Detergent system for improved piston cleanliness

Abstract

To provide a lubricating composition which achieves piston cleanliness according to CECL-C 117 - 20 (VWTDi3).SOLUTION: One or more base oils of lubricating viscosity, less than 2 weight percent total antioxidant compounds selected from aminic antioxidant compounds, phenolic antioxidant compounds, molybdenum antioxidant compounds, or combinations thereof, less than 100ppm of boron, and a total base number (TBN) of at least 5. 5mgKOH / g as measured by ASTMD2896; And having a soap content of greater than or equal to about 75 percent sulfonate soaps and less than or equal to about 25 percent phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof, wherein the lubricating composition exhibits an average piston cleanliness of greater than or equal to 53 merits in the CECL - 117 - 20 (RL276) piston cleanliness test of VWTDi3 - 5.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to lubricating compositions, and more particularly to lubricating compositions that exhibit improved piston cleanliness using selected detergent systems and lower levels of antioxidants. [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. Today's engines are often becoming smaller, lighter, and more efficient with technologies designed to improve fuel economy, performance, and power output. These requirements also mean that the performance of engine oils must evolve to meet the higher demands of such modern engines and the corresponding performance standards associated with their unique uses and applications. Due to such stringent demands on engine oils, lubricant manufacturers often tailor lubricants and their additives to meet certain performance requirements for industry and / or manufacturer 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 performance specifications of a different use or application.

[0003] For example, the selection of detergents in engine oil formulations has often been based on several factors, including, but not limited to, piston detergency, acid neutralization, TBN retention, oxidation, low-speed pre-ignition, wear, friction performance, fuel economy, supply, and / or cost factors, to name just a few relevant considerations. However, it has previously been accepted that piston detergency in diesel engines typically requires the use of detergent sources other than sulfonates; thus, diesel piston detergency has required, for example, a combination of phenate and sulfonate detergents. When other detergents (such as sulfonates, phenates, and / or salicylates) were included, traditional detergent systems often combined with base oil systems containing higher levels of antioxidants or higher levels of API Group IV base oils. Therefore, the combination required to achieve piston detergency has tended to limit the selection of auxiliary components in the formulation, resulting in formulation drawbacks and / or formulation trade-offs that can affect overall performance.

[0004] More specifically, the most stringent industry test for demonstrating diesel piston detergency was CEC L-078-99, commonly known as the VW TDi2 test. Because lubricants evaluated according to VW TDi2 showed clear responses to formulations containing phenate-based detergents, higher levels of antioxidants, and / or higher levels of API Group IV (e.g., PAO) base oils, preferred lubricants passing this performance standard included phenate detergents or other detergent combinations with phenate additives containing higher levels of antioxidants and / or higher levels of synthetic base oils. Recently, the VW TDi2 performance test was replaced by CEC L-117-20, or the so-called VW TDi3 test. This updated evaluation is based on newer engines, operating under even more severe conditions than the previous evaluation. Therefore, engine lubricants must now demonstrate passing performance when subjected to the more severe operating conditions of the new TDi3 test. However, in many situations, varying the components within a lubricant composition to meet newer performance characteristics tends to adversely affect one or more other performance characteristics, making it difficult for lubricant manufacturers to meet newer industrial performance demands while simultaneously maintaining traditional fluid performance. Summary of the Invention

[0005] The present disclosure relates to a lubricating composition that achieves passing piston cleanliness in the CEC L-117-20 (VW TDi3) test. In one approach or embodiment, the lubricating composition includes one or more base oils of lubricating viscosity (preferably less than 20 weight percent API Group IV base oil), less than 2 weight percent total antioxidant compounds selected from amine-based antioxidant compounds, phenolic antioxidant compounds, molybdenum antioxidant compounds, or combinations thereof, less than 100 ppm boron, and a detergent system having a total base number (TBN) of at least 5.5 mg KOH / g as measured by ASTM D2896, and having a soap content of about 75 percent or more sulfonate soaps and about 25 percent or less phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof. In some embodiments, the lubricating compositions exhibit an average piston cleanliness that is equal to or better than the RL 276-5 reference fluid merit, which in some embodiments is 53 merit or greater in the CEC L-117-20 (VW TDi3) piston cleanliness test of RL276-5.

[0006] In other approaches or embodiments, the lubricating composition of the preceding paragraph may include other features, embodiments, or elements in any combination. These other features, embodiments, or elements include one or more of the following: the detergent system has less than about 5 percent phenate soap, salicylate soap, calixarate soap, or a combination thereof; and / or the detergent system has a TBN (ASTM D2896) of 5.5 to 15 mg KOH / g and provides 0.3 to 0.7 weight percent sulfonate soap; and / or the lubricating composition has a detergent system TBN (ASTM D2896) of 13 to 18 mg KOH / g sulfonate soap content. D2896), and / or the detergent system consists essentially of one or more of magnesium sulfonate, sodium sulfonate, or calcium sulfonate in amounts to provide the detergent system TBN, and / or the detergent system includes only magnesium sulfonate, sodium sulfonate, calcium sulfonate, or combinations thereof in amounts to provide the detergent system TBN, and / or the detergent system provides from about 0.3 weight percent to about 0.7 weight percent sulfonate soap, and / or the detergent system has 1 percent or less of phenate soap, salicylate soap, calixarate soap, or combinations thereof (preferably no detectable amounts of phenate soap, salicylate soap, calixarate soap, or combinations thereof), and / or the detergent system has 1 percent or less of calcium sulfonate, magnesium sulfonate, sodium sulfonate, or combinations thereof (preferably no detectable amounts of calcium sulfonate, calcium sulfonate, or combinations thereof). and / or the lubricating composition has less than about 1.3 weight percent total antioxidant compounds; and / or the lubricating composition has less than about 5 weight percent API Group IV base oil; and / or the detergent system has a ratio of sulfonate soap to phenate soap of about 95:5 or greater; and / or the detergent system is a blend of neutral to low based sulfonate detergents and overbased sulfonate detergents in amounts to provide the detergent system TBN; and / or the detergent system includes from about 0 to about 7 weight percent sulfonate detergent from the neutral to low based sulfonate detergents and from about 0.1 to about 3.0 weight percent sulfonate detergent from the overbased sulfonate detergents.

