Detergent and dispersant systems for improved steel piston cleanliness in heavy duty lubricants

Abstract

To provide a method of lubricating a heavy-duty Diesel engine comprising steel pistons, and a crank-case lubricant composition achieving excellent piston cleanliness.SOLUTION: A method of lubricating a heavy duty Diesel engine includes lubricating steel pistons with a lubricant composition, which lubricant composition includes, (i) a detergent system consisting of one or more alkali earth metal sulfonate detergents delivering about 0.3 to about 1 wt.% of sulfonate soap to the lubricant composition, and (ii) a dispersant system including one or more polyisobutylene succinimide dispersants delivering at least about 5 wt.% of one or more dispersants to the lubricant composition, with one or more polyisobutylene succinimide dispersants having a number averaged molecular weight of from about 1200 to about 2500 and derived from a highly reactive polyisobutylene delivering more than 650 ppm of nitrogen to the lubricant composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] This disclosure relates to lubricating compositions, and in particular to heavy duty lubricating compositions that exhibit improved piston cleanliness when used with steel pistons and with select detergent and dispersant systems. [Background technology]

[0002] Automotive manufacturers continue to seek improvements in efficiency, fluid life, and fuel economy, which in turn increases the requirements for engines, lubricants, and their components. These requirements also mean that engine oil performance must evolve to meet the higher demands of such modern engines and their corresponding performance standards associated with their unique uses and applications. With such stringent demands on engine oils, lubricant manufacturers often tailor lubricants and their additives to meet certain performance requirements for the industry and / or manufacturer's applications. Typically, industry standards and / or automotive manufacturers require certain performance standards, where a lubricant designed for one use or application may not meet all the performance specifications of a different use or application.

[0003] For example, the selection of detergents and dispersants in engine oil formulations has often suggested only a few relevant considerations based on a number of factors, including but not limited to piston cleanliness, acid neutralization, TBN retention, oxidation, low speed pre-ignition, wear, friction performance, fuel economy, supply, and / or cost factors. However, it has previously been accepted that piston cleanliness in diesel engines typically requires the use of detergent sources other than sulfonates, and thus diesel piston cleanliness has generally required, for example, a combination of a phenate detergent with a sulfonate detergent. These combinations have tended to result in formulation disadvantages by limiting the choice of auxiliary components in the formulation and / or have tended to cause formulation trade-offs that may affect overall performance.

[0004] Traditional heavy-duty engines (i.e., engines configured for vehicles having a gross vehicle weight of about 6,000 pounds or more) often use aluminum pistons, and traditional phenate and sulfonate detergent systems have been effective in maintaining piston cleanliness in such engine configurations. Previously, piston cleanliness for a particular application was evaluated according to the OM501LA (CEC L-101-08) test using aluminum pistons. Recently, some heavy-duty engines, engines configured for vehicles having a gross vehicle weight of about 6,000 pounds or more, have generally transitioned to the use of steel pistons, which allow for increased pressure and temperature in the cylinder to help achieve improved fuel economy performance by having less friction, higher torque management, and / or long-term durability. However, with the transition to upgraded engines and steel pistons, the industry has also developed a more demanding piston cleanliness test, designated as the OM471 piston cleanliness test of CEC L-118-21. This test uses an engine with steel pistons and configured to provide more power and more torque than the engine used in the OM501LA test. This new piston cleanliness test, designed for steel pistons, is not only more demanding than the OM501LA test in terms of pressure and temperature, but also twice as long in test duration (about 600 hours instead of about 300 hours) and / or at higher maximum power and torque levels. The OM471 test produces a significantly increased engine power output of about 391 kW versus the OM501LA test, which produces an engine power output of about 358 kW.

[0005] Therefore, heavy duty engine lubricants must now demonstrate acceptable performance when subjected to the more severe operating conditions of the new OM471 test of CEC L-118-21. However, in many situations, varying ingredients within a lubricant composition to meet newer performance characteristics tends to adversely affect one or more other performance characteristics. Thus, it becomes difficult for lubricant manufacturers to meet newer industrial performance demands while at the same time maintaining traditional fluid performance. Summary of the Invention

[0006] In one approach or embodiment, the present disclosure relates to a method of lubricating a diesel engine, particularly a heavy duty diesel engine having steel pistons. The present invention is particularly suitable for lubricating engines having steel pistons, and in particular for lubricating heavy duty diesel engines having steel pistons. In one aspect, the method comprises lubricating a steel piston of a diesel engine, particularly a heavy duty diesel engine, with a lubricating oil composition. In another embodiment, the lubricating oil composition comprises: (i) a detergent system consisting of one or more alkaline earth metal sulfonate detergents providing up to about 1 weight percent of sulfonate soap to the lubricating oil composition (preferably, from about 0.3 to about 1 weight percent of the sulfonate soap); and (ii) a dispersant system comprising one or more polyisobutylene succinimide dispersants providing at least about 5 weight percent of one or more dispersants to the lubricating oil composition, wherein the one or more polyisobutylene succinimide dispersants are derived from highly reactive polyisobutylene having a number average molecular weight of from about 1,200 to about 2,500 and providing greater than 650 ppm of nitrogen to the lubricating oil composition. In some embodiments, the diesel engine, particularly a heavy duty diesel engine, is operated under conditions as specified in the OM471 piston cleanliness test of CEC L-118-21, and in some embodiments, for up to about 600 hours (or up to about 400 hours or from about 400 to about 600 hours), and / or up to about 391 kW of engine power.In some embodiments, the lubricating oil composition further comprises an antioxidant system of one or more ashless antioxidants (preferably alkylated diphenylamines and hindered phenols) and a molybdenum-containing antioxidant, the molybdenum-containing antioxidant comprises an oil-soluble molybdenum compound selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organo-molybdenum complexes of organic amides, or mixtures thereof, and the one or more ashless antioxidants are selected from hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof; in one embodiment, the lubricating oil composition comprises at least about 2 weight percent, at least about 2.2 weight percent, or at least about 2.5 weight percent of the antioxidant system. In one approach, the antioxidant system may include at least 1.0 weight percent of a diphenylamine, at least 1.0 weight percent of a hindered phenol, and less than 0.2 weight percent of a molybdenum-containing compound in the lubricating composition.

[0007] In yet a further approach or embodiment, the method of lubricating a diesel engine having steel pistons, particularly a heavy duty diesel engine, of the preceding paragraph may include any combination of optional features, steps, or embodiments, which may include one or more of the following: the diesel engine, particularly a heavy duty diesel engine, is configured to power a vehicle having a gross vehicle weight rating of about 6,000 pounds or more, and / or the detergent system consists of one or more overbased calcium sulfonate detergents and one or more lowbased calcium sulfonate detergents, the overbased detergents having a total base number (TBN) of at least about 200 mg KOH / g and the lowbased detergents having a total base number (TBN) of about 175 mg KOH / g or less, the total base number (TBN) being in accordance with ASTM D 1224 . D2896, and / or the detergent system comprises a weight ratio of one or more overbased sulfonate detergents to one or more underbased sulfonate detergents of from about 3:1 to about 8:1 (in other embodiments, from about 3:1 to about 6:1, from about 3:1 to about 5:1, or from about 3:1 to about 4:1), and / or the detergent system comprises a weight ratio of one or more overbased sulfonate detergents to one or more underbased sulfonate detergents of from about 2:1 to about 4:1 (in other embodiments, from about 2.1:1 to about 3.5:1, from about 2.2:1 to about 3:1, or from about 2.3:1 to about 2.and / or the detergent system comprises an effective amount of one or more overbased sulfonate detergents to provide the detergent system with at least about 5 mg KOH / g and an effective amount of one or more underbased sulfonate detergents to provide from about 25 to about 40 weight percent detergent soap, and / or the detergent system consists essentially of calcium sulfonate detergents, and / or the detergent system is substantially free of magnesium sulfonate detergents, substantially free of phenate detergents, or combinations thereof, and / or the lubricating oil composition comprises from about 50 ppm to about 200 ppm molybdenum provided by an oil-soluble molybdenum compound selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organo-molybdenum complexes of organic amides, or mixture ... The oil composition further comprises from about 0.5 to about 5 weight percent of one or more ashless antioxidants selected from hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof, and / or the lubricating oil composition comprises up to about 1200 ppm phosphorus from one or more metal dihydrocarbyl dithiophosphate compounds having hydrocarbyl groups derived from a mixture of linear or branched primary alcohols and linear or branched secondary alcohols, and / or the heavy duty crankcase lubricating composition has a negligible amount of magnesium, e.g., about 20 ppm or less, or about 10 ppm or less.

