Lubricating composition for motorcycle applications

Abstract

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

Description

Technical Field

[0001] The present disclosure relates to lubricating compositions, and in particular lubricating compositions suitable for use in motorcycle applications. Background Art

[0002] In motorcycles, common fluids provide lubrication to the engine and the transmission system components including transmission and / or clutch. Therefore, the lubricating composition used in motorcycle engines is formulated to have a balance of friction characteristics suitable for the transmission system and lubrication characteristics suitable for the engine. This is in contrast to lubricants used for other vehicles (such as passenger cars), in which the engine or crankcase is lubricated by one type of lubricant, and the transmission system is lubricated by a second type of lubricant. This dual-purpose fluid in motorcycle applications brings challenges in formulation, because it is usually necessary to reduce the viscosity and friction in the engine crankcase to improve fuel economy, but on the other hand, it is usually important to keep enough friction in the transmission and / or clutch assembly for proper operation. Therefore, lubricants formulated for passenger car applications are generally not suitable for motorcycle applications, because, among other features, passenger car fluids may show that the friction coefficient is too low for lubricating the transmission and / or clutch components of most motorcycles.

[0003] Given the unique challenges of motorcycle lubricants, standards have been developed within the industry to properly assess the quality and performance of lubricants for motorcycle applications. In particular, JASO T 903:2016 defines the performance requirements for motorcycle lubricants and specifies, among other standards, the amount of copper produced due to corrosion when measured using the Indiana Stirred Oxidation Test (ISOT) and when operating under the JIS K2514 test standard, the total base number (TBN) retention, and the sulfur retention. Dithiophosphate compounds, particularly metal dihydrocarbyl dithiophosphate compounds such as zinc dihydrocarbyl dithiophosphate (ZDDP), etc., are commonly used as anti-wear additives in passenger car crankcase lubricants, but these additives tend to be problematic in motorcycle lubricants in terms of negatively affecting copper corrosion, TBN retention, and / or sulfur retention. Summary of the invention

[0004] The present disclosure relates to a motorcycle lubricating composition that exhibits good copper corrosion, TBN retention, and / or sulfur retention that are typical of motorcycle fluids. In one embodiment or method, the motorcycle lubricant comprises: one or more base oils of lubricating viscosity; a small amount of an additive package, the additive package including a metal-containing sulfonate, salicylate, and / or phenate detergent; a dispersant that provides at least about 400 ppm 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 phosphorus to the motorcycle lubricating composition; and wherein the one or more metal dihydrocarbyl dithiophosphate compounds have an average of at least 14 total carbons per phosphorus atom, and wherein their hydrocarbyl groups are derived from at least about 80 mole percent of a straight or branched primary alcohol.

[0005] In other methods or embodiments, the motorcycle lubricant of the previous paragraph may include optional features or embodiments in any combination. These optional features or embodiments may include one or more of the following: wherein the hydrocarbyl groups of the one or more metal dihydrocarbyl dithiophosphate compounds are derived from about 100 mole % of a linear or branched primary alcohol; and / or wherein the one or more metal dihydrocarbyl dithiophosphate compounds have an average of at least 16 total carbons per phosphorus atom; and / or wherein the lubricating composition exhibits no more than about 90 ppm copper leaching, a TBN retention of up to about 25% (or about 10% to about 25%), and a sulfur retention of at least about 95% (or about 95% to 100%) when measured according to the Indiana Agitation Oxidation Test (ISOT) run in accordance with the JIS K2514 test standard; and / or wherein the metal dihydrocarbyl dithiophosphate compound has a structure of Formula I:

[0006]

[0007] wherein each R is independently a linear or branched 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 wherein each R is a linear or branched C8 to C10 hydrocarbyl group and is derived from a primary alcohol; and / or wherein A is zinc and wherein each R has about 100 mole % of a hydrocarbyl group derived from a C8 to C10 primary alcohol; and / or wherein the one or more metal dihydrocarbyl dithiophosphate compounds provide up to about 3,000 ppm of phosphorus to the motorcycle lubricating composition; and / or wherein the detergent is a calcium sulfonate detergent and / or a calcium phenate detergent having a TBN of 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; and / or wherein the lubricating composition comprises up to about 1 wt % of an aminic antioxidant; and / or wherein the aminic antioxidant is selected from aromatic amines, alkylated diphenylamines, nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, or combinations thereof; and / or wherein the lubricating composition comprises from about 0.5 wt % to about 5 wt % of a dispersant; and / or wherein the dispersant is obtainable by reacting a hydrocarbyl-substituted acylating agent with a nitrogen source; and / or wherein the acylating agent is maleic anhydride and the nitrogen source is selected from ammonia, polyalkylene polyamines, or combinations thereof; and / or wherein the nitrogen source is a polyalkylene polyamine selected from a mixture of polyethylene polyamines having an average of 5 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, or combinations thereof.

[0008] In other methods or embodiments, a method of lubricating a motorcycle engine, transmission and clutch assembly with a lubricating composition to achieve good copper corrosion, TBN retention and / or sulfur retention is described herein. In one aspect, the method includes lubricating a motorcycle engine, transmission and clutch assembly with a lubricating composition provided by a common lubricant reservoir; and wherein the lubricating composition comprises one or more base oils of lubricating viscosity; a small amount of an additive package, the additive package comprising a metal-containing sulfonate, salicylate and / or phenate detergent; a dispersant providing at least about 400 ppm nitrogen; at least one amine 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 wherein the one or more metal dihydrocarbyl dithiophosphate compounds have an average of at least 14 total carbons per phosphorus atom, and wherein their hydrocarbyl groups are derived from at least about 80 mole percent of a straight or branched primary alcohol.

[0009] In other methods or embodiments, the method described in the previous 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: wherein the hydrocarbyl groups of the one or more metal dihydrocarbyl dithiophosphate compounds are derived from about 100 mole % of a linear or branched primary alcohol; and / or wherein the one or more metal dihydrocarbyl dithiophosphate compounds have an average of at least 16 total carbons per phosphorus atom; and / or wherein the lubricating composition exhibits no more than about 90 ppm copper leaching, a TBN retention of up to about 25% (or about 10% to about 25%), and a sulfur retention of at least about 95% (or about 95% to about 100%) when measured according to the Indiana Agitation Oxidation Test (ISOT) run under the JIS K2514 test standard; and / or wherein the metal dihydrocarbyl dithiophosphate compound has a structure of Formula I:

[0010]

[0011] wherein each R is independently a linear or branched 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 wherein each R is a linear or branched C8 to C10 hydrocarbyl group and is derived primarily from primary alcohols; and / or wherein A is zinc and wherein each R has about 100 mole % of hydrocarbyl groups derived from C8 to C10 primary alcohols; and / or wherein the one or more metal dihydrocarbyl dithiophosphate compounds provide up to about 3,000 ppm phosphorus to the lubricating composition;

[0012] In yet other methods or embodiments, a lubricating composition is used, the lubricating composition comprising: one or more base oils of lubricating viscosity; a small amount of an 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; wherein the one or more metal dihydrocarbyl dithiophosphate compounds provide at least about 800 ppm phosphorus to the motorcycle lubricating composition; and wherein the one or more metal dihydrocarbyl dithiophosphate compounds have an average of at least 14 total carbons per phosphorus atom and wherein their hydrocarbyl groups are derived from at least about 80 mole percent of a linear or branched primary alcohol to achieve no more than about 90 ppm copper leaching, a TBN retention of up to about 25% (or about 10% to about 25%), and / or a sulfur retention of at least about 95% (or about 95% to 100%) when measured according to the Indiana Stirred Oxidation Test (ISOT) run in accordance with the JIS K2514 test standard. DETAILED DESCRIPTION

[0013] The present disclosure relates to lubricating compositions configured for motorcycles, and also to methods of lubricating motorcycle engines, transmissions, and clutch assemblies with a single lubricating composition typically provided by a common engine oil tank. As noted in the background, lubricants for motorcycles are required to lubricate more than just the engine crankcase. Motorcycle lubricants also lubricate drivetrain components, including transmissions and clutches. Therefore, the testing and requirements for the fluid are very different from typical lubricants used for passenger car motor oils.

[0014] In particular, copper leaching, TBN retention and sulfur retention of the Indiana Stirred Oxidation Test (ISOT) run under the JIS K2514 standard as listed in JASO T 903:2016 are fluid requirements that are not usually associated with crankcase lubricants for passenger car motor oils. Antiwear agents such as metal dihydrocarbyl dithiophosphate compounds (including but not limited to ZDDP compounds) are commonly used in passenger car motor oils, but when used in motorcycle oils, such additives traditionally result in less desirable performance in such ISOT tests. Unexpectedly, it has been found that certain metal dihydrocarbyl dithiophosphate compounds with a specific configuration provide ISOT performance that passes for motorcycle applications. More specifically, metal dihydrocarbyl dithiophosphate compounds having a minimum number of carbons per phosphorus atom and having a hydrocarbyl group primarily derived from a straight or branched primary alcohol surprisingly achieve ISOT performance that passes when used in motorcycle lubricants. On the other hand, lubricants containing metal dihydrocarbyl dithiophosphate compounds that do not meet such criteria fail to achieve passing ISOT performance suitable for motorcycle lubrication.