[0007] In yet another approach or embodiment, provided herein is a method for passing the CEC L-117-20 piston detergency test. In an aspect of this approach or embodiment, the method includes providing a lubricating composition comprising one or more base oils of lubricating viscosity, less than 2 weight percent total antioxidant compounds selected from amine-based antioxidant compounds, phenolic antioxidant compounds, molybdenum antioxidant compounds, or combinations thereof, less than 100 ppm boron, a detergent system having a total base number (TBN) of at least 5.5 mg KOH / g as measured by ASTM D2896 and having a soap content of about 75 percent or more sulfonate soaps and about 25 percent or less phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof, and less than 20 weight percent API Group IV base oil; and then measuring the piston detergency according to CEC L-117-20 (VW TDi3). In some embodiments, the method exhibits an average piston cleanliness that is equal to or better than the RL 276-5 reference fluid merit, which in some embodiments is 53 merit or better in the CEC L-117-20 (VW TDi3) piston cleanliness test for RL276-5.

[0008] In other approaches or embodiments, the method of the preceding paragraph may include other features, steps, or embodiments, in any combination. These other features, steps, or embodiments may include one or more of the following:The detergent system has about 5 percent or less of a phenate soap, a salicylate soap, a calixarate soap, or a combination thereof, and / or the detergent system has a TBN (ASTM D2896) of 5.5 to 15 mg KOH / g, providing 0.3 to 0.7 weight percent of a sulfonate soap, and / or the lubricating composition has a detergent system TBN (ASTM D2896) of 13 to 18 mg KOH / g of sulfonate soap content. D2896), and / or the detergent system consists essentially of one or more of magnesium sulfonate, sodium sulfonate, or calcium sulfonate in amounts to provide the detergent system TBN, and / or the detergent system includes only magnesium sulfonate, sodium sulfonate, calcium sulfonate, or combinations thereof in amounts to provide the detergent system TBN, and / or the detergent system is substantially free of detergents providing phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof, or the detergent system has about 5 percent or less of phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof, and / or the detergent system has 1 percent or less of phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof, and and / or the detergent system provides at least one of calcium, magnesium, sodium, or combinations thereof, individually or combined, in an amount up to about 5000 ppm; and / or the lubricating composition has less than about 1.3 weight percent total antioxidant compounds; and / or the detergent system has a ratio of sulfonate soap to phenate soap of about 95:5 or greater; and / or the detergent system is a blend of neutral to low based sulfonate detergents and overbased sulfonate detergents in amounts to provide the detergent system TBN; and / or the detergent system includes about 0 to about 7 weight percent sulfonate detergent from the neutral to low based sulfonate detergents and about 0.1 to about 3 weight percent sulfonate detergent from the overbased sulfonate detergents; and / or the lubricating composition has less than about 5 weight percent API Group IV base oil.

[0009] In yet another approach or embodiment, also provided herein is the use of a lubricating composition to achieve an average piston cleanliness in CEC L-276-20 (VW TDi3) that is equal to or better than the RL 276-5 reference fluid merit, which in some embodiments is 53 merit or greater in the CEC L-117-20 (VW TDi3) piston cleanliness test of RL276-5. By way of this embodiment, the lubricating composition is any embodiment described in this Summary, in particular a lubricating composition comprising one or more base oils of lubricating viscosity; less than 2 weight percent total antioxidant compounds selected from amine-based antioxidant compounds, phenolic antioxidant compounds, molybdenum antioxidant compounds, or combinations thereof; less than 100 ppm boron; a detergent system having a total base number (TBN) of at least 5.5 mg KOH / g as measured by ASTM D2896 and having a soap content of about 75 percent or more sulfonate soaps and about 25 percent or less phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof; and less than 20 weight percent API Group IV base oil. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure relates to lubricating compositions and methods of lubricating diesel internal combustion engines that are effective in achieving passing piston cleanliness according to CEC L-117-20 or the so-called VW TDi3 test. In an embodiment, the lubricating compositions and methods herein include one or more base oils of lubricating viscosity (preferably, the lubricant comprises less than about 20 weight percent API Group IV base oil); less than 2 weight percent total antioxidant compounds (e.g., amine-based antioxidant compounds, phenolic antioxidant compounds, molybdenum antioxidant compounds, or a combination thereof, more preferably less than about 1.5 weight percent total antioxidant compounds); less than 100 ppm boron (preferably, less than 50 ppm, or more preferably, less than 15 ppm boron); and a detergent system having a total base number (TBN) of at least 5.5 mg KOH / g as measured by ASTM D2896 (preferably, a TBN of 5.5 to 15) and providing a soap content of greater than or equal to about 75 percent sulfonate soaps and less than about 25 percent phenate or other types of soap other than sulfonates (preferably, providing substantially no phenate soaps or providing no soap content other than sulfonates). Surprisingly, even in compositions containing little or no phenate soap or other types of soap content other than sulfonates (previously required to achieve diesel piston detergency in previous industry tests), lower levels of total antioxidants, lower levels of total boron compounds, and little or no API Group IV base oil, the lubricating compositions herein meet or exceed the lubricant performance shown in the CEC L-117-20 (VW TDi3) piston detergency test.

[0011] In yet another approach or embodiment, the detergent system herein has a TBN (ASTM D2896) of 5.5 to 15 mg KOH / g, providing 0.3 to 0.7 weight percent sulfonate soaps (total soaps being at least about 75 percent sulfonate soaps, at least about 80 percent sulfonate soaps, at least about 90 percent sulfonate soaps, at least about 95 percent sulfonate soaps, at least about 98 percent sulfonate soaps, or about 100 percent sulfonate soaps). In some embodiments, it has also been discovered that the relative amounts of sulfonate soap content to detergent TBN contribution must be matched in a selected ratio to achieve acceptable TDi3 performance in conjunction with lubricants having lower antioxidant content, lower boron content, and / or lower levels of API Group IV base oils. For example, in some embodiments, it has been discovered that when the lubricating compositions herein have a ratio of detergent system TBN (ASTM D2896) to sulfonate soap content of from about 13 to about 18, more preferably from about 14 to about 16 (as shown in the examples), the lubricating compositions achieve acceptable TDi3 piston cleanliness using less antioxidant, less boron, and less Group IV base oil content.

[0012] In yet other embodiments, the lubricating oil compositions and methods herein consist essentially of, or alternatively consist of (e.g., consist only of), one or more of magnesium sulfonate, sodium sulfonate, or calcium sulfonate in amounts to provide the detergent system TBN and soap content. In other words, the detergent system of the present invention is primarily a sulfonate detergent, and most preferably a sulfonate-only detergent with little or no phenate or other detergent types (most preferably no phenate or other detergent additives) previously required to pass diesel piston detergency tests. Even with no phenate soap, lower levels of total antioxidants (e.g., less than about 2 weight percent, less than about 1.5 weight percent, or less than about 1.3 weight percent total antioxidants), lower levels of boron (e.g., less than 100 ppm, less than 50 ppm, less than 20 ppm, or less than 10 ppm boron), and little or no Group IV base oil (e.g., less than about 20 wt%, less than about 10 wt%, less than about 5 wt%, less than about 2 wt%, less than about 1 wt%, or none), the lubricants herein surprisingly pass the more stringent TDi3 piston detergency test. The detergent systems herein are substantially free of phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof, meaning no more than about 25 percent, no more than about 20 percent, no more than about 15 percent, no more than about 10 percent, no more than about 5 percent, no more than about 2.5 percent, no more than about 1 percent phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof, or none at all.

