Lubricating Composition for Reducing Low Temperature Valve Train Wear - Patent application

Abstract

To provide an engine lubricant composition that offers improved low-temperature valve train abrasion.SOLUTION: An engine lubricant composition with SAE J 300 viscosity grade of 0W-8, 0W-12, 0W-16, or 0W-20, includes: one or more base oils having lubricating viscosity; about 300 to about 1,000 ppm of molybdenum from an oil-soluble molybdenum compound; one or more metal-containing cleaning agents for providing a TBN greater than about 5 to the lubricant composition, wherein the TBN is measured using ASTM D4739, and at least one of the one or more metal-containing cleaning agents includes an overbasic magnesium cleaning agent providing an overbasic magnesium cleaning agent with a TBN greater than about 2 to the lubricant composition, and the TBN is measured using ASTM D4739; and less than about 0.2 wt.% of a polymer pour point depressant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to lubricating compositions, and in particular to lubricating compositions that provide improved low temperature valve train wear. [Background technology]

[0002] Automotive manufacturers continue to seek improvements in efficiency, fluid life, and fuel economy, which continues to increase the demands on engines, lubricants, and their components. Today's engines are often 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 their corresponding performance standards associated with their unique uses and applications. With such stringent demands on engine oils, lubricant manufacturers often tailor lubricants and their additives to meet certain performance requirements for industrial and / or industrial applications.

[0003] Typically, industry standards and / or automotive manufacturers require certain performance, with lubricants designed for one use or application not meeting all specifications for a different use or application. Modern automotive and / or industry standards impose increasingly stringent requirements on the composition and performance of such oils, which often leave little room for flexibility in lubricant formulations. For example, the Society of Automotive Engineers (SAE) or the Japanese Automobile Standards Organization (JASO) set performance standards for lubricants for use in a wide range of applications.

[0004] One of the goals in lubricant development is to help improve fuel efficiency by reducing friction loss, which is often targeted by designing lubricants with lower viscosity. However, as lubricant manufacturers strive to meet more stringent industry standards, it becomes a challenge to simultaneously achieve all the required performance and automotive industry standards in a cost-effective manner. In many situations, varying the ingredients in a lubricant composition to meet newer performance characteristics tends to adversely affect one or more other performance characteristics. Therefore, it becomes difficult for lubricant manufacturers to meet newer industrial performance requirements while simultaneously maintaining traditional fluid performance.

[0005] For example, molybdenum-based compounds are widely used as friction modifiers and, in some cases, help achieve passing performance in motor friction tests, such as the JASO M 365 motor friction test of the JASO GLV-1 specification. However, when low viscosity grade lubricants, such as 0W-8, 0W-12, 0W-16, or 0W-20 lubricants, are formulated with molybdenum levels to achieve passing motor friction performance, it also becomes difficult to achieve passing performance in the Sequence IVB engine test of ASTM D8350, which evaluates the effect of the lubricant on tappet wear in engines having direct-acting overhead cam valve trains. Summary of the Invention

[0006] The present disclosure relates to a lubricating composition for an engine oil composition that provides improved low temperature valve train wear according to the sequence IVB engine test of ASTM D8350. In one aspect, the engine oil lubricating composition comprises one or more base oils of lubricating viscosity, about 300 to about 1000 ppm of molybdenum from an oil-soluble molybdenum compound, and one or more metal-containing detergents providing the lubricating oil composition with a TBN of greater than about 5, the TBN being measured using ASTM D4739, and at least one of the one or more metal-containing detergents comprises an overbased magnesium detergent providing the lubricating oil composition with a TBN of greater than about 2, and the TBN being measured using ASTM D4739. In an embodiment, the engine oil lubricating composition may also comprise less than about 0.2 wt. % of a polymeric pour point depressant, and the engine oil composition has a viscosity grade according to SAE J 300 of 0W-8, 0W-12, 0W-16, or 0W-20.

[0007] In other embodiments or approaches, the lubricating composition of the preceding paragraph may include the optional features or embodiments in any combination. These optional features or embodiments may include one or more of the following: the one or more overbased magnesium-containing detergents comprise a magnesium sulfonate, and / or the lubricating oil composition further comprises a calcium-containing detergent, and / or the one or more overbased magnesium-containing detergents have a total base number (TBN) of at least about 250 mg KOH / g, and / or the polymeric pour point depressant is a poly(meth)acrylate based pour point depressant, and / or the polymeric pour point depressant is a poly(meth)acrylate copolymer having monomer units comprising (i) one or more monomer units selected from C1 to C16 (meth)acrylates, and (2) vinylpyrrolidone monomer units, and / or the engine lubricating oil composition is substantially free of a poly(meth)acrylate based dispersant pour point depressant, and / or the lubricating oil composition lubricates a hybrid gasoline-electric engine, and / or the hybrid gasoline-electric engine comprises a 2.0 liter or less gasoline engine, and / or the ... 2.7mm when measured according to D8350 Sequence IVB engine test 3 and a maximum end of test iron content of 400 ppm or less.

[0008] In another approach or embodiment, described herein is a method of lubricating a hybrid gasoline-electric engine to achieve improved low temperature valve train wear according to the Sequence IVB engine test of ASTM D8350. In one embodiment, the method includes lubricating a hybrid electric-gasoline engine with a lubricating oil composition having a viscosity grade of 0W-8, 0W-12, 0W-16, or 0W-20 by SAE J 300, the lubricating oil composition comprising one or more base oils of lubricating viscosity; about 300 to about 1000 ppm of molybdenum from an oil-soluble molybdenum compound; one or more metal-containing detergents providing the lubricating oil composition with a TBN of greater than about 5, wherein at least one of the one or more metal-containing detergents comprises an overbased magnesium detergent providing the lubricating oil composition with a TBN of greater than about 2, wherein the TBN is measured using ASTM D4739; and less than about 0.2 wt % of a polymeric pour point depressant.