[0015] In one method or embodiment, a motorcycle lubricating composition is described herein, the motorcycle lubricating composition comprising one or more base oils of lubricating viscosity and a small amount of an additive package, the 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. To achieve a passing ISOT performance, the one or more metal dihydrocarbyl dithiophosphate compounds provide at least about 800 ppm phosphorus to the motorcycle lubricating composition, and have an average of at least 14 total carbons per phosphorus atom, and wherein their hydrocarbyl groups are derived from at least about 80 mole percent of a straight or branched primary alcohol. In other methods or embodiments, the hydrocarbyl groups of the one or more metal dihydrocarbyl dithiophosphate compounds in the motorcycle lubricant are derived from about 100 mole percent of a straight or branched primary alcohol, and have an average of at least 16 total carbons per phosphorus atom. When a motorcycle lubricant includes such additives, the lubricating composition exhibits performance equal to or better than prior motorcycle lubricants with respect to copper corrosion / leaching, TBN retention, and / or sulfur retention, and in such context, the fluids herein exhibit no more than about 90 ppm copper leaching (preferably about 50 ppm to about 90 ppm), a TBN retention of up to about 25% (preferably about 10% to about 25% or about 14% to about 25%), and a sulfur retention of at least about 95% (preferably about 95% to about 100%) when measured according to the Indiana Agitation Oxidation Test (ISOT) run under the JIS K2514 test standard.

[0016] Metal dihydrocarbyl dithiophosphate compounds

[0017] The motorcycle lubricant herein may 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 herein provide at least about 800 ppm of phosphorus to the motorcycle lubricant, in other approaches, about 800 ppm to about 3,000 ppm of phosphorus, or about 900 ppm to about 2,500 ppm of phosphorus, or about 1000 ppm to about 2,000 ppm of phosphorus, or about 1000 ppm to about 1500 ppm of phosphorus. As described above, metal dihydrocarbyl dithiophosphate compounds suitable for motorcycle applications have a specific structure and contain at least 14 total carbons per phosphorus atom, and their hydrocarbyl groups are derived from at least about 80 mol% of a straight or branched primary alcohol. In other approaches or embodiments, the hydrocarbyl groups are derived from about 100 mol% of a straight or branched primary alcohol, and on average each phosphorus atom has at least 16 total carbons provided by a straight or branched primary alcohol. In yet other methods, the hydrocarbyl groups are derived from about 80 mol% to about 100 mol% of a linear or branched primary alcohol, and on average each phosphorus atom has 14 to 16 total carbons provided by a linear or branched primary alcohol, and preferably a branched primary alcohol. As used herein, the average total carbons per phosphorus atom of the metal dihydrocarbyl dithiophosphate is determined by the following equation: 2×[(carbons in alcohol 1)(mol%)+(carbons in alcohol 2)(mol%)+(carbons in alcohol 3)(mol%)+…], as long as the alcohol used to form the metal dihydrocarbyl dithiophosphate compound also meets the required amount of primary alcohol found herein.

[0018] Suitable metal dihydrocarbyl dithiophosphate compounds may include 5 wt % to about 10 wt % of metal (such as about 6 wt % to about 9 wt % of metal) and about 8 wt % to about 18 wt % of sulfur (such as about 12 wt % to about 18 wt % of sulfur or about 8 wt % to about 15 wt % of sulfur). Suitable metal dihydrocarbyl dithiophosphate compounds may include dihydrocarbyl dithiophosphate metal salts, wherein the metal may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc or a combination thereof. Preferably, the metal is zinc.

[0019] The alkyl groups on the metal dialkyl dithiophosphate compounds herein can be derived from primary alcohols, secondary alcohols, phenols and / or mixtures thereof, as long as the relationship of the average carbon number of each phosphorus atom and the mole % of the primary alcohol source is satisfied. For example, all alkyl groups of the metal dialkyl dithiophosphate compounds herein can be derived from primary alcohols (such as 2-ethylhexanol) or from mixtures of primary alcohols and secondary alcohols (such as 2-ethylhexanol, isobutyl alcohol and isopropyl alcohol), as long as the resulting metal dialkyl dithiophosphate compounds achieve the target carbon content per phosphorus atom and the primary alcohol content on the resulting molecule. For example and in one embodiment, about 80 mole % or more of the alkyl groups are derived from the primary alcohol of 2-ethylhexanol, and about 20 mole % or less of the alkyl groups are derived from secondary alcohols (such as isopropyl alcohol, methyl isobutyl carbinol, etc., and combinations thereof). In other embodiments, all alkyl groups on the metal dialkyl dithiophosphate compounds can be derived from primary alcohols, such as 2-ethylhexanol or other substances described below. Preferably, the metal dihydrocarbyl dithiophosphate compound is ZDDP obtained from 80 to 100 mole % of 2-ethylhexanol and may contain from about 6 to about 10 weight % phosphorus, from about 6 to about 9 weight % zinc, and from about 12 to about 18 weight % sulfur.

[0020] The metal dihydrocarbyl dithiophosphate compounds herein may be derived from, but are not limited to, alcohols selected from 2-ethylhexanol, methylheptanol, heptanol, octanol, nonanol, decanol, dodecanol, and / or variants thereof. Examples of suitable metal dihydrocarbyl dithiophosphate compounds include, but are not limited to: O,O-di(C 8-14 zinc dithiophosphate; zinc O,O-bis(2-ethylhexyl) dithiophosphate; zinc O,O-diisooctyl dithiophosphate; zinc O,O-bis(dodecylphenyl) dithiophosphate; zinc O,O-diisodecyl dithiophosphate; zinc O,O-bis(6-methylheptyl) dithiophosphate; zinc O,O-dioctyl dithiophosphate; zinc O,O-dipentyl dithiophosphate; zinc O-(2-methylbutyl)-O-(2-methylpropyl) dithiophosphate; and zinc O-(3-methylbutyl)-O-(2-methylpropyl) dithiophosphate, or a combination thereof.

[0021] In methods or embodiments, the metal dihydrocarbyl dithiophosphate compound suitable for use in motorcycle lubricants may also have the structure of Formula I:

[0022]

[0023] Each R in its formula I independently contains 6 to 18 carbon atoms, or 6 to 12 carbon atoms, or about 8 to 10 carbon atoms, as long as each phosphorus atom has at least 14 total carbons on average, and preferably at least 16 total carbons or 14 to 16 carbons. For example, each R can independently be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, amyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. The number of carbon atoms in each R group in the above formula is generally about 3 or more, about 4 or more, about 6 or more, or about 8 or more. Each R group can average 6 to 10 carbons, and preferably 8 to 10 carbons. Preferably, each R can be straight or branched 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, and preferably, A is zinc. When the metal dihydrocarbyl dithiophosphate compound has the structure shown in Formula I and A is zinc, the compound may have about 4 wt % to about 9 wt % phosphorus and about 6 wt % to about 9 wt % zinc.

[0024] In some methods or embodiments, it is understood in the art that a more precise representation of the sulfur-zinc coordination arrangement can be represented by the symmetrical arrangement shown below, i.e., the chemical structure of Formula II, which can be used interchangeably herein 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 (such as tetramers).

[0025]

[0026] Dialkyl dithiophosphate metal salts can be prepared according to known techniques, i.e., first, dialkyl dithiophosphoric acid (DDPA) is formed by reacting one or more alcohols or phenols with P2S5, and then the formed DDPA is neutralized with a metal compound such as zinc oxide. For example, DDPA can be prepared by reacting a mixture of alcohols with P2S5, the mixture of alcohols comprising a suitable amount of primary alcohol (and, if desired, a suitable blend of primary and secondary alcohols). In this case, DDPA comprises an alkyl group derived primarily from a primary alcohol or both a primary alcohol and a secondary alcohol as required to meet the primary alcohol content required in the final product. Alternatively, a variety of DDPAs can be prepared, wherein the alkyl group on one DDPA is completely derived from a secondary alcohol, and the alkyl group on another DDPA is completely derived from a primary alcohol. The DDPAs are then blended together to form a mixture of DDPAs having an alkyl group satisfying the primary alcohol content.

[0027] Detergent system

[0028] The motorcycle lubricating composition herein may also include a detergent or detergent system. In an embodiment, the detergent or detergent system generally comprises one or more detergent additives, including one or more basic salts or alkali metal salts of phenates, sulfonates, calixarates, salicylates, carboxylic acids, their sulfurized derivatives, or combinations thereof. Preferably, the detergent is a metal-containing sulfonate, salicylate, and / or phenate, and most preferably is calcium phenate, calcium sulfonate, or combinations thereof.

[0029] Suitable detergents and methods of making them are described in more detail in a number of patent publications, including US 7,732,390 and references cited therein, which are incorporated herein by reference. The lubricant compositions herein may contain from about 0.1 wt % to about 5 wt % of individual and / or total detergent additives, and from about 0.15 wt % to about 3 wt % in other approaches, and from about 0.5 wt % to 2.6 wt % of individual and / or total detergent additives in yet other approaches.

[0030] The detergent system provides total detergent metals in an amount of greater than about 1,000 ppm total metals, and 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 metal is calcium, sodium and / or magnesium, preferably calcium provided by phenates and sulfonates, and more preferably overbased calcium phenates and / or overbased calcium sulfonates.