[0013] Detergents The lubricating compositions herein include a detergent system that achieves VW TDi3 piston cleanliness with little or no phenate soap, salicylate soap, calixarate soap, or combinations thereof, preferably without any phenate soap, salicylate soap, calixarate soap, or combinations thereof. In some approaches, piston cleanliness is achieved with detergents when a minimum TBN level is maintained by a sulfonate additive, which may be a blend of neutral, underbased, or overbased sulfonate detergents. Preferred TBN levels contributed by sulfonate detergents are at least 5.5 mg KOH / g, at least 6 mg KOH / g, at least 7 mg KOH / g, or at least 8 mg KOH / g, up to about 15 mg KOH / g, up to about 12 mg KOH / g, or up to about 10 mg KOH / g. In embodiments, the detergent systems herein generally comprise one or more alkali or alkaline metal salts of sulfonates, and may contain small amounts, residual levels, or no other detergent additives such as phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof, so long as the minimum amounts of sulfonate soaps, TBN levels, soap content relationships, and / or low levels of other detergents described herein are satisfied.

[0014] 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 individual and / or total detergent additives, in other ways from about 0.15 to about 3 weight percent, and in yet other ways from about 0.15 to 2.6 weight percent of individual and / or total detergent additives, so long as the detergent additives satisfy the sulfonate amount and other relationships described herein.

[0015] As noted above, and in some approaches, the detergent system provides a selected amount of sulfonate soap and TBN level along with a certain amount of detergent metal. For example, the detergent system herein may provide an amount of total detergent metal greater than about 750 ppm total metal, or in other approaches from about 1000 ppm to about 5000 ppm total metal, from about 1200 ppm to about 3500 ppm total metal, from about 1400 to about 3000 ppm total metal, or from about 1500 ppm to about 2500 ppm total metal, based on the total lubricating composition. In other approaches, the detergent metal is calcium, sodium, and / or magnesium, preferably calcium, sodium, and magnesium provided by sulfonates, and more preferably only calcium, sodium, and / or magnesium sulfonates. Preferably, the metal is calcium, magnesium, or a combination thereof.

[0016] Generally, suitable detergents in the system may include linear or branched alkali or alkaline earth metal salts, such as calcium, sodium, or magnesium, of petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl, and / or various phenates or phenate derivatives. Examples of suitable detergents include low based / neutral and over based variations of the following detergents, in addition to the required amount of sulfonate soap: calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0017] The detergent additive may be neutral, underbased, or overbased, preferably overbased or a mixture of neutral to underbased and overbased detergents, as needed, meeting the minimum detergent TBN numbers set forth above. 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.

[0018] The term "overbased" refers to metal salts in which the amount of metal present exceeds the stoichiometric amount, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates. Such salts can have conversion levels greater than 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the MR is 1, while in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, highly based, or superbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

[0019] 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. Detergents can be neutral or overbased. For example, a neutral detergent may have a total base number (TBN) of less than about 200 mg KOH / gram. In another example, the overbased detergent of the lubricating oil composition herein may have a total base number (TBN) of about 200 mg KOH / gram or more, or about 250 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more. The overbased detergent may have a metal-to-substrate ratio of 1.1:1 or less, or 2:1 or less, or 4:1 or less, or 5:1 or less, or 7:1 or less, or 10:1 or less, or 12:1 or less, or 15:1 or less, or 20:1 or less.

[0020] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylic acid, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-coupled alkylphenol compound, overbased calcium methylene-bridged phenol, overbased magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-coupled alkylphenol compound, or overbased magnesium methylene-bridged phenol (so long as the sulfonate soap and other relationships described herein are satisfied).

[0021] Optionally, if a low-based or neutral detergent is incorporated into the detergent system, it generally has a TBN of less than 200 mg KOH / g, a maximum of 175 mg KOH / g, a maximum of 150 mg KOH / g, a maximum of 100 mg KOH / g, or a maximum of 50 mg KOH / g. The low-based / neutral detergent may include a calcium- or magnesium-containing detergent. Examples of suitable low-based / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate (as long as the sulfonate soap and other relationships described herein are satisfied).

[0022] In some embodiments, the detergents used in the lubricants herein comprise at least an overbased calcium sulfonate, an overbased sodium sulfonate, and / or an overbased magnesium sulfonate, each having a total base number of 200 to 400, or in another approach, from about 200 to about 350. The TBN values ​​above reflect the values ​​of the finished detergent components diluted in the base oil. In some approaches, the detergent system comprises a blend of neutral to low-based and overbased sulfonate detergents, and may include from about 0 to about 7.0 weight percent of the neutral to low-based sulfonate detergent and from about 0.1 to about 3.0 weight percent of the overbased sulfonate detergent (or in another approach, from about 0.2 to about 2.7 weight percent of the overbased sulfonate detergent). In yet another approach, the detergent system herein may have a ratio of low-based sulfonate detergent to overbased sulfonate detergent of from about 0:3 to about 35:1.

[0023] In other embodiments, the TBN of the detergents herein may reflect the neat or undiluted version of the detergent component. For example, the fluids herein may include an overbased calcium or sodium sulfonate as the neat additive having a TBN of from about 300 to about 450, or in other words from about 380 to about 420, and / or an overbased magnesium sulfonate as the neat additive having a TBN of from about 500 to about 700, or in other words from about 600 to about 700.