[0009] In other approaches or embodiments, the method of the preceding paragraph may include the optional features, embodiments, or method steps in any combination. These optional features, embodiments, or steps may include one or more of the following: the one or more overbased magnesium-containing detergents comprise magnesium sulfonate, and / or the lubricating oil composition further comprises a calcium-containing detergent, and / or the one or more overbased magnesium-containing detergents have a total base number (TBN) of at least about 250 mg KOH / g, and / or the polymeric pour point depressant is a poly(meth)acrylate based pour point depressant, and / or the polymeric pour point depressant is a poly(meth)acrylate copolymer having monomer units comprising (i) one or more monomer units selected from C1 to C16 (meth)acrylates and (ii) vinylpyrrolidone monomer units, and / or the lubricating oil composition is substantially free of poly(meth)acrylate based pour point depressants, and / or the hybrid gasoline-electric engine comprises a 2.0 liter or less gasoline engine, and / or the lubricating oil composition has ....7 mm when measured according to the Sequence IVB Engine Test of ASTM D8350. 3 and / or has an average intake lifter volume loss of 400 ppm or less and a maximum end of test iron content of 400 ppm or less, and / or has about 40% to about 100% of the detergent TBN provided by the overbased magnesium sulfonate.

[0010] In yet another embodiment, the present disclosure provides a composition having a viscosity of 2.7 mm or less when measured according to the Sequence IVB engine test of ASTM D8350 and using a viscosity grade according to SAE J 300 of 0W-8, 0W-12, 0W-16, or 0W-20. 3 The present invention provides for the use of any of the embodiments of the lubricant composition described in the Summary of the Invention to achieve an average intake lifter volume loss of 100% or less and a maximum end of test iron content of 400 ppm or less. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present disclosure relates to a lubricating composition and method for lubricating an internal combustion engine that is effective in maintaining acceptable engine friction performance according to JASO M365 while achieving improved low-temperature valve train wear in the ASTM D8350 Sequence IVB engine test. As mentioned in the Background, low-viscosity lubricants such as 0W-8, 0W-12, 0W-16, or 0W-20 grade lubricants may be preferred to target improved fuel economy, but such low-viscosity grade lubricants often require high amounts of molybdenum to achieve the desired motor friction performance. Unfortunately, such high levels of molybdenum cause problems with low-viscosity lubricants that also pass the valve train wear criteria of the ASTM D8350 Sequence IVB test.

[0012] Surprisingly, the lubricating compositions herein achieve passing performance in both performance tests by increasing the overbased magnesium detergent content relative to other fluid and detergent components. Since detergents, and the soap content from detergents, are primarily provided for acid neutralization, detergency, dispersancy, corrosion inhibition, and / or antiwear, it was unexpected that selection of specific amounts and relationships of detergent metal contributions in a fluid in combination with high molybdenum content would shift a lubricant with failing Sequence IVB performance to one with passing Sequence IVB performance that also achieves desired motor friction performance. As used herein, acceptable Sequence IVB performance means a lubricant with a 2.7mm overbased magnesium detergent content and ... 3 and a maximum end of test iron content of 400 ppm or less. Any embodiment of the lubricants herein is particularly suitable for lubricating hybrid gasoline-electric engines, and more particularly, hybrid gasoline-electric engines with gasoline engines of 2.0 liters or less.

[0013] In one aspect, all of the lubricants herein comprise an effective amount of molybdenum from an oil soluble molybdenum compound, such as a molybdenum dithiocarbamate, to achieve passing motor friction performance per JASO M 365. The lubricants herein also comprise a detergent system comprising one or more metal-containing detergents providing a TBN of greater than about 5 to the lubricating oil composition (TBN measured using ASTM D4739), wherein at least one of the one or more metal-containing detergents is an overbased magnesium detergent, e.g., an overbased magnesium sulfonate detergent, providing a TBN of greater than about 2 to the lubricating oil composition, a TBN of greater than about 3 to the lubricating oil composition, a TBN of greater than about 4 to the lubricating oil composition, and more preferably a TBN of greater than about 5 to the lubricating oil composition from the overbased magnesium detergent. In some approaches, the detergent systems herein may also include a ratio of TBN provided by the overbased magnesium component to TBN of the total detergent system of at least about 0.4:1 or more, such as from about 0.4:1 to about 1:1, or from about 0.6:1 to about 1:1, or from about 0.8:1 to about 1:1. In other approaches, the detergent systems herein may include at least about 40 percent of the detergent TBN provided by the overbased magnesium detergent, or from about 40 percent to about 100 percent of the TBN, or more preferably from about 40 to about 60 percent of the detergent TBN is provided by the overbased magnesium detergent, such as an overbased magnesium sulfonate.

[0014] Oil-soluble molybdenum compounds The lubricants herein include an effective amount of one or more oil-soluble molybdenum-containing compounds that provide sufficient molybdenum content to achieve a passing motor friction test, such as passing performance according to JASO M365. As used herein, an effective amount of molybdenum from oil-soluble molybdenum is at least about 300 ppm of molybdenum, or from about 300 ppm to about 1000 ppm, preferably from about 500 ppm to about 1000 ppm, more preferably from about 700 ppm to about 1000 ppm, or most preferably from about 800 ppm to about 1000 ppm of molybdenum from an oil-soluble molybdenum compound (e.g., a molybdenum dithiocarbamate, described below).

[0015] The oil-soluble molybdenum compound may be any of molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum sulfide, molybdenum disulfide, molybdenum dithiophosphinate, amine salt of molybdenum compound, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organomolybdenum compound, and / or mixtures thereof. The molybdenum-containing compound may be a sulfur-containing compound or a sulfur-free compound. The molybdenum disulfide may be in the form of a stable dispersion. Preferably, the oil-soluble molybdenum compound is a molybdenum dithiocarbamate or a molybdenum dialkyl dithiocarbamate having 1 to 20 carbons in the alkyl chain.

[0016] In one embodiment, the oil-soluble molybdenum compound can be selected from the group of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organomolybdenum complexes of organic amides, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be molybdenum dithiocarbamates. Exemplary sulfur-free organomolybdenum complexes of organic amides are disclosed in U.S. Patent No. 5,137,647.