[0008] In yet another approach or embodiment, the disclosure herein provides a crankcase lubricating oil composition, particularly a heavy duty crankcase lubricating oil composition, suitable for diesel engines having a gross vehicle weight of about 6,000 pounds or greater and having engines with steel pistons. In an aspect of this embodiment, the crankcase lubricating oil composition, particularly a heavy duty crankcase lubricating oil composition, comprises one or more base oils of lubricating viscosity, a detergent system consisting of one or more alkaline earth metal sulfonate detergents providing the lubricating oil composition with up to about 1 weight percent of sulfonate soap (preferably from about 0.3 to about 1 weight percent of sulfonate soap), and a dispersant system including one or more polyisobutylene succinimide dispersants providing the lubricating oil composition with at least about 5 weight percent of one or more dispersants, the one or more polyisobutylene succinimide dispersants being derived from a highly reactive polyisobutylene having a number average molecular weight of about 1,200 to about 2,500 and providing greater than 650 ppm of nitrogen to the lubricating oil composition. In some embodiments, the diesel engine, particularly a heavy duty diesel engine, is operated under conditions as set forth in the OM471 Piston Detergency Test of CEC L-118-21, and in some embodiments, for up to about 600 hours (or up to about 400 hours or from about 400 to about 600 hours), and / or up to about 391 kW of engine power. In some embodiments, the lubricating oil composition achieves a steel piston detergency rating of at least 90% (a higher percentage rating is a cleaner piston) as measured by the OM471 Piston Detergency Test (CEC L-118-21).In other embodiments, the crankcase lubricating oil composition, particularly the heavy duty crankcase lubricating oil composition, further comprises an antioxidant system of one or more ashless antioxidants (preferably alkylated diphenylamines and hindered phenols) and a molybdenum-containing antioxidant, the molybdenum-containing antioxidant comprises an oil-soluble molybdenum compound selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organo-molybdenum complexes of organic amides, or mixtures thereof, and the one or more ashless antioxidants are selected from hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof, and in one embodiment the lubricating oil composition comprises at least about 2 weight percent, at least about 2.2 weight percent, or at least about 2.5 weight percent of the antioxidant system. In one approach, the antioxidant system may include at least 1.0 weight percent of a diphenylamine, at least 1.0 weight percent of a hindered phenol, and less than 0.2 weight percent of a molybdenum-containing compound in the lubricating composition.

[0009] In yet another approach or embodiment, the crankcase lubricants, particularly the heavy duty crankcase lubricants, described in the preceding paragraph may include any combination of the optional features or embodiments. These optional features or embodiments may include one or more of the following: the detergent system consists of one or more overbased calcium sulfonate detergents and one or more lowbased calcium sulfonate detergents, the overbased detergents having a total base number (TBN) of at least about 200 mg KOH / g and the lowbased detergents having a total base number (TBN) of about 175 mg KOH / g or less, the total base number (TBN) being within the scope of ASTM A1224. D2896, and / or the detergent system comprises a weight ratio of one or more overbased sulfonate detergents to one or more low based sulfonate detergents of from about 3:1 to about 8:1 (in other embodiments from about 3:1 to about 6:1, from about 3:1 to about 5:1, or from about 3:1 to about 4:1), and / or the detergent system comprises a weight ratio of overbased sulfonate soap to low based sulfonate soap of from about 2:1 to about 4:1 (in other embodiments from about 2.1:1 to about 3.5:1, from about 2.2:1 to about 3:1, or from about 2.3:1 to about 2.8:1), and / or the detergent system comprises a weight ratio of overbased sulfonate soap to low based sulfonate soap of from about 2.1:1 to about 3.5:1, from about 2.2:1 to about 3:1, or from about 2.3:1 to about 2.8:1, ... and / or the detergent system consists essentially of a calcium sulfonate detergent, and / or the detergent system is substantially free of magnesium sulfonate detergents, substantially free of phenate detergents, or a combination thereof, and / or the lubricating oil composition comprises a molybdenum dithiocarbamate detergent, and / or a molybdenum dithiocarbamate detergent, and / or a molybdenum dithiocarbamate detergent. and / or the lubricating oil composition contains from about 50 ppm to about 200 ppm of molybdenum provided by an oil soluble molybdenum compound selected from the group consisting of hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof.5 to about 5 weight percent of one or more ashless antioxidants, and / or the lubricating oil composition contains up to about 1200 ppm of phosphorus from one or more metal dihydrocarbyl dithiophosphate compounds having hydrocarbyl groups derived from a mixture of linear or branched primary alcohols and linear or branched secondary alcohols, and / or the heavy duty crankcase lubricating composition contains a negligible amount of magnesium, e.g., about 20 ppm or less, or about 10 ppm or less.

[0010] In yet a further approach or embodiment, the disclosure herein provides for the use of the lubricating oil compositions, particularly any of the embodiments of the heavy duty lubricating oil compositions, of the present invention overview, to achieve improved steel piston detergency according to the OM471 Piston Detergency Test (CEC L-118-21), and in other embodiments a steel piston detergency rating of at least about 90% as measured by the OM471 Piston Detergency Test (CEC L-118-21). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present disclosure relates to heavy duty crankcase lubricant compositions and methods of lubricating heavy duty diesel engines having steel pistons, particularly those effective in achieving passing piston cleanliness according to the new OM471 piston cleanliness test of CEC L-118-21 consistent with ACEA E8 specifications. In an approach or embodiment, the heavy duty lubricant compositions herein are suitable for achieving passing piston cleanliness on steel pistons according to the OM471 test. Such heavy duty diesel engines and lubricants herein are configured to power vehicles having a gross vehicle weight rating of about 6,000 pounds or more. Such engines often have engine capacities of 10 liters or more, steel pistons, maximum power output of up to about 600 horsepower, maximum torque of up to about 1,900 ft-lbs, and / or exhaust gas recirculation systems. The present invention is particularly suitable for lubricating engines having steel pistons, more particularly, for lubricating heavy duty diesel engines having steel pistons.

[0012] In an approach or embodiment herein, the crankcase lubricating oil compositions of the present disclosure suitable for such engines and vehicles, particularly heavy duty crankcase lubricating oil compositions, preferably comprise at least (i) a detergent system comprising, consisting of, or consisting essentially of one or more alkaline earth metal sulfonate detergents providing up to about 1 weight percent of sulfonate soap to the lubricating oil composition, and (ii) a dispersant system comprising one or more polyisobutylene succinimide dispersants providing at least about 5 weight percent of one or more dispersants to the lubricating oil composition. In another approach or embodiment, the lubricating oil compositions herein may also comprise one or more optional ashless antioxidants, one or more optional oil-soluble molybdenum compounds, and one or more optional metal dihydrocarbyl dithiophosphate compounds in amounts effective to aid piston cleanliness when combined with the detergent and dispersant systems described above in the harsh environment of the OM471 piston cleanliness test. In some embodiments, the lubricating oil composition further comprises an antioxidant system of one or more ashless antioxidants (preferably alkylated diphenylamines and hindered phenols) and a molybdenum-containing antioxidant. The molybdenum-containing antioxidant may include an oil-soluble molybdenum compound selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organomolybdenum complexes of organic amides, or mixtures thereof. The one or more ashless antioxidants may be selected from hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof. In one embodiment, the lubricating oil composition comprises at least about 2 weight percent, at least about 2.2 weight percent, or at least about 2.5 weight percent of the antioxidant system, and in some embodiments, at most about 5 weight percent, at most about 4 weight percent, or at most about 3 weight percent of the antioxidant system.In one approach, the antioxidant system may include at least 1.0 weight percent of a diphenylamine, at least 1.0 weight percent of a hindered phenol, and less than 0.2 weight percent of a molybdenum-containing compound in the lubricating composition.

[0013] In some approaches, the one or more polyisobutylene succinimide dispersants of the dispersant system can be derived from a highly reactive polyisobutylene having a number average molecular weight of from about 1,200 to about 2,500, including at least one boronated polyisobutylene succinimide dispersant derived from a polyisobutylene having a number average molecular weight of from about 1,000 to about 1,500 and providing from about 100 to about 200 ppm of boron to the lubricating oil composition.

[0014] In other approaches or embodiments, the unique detergent systems herein comprise, consist of, or alternatively consist essentially of calcium sulfonate detergents in amounts that provide a TBN from the sulfonate detergent of about 3 to about 15 mg KOH / g, about 5 to about 15 mg KOH / g, or about 8 to about 15 mg KOH / g, and provide the detergent system TBN and soap content discussed herein. In other words, the detergent systems herein are primarily sulfonate detergents, and most preferably sulfonate-only detergents with little or no phenate or other detergent types (most preferably no phenate or other detergent additives) that were previously necessary to pass previous heavy duty diesel piston detergency tests when using aluminum pistons. Even without detergent soap types other than sulfonates, such as phenate soaps, the lubricants herein surprisingly pass the more stringent OM471 piston detergency test, even when using steel pistons. The detergent system herein is substantially free of non-sulfonate soaps, such as phenate soaps, meaning about 25 percent or less of phenate soaps, about 20 percent or less, about 15 percent or less, about 10 percent or less, about 5 percent or less, about 2.5 percent or less, about 1 percent or less, or a non-functional amount of phenate soaps.

[0015] As discussed further below, the detergent system herein can include a unique blend of overbased sulfonate detergents and neutral to low based sulfonate detergents configured to provide the TBN levels and soap content described. In some approaches or embodiments, the detergent system includes a weight ratio of one or more overbased sulfonate detergents to one or more low based sulfonate detergents of about 3:1 to about 8:1 (in other embodiments, about 3:1 to about 6:1, about 3:1 to about 5:1, or about 3:1 to about 4:1). In alternative approaches, the detergent system includes embodiments having a weight ratio of overbased sulfonate soap to low based sulfonate soap of about 2:1 to about 4:1 (in other embodiments, about 2.1:1 to about 3.5:1, about 2.2:1 to about 3:1, or about 2.3:1 to about 2.8:1). Preferably, the detergent system comprises one or more overbased sulfonate detergents in an amount effective to provide the detergent system with a minimum TBN of at least about 5 mg KOH / g, and one or more underbased sulfonate detergents in an amount effective to provide from about 25 to about 40 weight percent detergent soap in the detergent system.