[0024] More specifically, the detergent systems herein include neutral, underbased, and / or overbased detergents (preferably neutral to overbased calcium sulfonates, neutral to overbased sodium sulfonates, and / or neutral to overbased magnesium sulfonates) to achieve a detergent TBN as measured by ASTM D2896 of at least about 5.5 mg KOH / g, at least about 6 mg KOH / g, at least about 8 mg KOH / g up to about 15 mg KOH / g, up to about 12 mg KOH / g, or up to about 10 mg KOH / g.The detergent system may also contain at least one of calcium, sodium, magnesium, or a combination thereof, and thus one or more of the following metal contents: sodium: up to about 40 ppm sodium, at least about 40 ppm sodium, at least about 90 ppm sodium, at least about 180 ppm sodium, at least about 200 ppm sodium, at least 300 ppm sodium, or at least about 400 ppm sodium (preferably from about 40 to about 1,000 ppm sodium, from about 180 ppm to about 1,000 ppm, from about 200 ppm to about 1,000 ppm sodium, from 300 ppm to about 1,000 ppm sodium, or 400 ppm to about 1,000 ppm sodium); magnesium: up to about 90 ppm magnesium, at least about 90 ppm magnesium, at least about 180 ppm magnesium, at least about 200 ppm magnesium, at least 300 ppm sodium; ppm magnesium, or at least about 400 ppm magnesium (preferably about 90 to about 3,500 ppm magnesium, about 180 ppm to about 3,000 ppm magnesium, about 200 ppm to about 2,000 ppm magnesium, 300 ppm to about 1,500 ppm magnesium, or 400 ppm to about 1,000 ppm magnesium), or in some embodiments, calcium: up to about 90 ppm calcium, at least about 90 ppm The detergent system provides at least about 90 ppm of calcium, at least about 180 ppm of calcium, at least about 200 ppm of calcium, at least about 300 ppm of calcium, or at least about 400 ppm of calcium (preferably about 90 to about 3,500 ppm of calcium, about 180 ppm to about 3,000 ppm, about 200 ppm to about 2,000 ppm of calcium, 300 ppm to about 1,500 ppm of calcium, or 400 ppm to about 1,000 ppm of calcium). As shown in the examples below, lubricants meeting such detergent system contributions surprisingly achieve VW TDi3 piston cleanliness even with little or no levels of phenate detergent.

[0025] The detergent systems herein have a selected level of sulfonate soap content, particularly a soap content of at least about 75 percent sulfonate soap, or in other ways 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 ways, the detergent systems herein have a selected weight ratio of sulfonate soap to phenate soap, salicylate soap, calixylate soap, or combination thereof of about 75:25 or greater, about 80:20 or greater, about 85:15 or greater, about 90:10 or greater, or even about 95:5 or greater (greater in this ratio context means more sulfonate soap relative to phenate soap, salicylate soap, calixylate soap, or combination thereof). Preferably, the detergent systems herein contain only residual levels, if any, of phenate soaps, salicylate soaps, calixarate soaps, or soaps other than sulfonates.

[0026] In yet other embodiments or approaches, the amount of soap contributed by the detergent systems herein is balanced against a selected detergent TBN level to achieve VW TDi3 piston cleanliness with little or no phenate detergent, lower antioxidants, lower boron, and little or no Group IV base oil. For example, the detergent systems of the lubricants herein, in some embodiments, have a TBN (ASTM D2896) of 5.5 to 15 mg KOH / g (preferably about 5.5 to about 10 or other ranges above), providing 0.3 to 0.7 weight percent sulfonate soap. As shown in the examples below, when the detergent TBN and sulfonate soap relationship are balanced, such as in embodiments where the detergent system exhibits a ratio of detergent system TBN (ASTM D2896) to sulfonate soap content of from about 13 to about 18 (preferably, 14 to about 16), the lubricant surprisingly achieves passing piston cleanliness according to the TDi3 test, even while containing lower levels of total antioxidants, lower levels of total boron, and little or no API Group IV base oil.

[0027] Soap content generally refers to the amount of neutral organic acid salts and reflects the cleaning ability or cleaning power of the detergent and its ability to lift dirt. The soap content of a lubricant can be determined by ASTM D3712. Further discussion regarding the determination of soap content can be found in the relevant portions of FUELS AND LUBRICANTS HANDBOOK, TECHNOLOGY, PROPERTIES, PERFORMANCE, AND TESTING, George Totten, editor, ASTM International, 2003, which are incorporated herein by reference.

[0028] Antioxidants: The lubricating oil compositions herein may contain one or more antioxidants, but may contain limited amounts of total antioxidant compounds. As used herein, antioxidant compounds 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. Preferably, the antioxidant compounds include or are selected from amine antioxidant compounds, phenolic antioxidant compounds, and / or molybdenum antioxidant compounds.

[0029] In one approach, suitable hindered phenol antioxidants may contain secondary butyl groups 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, 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.

[0030] In other embodiments, useful antioxidants may include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition may contain a mixture of diarylamine and high molecular weight phenol antioxidants.

[0031] In yet another embodiment, other examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene, such as 1,3-butadiene, and an unsaturated ester, such as butyl acrylate.

[0032] The one or more antioxidants may be present in a total amount of less than about 2 wt%, preferably less than about 1.8 wt%, more preferably less than about 1.5 wt%, or most preferably less than about 1.3 wt%. In other embodiments, the total amount of antioxidants may range from about 0.1 weight percent to about 2 weight percent, or from about 0.2 weight percent to about 1.8 weight percent, or from about 0.5 weight percent to about 1.3 weight percent of the lubricating oil composition.

[0033] Boron-containing compounds: The lubricating oil compositions herein may contain limited amounts of one or more boron-containing compounds. Preferably, the lubricating oil compositions herein are substantially free of boron, meaning that the compositions herein have less than about 100 ppm boron, less than 80 ppm boron, less than 50 ppm boron, less than 20 ppm boron, less than 10 ppm boron, less than about 5 ppm boron, or no detectable amounts of boron. Examples of boron-containing compounds that may be used in the lubricating oil compositions herein in the above limited amounts include borate esters, borated fatty amines, borated epoxides, boron compounds for producing borated detergents, and boron compounds for producing borated dispersants, such as the borated succinimide dispersants disclosed in U.S. Pat. No. 5,883,057. The total boron-containing compounds, whether present individually or when used to borate detergents and / or dispersants, can be used in amounts sufficient to provide the above limited amount of total boron.

[0034] Dispersants The lubricating compositions herein also contain one or more optional dispersants. Dispersants are often known as ashless dispersants because they contain no ash-forming metals before mixing into the lubricant composition and typically do not contribute any ash when added to the lubricant. Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5000, or from about 3000, or from about 2,000, or from about 1,500, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 and U.S. Pat. No. 4,234,435, 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).

[0035] In this approach, preferred amines for dispersants can be selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologues such as pentaethylamine hexamine (PEHA). In some approaches, so-called heavy polyamines can be used, which are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily oligomers with six or more nitrogen atoms, two or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule.