[0017] In one approach or embodiment, a suitable molybdenum dithiocarbamate can be represented by the formula:

[0018] [ka] In the formula, R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, C 1 ~C 20 Alkyl group, C 6 ~C 20 C containing a cycloalkyl, aryl, alkylaryl, or aralkyl group, or optionally an ester, ether, alcohol, or carboxyl group 3 ~C 20is a hydrocarbyl group, X 1 , X 2 , Y 1 and Y 2 Each R is independently a sulfur atom or an oxygen atom. 5 , R 6 , R 7 , and R 8 Examples of suitable groups for each of R include 2-ethylhexyl, nonylphenyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-hexyl, n-octyl, nonyl, decyl, dodecyl, tridecyl, lauryl, oleyl, linoleyl, cyclohexyl, and phenylmethyl. 5 , R 6 , R 7 , and R 8 are C 6 ~C 18 X may have an alkyl group. 1 and X 2 can be identical, and Y 1 and Y 2 can be the same. X 1 and X 2 Both contain sulfur atoms, and Y 1 and Y 2 may both contain oxygen atoms. Further examples of molybdenum dithiocarbamates include C 6 ~C 18 Included are dialkyl or diaryl dithiocarbamates or alkyl-aryl dithiocarbamates such as dibutyl-, diamyl-di-(2-ethylhexyl)-, dilauryl-, dioleyl-, and dicyclohexyl-dithiocarbamate.

[0019] Suitable examples of molybdenum compounds that may be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, Molyvan® 807 and Molyvan® 855 manufactured by RT Vanderbilt Co., Ltd., Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381, U.S. Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entireties of which are incorporated herein by reference.

[0020] Detergents As noted above, with such high levels of molybdenum, conventional low viscosity lubricants tend to fail the Sequence IVB low temperature valve train wear test of ASTM D8350. In contrast, the lubricating compositions herein contain a unique detergent system that provides selected amounts and relationships of magnesium, preferably an overbased magnesium sulfonate, which, when combined with the high levels of molybdenum from the oil-soluble molybdenum compounds in the low viscosity lubricant, helps achieve low temperature valve train wear.

[0021] In an embodiment, the detergent systems herein generally include detergent additives such as one or more alkali or alkaline metal salts of phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof, so long as the magnesium content and TBN relationships herein are satisfied. Preferably, the detergent is a sulfonate, and most preferably includes at least one overbased magnesium sulfonate having the soap, metal, and / or TBN relationships discovered herein.

[0022] Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, such as U.S. Patent No. 7,732,390 and the references cited therein, which are incorporated herein by reference. The lubricant compositions herein may contain from about 0.1 to about 5 weight percent of individual and / or total detergent additives, in other approaches from about 0.15 to about 3 weight percent, and in yet other approaches from about 0.15 to 2.6 weight percent of individual and / or total detergent additives, so long as the detergent additives satisfy the metal content and TBN relationships described herein.

[0023] As noted above, and in some approaches, the detergent system provides selected amounts of detergent metals and TBN from detergent soaps, and in other approaches, magnesium, preferably magnesium and calcium in selected amounts and relationships provided by sulfonic acid soaps, with the detergent including a minimum amount of magnesium such that the magnesium detergent contribution provides at least about 40 percent of the detergent TBN in the fluid as measured in accordance with ASTM D 4739. As noted above, the detergent systems herein may include a ratio of TBN provided by the overbased magnesium component to the TBN of the total detergent system of at least about 0.4:1 or greater, such as from about 0.4:1 to about 1:1, or from about 0.6:1 to about 1:1, or from about 0.8:1 to about 1:1. In another approach, the detergent system herein has at least about 40 percent of the detergent TBN provided by the overbased magnesium detergent, or from about 40 percent to about 100 percent of the TBN, or more preferably from about 40 percent to about 60 percent of the detergent TBN provided by the overbased magnesium detergent, e.g., an overbased magnesium sulfonate.

[0024] As an example, the detergent system provides an amount of total detergent metals that is greater than about 1000 ppm metal based on the total lubricating composition, 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. In other approaches, the detergent metals are calcium, sodium and / or magnesium, preferably calcium and magnesium obtained by sulfonates, more preferably calcium and magnesium overbased sulfonates. The detergent may also optionally contain calcium phenates and / or other detergents as needed for a particular application, so long as the relationship between the amount of metal and the TBN of the detergent as described is met. More specifically, the detergent systems herein include neutral to overbased detergents (preferably neutral to overbased calcium sulfonates, neutral to overbased sodium sulfonates, and / or neutral to overbased magnesium sulfonates) that provide from about 300 to about 600 ppm magnesium (preferably from about 400 ppm to 600 ppm, or more preferably from about 500 ppm to 600 ppm magnesium), and in some embodiments at least about 500 ppm calcium (preferably from about 500 ppm to about 2,000 ppm calcium or from about 1000 ppm to about 1500 ppm calcium). In approaches or embodiments, the detergent systems herein may also include a particular weight relationship of calcium to magnesium of at least about 2 (i.e., at least about 2:1), at least about 2.1, at least about 2.2, or at least about 2.3 (in other approaches, from about 2 to about 3.0, from about 2.1 to about 2.5, from about 2.2 to about 2.5, or from about 2.3 to about 2.5).

[0025] In yet another approach or embodiment, the detergent system may also provide an amount of magnesium relative to the molybdenum from the oil soluble molybdenum component to achieve passing motor friction performance and passing Sequence IVB performance. In one embodiment, the weight relationship of magnesium to molybdenum that helps achieve such dual performance may be about 0.8:1 or less, about 0.6:1 or less, or from about 0.3:1 to about 0.8:1.

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

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

[0028] The term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "normal" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In normal or neutral salts, the MR is 1, and in overbased salts, the MR is greater than 1. They are generally referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0029] 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 D4739. 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.

[0030] 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 phosphoric acid, overbased calcium mono- and / or di-thiophosphoric acid, overbased calcium alkylphenol, overbased calcium sulfur-bound alkylphenol compound, overbased calcium methylene-bridged phenol, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphoric acid, overbased magnesium and / or di-thiophosphoric acid, overbased magnesium alkylphenol, overbased magnesium sulfur-bound alkylphenol compound, or overbased magnesium methylene-bridged phenol.Preferably, the detergent is overbased calcium and magnesium sulfonate.