[0016] Detergents The lubricating compositions herein include detergent systems that achieve piston cleanliness according to the demanding OM471 piston cleanliness test for steel pistons with little or no non-sulfonate soaps, such as phenate soaps, and preferably no phenate soaps at all. In some approaches, steel piston cleanliness is achieved with a detergent system that comprises, consists of, or consists essentially of one or more alkaline earth metal sulfonate detergents that provide the lubricant with up to about 1 weight percent soap, preferably up to 1 weight percent sulfonate soap with minimum TBN levels provided by the sulfonate detergent, which may be a blend of neutral, underbased, or overbased sulfonate detergents. Preferred TBN levels provided by the sulfonate detergents are at least about 3 mg KOH / g, at least about 4 mg KOH / g, at least about 5 mg KOH / g, from about 3 mg KOH / g to about 15 mg KOH / g, from about 5 mg KOH / g to about 9 mg KOH / g, not more than about 12 mg KOH / g, not more than about 10 mg KOH / g, or not more than about 7 mg KOH / g. In embodiments, the detergent systems herein generally comprise one or more alkali or alkali metal salts of a sulfonate and contain only small amounts, residual levels, or preferably no other functional detergent additives such as phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof, so long as the minimum amounts of sulfonate soaps, TBN levels, soap content relationships, and / or low levels of other detergents described herein are satisfied. Thus, in embodiments, the detergent systems herein comprise no more than about 0.5 weight percent, no more than about 0.2 weight percent, or no more than about 0.1 weight percent of a non-sulfonate detergent.

[0017] Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited therein, which are incorporated herein by reference. The lubricant compositions herein may contain from about 0.1 to about 5 weight percent of the individual and / or total detergent additives, in other approaches from about 0.15 to about 3 weight percent, and in yet other approaches from about 0.5 to 2.6 weight percent of the individual and / or total detergent additives, so long as the detergent additives satisfy the sulfonate amounts and other relationships described herein.

[0018] As mentioned above, and in some approaches, the detergent system provides a selected amount of sulfonate soap and TBN level with a certain amount of detergent metal. For example, the detergent system herein can provide an amount of total detergent metal that is greater than about 1200 ppm metal, or in other approaches, about 1200 ppm to about 3500 ppm total metal, about 1400 ppm to about 3000 ppm total metal, or about 2000 ppm to about 2500 ppm total metal. In some approaches, the detergent metal is calcium, magnesium, and / or sodium. In other approaches, the detergent metal is calcium and / or magnesium, and in still further approaches, the detergent metal is preferably only calcium.

[0019] In general, suitable detergents in the system may include petroleum sulfonic acids, long chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl, and / or linear or branched alkali or alkaline earth metal salts of various phenates or derivatives of phenates, such as calcium, sodium, or magnesium. Examples of suitable detergents include low based / neutral and overbased variations of the following detergents, in addition to the requisite amounts of sulfonate soaps listed above: calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compounds, calcium methylene bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixar ... mu salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkylphenol, magnesium sulfur-bound alkylphenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkylphenol, sodium sulfur-bound alkylphenol compound, or sodium methylene bridged phenol.

[0020] The detergent additives herein preferably comprise a blend of (i) an effective amount of a neutral to low based detergent to provide a minimum soap content, and (ii) an effective amount of an overbased detergent to meet a minimum detergent TBN number.

[0021] As will be appreciated, overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a 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.

[0022] The term "overbased" refers to metal salts in which the amount of metal present exceeds the stoichiometric amount, for example, metal salts of sulfonates, carboxylates, salicylates, and / or phenates. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the MR is 1, and in overbased salts, the MR is greater than 1. They are generally referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0023] As used herein, the term "TBN" is used to represent the total base number in mg KOH / g, as measured by the method of ASTM D2896. The detergent may be neutral or overbased. For example, a low-based or neutral detergent may have a total base number (TBN) of up to about 175 mg KOH / gram. In another example, the overbased detergent of the lubricating oil composition herein may have a total base number (TBN) of about 200 mg KOH / gram or more, or about 250 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more. The overbased detergent may have a metal to substrate ratio of 1.1:1 or less, or 2:1 or less, or 4:1 or less, or 5:1 or less, or 7:1 or less, or 10:1 or less, or 12:1 or less, or 15:1 or less, or 20:1 or less.

[0024] Examples of suitable overbased detergents include overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methacrylates ... overbased magnesium sulfur-containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-linked alkylphenol compounds, or overbased magnesium methylene bridged phenols.

[0025] Low-based or neutral detergents generally have a TBN of up to 175 mg KOH / g, up to 150 mg KOH / g, up to 100 mg KOH / g, or up to 50 mg KOH / g. Low-based / neutral detergents may include calcium-containing detergents. Examples of suitable low-based / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate (as long as they meet the sulfonate soap and other TBN relationships described herein).

[0026] In some embodiments, the detergent used in the lubricants herein comprises at least an overbased calcium sulfonate having a total base number of 200 to 400, in other approaches from about 250 to about 350. The above TBN values ​​reflect the value of the finished detergent component diluted in the base oil. In some approaches, the detergent system comprises a blend of neutral to low based and overbased sulfonate detergents, and the lubricants herein can comprise from about 0.1 to about 1.0 weight percent of the neutral to low based sulfonate detergent and from about 0.5 to about 3.0 weight percent of the overbased sulfonate detergent (or in other approaches from about 1.0 to about 2.5 weight percent of the overbased sulfonate detergent). In yet another approach, the detergent system herein can have a ratio of overbased sulfonate detergent to low based sulfonate detergent of from about 3:1 to about 8:1. As noted above, the overbased sulfonate detergent is in an amount effective to provide the detergent with a minimum TBN level, and the underbased or neutral sulfonate detergent is in an amount effective to provide a minimum soap level.

[0027] In other embodiments, the TBN of the detergents herein may reflect the neat or undiluted version of the detergent component. For example, the fluids herein may include overbased calcium sulfonates as a neat additive having a TBN of about 500 to about 650, and in other approaches about 550 to about 610. The fluids herein may also include neutral to low based calcium sulfonates as a neat additive having a TBN of up to 75, up to 70, or about 40 to about 75, or about 40 to about 70.

[0028] More specifically, the detergent systems herein include neutral, underbased, and / or overbased detergents (preferably neutral to overbased calcium sulfonates) to achieve a detergent TBN of at least about 3 mg KOH / g, at least about 4 mg KOH / g, at least about 5 mg KOH / g, from about 3 mg KOH / g to about 15 mg KOH / g or less, from about 5 mg KOH / g to about 9 mg KOH / g or less, as measured by ASTM D2896. Preferably, the detergent systems herein include an effective amount of one or more overbased sulfonate detergents to provide a total TBN of at least about 5 mg KOH / g to about 8 mg KOH / g for the detergent system.

[0029] The detergent system herein has a high level of sulfonate soap content relative to the total soap content, particularly the detergent system has at least about 75 percent sulfonate soap, in other approaches at least about 80 percent sulfonate soap, at least about 85 percent sulfonate soap, at least about 90 percent sulfonate soap, at least about 95 percent sulfonate soap, at least about 98 percent sulfonate soap, at least about 99 percent sulfonate soap, or about 100 percent sulfonate soap (or any range therebetween). In other approaches, the detergent soap amount is balanced with a selected detergent TBN level to achieve steel piston cleanliness with little or no phenate detergent. In some approaches, the detergent system of the lubricants herein, particularly the heavy duty lubricants, is substantially free of magnesium sulfonate detergent, substantially free of phenate detergent, or a combination thereof. As used herein, substantially free means about 1% by weight or less, 0.5% by weight or less, about 0.25% by weight or less, or about 0.1 weight percent or less, or completely free.

[0030] In another approach, the detergent system herein has a select weight ratio of sulfonate soap to phenate soap in the detergent system of about 75:25 or more, about 80:20 or more, about 85:15 or more, about 90:10 or more, even about 95:5, about 99:1 or more (in the context of this ratio, or more means more sulfonate soap relative to phenate soap). Preferably, the detergent system herein contains only residual levels, if any, of phenate soap, salicylate soap, calixarate soap, or non-sulfonate soap. Preferably, the detergent system contains an effective amount of one or more low-basing sulfonate detergents to provide about 30 to about 50 weight percent detergent soap.

[0031] Soap content generally refers to the amount of neutral organic acid salts and reflects the cleaning ability or cleaning power of the detergent and its ability to lift dirt. The soap content of a lubricant can be determined by ASTM D3712. A more detailed explanation of "soap content" is known to those skilled in the art and is described in the standard textbook entitled "Chemistry and Technology of Lubricants", Third Edition, edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 219-220, under the subheading 7.2.5. Detergent Classification, which is incorporated herein by reference.

[0032] Dispersant System The lubricating oil compositions herein, particularly the heavy duty crankcase lubricating oil compositions, also include a dispersant system including one or more polyisobutylene succinimide dispersants that provide at least about 5 weight percent of one or more dispersants to the lubricating oil composition (alternative approaches include from about 5 weight percent to about 15 weight percent, from about 6 weight percent to about 12 weight percent, or from about 6 weight percent to about 10 weight percent of one or more dispersants). Preferably, the one or more polyisobutylene succinimide dispersants are derived from a highly reactive polyisobutylene having a number average molecular weight of from about 1,200 to about 2,500, and in some embodiments may include at least one boronated polyisobutylene succinimide dispersant derived from a highly reactive polyisobutylene having a number average molecular weight of from about 1,000 to about 1,500, providing from about 100 to about 200 ppm of boron to the lubricating oil composition. In some embodiments, the dispersant provides greater than 650 ppm nitrogen to the lubricating oil composition, preferably from about 650 to about 1500 ppm nitrogen. In some approaches or embodiments, the dispersant may be diluted with from about 25 to about 50 weight percent of a suitable process oil.