[0036] In some embodiments, when included, polyisobutylene (PIB) is a preferred reactant for forming the dispersant and may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0037] HR-PIB having a number-average molecular weight ranging from about 900 to about 3,000 as determined by GPC may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Pat. Nos. 4,152,499 and 5,739,355. When used in the aforementioned thermal ene reaction, HR-PIB can result in higher conversion rates and less precipitate formation in the reaction due to its increased reactivity. A suitable method is described in U.S. Pat. No. 7,897,696. In one embodiment, the present disclosure further includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA may have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0038] In some approaches, the dispersants in the lubricants herein may optionally be post-treated by conventional methods by reaction with any of a variety of agents. Suitable post-treatment agents include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. (See, e.g., 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.)

[0039] The boron compounds used as post-treatment reagents can be selected from boron oxide, boron halides, boric acid, and esters of boric acid in amounts to provide from about 0.1 atomic percentage of boron per mole of nitrogen composition to about 20 atomic percentages of boron for each atomic percentage of nitrogen used. Dispersants post-treated with boron can contain from about 0.05 to about 2.0 weight percent, or in the alternative, from about 0.05 to about 0.7 weight percent, of boron, based on the total weight of the borate dispersant.

[0040] In another approach, carboxylic acids can also be used as post-treating reagents and can be saturated or unsaturated mono-, di-, or poly-carboxylic acids. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, and naphthalic diacids (e.g., 1,8-naphthalic diacid). Anhydrides can also be used as post-treating reagents and can be selected from the group consisting of mono-unsaturated anhydrides (e.g., maleic anhydride), alkyl- or alkylene-substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride), and aromatic carboxylic anhydrides (including naphthalic anhydrides, e.g., 1,8-naphthalic anhydride).

[0041] In one embodiment, the process for post-treating a dispersant includes first forming a succinimide product as described above, and then further reacting the succinimide product with a post-treating agent, such as a boron compound, such as boric acid. In some cases, the dispersants herein may be post-treated with more than one post-treating agent. For example, a dispersant may be post-treated with a boron compound, such as boric acid, and also with an anhydride, such as maleic anhydride and / or 1,8-naphthalic anhydride.

[0042] The dispersants may be used in an amount sufficient to provide up to about 20 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 500 ppm boron. In other approaches, the dispersants may be used in the lubricating composition in an amount of from about 0.1 weight percent to about 15 weight percent, or from about 0.1 weight percent to about 10 weight percent, or from about 0.1 weight percent to about 8 weight percent, or from about 1 weight percent to about 10 weight percent, or from about 1 weight percent to about 8 weight percent, or from about 1 weight percent to about 6 weight percent, based on the final weight of the lubricating oil composition. The dispersants may provide at least about 400 ppm nitrogen and up to about 1,500 ppm nitrogen.

[0043] Base oil or base oil blend: The base oil used in the lubricating compositions herein is an oil of lubricating viscosity and may be selected from any of API Groups I-V as defined in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines, but generally contains little or no API Group IV base oil (e.g., about 20 weight percent or less, about 10 weight percent or less, about 4 weight percent or less, about 2 weight percent or less, or about 1 weight percent or less, or most preferably, no API Group IV base oil). The five base oil groups are generally shown in Table 1 below.

[0044] [Table 1]

[0045] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but may also be natural oils such as vegetable oils. Group III base oils are derived from mineral oils, but it should be noted that the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Therefore, oils derived from Group III base oils may be referred to in industry as synthetic fluids. Group II+ may include high viscosity index Group II.

[0046] The base oil blends used in the disclosed lubricating oil compositions can be mineral, animal, vegetable, synthetic, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0047] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification processing. Refined oils are similar to unrefined oils except that they have been treated with one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable refining techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0048] Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often, these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

[0049] 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.

[0050] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as derivatives, analogs, and homologs thereof, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0051] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, oils may be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

[0052] 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 (in limited amounts as described above), Group V, or a combination of two or more of the foregoing, wherein the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, and a combination of two or more of the foregoing, wherein the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition.

[0053] The amount of oil of lubricating viscosity present can be the difference remaining after subtracting the sum of the amounts of performance additives, including viscosity index improver(s) and / or pour point depressant(s) 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.

[0054] 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, in other approaches from about 2.5 to about 6 cSt, in still other approaches from about 2.5 to about 3.5 cSt, and in other approaches from about 2.5 to about 4.5 cSt.

[0055] 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.

[0056] Optional Additives: The lubricating oil compositions herein may also contain a number of optional additives in combination with the detergent system, sulfurized additives, and borated detergents as needed to meet performance criteria, which optional additives are described in the following paragraphs.

[0057] Other Dispersants: The lubricating oil composition may optionally contain one or more other dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain ash-forming metals prior to incorporation into the lubricating oil composition and do not typically contribute ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0058] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylaminehexamine (PEHA).

[0059] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily oligomers with six or more nitrogen atoms, two or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., greater than 32% by weight) total nitrogen and an equivalent weight of 120 to 160 grams of primary amine groups per equivalent.

[0060] In some approaches, suitable polyamines are commonly known as PAM and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0061] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 gram equivalents per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers, which are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogen atoms and more extensive branching, may produce dispersants with improved dispersancy.

[0062] In embodiments, the present disclosure further includes at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight, as determined by GPC, ranging from about 350 to about 50,000, or from about 5,000, or from about 3,000. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0063] In some embodiments, when polyisobutylene is included, the polyisobutylene may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0064] HR-PIB having a number average molecular weight ranging from about 900 to about 3000, as determined by GPC, may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel et al. and U.S. Patent No. 5,739,355 to Gateau et al. When HR-PIB is used in the thermal ene reaction, it can result in higher conversion rates and less precipitate formation during the reaction due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0065] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of about 1.0 to about 2.0 succinic moieties per polymer.

[0066] The percent active ingredient of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0067] The percent polyolefin conversion is calculated from the % active ingredient using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0068] Unless otherwise stated, all percentages are weight percent and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0069] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0070] A suitable class of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0071] One class of suitable dispersants can also be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0072] A suitable class of dispersants may also be high molecular weight esters or half-ester amides. Suitable dispersants may also be post-treated by conventional methods with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patent Nos. 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entireties.