[0031] Optionally, when a low-based or neutral detergent is incorporated into the detergent system, the low-based or neutral detergent generally has a TBN of up to 175 mg KOH / g, up to 150 mg KOH / g, up to 100 mg KOH / g, or up to 50 mg KOH / g. The low-based / neutral detergent may include a calcium or magnesium-containing detergent. Examples of suitable low-based / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate.

[0032] In some embodiments, the detergents used in the lubricants herein include one or more of overbased calcium sulfonates, overbased sodium sulfonates, or overbased magnesium sulfonates (optionally also including overbased metal phenates), each having a total base number of 150 to 500, in other approaches about 200 to about 450, or about 300 to about 425. The TBN values ​​above reflect the values ​​of the finished detergent components diluted in the base oil. As noted above, the detergent systems herein preferably include overbased calcium sulfonates and overbased magnesium sulfonates, providing the detergent metal and TBN relationships herein.

[0033] In other embodiments, the TBN of the detergents herein may reflect the neat or undiluted version of the detergent components. For example, the fluids herein may include an overbased calcium or sodium sulfonate as an undiluted additive having a TBN of about 300 to about 450, or in other approaches about 380 to about 420, and / or an overbased magnesium sulfonate as an undiluted additive having a TBN of about 500 to about 700, or in other approaches about 600 to about 700.

[0034] In yet other embodiments, the lubricating compositions herein include amounts of sodium sulfonate, magnesium sulfonate, and / or calcium sulfonate to achieve the above metal amounts and relationships. The lubricating compositions may also include from about 0 to about 5 weight percent of any detergent, either individually or in combination. Other detergents may also be included as needed for a particular application, so long as the magnesium, sodium, and calcium amounts and relationships are met.

[0035] The detergent system herein also provides a selected level of soap content, particularly sulfonate soap content, to the lubricant composition, where the amount of soap provided is balanced with the level of metal for the desired performance. In one approach, the detergent provides a soap content of about 0.2 to about 1.0 weight percent in the final lubricant composition, in other approaches, the detergent system provides a soap content of about 0.2 to about 0.8 weight percent, about 0.25 to about 0.7 weight percent, or about 0.28 to about 0.6 weight percent, and in yet other approaches, the detergent system provides a soap content of about 0.4 to about 0.6 weight percent calcium, sodium, and / or magnesium metal (preferably, the soap content is a sulfonate soap) as described above. In some approaches, the detergent system may also include an optional phenate soap content, which, if included, may be provided in an amount up to about 0.7 weight percent, or up to about 0.1 weight percent (or any range therein).

[0036] The 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 is determined by the amount of an exemplary calcium sulfonate detergent (RSO) with v, w, x, and y indicating the number of sulfonate groups, the number of calcium atoms, the number of carbonate groups, and the number of hydroxyl groups, respectively. 3 (represented by v Ca w (CO 3 ) x (OH) y can be determined using ASTM D3712 and / or the following formula:

[0037]

number

[0038] As shown in the examples below, lubricants that meet the detergent system attributes described above surprisingly achieve acceptable motor friction and valve train wear performance.

[0039] Polymer Pour Point Additives In another aspect, the lubricants herein include low amounts of polymeric pour point additives that have been found to adversely affect low temperature valve train wear in low viscosity lubricants. In an approach or embodiment, for example, the lubricants herein may also include less than about 0.2 wt. % of a polymeric pour point depressant, preferably less than about 0.1 wt. %, more preferably less than about 0.05 wt. %, or may not include a polymeric pour point depressant. In some approaches, the lubricants herein are substantially free of any embodiment of a polymeric pour point depressant as described herein. In such a context, the lubricant may have less than about 0.1 wt. percent, less than about 0.05 wt. percent of a pour point depressant, or may have no functional amount of a pour point depressant. In one exemplary approach, the polymeric pour point additive is a poly(meth)acrylate copolymer including one or more (meth)acrylate monomer units and / or one or more optional heterocyclic monomer units derived from monomers including vinyl lactones, vinyl lactams, combinations thereof.

[0040] In embodiments, the polymeric pour point additive may have the structure of Formula I below, where z and p are integers sufficient to achieve a weight average molecular weight of from about 20,000 to about 1,500,000 (or from about 100,000 to about 500,000, or from about 200,000 to about 450,000, or from about 200,000 to about 300,000 in other approaches). The p monomer units may provide from about 0 to about 10 weight percent of the copolymer, more preferably from about 0.2 to about 5 weight percent, or from about 1 to about 4 weight percent of the copolymer. In formula I, R is hydrogen when the monomer unit is an acrylate or methyl when the monomer unit is a methacrylate, R' is a linear or branched hydrocarbyl group sized to achieve any arm molecular weight as described herein, and R'' is a heterocyclic moiety derived from a monomer such as vinyl lactone, vinyl lactam, combinations thereof, or derivatives thereof, which in some approaches may include heterocyclic moieties derived from vinyl pyrrolidone, vinyl pyridine, N-vinyl pyrrolidone, N-vinylimidazole, N-vinyl caprolactam, combinations thereof, or derivatives thereof.

[0041] [ka] The polymeric copolymers described herein may have varying monomer units randomly spaced throughout the polymer, as described below.

[0042] Suitable monomers or reactants for forming the copolymer include at least one, and optionally a blend of at least two different monomers or reactants selected from (1) (meth)acrylate monomers having a hydrocarbyl group in the ester portion of a low to medium weight average molecular weight of up to about 700, or preferably from about 100 to about 700 or from about 400 to about 700, and optionally (2) (meth)acrylate monomers having a hydrocarbyl group in the ester portion of the monomer of a high weight average molecular weight of about 6,000 to about 10,000 or from about 6,000 to about 8,000, and / or optionally (3) monomer units having a heterocyclic moiety derived from polymers such as vinyl lactones, vinyl lactams, combinations thereof, etc. As used herein, "(meth)acrylate" refers to both methacrylate and / or acrylate monomers or monomer units (or mixtures). Also, as used herein, the molecular weight of the hydrocarbyl group of any ester in a monomer includes the hydrocarbyl chain as well as the ester oxygen, but does not include the carbonyl group.