[0033] Dispersants are often known as ashless dispersants because they do not contain ash-forming metals prior to mixing into the lubricant composition and they do not usually contribute 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 nitrogen-substituted long chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 5,000, or about 3,000, or about 2,000, or about 1,500 as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 and U.S. Pat. No. 4,234,435, which are incorporated herein by reference. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0034] In the approach, the preferred amine for the dispersant may be selected from polyamines and hydroxylamines. Examples of polyamines that may be used include, but are not limited to, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and higher homologs such as pentaethylamine hexamine (PEHA). In some approaches, so-called heavy polyamines may be used, which are mixtures of polyalkylene-polyamines that contain small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylene hexamine), but mainly oligomers with 6 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers that contain 7 or more nitrogen atoms per molecule and have 2 or more primary amines per molecule.

[0035] In some embodiments, polyisobutylene (PIB), if included, is a preferred reactant for forming the dispersant and may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0036] HR-PIB having a number average molecular weight ranging from about 900 to about 3,000 as determined by GPC may be suitable. Such HR-PIB may be commercially available or may be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Pat. Nos. 4,152,499 and 5,739,355. When used in the aforementioned thermal ene reaction, HR-PIB may result in higher conversion rates in the reaction and less precipitate formation due to increased reactivity. A suitable method is described in U.S. Pat. No. 7,897,696. In one embodiment, the present disclosure further includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA may have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0037] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. In another embodiment, the dispersant may be described as poly-PIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0038] A suitable class of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants which may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds which may be reacted with the functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0039] A suitable class of dispersants can also be Mannich bases.Mannich bases are materials formed by 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.A suitable class of dispersants can also be high molecular weight esters or half-ester amides.

[0040] In some approaches, the dispersants in the lubricants herein may be optionally post-treated by conventional methods by reaction with any of a variety of agents. Suitable post-treatment agents include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. (See, for example, U.S. Pat. Nos. 7,645,726, 7,214,649, 8,048,831, and 5,241,003, all of which are incorporated herein by reference in their entirety.)

[0041] The boron compounds used as post-treatment reagents can be selected from boron oxides, boron halides, boric acid, and esters of boric acid in amounts to provide from about 0.1 atomic percentage of boron per mole of nitrogen composition to about 20 atomic percentages of boron for each atomic percentage of nitrogen used. Dispersants post-treated with boron can contain from about 0.05 to about 2.0 weight percent, or in other approaches, from about 0.5 weight percent to about 1.0 weight percent, of boron, based on the total weight of the borate dispersant.

[0042] In another approach, carboxylic acids can also be used as post-treatment reagents and can be saturated or unsaturated mono-, di-, or poly-carboxylic acids. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, and naphthalic diacids (e.g., 1,8-naphthalic diacid). Anhydrides can also be used as post-treatment reagents and can be selected from the group consisting of mono-unsaturated anhydrides (e.g., maleic anhydride), alkyl or alkylene substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride), and aromatic carboxylic anhydrides (including naphthalic anhydride, e.g., 1,8-naphthalic anhydride).

[0043] In one embodiment, the process 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 may be post-treated with more than one post-treating agent. For example, the dispersant may be post-treated with a boron compound, such as boric acid, and also with an anhydride, such as maleic anhydride. In some cases, the dispersant may be post-treated with an anhydride, such as maleic anhydride and / or 1,8-naphthalic anhydride.

[0044] In addition to the post-treatments mentioned above, dispersants may be post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with: inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); and / or carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980). Nos. 3,708,522 and 4,948,386; epoxides, polyepoxyates or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. No. 4,617,137); Nos. 3,312,619, 3,865,813, and British Patent No. 1,065,595; organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketenes (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); a Lucan 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. No. 3,954,639); cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. No. 4,612,132, U.S. Pat. No. 4,647,390, U.S. Pat. No. 4,648,886, U.S. Pat. No. 4,670,170); Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiocarbonates, etc. olactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. Nos. 4,379,064); , U.S. Pat. No. 3,185,647; combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chlorides (e.g., U.S. Pat. Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenols (e.g., U.S. Pat. No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenols and then glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); inorganic acids or anhydrides of phosphorus. or a combination of its partial or total sulfur analogue and a boron compound (e.g., U.S. Pat. No. 4,857,214); a combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are incorporated herein in their entirety;

[0045] In other approaches, the total amount of dispersants in the dispersant system can be present in an amount up to about 15 weight percent of the lubricating composition, with one or more of the dispersants being post-treated to provide the lubricating composition with at least about 40 ppm boron and up to 300 ppm boron (preferably about 100 to about 200 ppm boron). In other approaches, a total amount of dispersants can be used in the lubricating composition in an amount of about 5 weight percent to about 15 weight percent, or about 6 weight percent to about 10 weight percent, about 7.0 weight percent to about 10 weight percent, or about 7.0 weight percent to about 8 weight percent, based on the final weight of the lubricating oil composition. As noted above, the dispersant may be diluted with about 25 to about 50 weight percent of processing oil in some approaches. The dispersant is capable of providing at least about 400 ppm nitrogen, and up to about 1,500 ppm nitrogen, preferably from about 650 ppm to about 1500 ppm nitrogen, and more preferably from about 800 ppm to about 1200 ppm nitrogen.

[0046] Suitable dispersants may have a TBN of from about 10 to about 60 mg KOH / g of dispersant on an oil-free basis, which equates to a TBN of from about 5 to about 30 when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0047] Oil-soluble molybdenum compounds The crankcase lubricants, particularly heavy duty crankcase lubricants, of the present disclosure may optionally include one or more oil-soluble molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may be any of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum sulfides, molybdenum disulfides, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. The molybdenum-containing compounds may be sulfur-containing or sulfur-free compounds. The molybdenum disulfide may be in the form of a stable dispersion.

[0048] In one embodiment, the oil-soluble molybdenum compound can be selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organomolybdenum complexes of organic amides, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be molybdenum dithiocarbamates. Exemplary sulfur-free organomolybdenum complexes of organic amides are disclosed in U.S. Patent No. 5,137,647.

[0049] In one approach or embodiment, a suitable molybdenum dithiocarbamate may be represented by the formula:

[0050] [ka] In the formula, R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, C1 to C 20 Alkyl groups, C6-C 20 Cycloalkyl, aryl, alkylaryl, or aralkyl groups, or optionally C3-C containing ester, ether, alcohol, or carboxyl groups.20 R is a hydrocarbyl group, and X1, X2, Y1 and Y2 are each independently a sulfur atom or an oxygen atom. 5 , R 6 , R 7 , and R 8 Examples of suitable groups for each of R include 2-ethylhexyl, nonylphenyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-hexyl, n-octyl, nonyl, decyl, dodecyl, tridecyl, lauryl, oleyl, linoleyl, cyclohexyl, and phenylmethyl. 5 , R 6 , R 7 , and R 8 are C6 to C 18 X1 and X2 may be the same, and Y1 and Y2 may be the same. X1 and X2 may both contain sulfur atoms, and Y1 and Y2 may both contain oxygen atoms. Further examples of molybdenum dithiocarbamates include C6-C 18 Included are dialkyl or diaryl dithiocarbamates or alkyl-aryl dithiocarbamates such as dibutyl-, diamyl-di-(2-ethylhexyl)-, dilauryl-, dioleyl-, and dicyclohexyl-dithiocarbamate.

[0051] Suitable examples of molybdenum compounds which can be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, Molyvan® 807, Molyvan® 855, and Molyvan® 1055 from R.T. Vanderbilt Co., Ltd., and Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. Nos. 5,650,381, Re. 37,363 (E1), Re. 38,929 (E1), and Re. 40,595 (E1), the entireties of which are incorporated herein by reference.

[0052] In one embodiment, when included in the formulation, the oil soluble molybdenum compound may be present in the crankcase lubricants, particularly the heavy duty crankcase lubricants, herein in an amount to provide up to about 800 ppm molybdenum, or from about 5 ppm to 800 ppm molybdenum. In other embodiments, the oil soluble molybdenum compound may be present in an amount to provide from about 10 to about 500 ppm molybdenum, from about 20 to 250 ppm molybdenum, from about 30 to 175 ppm molybdenum, from about 40 to 150 ppm molybdenum, from about 50 to 125 ppm molybdenum, or from about 60 to 100 ppm molybdenum.

[0053] Antioxidants The crankcase lubricants herein, particularly the heavy duty crankcase lubricants, may also include one or more antioxidants, preferably one or more aminic antioxidants. If used, the antioxidants may be provided in an amount of about 1 to about 5 weight percent (alternatively about 1.2 to about 4 weight percent, or about 1.4 to about 3 weight percent, or about 2 to about 3 weight percent), which, when combined with the dispersant and detergent systems herein, may aid in piston cleanliness on steel pistons in the harsh environment of the OM471 test.