[0073] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with: inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,948,386); 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. 4,611,161); 7,137); urea, thiourea, or guanidine (e.g., U.S. Pat. Nos. 3,312,619, 3,865,813, and British Patent No. 1,065,595); organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketene (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkane sultones (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. 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, and 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxyl-protected carboxylic acids (e.g., U.S. Pat. Nos. 4,971,598 and 2,140,811); Protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and U.K. Pat. No. 4,670,170); No. 2,440,811; hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318, 4,713,189 No. 4,379,064), oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086, 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 followed by aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenols followed by glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by diisocyanates (e.g., U.S. Pat. No. 4,699,724); ,713,191); combinations of inorganic acids or anhydrides of phosphorus or their partial or total sulfur analogs and boron compounds (e.g., U.S. Pat. No. 4,857,214); combinations of organic diacids, followed by unsaturated fatty acids, followed by nitrosoaromatic amines, optionally followed by boron compounds, and then by glycosylating agents (e.g., U.S. Pat. No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Pat. No. 4,963,278); combinations of aldehydes and triazoles, followed by boron compounds (e.g., U.S. Pat. No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are incorporated herein in their entireties.

[0074] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g dispersant on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0075] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, wherein the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000 as determined by GPC using polystyrene as a calibration standard.

[0076] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0077] [ka] wherein each R and R' is independently a divalent C1-C6 alkylene linker, and each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0078] Dispersants, when present, may be used in an amount sufficient to provide up to about 20 wt. %, based on the final weight of the lubricating oil composition. Alternative amounts of dispersant that may be used may be from about 0.1 to about 15 wt. %, or from about 0.1 to about 10 wt. %, or from about 0.1 to about 8 wt. %, or from about 1 to about 10 wt. %, or from about 1 to about 8 wt. %, or from about 1 to about 6 wt. %, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.

[0079] Antiwear Agents: The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphoric acid esters or salts thereof; phosphoric acid ester(s); phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0080] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the antiwear agent may include citrates.

[0081] The antiwear agent may be present in ranges including from about 0 to about 15 weight percent, or from about 0.01 to about 10 weight percent, or from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent of the lubricating oil composition.

[0082] Additional Detergents: The lubricating oil composition may optionally further comprise one or more neutral, low-based, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and the references cited therein.

[0083] The detergent substrate may be salified with an alkali metal or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts of 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0084] Overbased detergent additives are well known in the art and can be alkali or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0085] The term "overbased" refers to metal salts, such as metal salts of sulfonic acids, carboxylic acids, and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts can have conversion levels greater than 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, highly based, or superbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

[0086] 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.

[0087] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylic acid, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bound alkylphenol compound, overbased calcium methylene-bridged phenol, overbased magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bound alkylphenol compound, or overbased magnesium methylene-bridged phenol.

[0088] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g, all measured by the method of ASTM D 2896. When such detergent compositions are formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials (e.g., accelerators, etc.) that may be included in the detergent composition.

[0089] Overbased detergents may have a metal-to-substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 to about 10 wt. %, or from about 0.1 to about 8 wt. %, or from about 1 to about 4 wt. %, or from greater than about 4 wt. % to about 8 wt. %.

[0090] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphate with propylene oxide; and mixtures thereof.

[0091] 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.

[0092] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a mono-ester, a di-ester, or a (tri)glyceride. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

[0093] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally may contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is generally known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0094] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0095] The amines and amides may be used per se or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, the entire contents of which are incorporated herein by reference.

[0096] Friction modifiers may optionally be present in ranges such as from about 0 to about 10 weight percent, or from about 0.01 to about 8 weight percent, or from about 0.1 to about 4 weight percent.

[0097] Molybdenum-Containing Component: The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0098] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, and Molyvan® 855 from R.T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381, U.S. Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entire contents of which are incorporated herein by reference.

[0099] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl, MoOBr, MoOCl, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0100] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula MoS k L n Q z and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donor compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. There may be at least 21 total carbon atoms among all of the ligand organic groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0101] The oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

[0102] Transition Metal-Containing Compound: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0103] In embodiments, the oil-soluble transition metal-containing compound may function as an anti-wear agent, a friction modifier, an antioxidant, a deposit control additive, or one or more of these functions. In embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound such as a titanium(IV) alkoxide. Among the titanium-containing compounds that may be used in or for preparing the oil-soluble material in the technology of the present disclosure include, but are not limited to, various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, and titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as titanium phenate; titanium carboxylates, such as titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzenesulfonates), or generally, reaction products of titanium compounds with various acid materials to form salts, such as oil-soluble salts. Thus, titanium compounds can be derived from organic acids, alcohols, and glycols, among others. Ti compounds can also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques apparent to those skilled in the art. They can exist at room temperature as solids or liquids, depending on the particular compound. They can also be provided in solution form in a suitable inert solvent.

[0104] In one embodiment, titanium can be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly or reacted with any of several materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable —NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl-(or alkyl) succinic anhydrides and polyamines; or (c) hydroxy-containing polyester dispersants prepared by reacting a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to lubricating oils or further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with approximately two parts (mole) of polyisobutene-substituted succinic anhydride 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.

[0105] Another titanium-containing compound is titanium alkoxide and C6-C 25 The reaction product may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0106] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or may be represented by the following formula:

[0107] [ka] or the titanium compound may be represented by the formula: wherein m+n=4, n ranging from 1 to 3, R4 is an alkyl moiety having from 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms;

[0108] [ka] wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; and R4 is selected from H, C6 to C8 25 and the carboxylic acid moiety of

[0109] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0110] In embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 ppm to about 500 ppm by weight of titanium, or from about 50 ppm to about 300 ppm.

[0111] Viscosity Index Improver: The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 20120101017(A1).

[0112] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or in place of a viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0113] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0 to about 20 wt %, from about 0.1 to about 15 wt %, from about 0.1 to about 12 wt %, or from about 0.5 to about 10 wt % of the lubricating oil composition.

[0114] 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.

[0115] Lubricating oil compositions according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, fully formulated lubricating oils will contain one or more of these performance additives.

[0116] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylate, polyacrylate, or polyacrylamide.

[0117] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0118] 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.

[0119] Suitable rust inhibitors can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids, including dimer and trimer acids such as those produced from tall oil fatty acid, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0120] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 to about 5 wt. %, from about 0.01 to about 3 wt. %, from about 0.1 to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0121] Generally speaking, suitable lubricants containing detergent metals herein may contain additive components in the ranges listed in the table below.

[0122] [Table 2]

[0123] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that supplies the properties required in the formulation.

[0124] definition For purposes of this disclosure, chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. Additionally, general principles of organic chemistry are described in "Organic Chemistry," Thomas Sorrell, University Science Books, Sausolito: 1999, and "March's Advanced Organic Chemistry," 5th Ed., Ed.: Smith, M.B. and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0125] As described herein, compounds can be optionally substituted with one or more substituents as illustrated generally above or as illustrated by the specific classes, subclasses, and species of the present disclosure.