[0043] Typically, the formed or resulting poly(meth)acrylate copolymer has an amount of monomers effective to achieve an overall copolymer number average molecular weight of about 20,000 or more, and in some cases about 250,000 or less, or about 225,000 or less, such as about 140,000 to about 240,000 or about 140,000 to about 225,000. The poly(meth)acrylate copolymer may also have a polydispersity index (Mw / Mn) of about 2.8 or less, or about 2.6 or less, and in other approaches, in the range of about 1.8 to about 2.6. In yet other approaches, the copolymers herein may optionally have two differently sized pendant arms and / or may have pendant heterocyclic groups, in such circumstances having a molecular weight ratio between the higher and lower arms of about 10:1 to about 50:1, in other approaches about 11:1 to about 30:1, and in still other approaches about 12:1 to about 25:1. In other cases, the copolymers herein have a molecular weight ratio between the higher and lower arms of about 1.5:1 to about 25:1, and in other approaches about 1.5:1 to about 16:1.

[0044] In an approach or embodiment, the poly(meth)acrylate copolymers herein comprise the reaction product in the form of a linear, random copolymer of selected amounts of low to medium molecular weight (meth)acrylate monomers, optional heterocyclic monomers, and / or optional higher molecular weight pendant hydrocarbyl (meth)acrylate monomers. These monomers and monomer units are further described below and contain both linear and / or branched hydrocarbyl groups on the respective ester chains, forming in some embodiments a comb copolymer having at least one, and optionally at least two, distinct molecular weight pendant arms.

[0045] In an embodiment or approach, the low molecular weight hydrocarbyl (meth)acrylate units or monomers are derived from alkyl (meth)acrylates having linear or branched hydrocarbyl groups in the ester portion, linear or branched alkyl groups in the ester portion having a total carbon chain length in the monomer ester portion (including any branching) of 1 to 20 carbons, preferably 6 to 20 carbons, and more preferably 12 to 16 carbons. Exemplary low molecular weight hydrocarbyl (meth)acrylate monomers can be methyl (meth)acrylate or lauryl (meth)acrylate (which can include a blend of (meth)acrylate monomers or monomer units having alkyl chain lengths in the range of C12 to C16 in the blend, specifically alkyl chains of 12, 14, and 16 carbons, of which C12 alkyl (meth)acrylates are in the majority). In another embodiment or approach, the low or medium molecular weight hydrocarbyl (meth)acrylate units are derived from hydrocarbyl (meth)acrylate monomers having hydrocarbyl groups or total hydrocarbyl ester length (including any branching) and have a weight average molecular weight of at least about 500 up to about 700. These molecular weight chains can be derived from macromonomers of olefins or polymeric alcohols, optionally esterified with (meth)acrylic acid. The macromonomers can be derived from alkenes or alkadienes, including ethylene, propylene, butene, butadiene, isoprene, or combinations thereof, and have a molecular weight of about 700 or less, such as about 500 to about 700.

[0046] In yet another embodiment or approach, the optional high molecular weight hydrocarbyl (meth)acrylate units, or monomers, are derived from hydrocarbyl (meth)acrylate monomers having hydrocarbyl groups or total hydrocarbyl ester lengths (including any branching) having a weight average molecular weight of at least about 6,000 and up to about 10,000, or from about 6,000 to about 8,000. These high molecular weight chains can be derived from macromonomers of polymeric alcohols esterified with (meth)acrylic acid. The macromonomers can be derived from alkenes or alkadienes, including ethylene, propylene, butene, butadiene, isoprene, or combinations thereof, and have a molecular weight of about 10,000 or less, or about 8,000 or less, such as about 500 to about 10,000, or from about 6,000 to about 8,000.

[0047] In other optional embodiments, the polymer copolymers herein may also include other optional monomers and monomer units, including, for example, hydroxyalkyl (meth)acrylates and / or various dispersant monomers and monomer units. The poly(meth)acrylate copolymers herein may also be optionally functionalized with one or more dispersant monomers or monomer units. For example, the copolymers may include heterocyclic moieties derived from monomers such as vinyl lactones, vinyl lactams, combinations thereof, or derivatives thereof, and in some approaches may include heterocyclic moieties derived from vinyl pyrrolidone, vinyl pyridine, N-vinyl pyrrolidone, N-vinylimidazole, N-vinyl caprolactam, combinations thereof, or derivatives thereof.

[0048] In one optional approach, the dispersant monomer or monomer unit may be a nitrogen-containing monomer or unit thereof. Such monomers, when used, may impart dispersant functionality to the polymer. In some approaches, the nitrogen-containing monomer may be a (meth)acrylic monomer, such as a methacrylate, methacrylamide, or the like. In some approaches, the attachment of the nitrogen-containing moiety to the acrylic moiety may be through a nitrogen atom or alternatively an oxygen atom, in which case the nitrogen of the monomer will be located elsewhere in the monomer. The nitrogen-containing monomer may be other than a (meth)acrylic monomer, such as a vinyl-substituted nitrogen heterocyclic monomer and a vinyl-substituted amine. Nitrogen-containing monomers include, for example, those in U.S. Pat. No. 6,331,603. Other suitable dispersant monomers include, but are not limited to, dialkylaminoalkyl acrylates, dialkylaminoalkyl (meth)acrylates, dialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides, N-tertiary alkyl acrylamides, and N-tertiary alkyl methacrylamides, where the alkyl or aminoalkyl groups may independently contain 1 to 8 carbon atoms. For example, the dispersant monomer can be dimethylaminoethyl (meth)acrylate. The nitrogen-containing monomer can be, for example, t-butylacrylamide, dimethylaminopropyl (meth)acrylamide, dimethylaminoethyl methacrylamide, N-vinylpyrrolidone, N-vinylimidazole, or N-vinylcaprolactam. It may also be a (meth)acrylamide based on any of the aromatic amines disclosed in WO 2005 / 087821, including 4-phenylazoaniline, 4-aminodiphenylamine, 2-aminobenzimidazole, 3-nitroaniline, 4-(4-nitrophenylazo)aniline, N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide, N-(4-amino-2,5-dimethoxy-phenyl)-benzamide, N-(4-amino-2,5-diethoxy-phenyl)-benzamide, N-(4-amino-phenyl)-benzamide, 4-amino-2-hydroxy-benzoic acid.