[0054] Suitable antioxidants may include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0055] In some approaches or embodiments, suitable aminic antioxidants may include, but are not limited to, antioxidants selected from aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, and the like, or combinations thereof. The total amount of antioxidant in the lubricating compositions herein may be present in an amount that provides up to about 400 ppm nitrogen, or up to about 300 ppm nitrogen, or up to about 200 ppm nitrogen, or from about 50 to about 400 ppm nitrogen, from about 60 to about 300 ppm nitrogen, from about 70 to about 200 ppm nitrogen, or from about 80 to about 100 ppm nitrogen. In other approaches, the lubricating compositions herein may include up to about 5 weight percent aminic antioxidant, or from about 0.1 to about 5 weight percent aminic antioxidant, and in other approaches, from about 0.2 to about 3 weight percent, or from about 0.2 to about 2.0 weight percent aminic antioxidant.

[0056] In some approaches, the amine antioxidant may be one or more aromatic amine antioxidants, including, but not limited to, diarylamines having the formula:

[0057] [ka] wherein R' and R" each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. If substituted, suitable substituents on the aryl groups of R' and R" include an aliphatic hydrocarbon group such as an alkyl having 1 to 30 carbon atoms, a hydroxy group, a halogen radical, a carboxylic acid or ester group, or a nitro group. The aryl group may be a substituted or unsubstituted phenyl or naphthyl, particularly one in which one or both aryl groups are substituted with at least one alkyl having 4 to 30, preferably 4 to 18, and most preferably 4 to 9 carbon atoms. In an approach, one or both aryl groups may be substituted, such as mono-alkylated diphenylamine, di-alkylated diphenylamine, C9 alkylated diphenylamines, or a mixture of mono- and dialkylated diphenylamines.

[0058] Examples of diarylamines that may be used include, but are not limited to, diphenylamine; the various alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, monobutyldiphenyl-amine, dibutyldiphenylamine, monooctyldiphenylamine, dioctyldiphenylamine, monononyldiphenylamine, dinonyldiphenylamine, monotetradecyldiphenylamine, ditetradecyldiphenylamine, phenyl-alpha-naphthylamine, monooctylphenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, monoheptyldiphenylamine, diheptyl-diphenylamine, p-oriented styrenated diphenylamines, mixed butyloctyldi-phenylamines, and mixed octylstyryldiphenylamines.

[0059] In another approach, suitable antioxidants may include aromatic amine antioxidants. Examples of phenolic antioxidants include N,N'-di-sec-butyl-phenylene-diamine, 4-isopropylaminodiphenylamine, phenyl-alpha-naphthylamine, phenyl-alpha-naphthylamine, and ring-alkylated diphenylamines.

[0060] The hindered phenol antioxidant may contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group that connects 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 but may include, for example, Irganox™ L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester but may include Ethanox™ 4716 available from Albemarle Corporation.

[0061] Useful antioxidants may include diarylamines and high molecular weight phenols. In an embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In an embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0062] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefins can be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0063] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with olefins, such as α-olefins.

[0064] Metal dihydrocarbyl dithiophosphate compounds The crankcase lubricants herein, particularly heavy duty crankcase lubricants, may optionally include one or more metal dihydrocarbyl dithiophosphate compounds, such as, but not limited to, zinc dihydrocarbyl dithiophosphate (ZDDP). When used, the one or more metal dihydrocarbyl dithiophosphate compounds can provide the lubricant, particularly the heavy duty lubricant, with at least about 500 ppm phosphorus, and in other approaches, from about 600 ppm to about 1200 ppm phosphorus, or from about 700 ppm to about 1,000 ppm phosphorus, or from about 700 ppm to about 1,200 ppm phosphorus. As used herein, the metal dihydrocarbyl dithiophosphate compounds preferably include hydrocarbyl groups derived from a mixture of primary and secondary alcohols.

[0065] Suitable metal dihydrocarbyl dithiophosphate compounds may contain 5 to about 10 weight percent metal (e.g., about 6 to about 9 weight percent metal, such as zinc) and about 8 to about 18 weight percent sulfur (e.g., about 12 to about 18 weight percent sulfur, or about 8 to about 15 weight percent sulfur). Suitable metal dihydrocarbyl dithiophosphate compounds can include dihydrocarbyl dithiophosphate metal salts, where the metal can be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or combinations thereof. Preferably, the metal is zinc.

[0066] The alkyl groups on the metal dihydrocarbyl dithiophosphate compounds herein may be derived from primary alcohols, secondary alcohols, phenols, and / or mixtures thereof, preferably mixtures of primary and secondary alcohols. For example, all of the alkyl or hydrocarbyl groups on the metal dihydrocarbyl dithiophosphate compounds herein may be derived from primary alcohols (such as 2-ethylhexyl alcohol) and / or mixtures of primary and secondary alcohols (such as 2-ethylhexanol, isobutanol, and isopropanol). For example, in one embodiment, about 60 mole percent or more of the alkyl groups are derived from primary alcohols such as 2-ethylhexanol and / or isobutyl alcohol, and about 40 mole percent or less of the alkyl groups are derived from secondary alcohols (such as isopropyl alcohol, methyl isobutyl carbinol, and / or combinations thereof). In an optional embodiment, all of the alkyl groups on the metal dihydrocarbyl dithiophosphate compounds may be derived from primary alcohols such as 2-ethylhexanol or others described below. Preferably, the metal dihydrocarbyl dithiophosphate compound is a ZDDP derived from 60 to 80 mole percent 2-ethylhexanol and / or isobutyl alcohol and 20 to 40 mole percent isopropyl alcohol, and may contain about 6 to about 10 weight percent phosphorus, about 7 to about 9 weight percent zinc, and about 15 to about 20 weight percent sulfur.

[0067] The metal dihydrocarbyl dithiophosphate compounds herein may be derived from an alcohol selected from, but not limited to, 2-ethylhexanol, methylheptanol, heptanol, octanol, nonanol, decanol, dodecanol, and / or their isovariants. Examples of suitable metal dihydrocarbyl dithiophosphate compounds include zinc O,O-di(C 8~14zinc O,O-bis(6-ethylhexyl)dithiophosphate; zinc O,O-dioctyldithiophosphate; zinc O,O-dipentyldithiophosphate; zinc O-(2-methylbutyl)-O-(2-methylpropyl)dithiophosphate; and zinc O-(3-methylbutyl)-O-(2-methylpropyl)dithiophosphate, or combinations thereof.

[0068] In one approach or embodiment, the metal dihydrocarbyl dithiophosphate compounds suitable for the heavy duty crankcase lubricants herein have Formula I:

[0069] [ka] wherein each R in formula I independently contains 6-18 carbon atoms, or 6-12 carbon atoms, or about 8-10 carbon atoms, provided that each phosphorus atom has an average of at least 14 total carbons per phosphorus atom, preferably at least 8 total carbons or 8-16 total carbons. For example, each R can independently be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, 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 have an average of 6-10 carbons, preferably 8-10 carbons. Preferably, each R may be a linear or branched C8 or 2-ethylhexyl group, a C3 or isopropyl group, and / or a C4 or isobutyl group. In formula I, A is a metal, such as aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof, preferably A is zinc. When the metal dihydrocarbyl dithiophosphate compound has the structure shown in formula I and A is zinc, the compound may have about 6 to about 9 weight percent phosphorus and about 7 to about 9 weight percent zinc, and a zinc to phosphorus ratio of about 1.0 to about 1.5. In some approaches or embodiments, it is understood in the art that a more accurate representation of the sulfur-zinc coordination arrangement may be represented by the symmetrical arrangement shown below, which has the chemical structure of formula II, which may be used herein interchangeably with formula I shown above. It is also understood that the structures depicted in Formulas I and II can exist as monomers, dimers, trimers, or oligomers (eg, tetramers).

[0070] [ka]

[0071] Dihydrocarbyl dithiophosphate metal salts can be prepared according to known techniques, typically by first forming dihydrocarbyl dithiophosphoric acid (DDPA) by reacting one or more alcohols or phenols with P2S5, and then neutralizing the formed DDPA with a metal compound such as zinc oxide. For example, DDPA can be produced by reacting a mixture of alcohols containing a suitable amount of primary alcohol (and a suitable blend of primary and secondary alcohols, if necessary) with P2S5. In this case, the DDPA contains alkyl groups derived primarily from primary alcohols, or from both primary and secondary alcohols, as necessary to meet the required primary alcohol content in the final product. Alternatively, multiple DDPAs can be prepared, with the alkyl groups on one DDPA derived entirely from secondary alcohols and the alkyl groups on another DDPA derived entirely from primary alcohols. The DDPAs are then blended together to form a mixture of DDPAs with alkyl groups that meet the above-mentioned primary alcohol content.

[0072] Base oil or base oil blend: The base oil used in the crankcase lubricant compositions herein, particularly the heavy duty crankcase lubricant compositions, may be an oil of lubricating viscosity and may be selected from any of the base oils in API Groups I-V as set forth in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. Heavy duty crankcase lubricants may have a kV100 (ASTM D445) of about 9 to about 20 cSt. In some cases, even lower viscosities are targeted, with crankcase lubricants, particularly heavy duty crankcase lubricants, having a kV100 (ASTM D445) of about 5 to about 9 cSt. The five base oil groups are generally set forth in Table 1 below.

[0073] [Table 1]

[0074] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, etc., but may also be natural oils, such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Thus, oils derived from Group III base oils may be referred to as synthetic fluids in the industry. Group II+ may include high viscosity index Group II.

[0075] The base oil blends used in the disclosed lubricating oil compositions can be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0076] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further refinement processing. Refined oils are similar to unrefined oils, except that they have been treated with one or more refining steps, which may result in the improvement of one or more properties. Examples of suitable refining 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 called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0077] Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often, these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

[0078] Mineral oils may include oils obtained by drilling or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils, and solvent- or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0079] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as alpha-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, and derivatives, analogs, and homologs thereof, or mixtures thereof. The polyalphaolefins are typically hydrogenated materials.