[0031] Generally, suitable detergents in the system may include linear or branched alkali or alkaline earth metal salts, such as calcium, sodium or magnesium salts, of petroleum sulfonic acids and long chain mono- or di-alkyl aryl sulfonic acids, wherein the aryl groups are benzyl, tolyl and xylyl, and / or various phenates or phenate derivatives. Examples of suitable detergents include, but are not limited to, low base / neutral and high base forms of calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calcium calixarate, calcium salicyclic acid, calcium salicylate, calcium carboxylate, calcium phosphate, calcium monothiophosphate and / or dithiophosphate, calcium alkyl phenate, sulfur-coupled alkyl phenate calcium compounds, methylene-bridged calcium phenate, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salicyclic acid, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium monothiophosphate and / or dithiophosphate, magnesium alkyl phenate, sulfur-coupled alkyl phenate magnesium compounds, methylene-bridged magnesium phenate, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixarate, sodium salicyclic acid, sodium salicylate, sodium carboxylate, sodium phosphate, sodium monothiophosphate and / or dithiophosphate, sodium alkyl phenate, sulfur-coupled sodium alkyl phenate compounds, or methylene-bridged sodium phenate.

[0032] The detergent additive may be neutral, low basic or high basic, and is preferably high basic as described above. It should be understood that high basic detergent additives are well known in the art and may be alkali metal or alkaline earth metal high basic 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 acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid or an aliphatic substituted phenol.

[0033] The term "overbased" relates to metal salts, such as metal salts of sulfonic acids, carboxylic acids, salicylic acids and / or phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level exceeding 100% (i.e., they may contain 100% of the theoretical amount of metal required to convert the acid into its "normal" salt, "neutral" salt). The expression "metal ratio" is usually abbreviated as MR, which is used to represent the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, MR is one, and in overbased salts MR is greater than one. They are often referred to as overbased, superbased or super-based salts, and may be salts of organic sulfuric acid, carboxylic acid, or phenol.

[0034] As used herein, the term "TBN" is used to represent the total base number in mg KOH / g as measured by the ASTM D2896 method. The total base number (TBN) of the overbased detergent of the lubricating oil composition herein can be about 200 mg KOH / gram or greater, or about 250 mg KOH / gram or greater, or about 350 mg KOH / gram or greater, or about 375 mg KOH / gram or greater, or about 400 mg KOH / gram or greater, or about 200 mg KOH / gram to about 400 mg KOH / gram, or any range therein. The overbased detergent can have a metal to matrix 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.

[0035] 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 salicylates, overbased calcium carboxylates, overbased calcium phosphates, overbased calcium monothiophosphates and / or dithiophosphates, overbased calcium alkylphenates, overbased sulfur-coupled alkylphenate calcium compounds, overbased methylene-bridged calcium phenates, overbased magnesium phenates, overbased sulfur-containing magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salicylates, overbased magnesium carboxylates, overbased magnesium phosphates, overbased magnesium monothiophosphates and / or dithiophosphates, overbased magnesium alkylphenates, overbased sulfur-coupled alkylphenate magnesium compounds, or overbased methylene-bridged magnesium phenates.

[0036] Preferably, the detergent is highly alkaline, but the motorcycle lubricant herein may also include low-base or neutral detergents. When low-base or neutral detergents are incorporated into the detergent system, they typically have a TBN of at most 175 mg KOH / g, at most 150 mg KOH / g, at most 100 mg KOH / g, or at most 50 mg KOH / g. Low-base / neutral detergents may include calcium-containing, sodium-containing, or magnesium-containing detergents. Examples of suitable low-base / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate.

[0037] In some embodiments, the detergent used in the lubricants herein is an overbased calcium sulfonate, an overbased calcium phenate, or a combination thereof, each having a total base number of 200 to 400, and in other approaches from about 200 to about 350. The above TBN values ​​reflect the values ​​of the finished detergent component that has been diluted in a base oil.

[0038] In other embodiments, the TBN of the detergents herein may reflect the neat or undiluted form of the detergent components. For example, the fluids herein may include an overbased calcium or sodium sulfonate or an overbased calcium or sodium phenate as a neat additive having a TBN of about 300 to about 450, and in other approaches from about 380 to about 420, and / or an overbased magnesium sulfonate as a neat additive having a TBN of about 500 to about 700, and in other approaches from about 600 to about 700.

[0039] More specifically, the detergent systems herein comprise neutral to overbased calcium sulfonates or calcium phenates, neutral to overbased sodium sulfonates or sodium phenates, or neutral to overbased magnesium sulfonates or magnesium phenates. Preferably, the detergent provides at least about 1000 ppm of calcium from the overbased phenates or sulfonates (preferably about 1500 ppm to about 5,000 ppm of calcium). If the detergents provide sodium, they can provide at least about 90 ppm of sodium, at least about 180 ppm of sodium (preferably about 90 ppm to about 1,000 ppm of sodium or about 180 ppm to about 1,000 ppm of sodium). If the detergent provides magnesium, the detergent will provide about 90 ppm of magnesium, at least about 180 ppm of magnesium (preferably about 90 ppm to about 1,000 ppm of magnesium or about 180 ppm to about 1,000 ppm of magnesium).

[0040] Amine antioxidants

[0041] The motorcycle lubricant may also include one or more antioxidants, and preferably one or more aminic antioxidants. In methods or embodiments, the aminic antioxidant may include, but is 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 composition herein may be present in an amount to deliver up to about 400 ppm of nitrogen, or up to about 300 ppm of nitrogen, or up to about 200 ppm of nitrogen, or about 50 ppm to about 400 ppm of nitrogen, about 60 ppm to about 300 ppm of nitrogen, about 70 ppm to about 200 ppm of nitrogen, or about 80 ppm to about 100 ppm of nitrogen. In other approaches, the lubricating compositions herein may include up to about 1 wt % aminic antioxidant, or from about 0.1 wt % to about 1.0 wt % aminic antioxidant, in other approaches, from about 0.2 wt % to about 0.8 wt % or from about 0.2 wt % to about 0.6 wt % aminic antioxidant.

[0042] In some methods, the amine antioxidant may be one or more aromatic amine antioxidants, and may include, but are not limited to, diarylamines having the formula:

[0043]

[0044] wherein R' and R" each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. If substituted, suitable substituents for the aryl groups of R' and R" include aliphatic hydrocarbon groups such as alkyl groups having 1 to 30 carbon atoms, hydroxyl groups, halogen groups, carboxylic acid or ester groups or nitro groups. The aryl groups may be substituted or unsubstituted phenyl or naphthyl, in particular wherein one or both of these aryl groups are substituted with at least one alkyl group having 4 to 30 carbon atoms, preferably 4 to 18 carbon atoms, most preferably 4 to 9 carbon atoms. In the method, one or both aryl groups are substituted, for example monoalkylated diphenylamine, dialkylated diphenylamine, C9 alkylated diphenylamine or a mixture of monoalkylated diphenylamine and dialkylated diphenylamine.

[0045] 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, tetracosyldiphenylamine, benzene-α-naphthylamine, monooctylbenzene-α-naphthylamine, benzene-β-naphthylamine, monoheptyldiphenylamine, diheptyldiphenylamine, para-oriented styrenated diphenylamines, mixed butyloctyldiphenylamines, and mixed octylstyryldiphenylamines.

[0046] In other methods, suitable antioxidants may include aromatic amine antioxidants. Examples of phenolic antioxidants include N,N'-di-sec-butylphenylenediamine, 4-isopropylaminodiphenylamine, phenyl-α-naphthylamine, phenyl-α-naphthylamine, and cycloalkylated diphenylamine.

[0047] Dispersants

[0048] The lubricating composition of this paper also comprises one or more dispersants. In the method, one or more dispersants provide at least about 400ppm of nitrogen or at most about 1200ppm of nitrogen. In other methods, one or more dispersants provide about 400ppm to about 1000ppm of nitrogen or about 450ppm to about 950ppm of nitrogen. In some methods, one or more dispersants can be post-treated with boron compounds, and in such methods, at least about 40ppm of boron or at least about 80ppm of boron can also be provided to the lubricating composition, and in other methods, about 40ppm to about 700ppm, about 80ppm to about 700ppm, about 100ppm to about 700ppm, about 40ppm to about 500ppm, about 80ppm to about 500ppm, about 100ppm to about 500ppm, about 150ppm to about 700ppm or about 150ppm to about 500ppm of boron is provided. In other methods, the lubricating composition comprises up to about 5 wt % dispersant, or about 0.5 wt % to about 5.0 wt % dispersant, about 1 wt % to about 4 wt %, about 2 wt % to about 4 wt %, or about 2.5 wt % to about 3.5 wt % dispersant.

[0049] Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to being mixed into the lubricating composition and they generally do not provide any ash when added to the lubricant. Ashless dispersants are characterized by having 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, wherein the number average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000, or to about 5,000, or to about 3,000, or to about 2,000, or to about 1,500 as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in US 7,897,696 or US 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(ethylene amines).