[0049] The (meth)acrylate copolymers of the present disclosure are typically synthesized to have a number average molecular weight of about 20,000 or more, and in other approaches, about 250,000 or less, or about 200,000 or less. Suitable ranges of number average molecular weight include about 140,000 to about 250,000, and in other approaches, about 150,000 to about 200,000. Such copolymers herein typically have a polydispersity index in the range of about 1 to about 4, and in other approaches, about 1.2 to about 3.5, and in yet other approaches, about 1.5 to about 3, and in yet other approaches, about 1.6 to about 2.5.

[0050] The (meth)acrylate copolymers may be prepared by any suitable conventional or controlled free radical polymerization technique. Examples include conventional free radical polymerization (FRP), reversible addition-fragmentation chain transfer (RAFT), atom transfer radial polymerization (ATRP), and other controlled types of polymerization known in the art. Polymerization procedures are known to those skilled in the art and include, for example, the use of common polymerization initiators (such as Vazo™ 67 (2.2′-azobis(2-methylbutyronitrile)), chain transfer agents (such as dodecyl mercaptan) when using conventional FRP, or RAFT agents (such as 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid) when using RAFT polymerization. Other initiators, chain transfer agents, RAFT agents, ATRP catalysts, and initiator systems may be used as known in the art, depending on the polymerization method selected, as needed for a particular application.

[0051] Amine or phenolic antioxidants The lubricants herein may also include one or more antioxidants, preferably one or more amine-based or phenol-based antioxidants. Similar to the polymeric pour point additives discussed above, the lubricants herein include low amounts of amine-based and / or phenol-based antioxidants that have been found to adversely affect low temperature valve train wear in low viscosity lubricants. In an approach or embodiment, the amine-based antioxidant may include, but is not limited to, antioxidants selected from aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, and the like, or combinations thereof. The total amount of antioxidant in the lubricating compositions herein may be present in an amount to deliver, for example, about 400 ppm or less of nitrogen, or about 300 ppm or less of nitrogen, or about 200 ppm or less of nitrogen, or about 50 to about 400 ppm of nitrogen, about 60 to about 300 ppm of nitrogen, about 70 to about 200 ppm of nitrogen, or about 80 to about 100 ppm of nitrogen. In other approaches, the lubricating compositions herein may include up to about 2 weight percent of the aminic antioxidant, or from about 0.1 to about 2.0 weight percent of the aminic antioxidant, and in other approaches, from about 0.1 to about 1.0 weight percent, or from about 0.2 to about 0.8 weight percent, or from about 0.2 to about 0.6 weight percent of the aminic antioxidant.

[0052] In some approaches, the amine antioxidant can be one or more aromatic amine antioxidants, which can include, but are not limited to, diarylamines having the following formula:

[0053] [ka] where R' and R'' each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. If substituted, suitable substituents on the aryl groups of R' and R'' include an aliphatic hydrocarbon group such as an alkyl having 1 to 30 carbon atoms, a hydroxy group, a halogen radical, a carboxylic acid or ester group, or a nitro group. The aryl group may be a substituted or unsubstituted phenyl or naphthyl, particularly one in which one or both aryl groups are substituted with at least one alkyl having 4 to 30, preferably 4 to 18, and most preferably 4 to 9 carbon atoms. In an approach, one or both aryl groups may be substituted, such as mono-alkylated diphenylamine, di-alkylated diphenylamine, C9 alkylated diphenylamines, or a mixture of mono- and dialkylated diphenylamines.

[0054] Examples of diarylamines that may be used include, but are not limited to, diphenylamine; the various alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, monobutyldiphenyl-amine, dibutyldiphenylamine, monooctyldiphenylamine, dioctyldiphenylamine, monononyldiphenylamine, dinonyldiphenylamine, monotetradecyldiphenylamine, ditetradecyldiphenylamine, phenyl-alpha-naphthylamine, monooctylphenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, monoheptyldiphenylamine, diheptyl-diphenylamine, p-oriented styrenated diphenylamines, mixed butyloctyldi-phenylamines, and mixed octylstyryldiphenylamines.

[0055] In another approach, suitable antioxidants may include aromatic amine antioxidants. Examples of phenolic antioxidants include N,N'-di-sec-butyl-phenylene-diamine, 4-isopropylaminodiphenylamine, phenyl-alpha-naphthylamine, phenyl-alpha-naphthylamine, and ring-alkylated diphenylamines.

[0056] Base oil or base oil blend: The base oil used in the lubricating compositions herein may be an oil of lubricating viscosity and may be selected from any of the base oils in American Petroleum Institute (API) Groups I to V as set forth in the API Base Oil Interchangeability Guidelines. The five base oil groups are generally set forth in Table 1 below.

[0057] [Table 1]

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

[0059] The base oil blends used in the disclosed lubricating oil compositions can be mineral, animal, vegetable, synthetic, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0060] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification treatment. Refined oils are similar to unrefined oils, except that they have been treated with one or more purification steps that may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

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

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

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

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

[0065] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, where the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, where the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition.

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

[0067] In some approaches or embodiments, the base oil system herein comprises one or more of Group I through Group V base oils and may have a KV100 of from about 2 to about 20 cSt, in other approaches from about 2 to about 10 cSt, from about 2.5 to about 6 cSt, in yet other approaches from about 2.5 to about 3.5 cSt, and in yet other approaches from about 2.5 to about 4.5 cSt.

[0068] As used herein, the terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "fully formulated lubricant composition," "lubricant," and "lubricating and cooling fluid" are considered synonymous and fully interchangeable terms that refer to a finished lubricating product that includes a majority of a base oil component and minor amounts of detergents and other optional components.

[0069] Optional Additives: The lubricating oil compositions herein may also contain a number of optional additives in combination with the detergent system, the sulfurized additives, and the boronated detergents as needed to meet performance criteria, which optional additives are described in the following paragraphs.

[0070] Dispersants: The lubricating oil composition may optionally contain one or more dispersants or mixtures thereof. Dispersants are often referred to as ashless type dispersants because they do not contain ash-forming metals prior to mixing with the lubricating oil composition and do not normally contribute to ash when added to the lubricant. Ashless type dispersants are characterized in that polar groups are 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).