[0080] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

[0081] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition.

[0082] The amount of oil of lubricating viscosity present may be the remainder remaining after subtracting the sum of the amounts of performance additives, including viscosity index improvers and / or pour point depressants and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a major amount, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0083] In some approaches or embodiments, the base oil system herein comprises one or more of Group I through Group V base oils and may have a KV100 of from about 2 to about 20 cSt, in other approaches from about 2 to about 10 cSt, from about 2.5 to about 6 cSt, in yet other approaches from about 2.5 to about 3.5 cSt, and in other approaches from about 2.5 to about 4.5 cSt. As used herein, the terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "fully formulated lubricant composition," "lubricant," and "lubricating and cooling fluid" are considered synonymous and fully interchangeable terms that refer to a finished lubricating product that includes a major amount of a base oil component and minor amounts of detergents and other optional components.

[0084] Optional Additives: The lubricating oil compositions herein, particularly the heavy duty lubricating oil compositions, may also contain a number of optional additives in combination with the detergent and dispersant systems discussed above as necessary to meet performance criteria, which optional additives are described in the following paragraphs.

[0085] Antiwear agents: The lubricating oil compositions herein may also optionally contain additional antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphoric acid esters or salts thereof; phosphoric acid esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0086] Further examples of suitable additional antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, and the total of carbon atoms on the alkyl group may be at least 8. The antiwear agent may include citrates in one embodiment.

[0087] The additional antiwear agent may be present in a range including from about 0% to about 15% by weight, or from about 0.01% to about 10% by weight, or from about 0.05% to about 5% by weight, or from about 0.1% to about 3% by weight of the lubricating oil composition.

[0088] Boron-containing compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, borated dispersants such as borated hydrated sodium or potassium borates in dispersion, and borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057. The boron-containing compounds, when present, may be used in an amount sufficient to provide up to about 8% by weight of the lubricating oil composition, about 0.01% to about 7% by weight, about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight.

[0089] Additional detergents: The lubricating oil composition may optionally further comprise one or more neutral detergents, low-based detergents, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-bound alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and their preparation methods are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein.

[0090] The detergent substrate may be salified with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkylphenol, calcium sulfur-bound alkylphenol compound, calcium methylene bridged phenol, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkylphenol, magnesium sulfur-bound alkylphenol compound, magnesium methylene bridged phenol, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkylphenol, sodium sulfur-bound alkylphenol compound, or sodium methylene bridged phenol.

[0091] Overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a 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.

[0092] The overbased detergent of the lubricating oil composition may have a Total Base Number (TBN) of about 200 mg KOH / g or greater, or, as a further example, about 250 mg KOH / g or greater, or about 350 mg KOH / g or greater, or about 375 mg KOH / g or greater, or about 400 mg KOH / g or greater, as measured by the method of ASTM D2896.

[0093] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene bridged phenols, overbased magnesium phenates, overbased magnesium sulfur-containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene bridged phenols.

[0094] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH to about 400 mg KOH / g, at least about 225 mg KOH to about 350 mg KOH / g, or from about 230 mg KOH to about 350 mg KOH / g, all measured by the method of ASTM D 2896. When such detergent compositions are formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials that may be included in the detergent composition (e.g., accelerators, etc.).

[0095] The overbased detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 wt.% to about 10 wt.%, or from about 0.1 wt.% to about 8 wt.%, or from about 1 wt.% to about 4 wt.%, or from greater than about 4 wt.% to about 8 wt.%.

[0096] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme Pressure (EP) agents that are soluble in oil include sulfur and chlorosulfur containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphoric acid with propylene oxide; and mixtures thereof.

[0097] Friction modifiers: The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, but may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0098] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In other embodiments, the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

[0099] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free mechanical friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and may generally include polar end groups (e.g., carboxyl or hydroxyl) covalently attached to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is generally known as glycerol monooleate (GMO), which may include mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entirety of which is incorporated herein by reference.

[0100] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0101] The amines and amides may be used by themselves or in the form of adducts or reaction products with boron compounds such as boron oxides, boron halides, metaborates, boric acid or mono-, di-, or tri-alkyl borates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0102] Friction modifiers may optionally be present in a range such as from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from about 0.1% to about 4% by weight.

[0103] Transition metal-containing compounds: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0104] In some embodiments, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium (IV) alkoxide. Among the titanium-containing compounds that may be used in or for the preparation of oil-soluble materials in the technology of the present disclosure are various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as, but not limited to, titanium phenate; titanium carboxylates, such as titanium (IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolaminato) isopropoxide. Other forms of titanium encompassed within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyl dithiophosphates) and titanium sulfonates (e.g., alkyl benzene sulfonates), or generally reaction products of titanium compounds with various acid materials to form salts, such as oil-soluble salts. Thus, titanium compounds may be derived from organic acids, alcohols, and glycols, among others. Ti compounds may also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques that will be apparent to those skilled in the art. They may exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

[0105] In one embodiment, titanium may be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or may be reacted with any of a number of materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable -NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl (or alkyl) succinic anhydrides and polyamines; (c) hydroxy-containing polyester dispersants prepared by reaction of substituted succinic anhydrides with polyols, amino alcohols, polyamines, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to a lubricant or can be further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with about two parts (mole) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to produce a titanium modified succinimide dispersant.

[0106] Another titanium-containing compound is titanium alkoxide and C6-C 25 It may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0107] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or the following formula:

[0108] [ka] or the titanium compound may be represented by the formula:

[0109] [ka] (wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; R4 is H, C6 to C 25 The carboxylic acid moiety may be selected from the group consisting of

[0110] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0111] In some embodiments, the oil soluble titanium compound may be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 ppm to about 500 ppm by weight of titanium, or from about 50 ppm to about 300 ppm.

[0112] Viscosity index improver: The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in US Patent Application Publication No. 20120101017(A1).

[0113] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead of the viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) with an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0114] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0% to about 20% by weight, from about 0.1% to about 15% by weight, from about 0.1% to about 12% by weight, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0115] Other optional additives: Other additives may be selected to perform one or more functions required in a lubricating fluid. Additionally, one or more of the aforementioned additives may be multifunctional and may provide functions in addition to or other than those described herein.

[0116] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0117] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate 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.

[0118] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0119] 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.

[0120] A suitable rust inhibitor can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful.Useful rust inhibitors are high molecular weight organic acids.

[0121] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 wt. % to about 5 wt. %, from about 0.01 wt. % to about 3 wt. %, from about 0.1 wt. % to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0122] Generally speaking, suitable lubricants containing detergent metals herein may contain additive components in the ranges listed in the table below.

[0123] [Table 2]

[0124] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives and a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that supplies the properties required in the formulation.

[0125] definition For purposes of this disclosure, the chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. Additionally, general principles of organic chemistry are described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausolito: 1999, and "March's Advanced Organic Chemistry", 5th Ed., Ed.: Smith, M. B. and March, J., John Wiley & Sons, New York: 2001, the entireties of which are incorporated herein by reference.

[0126] As described herein, compounds may be optionally substituted with one or more substituents as illustrated generally above, or as illustrated by the specific classes, subclasses, and species of the present disclosure.

[0127] Unless otherwise clear from the context, the term "major amount" is understood to mean an amount of 50 weight percent or more, for example, about 80 to about 98 weight percent, based on the total weight of the composition, and the term "minor amount" as used herein is understood to mean an amount of less than 50 weight percent, based on the total weight of the composition.

[0128] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense, well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) and aromatic, aliphatic and alicyclic substituted aromatic substituents, as well as cyclic substituents in which a ring is completed through another portion of the molecule (e.g., two substituents taken together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy) that do not alter the predominantly hydrocarbon substituent in the context of this disclosure; (3) hetero substituents, i.e., substituents that, while having predominantly hydrocarbon character in the context of this disclosure, contain other than carbon in the ring or chain or are otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and encompass such substituents as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than 2, or as a further example, only one non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group, and in some embodiments, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0129] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0130] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be linear or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. An alkyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino,

[0046] The aryloxy group may be substituted (i.e., optionally substituted) with alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic -SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy.Without being limiting, some examples of substituted alkyl include carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO2-amino)alkyl), aminoalkyl, amidoalkyl, (alicyclic)alkyl, or haloalkyl.

[0131] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be linear or branched. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. An alkenyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbonyl], or heteroarylcarbonylamino. nyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO2-, alicyclic-SO2-, or aryl-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heteroalicyclicoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Without limitation, some examples of substituted alkenyls include cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (alicyclic)alkenyl, or haloalkenyl.

[0132] As used herein, an "alkynyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. Alkynyl groups can be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. Alkynyl groups can be substituted with one or more substituents, such as, for example, aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or cycloaliphatic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or cycloaliphatic finyl], sulfonyl [e.g., aliphatic -SO2-, aliphatic amino-SO2-, or cycloaliphatic -SO2-], amido [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, aryl and optionally substituted with aminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamido, alkoxycarbonyl, alkylcarbonyloxy, alicyclic, heteroalicyclic, aryl, heteroaryl, acyl [e.g., (alicyclic)carbonyl or (heteroalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heteroalicyclic)oxy, or (heteroaryl)alkoxy.

[0133] As used herein, an "amino" group refers to an -NR X R Y In the formula, R X and R YEach of is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaralkyl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is not limited to -NR X - Represented by R X is as defined above.