[0050] In the method, the preferred amine for dispersant can be selected from polyamines and hydroxylamines. The example of usable polyamines includes but is not limited to diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and higher homologues, such as pentaethylamine hexamine (PEHA) etc. In some methods, so-called heavy polyamines that can be used are mixtures of polyalkylene-polyamines containing a small amount of low-level polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine) but mainly having 6 or more nitrogen atoms, 2 or more primary amines and oligomers more widely branched than conventional polyamine mixtures per molecule. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogens per molecule and having 2 or more primary amines per molecule.

[0051] In some embodiments, when polyisobutylene (PIB) is included, it is a preferred reactant for forming a 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 PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for embodiments of the present disclosure. Conventional PIBs typically have 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%.

[0052] As determined by GPC, HR-PIB with a number average molecular weight in the range of about 900 to about 3,000 may be suitable. Such HR-PIB is commercially available, or can be synthesized by polymerization of isobutylene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in US 4,152,499 and US 5,739,355. When used in the aforementioned thermal olefin reaction, HR-PIB can increase the conversion rate in the reaction and reduce the amount of sediment formation due to enhanced reactivity. Suitable methods are described in U.S. Patent No. 7,897,696. In one embodiment, the present disclosure also includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). PIBSA may have an average of about 1.0 and about 2.0 succinic acid moieties per polymer.

[0053] In some methods, any dispersant herein may also be post-treated by conventional methods by reacting with any of a variety of agents. Suitable post-treatment agents include boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. (See, e.g., US 7,645,726; US 7,214,649; US 8,048,831; and US 5,241,003, which are incorporated herein by reference in their entirety.)

[0054] When a boron compound is used as a post-treatment agent, the boron compound can be selected from boron oxides, boron halides, boric acids, and boric acid esters in an amount to provide about 0.1 atomic proportion of boron per mole of nitrogen composition to about 20 atomic proportion of boron per atomic proportion of nitrogen used. The dispersant post-treated with boron can contain from about 0.05 wt % to about 2.0 wt % boron, or in other approaches, from about 0.05 wt % to about 0.7 wt % boron, based on the total weight of the borated dispersant.

[0055] In other methods, carboxylic acids can be used as post-treatment agents and can be saturated or unsaturated mono-, di- or poly-carboxylic acids. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid and naphthalene dicarboxylic acid (e.g., 1,8-naphthalene dicarboxylic acid). Anhydrides can be used as post-treatment agents and can be selected from the group consisting of monounsaturated anhydrides (e.g., maleic anhydride), alkyl or alkylene substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride) and aromatic carboxylic anhydrides (including naphthalene dicarboxylic anhydride, e.g., 1,8-naphthalene dicarboxylic anhydride).

[0056] In one embodiment, the method of post-treating the 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 dispersant herein can be post-treated with more than one post-treating agent. For example, the copolymer can be post-treated with an amine first and then post-treated with a boron compound such as boric acid and an anhydride such as maleic anhydride and / or 1,8-naphthalic anhydride.

[0057] Base oil or base oil blend:

[0058] The base oil used in the motorcycle lubricating oil composition herein may be an oil of lubricating viscosity and is selected from any one of Group I to Group V base oils as specified by the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are generally listed in Table 1 below:

[0059] Table 1

[0060]

[0061] Class I, Class II and Class III are mineral oil treated raw materials.Class IV base oil contains real synthetic molecular substances, and these synthetic molecular substances are prepared by the polymerization of olefinically unsaturated hydrocarbons.Many Class V base oils are also real synthetic products, and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatic compounds, polyphosphates, polyvinyl ethers and / or polyphenylene ethers etc., but can also be naturally occurring oils, such as vegetable oils.It should be noted that although Class III base oil is derived from mineral oil, the strict treatment of these fluid experiences causes their physical properties to be very similar to some real synthetic oils, such as PAO.Therefore, the oil derived from Class III base oil can be called synthetic fluid in industry.The II+ class can include high viscosity index Class II.

[0062] The base oil blend used in the disclosed lubricating oil composition can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, a synthetic oil blend, or a mixture thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrorefined, unrefined, refined and re-refined oils and mixtures thereof.

[0063] Unrefined oils are those derived from natural, mineral or synthetic sources with little or no further purification. Refined oils are similar to unrefined oils, except that they have been subjected to one or more purification steps, which may result in improvements in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition does not contain edible oils or white oils.

[0064] Re-refined oils are also called reclaimed oils or reprocessed oils. Similar to refined oils, these oils are obtained using the same or similar processes. Typically these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0065] Mineral oil can include oil obtained by drilling or oil from plants and animals or any mixture thereof. For example, such oil can include but is not limited to castor oil, lard, olive oil, peanut oil, corn oil, soybean oil and linseed oil, and mineral lubricating oils, such as liquid petroleum and solvent-treated or acid-treated paraffin, cycloalkane or mixed paraffin-cycloalkane type mineral lubricating oils. If desired, such oil can be partially or completely hydrogenated. Oil derived from coal or shale can also be useful.

[0066] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomeric or copolymerized olefins (e.g., polybutene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), 1-decene trimers or oligomers, such as poly(1-decene), such materials are generally referred to as alpha-olefins, and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenylenes (e.g., biphenyl, terphenyl, alkylated polyphenylenes); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof or mixtures thereof. Polyalpha-olefins are typically hydrogenated materials.

[0067] Other synthetic lubricating oils include polyol esters, diesters, liquid esters (e.g., toluene phosphate, trioctyl phosphate, and diethyl ester of decanephosphonic acid) or polytetrahydrofuran containing phosphoric acid. Synthetic oils can be produced by Fischer-Tropsch reaction and can typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil can be prepared by Fischer-Tropsch gas-liquid synthesis procedures and other gas-liquid oils.

[0068] The major amount of the base oil included in the lubricating composition may be selected from Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the major amount of the base oil is different from the base oil resulting from providing an additive component or a viscosity index improver in the composition. In another embodiment, the major amount of the base oil included in the lubricating composition may be selected from Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the major amount of the base oil is different from the base oil resulting from providing an additive component or a viscosity index improver in the composition.

[0069] The oil of lubricating viscosity may be present in an amount that is the remainder remaining after the total amount of performance additives (including viscosity index improvers and / or pour point depressants and / or other top treatment additives) is subtracted from 100 wt %. For example, the oil of lubricating viscosity that may be present in the finished fluid may be a major amount, such as greater than about 50 wt %, greater than about 60 wt %, greater than about 70 wt %, greater than about 80 wt %, greater than about 85 wt %, or greater than about 90 wt %.

[0070] In some methods or embodiments, the base oil system herein comprises one or more of Group I to Group V base oils, and the lubricating composition herein may have a KV100 of about 2 cSt to about 20 cSt, in other methods about 2 cSt to about 15 cSt, about 3 cSt to about 12 cSt, in still other methods about 4 cSt to about 12 cSt, and in other methods about 6 cSt to about 12 cSt.

[0071] 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 to be synonymous and fully interchangeable terms that refer to a finished lubricating product comprising a major amount of a base oil component plus minor amounts of detergents and other optional components.

[0072] Optional additives

[0073] The lubricating oil compositions herein may also include a variety of optional additives to meet performance criteria. Those optional additives are described in the following paragraphs.

[0074] Other dispersants

[0075] The lubricating oil composition may optionally include one or more other dispersants or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals before being mixed into the lubricating oil composition, and they generally do not provide any ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides, wherein the number average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000 or to about 5,000 or to about 3,000 as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethylene amines).

[0076] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that may be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and higher homologues such as pentaethylaminehexamine (PEHA) and the like.

[0077] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of low polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine) but predominantly oligomers having 6 or more nitrogen atoms per molecule, 2 or more primary amines and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogen atoms per molecule and 2 or more primary amines per molecule. Heavy polyamines contain greater than 28 wt% (e.g., >32 wt%) total nitrogen and an equivalent weight of primary amine groups of 120 g / equivalent to 160 g / equivalent.

[0078] In some processes, suitable polyamines are generally referred to as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, typically less than about 80%.

[0079] Typically, PAM has 8.7 to 8.9 milliequivalents / gram of primary amine (equivalent weight of primary amine is 115 to 112 grams / equivalent) and a total nitrogen content of about 33 to 34 weight percent. Heavier PAM oligomer cuts have little TEPA, only very small amounts of PEHA, but contain predominantly oligomers with more than 6 nitrogens and more extensive branching, producing dispersants with improved dispersibility.

[0080] In one embodiment, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or to about 5000, or to about 3000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0081] In some embodiments, polyisobutylene (when included) 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 PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for use in embodiments of the present disclosure. Conventional PIBs typically have 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%.

[0082] HR-PIB with a number average molecular weight in the range of about 900 to about 3000 as determined by GPC may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerizing isobutylene in the presence of a non-chlorinated catalyst (such as boron trifluoride), as described in U.S. Pat. No. 4,152,499 to Boerzel et al. and U.S. Pat. No. 5,739,355 to Gateau et al. When used in the aforementioned hot olefin reaction, HR-PIB can increase the conversion rate in the reaction due to enhanced reactivity, as well as reduce the amount of sediment formation. Suitable methods are described in U.S. Pat. No. 7,897,696.

[0083] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA may have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.