[0071] Preferred amines are selected from polyamines and hydroxyamines. Examples of polyamines that may be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylaminehexamine (PEHA).

[0072] 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 6 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogen atoms per molecule and having 2 or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., >32% by weight) total nitrogen and an equivalent weight of 120-160 grams of primary amine groups per equivalent.

[0073] In some approaches, suitable polyamines, commonly known as PAM, contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0074] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 grams equivalent per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than 6 nitrogens and more extensive branching, may produce dispersants with improved dispersancy.

[0075] In an embodiment, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from a polyisobutylene having a number average molecular weight, as determined by GPC, in the range of from about 350 to about 50,000, or to about 5000, or to about 3000. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0076] In some embodiments, polyisobutylene, if present, 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%.

[0077] 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 used in the thermal ene reaction, HR-PIB can result in higher conversion during the reaction and less precipitate formation due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0078] 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.

[0079] The percent actives of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in U.S. Patent No. 5,334,321, columns 5 and 6.

[0080] Polyolefin conversion is calculated from the percent actives using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0081] Unless otherwise specified, 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.

[0082] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0083] A suitable class of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants that may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that may be reacted with the functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0084] One class of suitable dispersants may also be Mannich bases. Mannich bases are materials formed by condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0085] A suitable class of dispersants may also be high molecular weight esters or half ester amides.Suitable dispersants may also be post-treated by reacting with any of a variety of agents by conventional methods.Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds.U.S. Patent No. 7,645,726, U.S. Patent No. 7,214,649, and U.S. Patent No. 8,048,831 are incorporated herein by reference in their entirety.

[0086] 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. Patent No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980), organic phosphorus compounds (e.g., U.S. Patent No. 3,502,677), phosphorus pentasulfide, boron compounds as already mentioned above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387), carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948,386), epoxides, polyepoxy compounds, and the like. esters or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495), aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530), carbon disulfide (e.g., U.S. Pat. No. 3,256,185), glycidol (e.g., U.S. Pat. No. 4,617,137), urea, thiourea, or guanidine (e.g., U.S. Pat. Nos. 3,312,619, 3,865,813, and British Patent No. 1,065,595), organic sulfones, acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811), alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569), diketenes (e.g., U.S. Pat. No. 3,546,243), diisocyanates (e.g., U.S. Pat. No. 3,573,205), alkanesultones (e.g., U.S. Pat. No. 3,749,695), 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675), alkane sultones (e.g., U.S. Pat. No. 4,579,675), alkane nitriles ... No. 3,954,639), cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711), cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811), hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522), lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460), cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460). Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811), hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522), lactams, 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. 4,612,132, 4,647,390, 4,646,860, and 4,670,170), For example, U.S. Pat. Nos. 4,663,062 and 4,666,459), hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318, and 4,713,189), oxidizing agents (e.g., U.S. Pat. No. 4,379,064), combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. No. 3,185,647), combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086 and 3,470,098), hydrazine and carbon disulfide. No. 3,519,564), combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, and 5,039,307), combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740), combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086), combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenols (e.g., U.S. Pat. No. 4,636,No. 322), combinations of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064), combinations of formaldehyde and phenols and then glycolic acid (e.g., U.S. Pat. No. 4,699,724), combinations of hydroxyaliphatic carboxylic acids or oxalic acid and then a diisocyanate (e.g., U.S. Pat. No. 4,713,191), combinations of inorganic acids or anhydrides of phosphorus or their partial or total sulfur analogs and boron compounds (e.g., U.S. Pat. No. 4,857,21 No. 4), an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412), an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278), an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492), a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are hereby incorporated in their entirety.

[0087] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0088] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In this approach, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, where the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 as determined by GPC using polystyrene as the calibration standard.

[0089] In some approaches, the polyalkylene polyamine used to form the dispersant has the formula:

[0090] [ka] wherein each R and R' is independently a divalent C1-C6 alkylene linker; 1 and R 2 are 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.

[0091] Dispersants, when present, may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Alternative amounts of dispersants that may be used may be from about 0.1% to about 15% by weight, or from about 0.1% to about 10% by weight, or from about 0.1 to about 8% by weight, or from about 1% to about 10% by weight, or from about 1% to about 8% by weight, or from about 1% to about 6% by weight, 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.

[0092] Antioxidants: The lubricating oil composition herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0093] The hindered phenol antioxidant may contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group that connects to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and 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 and may include Ethanox™ 4716 available from Albemarle Corporation.

[0094] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0095] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefins can be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0096] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with olefins, such as α-olefins.

[0097] In another alternative embodiment, the antioxidant composition contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the treat rate ratio of the phenolic to the amine to the molybdenum-containing components is (0-3):(0-3):(0-3).

[0098] The one or more antioxidants may be present in the range of from about 0% to about 20%, or from about 0.1% to about 10%, or from about 1% to about 5% by weight of the lubricating oil composition.

[0099] Anti-wear agents: The lubricating oil composition herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates, metal dialkyldithiophosphates; phosphate esters or salts thereof; phosphoric acid esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0100] 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, and the total of carbon atoms on the alkyl group may be at least 8. The antiwear agent may, in one embodiment, include citrates.

[0101] The antiwear agent may be present in a range including from about 0% to about 15%, or from about 0.01% to about 10%, or from about 0.05% to about 5%, or from about 0.1% to about 3% by weight of the lubricating oil composition.

[0102] Boron-containing compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057. The boron-containing compounds, when present, may be used in an amount sufficient to provide up to about 8 wt. %, about 0.01 wt. % to about 7 wt. %, about 0.05 wt. % to about 5 wt. %, or about 0.1 wt. % to about 3 wt. % of the lubricating oil composition.

[0103] Additional cleaning agents: 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 dithiophosphoric acids, alkylphenols, sulfur-bound alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and their preparation methods are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein.

[0104] The detergent substrate may be salified with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphoric acid, calcium mono- and / or dithiophosphoric acid, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphoric acid, magnesium mono- and / or dithiophosphoric acid, 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 phosphoric acid, sodium mono- and / or dithiophosphoric acid, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0105] 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.