[0126] 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.

[0127] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl) substituents, alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic-substituted aromatic substituents, as well as cyclic substituents in which the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy) that do not alter the predominantly hydrocarbon substituent in the context of this disclosure; and (3) heterosubstituents, i.e., substituents that, while predominantly hydrocarbon in the context of this disclosure, contain other than carbon atoms in the ring or chain or are otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and encompass substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than two, or as a further example, only one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group, and in some embodiments, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0128] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0129] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be linear or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. An alkyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino], or the like.

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

[0130] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be linear or branched. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. Alkenyl groups can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbonyl], or heteroarylcarbonylamino. and optionally substituted by alkyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO2-, alicyclic-SO2-, or aryl-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heteroalicyclicoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Some examples of substituted alkenyls include, but are not limited to, cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (alicyclic)alkenyl, or haloalkenyl.

[0131] As used herein, an "alkynyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. Alkynyl groups can be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. Alkynyl groups can be substituted with one or more groups, such as aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or alicyclic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or alicyclic sulfinyl], sulfonyl [e.g., aliphatic -SO2-, aliphatic amino-SO2-, or alicyclic -SO2-], amido [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, aryl aminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamido, alkoxycarbonyl, alkylcarbonyloxy, alicyclic, heteroalicyclic, aryl, heteroaryl, acyl [e.g., (alicyclic)carbonyl or (heteroalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heteroalicyclic)oxy, or (heteroaryl)alkoxy.

[0132] As used herein, an "amino" group refers to an -NR X R Y In the formula, R X and R Yis independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaralkyl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is not -NR X - represented by R X is as defined above.

[0133] 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.

[0134] 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.

[0135] As used herein, a "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or a combination thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fused ring systems having 2 to 3 rings. For example, a benzo-fused group includes benzo fused to one or two 4- to 8-membered heterocyclic aliphatic moieties (e.g., indolyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzthiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzthiazolyl, puryl, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthyridyl.

[0136] Monocyclic heteroaryls include, but are not limited to, furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4H-pyranyl, pyridyl, pyridazyl, pyrimidyl, pyrazolyl, pyrazyl, or 1,3,5-triazyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0137] 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.

[0138] As used herein, the term "treat rate" refers to the weight percent of a component in a lubricating and cooling fluid.

[0139] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined using a gel permeation chromatography (GPC) instrument from Waters or similar equipment and Waters Empower Software or similar software. The GPC instrument can be equipped with a Waters Separation Module and a Waters Refractive Index Detector (or similar optional equipment). GPC operating conditions can include a guard column, four Agilent PLgel columns (300 x 7.5 mm long, 5 μm particle size, and pore sizes ranging from 100 to 10,000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) can be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument can be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards with narrow molecular weight distributions ranging from 960 to 1,568,000 g / mol. The calibration curve can be extrapolated for samples with masses less than 500 g / mol. Samples and PMMA standards are dissolved in THF at concentrations of 0.1 to 0.5% by weight and can be used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method additionally provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland, and D.D. Bly, "Modern Size Exclusion Liquid Chromatography," John Wiley and Sons, New York, 1979, which is incorporated herein by reference. [Example]

[0140] A better understanding of the present disclosure and its many advantages may be clarified with the following examples. The following examples are illustrative and not limiting in scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise specified or apparent from the context of the following examples and discussion throughout this disclosure, all percentages, ratios, and parts described in this disclosure are by weight. Any standardized test method described in the examples, disclosure, or claims refers to the version of the test method publicly available at the time of filing this disclosure, unless apparent from the context of its use.

[0141] Example 1 The lubricating compositions were evaluated for piston cleanliness according to CEC L-117-20 (TDi3). The lubricating compositions evaluated for this example contained sulfonate and / or phenate detergents to provide the fluid relationships in Table 3 below, as well as similar additive packages including dispersants, antiwear additives, aminic antioxidants, phenolic antioxidants, molybdenum antioxidants, friction modifiers, antifoam agents, pour point depressants, viscosity modifiers, and the balance base oil to achieve a KV100 of about 4.0 to about 26.1 cSt. (KV100 was measured according to ASTM D445.) Table 4 provides the VW TDi3 piston cleanliness results.

[0142] [Table 3] * Wt% soap in final formulation ** The ratio is the detergent TBN (D2896) divided by the weight percent of sulfonate soap in the final formulation. Thus, Comparative Example 1 has a ratio of 5.1 / 0.5 or 10.5, reflecting the balance of detergent TBN contribution to sulfonate soap contribution. Preferred lubricants have ratios of 13-18 or 14-16.

[0143] [Table 4]

[0144] Piston cleanliness was measured to RL276-5, with passing piston cleanliness being equal to or better than the RL 276-5 reference fluid merit. Comparative Examples 1 and 2, with blends of sulfonate and phenate soaps, failed to achieve passing piston cleanliness under the TDi3 performance criteria. Comparative Example 3, with only sulfonate soap, still failed TDi3 performance because the lubricant did not balance the detergent TBN (ASTM D2896) contribution to the sulfonate soap level. While inventive Lubricant 1 passed TDi3 piston cleanliness using only sulfonate soap when it had limited amounts of boron and a lower total antioxidant content, it was unexpected that such a lubricant achieved passing TDi3 performance when selecting a sulfonate-only detergent with a selected detergent TBN contribution (ASTM D2896).

[0145] Comparative Lubricant 4, which had a blend of sulfonate and phenate soaps, surprisingly failed TDi3 performance despite its higher detergent TBN contribution (ASTM D2896) because it did not balance the TBN to the sulfonate soap contribution. Invention 2 demonstrates that passing TDi3 performance was achieved by switching lubricants from mixed phenate and sulfonate formulations when the detergent TBN was also matched with sulfonate soap content, antioxidant content, and less than about 20 wt.% Group IV base oil. The lubricants herein also contained lower levels of total antioxidants (e.g., less than about 2 weight percent amine antioxidants, phenolic antioxidants, and molybdenum antioxidants), less boron content (e.g., about 100 ppm or less), and little or no API Group IV base oil (e.g., about 20 weight percent or less).

[0146] Example 2 Additional lubricating compositions containing the detergent additive of Example 1 were evaluated for piston cleanliness using the older CEC L-078-99 or VW TDi2 test. The lubricants in this example contained the same additive package of antioxidant, antiwear additive, phenolic antioxidant, molybdenum antioxidant, friction modifier, antifoam additive, pour point depressant, viscosity modifier, and the balance of the base oil, plus the fluid relationships in Table 5 below, to achieve a KV100 of about 4 to about 26.1 cSt (KV100 measured according to ASTM D445). Table 6 provides the VW TDi2 piston cleanliness.