[0134] As used herein, a "cycloalkyl" group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cubyl, octahydroindenyl, decahydronaphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2.]decyl, bicyclo[2.2.2]octyl, adamantyl, or ((aminocarbonyl)cycloalkyl)cycloalkyl.

[0135] As used herein, a "heterocycloalkyl" group refers to a 3- to 10-membered mono- or bicyclic (fused or bridged) (e.g., 5- to 10-membered mono- or bicyclic) saturated ring structure in which one or more of the ring atoms is a heteroatom (e.g., N, O, S, or combinations thereof). Examples of heterocycloalkyl groups include piperidyl, piperazyl, tetrahydropyranyl, tetrahydrofuryl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidyl, isoxazolidyl, morpholinyl, thiomorpholyl, octahydrobenzofuryl, octahydrochromenyl, octahydrothiochromenyl, octahydroindolyl, octahydropyrindinyl, decahydroquinolinyl, octahydrobenzo[b]thiophenyl, 2-oxa-bicyclo[2.2.2]octyl, 1-aza-bicyclo[2.2.2]octyl, 3-aza-bicyclo[3.2.1]octyl, and 2,6-dioxa-tricyclo[3.3.1.0]nonyl. Monocyclic heterocycloalkyl groups can be fused with a phenyl moiety to form structures such as tetrahydroisoquinoline, which would be classified as heteroaryls.

[0136] As used herein, a "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or combinations thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fused ring systems having 2 to 3 rings. For example, benzo-fused groups include benzo fused to one or two 4-8 membered heterocyclic aliphatic moieties (e.g., indolisyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzthiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzthiazolyl, puryl, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthyridyl.

[0137] Monocyclic heteroaryls include, but are not limited to, furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridyl, pyridazyl, pyrimidyl, pyrazolyl, pyrazyl, or 1,3,5-triazyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0138] Bicyclic heteroaryls include indolizyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolizinyl, isoindolyl, indolyl, benzo[b]furyl, bexo[b]thiophenyl, indazolyl, benzimidazyl, benzthiazolyl, purinyl, 4H-quinolizyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, 1,8-naphthyridyl, or pteridyl. Bicyclic heteroaryls are numbered according to standard chemical nomenclature.

[0139] As used herein, the term "treat rate" refers to the weight percentage of a component in a lubricating composition.

[0140] Weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined using a gel permeation chromatography (GPC) instrument from Waters or similar instrument and data processed with Waters Empower Software or similar software using commercially available polystyrene standards (having Mn of 180 to about 18,000 as calibration standards). See, for example, W.W. Yau, J.J. Kirkland and D.D. Ly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, also incorporated herein by reference. EXAMPLES

[0141] A better understanding of the present disclosure and its many advantages can be made clear with the following examples. The following examples are illustrative and are not intended to be limiting in scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise stated or apparent from the context of the following examples and discussion throughout this disclosure, all percentages, ratios, and parts described in this disclosure are by weight.

[0142] The heavy duty crankcase lubricating oil compositions of the comparative example and the present invention were evaluated for piston detergency on a steel piston according to the OM471 piston detergency test of CEC L-118-21. The lubricating compositions evaluated for this example contained sulfonate and / or phenate detergents and provided the fluid relations in Table 3 below. Except for the change in detergent system, Inventive 1 and Comparative Example 1 otherwise contained identical additive packages (with identical treat rates) and thus had identical dispersant systems, antiwear systems, antioxidant systems, antifoam agents, pour point depressants, viscosity modifiers, with a balance of API Group III base oil, and achieved a target KV100 of 11.4 to about 11.7 cSt measured according to ASTM D445. The antioxidant systems of Inventive 1 and Comparative Example 1 contained at least 1.0 weight percent diphenylamine, at least 1.0 weight percent hindered phenol, and less than 0.2 weight percent molybdenum-containing compound. In addition to the detergent system changes, Comparative Example 2 also contained a reduction in the treat rate of dispersant in its dispersant system, a reduction in the treat rate of antioxidant in its antioxidant system, and an increase in the treat rate of zinc dithiophosphate in its antiwear system. Note that each fluid also contained slight changes in the process oil due to differences in the amounts of additives provided. Soap content was calculated as explained under subheading 7.2.5. Detergent Classification in the textbook entitled "Chemistry and Technology of Lubricants", Third Edition, edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 219-220.

[0143] [Table 3] * The TBN of each sulfonate and phenate detergent is measured by ASTM D2896, and the TBN contribution from the sulfonate is calculated based on the treat rate in the lubricating oil composition.

[0144] The detergent and dispersant systems for the heavy duty crankcase lubricants in Table 3 above contained the following components: Detergent A was an overbased calcium phenate having a TBN of about 250 and about 9.3 weight percent calcium. · Detergent B was an overbased calcium sulfonate having a TBN of about 307 and about 11.9 weight percent calcium. Detergent C was a low based calcium sulfonate having a TBN of about 28 and about 2.6 weight percent calcium. The dispersant system contained a combination of polyisobutylene succinimide dispersants derived from highly reactive polyisobutylenes, each having a number average molecular weight of 1000 to 2500. Each dispersant had 1.0 to 1.7 weight percent nitrogen. The antioxidant system contained a mixture of alkylated diphenylamines, hindered phenolic antioxidants, and molybdenum-containing compounds. · The antiwear system contained one or more zinc dithiophosphates which contributed phosphorus to the fluid.

[0145] The heavy duty lubricants in Table 3 were evaluated for piston cleanliness according to the OM471 piston cleanliness test (CEC L-118-21) using steel pistons. The results are provided in Table 4 below. Comparative Example 1 was previously acceptable in the previous piston cleanliness test of OM501LA (CEC L-101-08) when using aluminum pistons, but Comparative Example 1 did not achieve high piston cleanliness when tested using the new OM471 test for steel pistons. It was unexpected that Invention 1, which contains only sulfonate soap, achieved high piston cleanliness on steel pistons under the newer, more stringent OM471 test. Invention 1 is further expected to achieve high piston cleanliness in a modified version of the OM471 test using a shorter test period.

[0146] [Table 4] * Comparative Example 1 and 2 fluids were not able to complete the full test, recording the results reported after only 400 hours.

[0147] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list excludes other similar items that may be substituted for or added to the items in the list.

[0148] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0149] It is understood that each component, compound, substituent, or parameter disclosed herein should be construed as disclosed for use alone or in combination with one or more of any and all other components, compounds, substituents, or parameters disclosed herein.

[0150] It is further to be understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but any range of such values.