[0084] Chromatographic techniques may be used to determine the % activity of the alkenyl or alkyl succinic anhydride. This method is described in columns 5 and 6 of US Pat. No. 5,334,321.

[0085] The percent conversion of the polyolefin was calculated from the % activity using the equations in columns 5 and 6 of US Patent No. 5,334,321.

[0086] Unless otherwise indicated, all percentages are by weight (wt%) and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards with number average molecular weights ranging from 180 to about 18,000 as calibration reference.

[0087] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from olefin maleic anhydride copolymers. For example, the dispersant may be described as polyPIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0088] Suitable classes of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants, which can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can react with functionalized OCPs is described in U.S. Pat. Nos. 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383; and / or are commercially available.

[0089] One class of suitable dispersants is also 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.

[0090] A class of suitable dispersants may also be high molecular weight esters or half ester amides. Suitable dispersants may also be post-treated by conventional methods by reaction with any of a variety of reagents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. US 7,645,726; US 7,214,649; and US 8,048,831 are incorporated herein by reference in their entirety.

[0091] In addition to carbonate and boric acid post-treatments, both compounds can 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 outlined in columns 27 to 29 of U.S. Patent No. 5,241,003, incorporated herein by reference. Such treatments include treatment with: inorganic phosphorous acid or anhydrous (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as described above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948, 386); epoxides, polyepoxides or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea or guanidine (e.g., U.S. Pat. Nos. 3,312,619; 3,865,813; and GB 1,065,595); organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and GB 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketenes (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkane sultones (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. Nos. 3,954,6 39); 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 GB Patent No. 2,140,811); hydroxy protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,646,860; and 4,670,170);Nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent GB 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxy aliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; 4,713,189); oxidants (e.g., combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. No. 4,379,064); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086; 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229; 5,030,249; 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. Nos. 3,865,000; 3,986,010); ,740); a combination of a hydroxyaliphatic carboxylic acid and boric acid (e.g., U.S. Pat. No. 4,554,086); a combination of a hydroxyaliphatic carboxylic acid, then formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322); a combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064); a combination of formaldehyde and phenol and then glycolic acid (e.g., U.S. Pat. No. 4,699,724); a combination of a hydroxyaliphatic carboxylic acid or oxalic acid, and then a diisocyanate (e.g., U.S. Pat. No. 4,713,191); an inorganic acid or anhydride of phosphorus or a portion thereof Combinations of part or all of the sulfur analogues with boron compounds (e.g., U.S. Pat. No. 4,857,214); organic diacids, then unsaturated fatty acids, then nitrosoaromatic amines, optionally followed by boron compounds, and then ethanolating agents (e.g., U.S. Pat. No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Pat. No. 4,963,278); combinations of aldehydes and triazoles, then boron compounds (e.g., U.S. Pat. No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are incorporated herein in their entirety. ;

[0092] The TBN of a suitable dispersant may be from about 10 mg KOH / g to about 65 mg KOH / g dispersant on an oil-free basis, which is comparable to about 5 TBN to about 30 TBN if measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0093] In yet other embodiments, the optional dispersant additive can be a hydrocarbyl-substituted succinamide or succinimide dispersant. In the method, the hydrocarbyl-substituted succinamide or succinimide dispersant is derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, and wherein the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear chain hydrocarbyl group or a branched chain hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 as measured by GPC using polystyrene as a calibration reference.

[0094] In some methods, the polyalkylene polyamine used to form the dispersant has the formula

[0095]

[0096] wherein each R and R' is independently a divalent C1 to C6 alkylene linking group, each R1 and R2 is independently hydrogen, a C1 to C6 alkyl group, or together with the nitrogen atom to which they are attached, forms a 5-membered or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer between 0 and 8. In other methods, 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.

[0097] Dispersants, if present, can be used in an amount sufficient to provide up to about 20 wt % based on the final weight of the lubricating oil composition. Another amount of dispersant that can be used can be about 0.1 wt % to about 15 wt %, or about 0.1 wt % to about 10 wt %, or about 0.1 wt % to about 8 wt %, or about 1 wt % to about 10 wt %, or about 1 wt % to about 8 wt %, or about 1 wt % to about 6 wt %, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type of dispersant or a mixture of two or more types of dispersants can be used in any desired ratio.

[0098] Other antioxidants

[0099] The lubricating oil composition herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfided olefins, phosphorus sulfided terpenes, sulfided esters, aromatic amines, alkylated diphenylamines (e.g., nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine), phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

[0100] Hindered phenol antioxidants may contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group may also be substituted with a hydrocarbyl group and / or a bridging group connected to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, Irganox®, which may be purchased from BASF. TM L-135 or the addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein 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 and may include Ethanox acrylate available from Albemarle Corporation. TM 4716.

[0101] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols such that each antioxidant may be present in an amount sufficient to provide up to about 5 weight percent based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 weight percent to about 1.5 weight percent diarylamine and about 0.4 weight percent to about 2.5 weight percent high molecular weight phenol based on the final weight of the lubricating oil composition.

[0102] 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, nonadecaene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecaene, or mixtures thereof, and dimers, trimers, and tetramers thereof are particularly suitable olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene (such as 1,3-butadiene) and an unsaturated ester (such as butyl acrylate).

[0103] Another class of sulphurized olefins includes sulphurized fatty acids and esters thereof. Fatty acids are usually obtained from vegetable oils or animal oils and usually contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Usually, fatty acids are obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as alpha-olefins.

[0104] In another alternative embodiment, the antioxidant composition contains a platinum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the ratio of the phenolic to amine to platinum-containing component treatment rate is (0 to 3):(0 to 3):(0 to 3).

[0105] The one or more antioxidants may be present in a range from about 0 wt % to about 20 wt %, or from about 0.1 wt % to about 10 wt %, or from about 1 wt % to about 5 wt % of the lubricating oil composition.

[0106] Other anti-wear agents

[0107] The lubricating oil composition herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyl dithiophosphates; phosphates or their salts; phosphate esters; phosphites; phosphorus-containing carboxylates, ethers or amides; sulphurized olefins; compounds containing thiocarbamates, including thiocarbamates, alkylene coupled thiocarbamates and bis(S-alkyl dithiocarbamoyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamates. Phosphorus-containing antiwear agents are more fully described in European Patent 612 839. The metal in the dialkyl dithiophosphate may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. A suitable antiwear agent may be zinc dialkyl dithiophosphate.

[0108] Other examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulphurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene coupled thiocarbamates and bis(S-alkyldithiocarbamoyl) disulfides). The tartrate or tartrimide may contain an alkyl ester group, wherein the total number of carbon atoms in the alkyl group may be at least 8. In one embodiment, the antiwear agent may include a citrate ester.

[0109] The antiwear agent may be present in a range comprising about 0 wt % to about 15 wt %, or about 0.01 wt % to about 10 wt %, or about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % of the lubricating oil composition.

[0110] Boron compounds

[0111] The lubricating oil composition herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057. The boron-containing compound, if present, may be used in an amount sufficient to provide up to about 8 wt %, about 0.01 wt % to about 7 wt %, about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % of the lubricating oil composition.

[0112] Additional detergent

[0113] The lubricating oil composition may optionally further comprise one or more neutral, low-basic or high-basic detergents and mixtures thereof. Suitable detergent bases include benzoates, sulfur-containing benzoates, sulfonates, calixformates, salicylates, salicylates, carboxylic acids, phosphoric acid, monothiophosphoric acid and / or dithiophosphoric acid, alkylphenols, sulfur-coupled alkylphenol compounds or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in a number of patent publications, including US 7,732,390 and references cited therein.

[0114] The detergent matrix may be salified with an alkali metal or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals such as magnesium or calcium, such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or dialkyl aryl sulfonic acids, wherein the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenates, sulfur-containing calcium phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylates, calcium phosphates, calcium monothiophosphates and / or dithiophosphates, calcium alkyl phenates, sulfur-coupled alkyl phenate calcium compounds, methylene-bridged calcium phenates, magnesium phenates, sulfur-containing magnesium phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylates, magnesium phosphates, magnesium monothiophosphates and / or dithiophosphates, magnesium alkyl phenates, sulfur-coupled alkyl phenate magnesium compounds, methylene-bridged magnesium phenates, sodium phenates, sulfur-containing sodium phenates, sodium sulfonates, sodium calixarates, sodium salixarates, salixarates), sodium salicylates, sodium carboxylates, sodium phosphates, sodium monothiophosphates and / or sodium dithiophosphates, sodium alkylphenols, sodium sulfur-coupled alkylphenol compounds, or sodium methylene-bridged phenols.

[0115] 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.

[0116] The term "overbased" relates to metal salts, such as metal salts with sulfonic acids, carboxylic acids and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level exceeding 100% (i.e., they may contain 100% of the theoretical amount of metal required to convert the acid into its "normal" salt, "neutral" salt). The expression "metal ratio" is usually abbreviated as MR, which is used to represent the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in overbased salts, MR is greater than one. They are often referred to as overbased, superbased or super-based salts, and may be salts of organic sulfuric acid, carboxylic acid, or phenol.

[0117] The total base number (TBN) of the overbased detergent of the lubricating oil composition may be about 200 mg KOH / g or greater, or as other examples, 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. TBN is measured by the method of ASTM D2896.