[0147] [Table 5]

[0148] [Table 6]

[0149] Passing piston cleanliness for TDi2 was comparable to or better than that of the reference fluids, which generally had piston cleanliness ratings above about 65. The data in Table 6 show that detergent systems with most sulfonate soaps (e.g., Comparative Examples 5, 7, and 8) failed to provide adequate piston cleanliness when evaluated using the older VW TDi2 performance standards. However, the data in Table 4 from Example 1 show that when sufficiently high TBN levels are balanced in lubricants with a predominantly sulfonate (preferably sulfonate-only) detergent system, the lubricant can surprisingly achieve the desired piston cleanliness according to the newer, more stringent VW TDi3 performance standards, even when the lubricant has lower levels of total antioxidants (e.g., less than 2.0 weight percent), lower levels of boron (e.g., less than about 100 ppm), and / or lower levels of API Group IV base oil (e.g., less than about 20 weight percent).

[0150] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, a reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprises" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list does not exclude other similar items that may be substituted for or added to the listed items.

[0151] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages, or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0152] 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.

[0153] It is further understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but also any range of such values.

[0154] It should be further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range, or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. In other words, it should also be understood that any range between the endpoints within a broad range is also contemplated herein. Thus, a range of 1 to 4 also means ranges of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0155] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the details or examples should be construed as disclosing either a lower or upper limit of a range and, therefore, can be combined with any other lower or upper limit or specific amount / value in a range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0156] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or presently unforeseeable to Applicants or others skilled in the art. Accordingly, the appended claims as filed, and the appended claims as they may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 1. A lubricating composition comprising: one or more base oils of lubricating viscosity; less than 2 weight percent total antioxidant compounds selected from amine antioxidant compounds, phenolic antioxidant compounds, molybdenum antioxidant compounds, or combinations thereof; less than 100 ppm of boron; a detergent system having a total base number (TBN) of at least 5.5 mg KOH / g as measured by ASTM D2896 and having a soap content of greater than or equal to about 75 percent sulfonate soaps and less than or equal to about 25 percent phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof; the lubricating composition comprising less than 20 weight percent of an API Group IV base oil; The lubricating composition exhibits an average piston detergency of 53 merits or greater in the CEC L-117-20 (VW TDi3) piston detergency test of RL276-5.

2. 10. The lubricating composition of claim 1, wherein the detergent system has less than about 5 percent of a phenate soap, a salicylate soap, a calixarate soap, or a combination thereof, preferably about 1 percent or less of a phenate soap, a salicylate soap, a calixarate soap, or a combination thereof.

3. 10. The lubricating composition of claim 1, wherein the detergent system has a TBN (ASTM D2896) of 5.5 to 15 mg KOH / g and provides 0.3 to 0.7 weight percent sulfonate soap.

4. 10. The lubricating composition of claim 1, wherein the lubricating composition has a detergent system TBN (ASTM D2896) to sulfonate soap content ratio of 13-18.

5. 10. The lubricating composition of claim 1, wherein the detergent system includes only magnesium sulfonate, sodium sulfonate, calcium sulfonate, or combinations thereof in amounts to provide the detergent system TBN, and / or the detergent system provides from about 0.3 weight percent to about 0.7 weight percent of a sulfonate soap.

6. 10. The lubricating composition of claim 1, wherein the lubricating composition has less than about 1.3 weight percent total antioxidant compounds.

7. 10. The lubricating composition of claim 1, wherein the lubricating composition has less than about 5 weight percent API Group IV base oil.

8. 10. The lubricating composition of claim 1, wherein the detergent system has a ratio of sulfonate soap to phenate soap of about 95:5 or greater, and / or the detergent system is a blend of neutral to low based sulfonate detergents and overbased sulfonate detergents in amounts to provide the detergent system TBN, and / or the detergent system comprises about 0 to about 7 weight percent sulfonate detergent from the neutral to low based sulfonate detergent and about 0.1 to about 3.0 weight percent sulfonate detergent from the overbased sulfonate detergent.

9. 1. A method for passing the CEC L-117-20 piston cleanliness test, comprising: providing a lubricating composition comprising one or more base oils of lubricating viscosity; less than 2 weight percent total antioxidant compounds selected from amine-based antioxidant compounds, phenolic-based antioxidant compounds, molybdenum antioxidant compounds, or combinations thereof; less than 100 ppm boron; a detergent system having a total base number (TBN) of at least 5.5 mg KOH / g as measured by ASTM D2896 and having a soap content of greater than or equal to about 75 percent sulfonate soaps and less than or equal to about 25 percent phenate soaps, salicylate soaps, calixarate soaps, or combinations thereof; and less than 20 weight percent API Group IV base oil; and measuring piston cleanliness according to CEC L-117-20 (VW TDi3), wherein the lubricating composition has an average piston cleanliness of 53 Merit or greater in the CEC L-117-20 test of RL276-5.

10. 10. The method of claim 9, wherein the detergent system has about 5 percent or less of a phenate soap, salicylate soap, calixarate soap, or combination thereof, preferably about 1 percent or less of a phenate soap, salicylate soap, calixarate soap, or combination thereof, more preferably the detergent system is substantially free of detergents that provide a phenate soap, salicylate soap, calixarate soap, or combination thereof, and / or the detergent system includes only magnesium sulfonate, sodium sulfonate, calcium sulfonate, or combinations thereof in amounts to provide a detergent system TBN.

11. 10. The method of claim 9, wherein the detergent system has a TBN (ASTM D2896) of 5.5 to 15 mg KOH / g and provides 0.3 to 0.7 weight percent sulfonate soap.

12. 10. The method of claim 9, wherein the lubricating composition has a detergent system TBN (ASTM D2896) to sulfonate soap content ratio of 13 to 18.

13. 10. The method of claim 9, wherein the lubricating composition has less than about 1.3 weight percent total antioxidant compounds.

14. 10. The method of claim 9, wherein the detergent system has a ratio of sulfonate soap to phenate soap of about 95:5 or greater, and / or the detergent system is a blend of neutral to low based sulfonate detergent and overbased sulfonate detergent in amounts to provide the detergent system TBN, and / or the detergent system comprises from about 0 to about 7 weight percent sulfonate detergent from the neutral to low based sulfonate detergent and from about 0.1 to about 3 weight percent sulfonate detergent from the overbased sulfonate detergent.

15. 10. The method of claim 9, wherein the lubricating composition has less than about 5 weight percent API Group IV base oil.

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