[0151] It is further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is further understood that any range between the endpoint values ​​within the broad range is also contemplated herein. Thus, a range of 1 to 4 also means a range of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0152] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and therefore can be combined with any other lower or upper limit or specific amount / value in a range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0153] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or that cannot be currently anticipated by the applicants or others skilled in the art. It is therefore intended that the appended claims as filed, and the appended claims as they may be amended, cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0154] The present disclosure also relates to the following numbered embodiments: 1. A method of lubricating a heavy duty diesel engine having steel pistons, comprising: lubricating a steel piston of a heavy duty diesel engine with a lubricating oil composition; a lubricating oil composition comprising: (i) a detergent system consisting of one or more alkaline earth metal sulfonate detergents providing from 0.3 to about 1 weight percent of a sulfonate soap to the lubricating oil composition; and (ii) a dispersant system comprising one or more polyisobutylene succinimide dispersants providing at least about 5 weight percent of one or more dispersants to the lubricating oil composition; The method of claim 1, wherein the one or more polyisobutylene succinimide dispersants are derived from a highly reactive polyisobutylene having a number average molecular weight of from about 1,200 to about 2,500 and providing greater than 650 ppm nitrogen to the lubricating oil composition. 2. A method of lubricating a heavy duty diesel engine having a steel piston as described in embodiment 1, wherein the heavy duty diesel engine is operated under conditions set forth in the OM471 Piston Detergency Test of CEC L-118-21. 3. A method of lubricating a heavy duty diesel engine having a steel piston as described in embodiment 1, wherein the heavy duty diesel engine is configured to power a vehicle having a gross vehicle weight rating of about 6,000 pounds or greater. 4. A method of lubricating a heavy duty diesel engine having a steel piston according to embodiment 1, wherein the detergent system consists of one or more overbased calcium sulfonate detergents and one or more low based calcium sulfonate detergents, the overbased detergents having a total base number (TBN) of at least about 300 mg KOH / g and the low based detergents having a total base number (TBN) of about 175 mg KOH / g or less, the total base numbers (TBN) being determined by ASTM D2896. 5. A method of lubricating a heavy duty diesel engine having steel pistons according to embodiment 4, wherein the lubricating composition comprises from about 0.3 to about 0.7 weight percent of the sulfonate soap. 6. A method of lubricating a heavy duty diesel engine having steel pistons as described in embodiment 4, wherein the detergent system comprises one or more overbased sulfonate detergents in an effective amount to provide the detergent system with at least about 5 mg KOH / g, and one or more underbased sulfonate detergents in an effective amount to provide about 25 to about 40 weight percent detergent soap. 7. A method of lubricating a heavy duty diesel engine having steel pistons as described in embodiment 1, wherein the detergent system consists essentially of a calcium sulfonate detergent. 8. A method of lubricating a heavy duty diesel engine having steel pistons as described in embodiment 1, wherein the detergent system is substantially free of magnesium sulfonate detergents, substantially free of phenate detergents, or a combination thereof. 9. A method of lubricating a heavy duty diesel engine having steel pistons as recited in embodiment 1, wherein the lubricating oil composition contains from about 50 ppm to about 200 ppm of molybdenum provided by an oil-soluble molybdenum compound selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organo-molybdenum complexes of organic amides, or mixtures thereof. 10. A method for lubricating a heavy duty diesel engine having steel pistons according to claim 1, wherein the lubricating oil composition further comprises from about 0.5 to about 5 weight percent of one or more ashless antioxidants selected from hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof. 11. A method of lubricating a heavy duty diesel engine having steel pistons as described in embodiment 1, wherein the lubricating oil composition contains up to about 1200 ppm phosphorus from one or more metal dihydrocarbyl dithiophosphate compounds having hydrocarbyl groups derived from a mixture of linear or branched primary alcohols and linear or branched secondary alcohols. 12. A heavy duty crankcase lubricating oil composition suitable for diesel engines having a gross vehicle weight of about 6,000 pounds or more, comprising: one or more base oils of lubricating viscosity; a detergent system comprising one or more alkaline earth metal sulfonate detergents providing up to about 1 weight percent of a sulfonate soap to the lubricating oil composition; a dispersant system comprising one or more polyisobutylene succinimide dispersants providing at least about 5 weight percent of the one or more dispersants to the lubricating composition; 1. A heavy duty crankcase lubricating oil composition, wherein one or more polyisobutylene succinimide dispersants are derived from a highly reactive polyisobutylene having a number average molecular weight of from about 1,200 to about 2,500 and providing greater than 650 ppm nitrogen to the lubricating oil composition. 13. The heavy duty crankcase lubricating oil composition of embodiment 12, wherein the lubricating oil composition achieves a steel piston detergency rating of at least about 90% as measured by the OM471 piston detergency test (CEC L-118-21). 14. The heavy duty crankcase lubricating oil composition of embodiment 12, wherein the detergent system consists of one or more overbased calcium sulfonate detergents and one or more lowbased calcium sulfonate detergents, the overbased detergents having a total base number (TBN) of at least about 200 mg KOH / g and the lowbased detergents having a total base number (TBN) of about 175 mg KOH / g or less, the total base numbers (TBN) being determined by ASTM D2896. 15. The heavy duty crankcase lubricating oil composition of embodiment 13, wherein the detergent system comprises one or more overbased sulfonate detergents in an effective amount to provide the detergent system with at least about 5 mg KOH / g, and one or more underbased sulfonate detergents in an effective amount to provide from about 25 to about 40 weight percent detergent soap. 16. The heavy duty crankcase lubricating oil composition according to embodiment 12, wherein the detergent system consists essentially of a calcium sulfonate detergent. 17. The heavy duty crankcase lubricating oil composition of embodiment 12, wherein the detergent system is substantially free of magnesium sulfonate detergents, substantially free of phenate detergents, or a combination thereof. 18. The heavy duty crankcase lubricating oil composition of embodiment 12, wherein the lubricating oil composition contains from about 50 ppm to about 200 ppm of molybdenum provided by an oil-soluble molybdenum compound selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organo-molybdenum complexes of organic amides, or mixtures thereof. 19. The heavy duty crankcase lubricating oil composition of embodiment 12, wherein the lubricating oil composition further comprises from about 0.5 to about 5 weight percent of one or more ashless antioxidants selected from hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof. 20. The heavy duty crankcase lubricating oil composition according to embodiment 1, wherein the lubricating oil composition contains up to about 1200 ppm phosphorus from one or more metal dihydrocarbyl dithiophosphate compounds having hydrocarbyl groups derived from a mixture of linear or branched primary alcohols and linear or branched secondary alcohols.

Claims

1. 1. A method of lubricating a heavy duty diesel engine having steel pistons, comprising: lubricating said steel piston of said heavy duty diesel engine with a lubricating oil composition; the lubricating oil composition comprises: (i) a detergent system consisting of one or more alkaline earth metal sulfonate detergents providing from 0.3 to about 1 weight percent of a sulfonate soap to the lubricating oil composition; and (ii) a dispersant system comprising one or more polyisobutylene succinimide dispersants providing at least about 5 weight percent of one or more dispersants to the lubricating oil composition; The method of claim 1, wherein said one or more polyisobutylene succinimide dispersants are derived from a highly reactive polyisobutylene having a number average molecular weight of about 1,200 to about 2,500 and providing greater than 650 ppm nitrogen to said lubricating oil composition.

2. 10. The method of lubricating a heavy duty diesel engine having steel pistons as set forth in claim 1, wherein the heavy duty diesel engine is operated under conditions set forth in the OM471 Piston Cleanliness Test of CEC L-118-21 and / or the heavy duty diesel engine is configured to power a vehicle having a gross vehicle weight rating of about 6,000 pounds or greater.

3. 2. The method of lubricating a heavy duty diesel engine having steel pistons according to claim 1, wherein the detergent system consists of one or more overbased calcium sulfonate detergents and one or more lowbased calcium sulfonate detergents, the overbased detergents having a total base number (TBN) of at least about 300 mg KOH / g and the lowbased detergents having a total base number (TBN) of about 175 mg KOH / g or less, the total base number (TBN) being determined by ASTM D2896.

4. 4. A method for lubricating a heavy duty diesel engine having steel pistons as recited in claim 3, wherein the lubricating composition comprises from about 0.3 to about 0.7 weight percent of the sulfonate soap.

5. 4. A method of lubricating a heavy duty diesel engine having steel pistons as recited in claim 3, wherein said detergent system comprises an effective amount of said one or more overbased sulfonate detergents to provide said detergent system with at least about 5 mg KOH / g, and an effective amount of said one or more underbased sulfonate detergents to provide from about 25 to about 40 weight percent detergent soap.

6. 2. A method of lubricating a heavy duty diesel engine having steel pistons as claimed in claim 1, wherein the detergent system consists essentially of a calcium sulfonate detergent and / or the detergent system is substantially free of magnesium sulfonate detergents, substantially free of phenate detergents, or a combination thereof.

7. 2. A method for lubricating a heavy duty diesel engine having steel pistons as recited in claim 1, wherein the lubricating oil composition contains from about 50 ppm to about 200 ppm molybdenum provided by an oil-soluble molybdenum compound selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organo-molybdenum complexes of organic amides, or mixtures thereof.

8. 2. The method of lubricating a heavy duty diesel engine having steel pistons according to claim 1, wherein the lubricating oil composition further comprises from about 0.5 to about 5 weight percent of one or more ashless antioxidants selected from hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof.

9. 2. A method for lubricating a heavy duty diesel engine having steel pistons as claimed in claim 1, wherein the lubricating oil composition contains up to about 1200 ppm phosphorus from one or more metal dihydrocarbyl dithiophosphate compounds having hydrocarbyl groups derived from a mixture of linear or branched primary alcohols and linear or branched secondary alcohols.

10. 1. A heavy duty crankcase lubricating oil composition suitable for diesel engines having a gross vehicle weight of about 6,000 pounds or more, comprising: one or more base oils of lubricating viscosity; a detergent system comprising one or more alkaline earth metal sulfonate detergents providing up to about 1 weight percent of a sulfonate soap to said lubricating oil composition; a dispersant system comprising one or more polyisobutylene succinimide dispersants providing at least about 5 weight percent of said one or more dispersants in said lubricating composition; A heavy duty crankcase lubricating oil composition, wherein the one or more polyisobutylene succinimide dispersants are derived from a highly reactive polyisobutylene having a number average molecular weight of about 1,200 to about 2,500 and providing greater than 650 ppm nitrogen to the lubricating oil composition.

11. 11. The heavy duty crankcase lubricating oil composition of claim 10, wherein the lubricating oil composition achieves a steel piston detergency rating of at least about 90% as measured by the OM471 piston detergency test (CEC L-118-21).

12. 11. The heavy duty crankcase lubricating oil composition of claim 10, wherein the detergent system consists of one or more overbased calcium sulfonate detergents and one or more lowbased calcium sulfonate detergents, the overbased detergents having a total base number (TBN) of at least about 200 mg KOH / g and the lowbased detergents having a total base number (TBN) of about 175 mg KOH / g or less, the total base number (TBN) being determined by ASTM D2896.

13. 11. The heavy duty crankcase lubricating oil composition of claim 10, wherein the detergent system comprises the one or more overbased sulfonate detergents in an effective amount to provide the detergent system with at least about 5 mg KOH / g, and the one or more low based sulfonate detergents in an effective amount to provide from about 25 to about 40 weight percent detergent soap, and / or the detergent system consists essentially of a calcium sulfonate detergent, and / or the detergent system is substantially free of magnesium sulfonate detergents, substantially free of phenate detergents, or combinations thereof.

14. 11. The heavy duty crankcase lubricating oil composition of claim 10, wherein the lubricating oil composition contains from about 50 ppm to about 200 ppm molybdenum provided by an oil soluble molybdenum compound selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organo-molybdenum complexes of organic amides, or mixtures thereof.

15. 11. The heavy duty crankcase lubricating oil composition of claim 10, wherein the lubricating oil composition further comprises from about 0.5 to about 5 weight percent of one or more ashless antioxidants selected from hindered phenols, aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, sulfurized olefins, or mixtures thereof, and / or the lubricating oil composition comprises up to about 1200 ppm phosphorus from one or more metal dihydrocarbyl dithiophosphate compounds having hydrocarbyl groups derived from mixtures of linear or branched primary alcohols and linear or branched secondary alcohols.

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