[0118] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased sulfur-containing calcium phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salicylates, overbased calcium carboxylates, overbased calcium phosphates, overbased calcium monothiophosphates and / or dithiophosphates, overbased calcium alkylphenates, overbased sulfur-coupled alkylphenate calcium compounds, overbased methylene-bridged calcium phenates, overbased magnesium phenates, overbased sulfur-containing magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salicylates, overbased magnesium carboxylates, overbased magnesium phosphates, overbased magnesium monothiophosphates and / or dithiophosphates, overbased magnesium alkylphenates, overbased sulfur-coupled alkylphenate magnesium compounds, or overbased methylene-bridged magnesium phenates.

[0119] The overbased calcium phenate detergent has a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g, all as measured by the method of ASTM D 2896. When such detergent compositions are formed in an inert diluent (e.g., process oil, typically mineral oil), the total base number reflects the basicity of the overall composition, which includes the diluent and any other materials that may be contained in the detergent composition (e.g., accelerators, etc.).

[0120] The metal to matrix ratio of the overbased detergent may be 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10:1. In some embodiments, the detergent is effective in reducing or preventing rust in the engine or other automotive parts (such as transmissions or gears). The detergent may be present in the lubricating composition at about 0 wt % to about 10 wt %, or about 0.1 wt % to about 8 wt %, or about 1 wt % to about 4 wt %, or greater than about 4 wt % to about 8 wt %.

[0121] Extreme Pressure Agents

[0122] The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme pressure (EP) agents soluble in oil include sulfur-containing and chlorine-containing sulfur-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 bisdibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl oleate, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphites such as dialkyl phosphites and trialkyl phosphites, for example, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, amylphenyl phosphite; diamylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol dioate; amine salts of alkyl and dialkyl phosphoric acids, including, for example, amine salts of the reaction product of dialkyldithiophosphoric acids with propylene oxide; and mixtures thereof.

[0123] Friction modifiers

[0124] The lubricating oil composition 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, glycerides, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of polyols, and one or more aliphatic or aromatic carboxylic acids, and the like.

[0125] Suitable friction modifiers may contain a hydrocarbyl group selected from a linear, branched or aromatic hydrocarbyl group or a mixture thereof, and may be saturated or unsaturated. The hydrocarbyl group may be composed of carbon and hydrogen or heteroatoms (such as sulfur or oxygen). The hydrocarbyl group may be in the range of about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester or a diester 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.

[0126] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally contain polar terminal groups (e.g., carboxyl or hydroxyl groups) covalently bonded to oleophilic hydrocarbon chains. An example of an organic ashless, nitrogen-free friction modifier is generally known as glyceryl monooleate (GMO), which may contain monoesters, diesters, and triesters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0127] Amine friction modifiers may include amines or polyamines. Such compounds may have linear chains, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and may contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have linear chains, saturated or unsaturated hydrocarbon groups, or mixtures thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0128] The amines and amides can be used as such or as adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid or mono-, di- or tri-alkyl borate esters. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, which is incorporated herein by reference in its entirety.

[0129] Friction modifiers may optionally be present in a range such as from about 0 wt % to about 10 wt %, or from about 0.01 wt % to about 8 wt %, or from about 0.1 wt % to about 4 wt %.

[0130] Molybdenum-containing components

[0131] The lubricating oil composition herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compound may have the functional properties of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil-soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organic molybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamates.

[0132] Suitable examples of molybdenum compounds that can be used include commercial materials sold under trade names such as: 822, A. 2000 and 855, and commercially available from Adeka Corporation S-165, S-200, S-300, S-310G, S-525, S-600, S-700 and S-710, and mixtures thereof. Suitable molybdenum components are described in US 5,650,381; US ​​RE 37,363 E1; US ​​RE 38,929 E1; and US RE 40,595 E1, the entireties of which are incorporated herein by reference.

[0133] In addition, the molybdenum compound can be an acidic molybdenum compound. Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, these compositions can provide molybdenum through molybdenum / sulfur complexes of basic nitrogen compounds, such as, for example, U.S. Patent Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94 / 06897, the entirety of which is incorporated herein by reference.

[0134] Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds such as those of the formula Mo3S k L n Q z Those and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having organic groups having a sufficient number of carbon atoms to make the compound soluble or dispersible in oil, n is 1 to 4, k is 4 to 7, Q is selected from neutral electron-donating compounds such as water, amines, alcohols, phosphines and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. There may be a total of at least 21 carbon atoms, such as at least 25, at least 30 or at least 35 carbon atoms in the organic groups of all ligands. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0135] 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.

[0136] Compounds containing transition metals

[0137] In another embodiment, the oil-soluble compound may be a compound containing a transition metal or a metalloid. The transition metal may include, but is 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.

[0138] In one embodiment, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or more than one of these functions. In one embodiment, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as a titanium (IV) alkoxide. Among the titanium-containing compounds that may be used in the disclosed technology or may be used to prepare the oil-soluble materials of the disclosed technology are various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, 2-ethylhexyl titanium; and other titanium compounds or complexes, including but not limited to titanium phenolate; titanium carboxylates, such as 2-ethyl-1-3-adipate titanium (IV) or titanium citrate or titanium oleate; and (triethanolamine) isopropoxide titanium (IV). Other forms of titanium encompassed within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., titanium dialkyl dithiophosphates), and titanium sulfonates (e.g., titanium alkylbenzene sulfonates), or generally, the reaction products of titanium compounds reacting with various acidic materials to form salts (e.g., oil-soluble salts). Titanium compounds can therefore be derived, in particular, from organic acids, alcohols, and glycols. Ti compounds can also exist in dimerized or oligomeric forms, containing Ti--O--Ti structures. Such titanium materials are commercially available or can be readily prepared by appropriate synthesis techniques that are readily known to those skilled in the art. They exist at room temperature in solid or liquid form, depending on the specific compound. They can also be provided in the form of solutions in suitable inert solvents.

[0139] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly, or it can be reacted with any of a number of materials, such as (a) a polyamine-based succinimide / amide dispersant having free, condensable-NH functional groups; (b) components of a polyamine-based succinimide / amide dispersant, i.e., alkenyl (or alkyl) succinic anhydride and a polyamine, (c) a hydroxyl-containing polyester dispersant prepared by reacting a substituted succinic anhydride with a polyol, an amino alcohol, a polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate can be reacted with other reagents, such as an alcohol, an amino alcohol, an ether alcohol, a polyether alcohol, or a polyol or a fatty acid, and the product thereof can be used directly to impart Ti to the lubricant, or alternatively, reacted with a succinic acid dispersant as described herein. As an example, 1 part (by mole) of tetraisopropyl titanate can be reacted with about 2 parts (by mole) of polyisobutylene-substituted succinic anhydride at 140°C to 150°C for 5 to 6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can also be reacted with a succinimide dispersant from polyisobutylene-substituted succinic anhydride and a polyethylene polyamine mixture (127 g + diluent oil) at 150°C for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0140] Another titanium-containing compound can be a titanium alkoxide with a C6 to C 25 The reaction product of carboxylic acid. The reaction product can be represented by the following formula:

[0141]

[0142] 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 is represented by the formula:

[0143]

[0144] wherein m+n=4 and n is in the range of 1 to 3, R4 is an alkyl moiety having a carbon atom range of 1 to 8, R1 is selected from a hydrocarbon group containing about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from a hydrocarbon group containing about 1 to 6 carbon atoms, or the titanium compound can be represented by the following formula:

[0145]

[0146] wherein x is in the range of 0 to 3, R1 is selected from a hydrocarbon group containing about 6 to 25 carbon atoms, R2 and R3 are the same or different and are selected from a hydrocarbon group containing about 1 to 6 carbon atoms, and R4 is selected from H, or C6 to C 25 A group consisting of carboxylic acid moieties.

[0147] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0148] In one embodiment, the oil soluble titanium compound may be present in the lubricating oil composition in an amount providing 0 ppm to 3000 ppm by weight titanium, or 25 ppm to about 1500 ppm by weight titanium, or about 35 ppm to 500 ppm by weight titanium, or about 50 ppm to about 300 ppm by weight.

[0149] Viscosity Index Improver

[0150] The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutylene, 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 alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, and suitable examples are described in U.S. Publication No. 20120101017A1.

[0151] The lubricating oil compositions herein may optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with amines, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0152] Viscosity Index Improvers and / or Dispersants The total amount of viscosity index improvers can be from about 0 wt % to about 20 wt %, from about 0.1 wt % to about 15 wt %, from about 0.1 wt % to about 12 wt %, or from about 0.5 wt % to about 10 wt % of the lubricating oil composition.

[0153] Other optional additives

[0154] Other additives may be selected to perform one or more functions required of the lubricating fluid.In addition, one or more of the mentioned additives may be multifunctional and provide functionality in addition to or different from the functionality described herein.

[0155] Lubricating oil compositions according to the present disclosure may optionally include other performance additives. Other performance additives may be additives other than the specified additives of the present disclosure and / or may include one or more of the following: metal passivators, viscosity index improvers, detergents, ashless TBN promoters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0156] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dithiothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

[0157] Suitable foam suppressors include silicon-based compounds such as siloxanes.

[0158] 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.

[0159] Suitable rust inhibitors can be single compounds or compound mixtures having properties that inhibit corrosion of ferrous metal surfaces. Non-limiting examples of useful rust inhibitors 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; and oil-soluble polycarboxylic acids including dimer acids and trimer acids, such as those produced by pine oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain α, ω-dicarboxylic acids with a molecular weight ranging from about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropylene succinic acid, tetradecene succinic acid, and hexadecene succinic acid. Another type of acidic corrosion inhibitor available is a half ester of alkenyl succinic acid and an alcohol (such as polyethylene glycol) having about 8 to about 24 carbon atoms in the alkenyl group. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0160] Rust inhibitors, if present, may be used in amounts 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.

[0161] Generally speaking, suitable lubricants including the detergent metals herein may include additive components within the ranges listed in the following table.

[0162] Table 2: Suitable lubricating compositions

[0163]

[0164]

[0165] The percentages (weight %) of each component above represent the weight percentage 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 to formulate the compositions described herein can be blended into the base oils individually or in various sub-combinations. However, it may be appropriate to blend all components simultaneously using an additive concentrate (i.e., additives plus diluents, such as hydrocarbon solvents). A fully formulated lubricant typically contains an additive package, referred to herein as a dispersant / inhibitor package or DI package, which will supply the desired features in the formulation.

[0166] definition

[0167] 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 edition. In addition, general principles of organic chemistry are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausolito: 1999 and March's Advanced Organic Chemistry, 5th edition, eds.: Smith, MB and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0168] As described herein, compounds may be optionally substituted with one or more substituents, such as described generally above, or as exemplified by particular classes, subclasses, and species of the present disclosure.

[0169] Unless it is obvious from the context, the term "major amount" should be understood to mean an amount greater than or equal to 50% by weight, such as from about 80% by weight to about 98% by weight, relative to the total weight of the composition. In addition, as used herein, the term "minor amount" should be understood to mean an amount less than 50% by weight relative to the total weight of the composition.

[0170] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense as is known to those skilled in the art. Specifically, it refers to a group having carbon atoms directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic substituted aromatic substituents, as well as cyclic substituents in which the ring is completed by another part of the molecule (e.g., two substituents together form an alicyclic group); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbyl groups which, in the context described herein, do not alter the predominant hydrocarbon substituent (e.g., halogens (especially chlorine and fluorine), hydroxyl, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxyl); (3) heterosubstituents, i.e., substituents which, in the context of this specification, although predominantly hydrocarbon in character, contain atoms other than carbon in a ring or chain that is otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents such as pyridyl, furanyl, thienyl, and imidazolyl. Generally, for every ten carbon atoms in the hydrocarbyl group, there are no more than two, or as another example, no more than one, non-hydrocarbon substituent group; in some embodiments, there are no non-hydrocarbon substituent groups in the hydrocarbyl group.

[0171] As used herein, the term "aliphatic" includes the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0172] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1-12 (e.g., 1-8, 1-6, or 1-4) carbon atoms. The alkyl group can be straight chain or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, n-pentyl, n-heptyl, or 2-ethylhexyl. The alkyl group may be substituted (i.e., optionally substituted) with one or more substituents such as halo, phosphate, cycloaliphatic [e.g., cycloalkyl or cycloalkenyl], heterocycloaliphatic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (cycloaliphatic)carbonyl, or (heterocycloaliphatic)carbonyl], nitro, cyano, acylamino [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino] The invention can be substituted with any of the following: alkyl, heteroarylcarbonylamino, heteroaralkylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl or heteroarylaminocarbonyl], amino [e.g., aliphatic amino, cycloaliphatic amino or heterocycloaliphatic amino], sulfonyl [e.g., aliphatic -SO2-], sulfinyl, sulfhydryl, sulfoxy, urea, thiourea, sulfamoyl, sulfonamide, pendant oxy, carboxyl, carbamoyl, cycloaliphatic oxy, heterocycloaliphatic oxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkyloxy, alkoxycarbonyl, alkylcarbonyloxy or hydroxy. Without limitation, some examples of substituted alkyl groups include carboxyalkyl (such as HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (such as (alkyl-SO2-amino)alkyl), aminoalkyl, amidoalkyl, (cycloaliphatic)alkyl, or haloalkyl.

[0173] 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 alkyl groups, alkenyl groups can be straight or branched. Examples of alkenyl groups include, but are not limited to, allyl, isopropenyl, 2-butenyl, and 2-hexenyl. The alkenyl group may be optionally substituted with one or more substituents such as halo, phosphate, cycloaliphatic [e.g., cycloalkyl or cycloalkenyl], heterocycloaliphatic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (cycloaliphatic)carbonyl, or (heterocycloaliphatic)carbonyl], nitro, cyano, amide [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino,

[0013] The invention further comprises a cycloalkylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl or heteroarylaminocarbonyl group, an amino group [e.g., an aliphatic amino, a cycloaliphatic amino, a heterocycloaliphatic amino or an aliphatic sulfonylamino group], a sulfonyl group [e.g., an alkyl-SO2-, a cycloaliphatic-SO2- or an aryl-SO2-], a sulfinyl group, a sulfhydryl group, a sulfoxy group, a urea, a thiourea, a sulfamoyl group, a sulfonamide group, a pendant oxy group, a carboxyl group, a carbamoyl group, a cycloaliphatic oxy group, a heterocycloaliphatic oxy group, an aryloxy group, a heteroaryloxy group, an aralkyloxy group, a heteroaralkyloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group or a hydroxyl group. Without limitation, some examples of substituted alkenyl groups include cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, arylalkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (such as (alkyl-SO2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (cycloaliphatic)alkenyl, or haloalkenyl.

[0174] 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. The alkynyl group may be straight or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. The alkynyl group may be optionally substituted with one or more substituents such as aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkoxy, aryloxy, heteroaryloxy, aralkoxy, nitro, carboxyl, cyano, halide, hydroxyl, sulfonic acid, mercapto, sulfenyl [e.g., aliphatic sulfenyl or cycloaliphatic sulfenyl], sulfinyl [e.g., aliphatic sulfinyl or cycloaliphatic sulfinyl], sulfonyl [e.g., aliphatic-SO2-, aliphatic amino-SO2-, or cycloaliphatic-SO2-], acylamino [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, , cycloalkylcarbonylamino, arylaminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfonamide, alkoxycarbonyl, alkylcarbonyloxy, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, acyl [e.g., (cycloaliphatic)carbonyl or (heterocycloaliphatic)carbonyl], amino [e.g., aliphaticamino], sulfoxy, pendant, carboxyl, carbamoyl, (cycloaliphatic)oxy, (heterocycloaliphatic)oxy or (heteroaryl)alkoxy.

[0175] As used herein, an "amino" group refers to an -NR X R Y , where R X and R Y Each of the amino groups is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxyl, thio, 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 is 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 represented by -NR X - indicates. X has the same meaning as defined above.

[0176] As used herein, a "cycloalkyl" group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3-10 (e.g., 5-10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cycloheptyl, octahydro-indenyl, 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.

[0177] As used herein, a "heterocycloalkyl" group refers to a 3-10 membered mono- or bicyclic (fused or bridged) (e.g., a 5- to 10-membered mono- or bicyclic) saturated ring structure in which one or more ring atoms is a heteroatom (e.g., N, O, S, or a combination thereof). Examples of heterocycloalkyl groups include piperidinyl, piperazinyl, tetrahydropyranyl, tetrahydrofuranyl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, octahydrobenzofuranyl, octahydrochromenyl, octahydrothiochromenyl, octahydroindolyl, octahydropyridinyl, decahydroquinolinyl, octahydrobenzo[b]thienyl, 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 may be fused with a phenyl moiety to form a structure such as tetrahydroisoquinoline, which would be classified as a heteroaryl.

[0178] As used herein, a "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, wherein one or more of the ring atoms is a heteroatom (e.g., N, O, S, or a combination thereof), and wherein the monocyclic ring system is aromatic, or at least one of the bicyclic or tricyclic ring systems is aromatic. Heteroaryl groups include benzo-fused ring systems having 2 to 3 rings. For example, benzo-fused groups include benzo fused to one or two 4 to 8-membered heterocyclic aliphatic moieties (e.g., indolizyl, indolyl, isoindolyl, 3H-indolyl, dihydroindole, benzo[b]furanyl, benzo[b]thienyl, quinolyl, or isoquinolyl). Some examples of heteroaryl groups are pyridinyl, 1H-indazolyl, furanyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuranyl, isoquinolyl, benzothiazolyl, xanthene, thioxanthene, phenothiazine, indoline, benzo[1,3]dioxole, benzo[b]furanyl, benzo[b]thienyl, indazolyl, benzimidazolyl, benzothiazolyl, furanyl, cinnolyl, quinolyl, quinazolinyl, cinnolyl, phthalazyl, quinazolinyl, quinoxalinyl, isoquinolyl, 4H-quinolizyl, benzo-1,2,5-thiadiazolyl, or 1,8-naphthyridyl.

[0179] Without limitation, monocyclic heteroaryl groups include furanyl, thienyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazolyl, pyrazinyl or 1,3,5-triazinyl. Monocyclic heteroaryl groups are numbered according to standard chemical nomenclature.

[0180] Without limitation, bicyclic heteroaryl groups include indolizinyl, indolyl, isoindolyl, 3H-indolyl, dihydroindole, benzo[b]furanyl, benzo[b]thienyl, quinolyl, isoquinolyl, indolizinyl, isoindolyl, indolyl, benzo[b]furanyl, benzo[b]thienyl, indazolyl, benzimidazolyl, benzothiazolyl, purinyl, 4H-quinolizinyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 1,8-naphthyridinyl or pteridyl. Bicyclic heteroaryl groups are numbered according to standard chemical nomenclature.

[0181] As used herein, the term "treaty rate" refers to the weight percentage of a component in a lubricating fluid.

[0182] Both the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured using a gel permeation chromatography (GPC) instrument available from Waters or a similar instrument, and the data are processed using Waters Empower software or a similar software. The GPC instrument can be equipped with a Waters separation module and a Waters refractive index detector (or similar optional equipment). GPC operating conditions may include a guard column, 4 Agilent PLgel columns (length is 300×7.5 mm; particle size is 5 μm, and pore size range is ), the column temperature is about 40°C. Unstabilized HPLC grade tetrahydrofuran (THF) can be used as a solvent, and the flow rate is 1.0 mL / min. The GPC instrument can be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards having a narrow molecular weight distribution range of 960-1,568,000 g / mol. For samples with a mass of less than 500 g / mol, the calibration curve can be extrapolated. Samples and PMMA standards can be dissolved in THF and prepared at a concentration of 0.1 wt % to 0.5 wt % and used without filtering. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information; see, for example, WW Yau, JJ Kirkland and DD Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is also incorporated herein by reference.

[0183] Example

[0184] The present disclosure and its many advantages can be better understood by the following examples. The following examples are illustrative and do not limit their scope or spirit. It will be readily appreciated by those skilled in the art that variations of the parts, methods, steps and equipment described in these examples can be used. Unless otherwise indicated or apparent from the context of the following examples and the entire disclosure, all percentages, ratios and parts mentioned in the present disclosure are by weight.

[0185] Example 1

[0186] The motorcycle lubricants were evaluated for copper leaching, TBN retention, sulfur retention, and varnish formation by the hot tube test (HTT) at 280°C when run according to the standards of JASO T 903:2016, Indiana Stirred Oxidation Test (ISOT), and / or JIS K2514. The lubricants are specified 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 additive of Table 3, each fluid contained the same basic additive package of dispersants, detergents, antioxidants, and viscosity index improvers and base oil blends to achieve a KV100 (ASTM D425) of about 10.9 cSt.

[0187] Table 3: Motorcycle lubricants

[0188]

[0189] The antiwear additives of Table 3 include the following zinc dihydrocarbyl dithiophosphate additives:

[0190] ZDDP1 is a zinc dihydrocarbyl dithiophosphate compound having an average of 8.8 total carbons per phosphorus atom and having 60 mole % primary alcohols, 40 mole % secondary alcohols.

[0191] ZDDP2 is a zinc dihydrocarbyl dithiophosphate compound having an average of 16 total carbons per phosphorus atom and having 100 mole % primary alcohols.

[0192] - ZDDP3 is a zinc dihydrocarbyl dithiophosphate compound having an average of 16 total carbons per phosphorus atom and having 100 mole % primary alcohols.

[0193] ZDDP4 is a zinc dihydrocarbyl dithiophosphate compound having an average of 9 total carbons per phosphorus atom and having 100% secondary alcohols.

[0194] ZDDP5 is a zinc dihydrocarbyl dithiophosphate compound having an average of 9.3 total carbons per phosphorus atom and having 100 mole % primary alcohols.

[0195] ZDDP6 is a zinc dihydrocarbyl dithiophosphate compound having an average of 12 total carbons per phosphorus atom and having 100 mole % secondary alcohols.

[0196] Table 4

[0197]

[0198] The fluids summarized in Tables 3 and 4 were evaluated for copper leaching, TBN retention, sulfur retention, and varnish formation in the hot pipe test as described above. The results are provided in Table 5.

[0199] Table 5: Results

[0200]

[0201] *HClO4 method

[0202] **HCL

[0203] ***TBN retention and sulfur retention are the TBN or sulfur at the beginning of the test divided by the TNB or sulfur at the end of the test.

[0204] Multiply that by 100.

[0205] As shown in Table 5 above, the inventive fluids have lower ISOT copper corrosion, better TNB retention, and higher or equivalent Hot Pipe Test (HTT) ratings than the comparative fluids.

[0206] 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 affirmatively limited to one referent. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. The term "comprising" and its grammatical variations as used herein are intended to be non-limiting, such that recitation of items in a list does not exclude other similar items that can be substituted or added to the listed items.

[0207] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers and other numerical values ​​used in the specification and claims indicating quantities, percentages or ratios should be understood to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that may vary depending on the desired properties attempted to be obtained by the present disclosure. At a minimum, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of reported significant figures and by applying ordinary rounding techniques.

[0208] It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as disclosed for use alone or in combination with one or more of each of the other components, compounds, substituents or parameters disclosed herein.

[0209] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range with the same number of significant figures. Thus, for example, a range of 1 to 4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, as well as any range of such values.

[0210] It should be further understood that each lower limit of each scope disclosed herein should be interpreted as being disclosed in combination with each upper limit of each scope disclosed herein for the same component, compound, substituent or parameter and each specific value in each scope. Therefore, the disclosure should be interpreted as being disclosed by combining each lower limit of each scope with each upper limit of each scope or with each specific value in each scope, or by combining each upper limit of each scope with each specific value in each scope. That is, it should also be further understood that any scope between the endpoint values ​​in a wide range is also discussed herein. Therefore, the scope of 1 to 4 also means the scope of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0211] In addition, a specific amount / value of a component, compound, substituent or parameter disclosed in this specification or the examples should be interpreted as a disclosure of a lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or specific amount / value of a range for the same component, compound, substituent or parameter disclosed elsewhere in this disclosure to form a range for that component, compound, substituent or parameter.

[0212] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseen or may not currently be foreseen may occur to applicants or other persons skilled in the art. Therefore, the appended claims as filed and as they may be amended are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A motorcycle 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; wherein the one or more metal dihydrocarbyl dithiophosphate compounds provide at least about 800 ppm phosphorus to the motorcycle lubricating composition; and wherein the one or more metal dihydrocarbyl dithiophosphate compounds have an average of at least 14 total carbons per phosphorus atom and wherein their hydrocarbyl groups are derived from at least about 80 mole percent of a straight or branched chain primary alcohol.

2. 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 of a linear or branched primary alcohol.

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

4. The motorcycle lubricating composition of claim 1, wherein the lubricating composition exhibits no more than about 90 ppm copper leaching, a TBN retention of about 10% to about 25%, and a sulfur retention of at least about 95% when measured according to the Indiana Agitation Oxidation Test (ISOT) run in accordance with JIS K2514 test standard.

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

6. The motorcycle lubricating composition of claim 1, wherein the detergent is a calcium sulfonate detergent and / or a calcium phenate detergent having a TBN of 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. The motorcycle lubricating composition of claim 1, wherein the lubricating composition comprises up to about 1 wt. % of the aminic antioxidant; and / or wherein the aminic antioxidant is selected from aromatic amines, alkylated diphenylamines, nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, or combinations thereof.

8. The motorcycle lubricating composition of claim 1, wherein the lubricating composition comprises from about 0.5 wt. % to about 5 wt. % of the dispersant; and / or wherein the dispersant is obtainable by reacting a hydrocarbyl-substituted acylating agent with a nitrogen source; and / or wherein the acylating agent is maleic anhydride and the nitrogen source is selected from ammonia, polyalkylene polyamines, or combinations thereof; and / or wherein the nitrogen source is a polyalkylene polyamine selected from a mixture of polyethylene polyamines having an average of 5 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, or combinations thereof.

9. A method of lubricating a motorcycle engine, transmission and clutch assembly with a lubricating composition, the method comprising: lubricating the motorcycle engine, the transmission, and the clutch assembly with a lubricating composition provided from a common lubricant reservoir; and The lubricating composition comprises 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; wherein the one or more metal dihydrocarbyl dithiophosphate compounds provide at least about 800 ppm phosphorus to the motorcycle lubricating composition; and wherein the one or more metal dihydrocarbyl dithiophosphate compounds have an average of at least 14 total carbons per phosphorus atom and wherein their hydrocarbyl groups are derived from at least about 80 mole percent of a straight or branched primary alcohol.

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 of a linear or branched primary alcohol.

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

12. The method of claim 9, wherein the lubricating composition exhibits no more than about 90 ppm copper leaching, a TBN retention of about 10% to about 25%, and a sulfur retention of at least about 95% when measured according to the Indiana Agitation Oxidation Test (ISOT) run under JIS K2514 testing standards.

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

14. The method of claim 13, wherein each R is a linear or branched C8 to C10 hydrocarbyl group and is derived primarily from primary alcohols; and / or wherein A is zinc and wherein each R has about 100 mole % of a hydrocarbyl group derived from a C8 to C10 primary alcohol.

15. 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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