[0106] The term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "normal" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is 1, while in overbased salts the MR is greater than 1. They are generally referred to as overbased, hyperbasic, or superbasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0107] 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.

[0108] 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 dithiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bound alkylphenol compound, overbased calcium methylene bridged phenol, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphate, overbased magnesium and / or dithiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bound alkylphenol compound, or overbased magnesium methylene bridged phenol.

[0109] 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, from about 225 mg KOH / g to about 400 mg KOH / g, from at least about 225 mg KOH / g to about 350 mg KOH / g, or from 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 that may be included in the detergent composition (e.g., accelerators, etc.).

[0110] The overbased detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 wt.% to about 10 wt.%, or from about 0.1 wt.% to about 8 wt.%, or from about 1 wt.% to about 4 wt.%, or from greater than about 4 wt.% to about 8 wt.%.

[0111] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme pressure (EP) agents that are soluble in oil include sulfur and chlorosulfur containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes, organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts, phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphoric acids, including, for example, the amine salts of the reaction products of dialkyl dithiophosphoric acids with propylene oxide, and mixtures thereof.

[0112] Friction Modifiers: The lubricating oil composition herein may optionally contain one or more friction modifiers.Suitable friction modifiers may include metal-containing and metal-free friction modifiers, including, but 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.

[0113] 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 another embodiment, the long chain fatty acid ester may be a monoester, or a diester, or a (tri)glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

[0114] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free mechanical friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and may generally include polar end groups (e.g., carboxyl or hydroxyl) covalently attached to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is generally known as glycerol monooleate (GMO), which may include mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entirety of which is incorporated herein by reference.

[0115] 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.

[0116] The amines and amides may be used by themselves or in the form of adducts or reaction products with boron compounds such as boron oxides, boron halides, metaborates, boric acid or mono-, di-, or tri-alkyl borates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0117] Friction modifiers may optionally be present in ranges such as from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from about 0.1% to about 4% by weight.

[0118] Molybdenum-containing ingredients: The lubricating oil composition herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compounds may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0119] Suitable examples of molybdenum compounds that may 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 entireties of which are incorporated herein by reference.

[0120] 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 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide, or a similar acidic molybdenum compound. Alternatively, the composition can provide the molybdenum via a molybdenum / sulfur complex of a basic nitrogen compound, 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.

[0121] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula Mo 3 S k L n Q z and mixtures thereof, where 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 1-4, k varies from 4-7, Q is selected from the group of neutral electron donor compounds, such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0-5, including non-stoichiometric values. There may be at least 21 total carbon atoms in the organic groups of all the ligands, 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, which is incorporated herein by reference in its entirety.

[0122] 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.

[0123] Transition metal-containing compounds: In another embodiment, the oil-soluble compound can be a transition metal-containing compound or metalloid. Transition metals can 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.

[0124] In some embodiments, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium (IV) alkoxide. Among the titanium-containing compounds that may be used in or for the preparation of the oil-soluble material of the technology of the present disclosure are various Ti (IV) compounds, such as titanium (IV) oxide, titanium (IV) sulfide, titanium (IV) nitrate, titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide, and other titanium compounds or complexes, such as, but not limited to, titanium phenate, titanium carboxylate, 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., dialkyl dithiophosphates) and titanium sulfonates (e.g., alkyl benzene sulfonates), or generally reaction products of titanium compounds with various acidic materials to form salts, such as oil-soluble salts. Thus, titanium compounds may be derived from organic acids, alcohols, and glycols, among others. Ti compounds may also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques that will be apparent to those skilled in the art. They may exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

[0125] In one embodiment, titanium may be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or may be reacted with any of 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, (c) hydroxy-containing polyester dispersants prepared by reaction of substituted succinic anhydrides with polyols, amino alcohols, polyamines, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to a lubricant or can be further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with about two parts (mole) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to produce a titanium modified succinimide dispersant.

[0126] Another titanium-containing compound is titanium alkoxide and C 6 ~C 25 The reaction product may be a reaction product with a carboxylic acid. The reaction product may be represented by the formula:

[0127] [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 formula:

[0128] [ka] In the formula, m+n=4, n is in the range of 1 to 3, and R 4 is an alkyl moiety having in the range of 1 to 8 carbon atoms, R 1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms; R 2 and R 3 are the same or different and are selected from hydrocarbyl groups containing 1 to 6 carbon atoms, or the titanium compound may be represented by the formula:

[0129] [ka] In the formula, x ranges from 0 to 3; R 1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms; R 2 , and R 3 are the same or different and are selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms; R 4 , H, C 6 ~C 25 The carboxylic acid moiety is selected from the group consisting of:

[0130] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0131] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 to about 500 ppm by weight of titanium, or from about 50 to about 300 ppm by weight of titanium.

[0132] 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. Publication No. 2012 / 0101017(A1).

[0133] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead of the viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) with an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0134] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0% to about 20%, from about 0.1% to about 15%, from about 0.1% to about 12%, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0135] 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.

[0136] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0137] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates, or polyacrylamides.

[0138] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0139] 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.

[0140] A suitable rust inhibitor can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful class of acidic corrosion inhibitors are the half esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as polyglycols. The corresponding half amides of such alkenyl succinic acids are also useful.Useful rust inhibitors are high molecular weight organic acids.

[0141] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 wt. % to about 5 wt. %, from about 0.01 wt. % to about 3 wt. %, from about 0.1 wt. % to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0142] Generally speaking, suitable lubricants containing detergent metals herein may contain additive components in the ranges listed in the table below.

[0143] [Table 2]

[0144] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricant composition. The remainder of the lubricant 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 provides the characteristics required in the formulation.

[0145] definition For purposes of this disclosure, the chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. Additionally, general principles of organic chemistry are described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausolito: 1999, and "March's Advanced Organic Chemistry", 5th Ed., Ed.: Smith, M. B. and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0146] As described herein, compounds may be optionally substituted with one or more substituents as illustrated generally above, or as illustrated by the specific classes, subclasses, and species of the present disclosure.

[0147] 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. Also, as used herein, the term "minor amount" is understood to mean an amount of less than 50 weight percent, based on the total weight of the composition.

[0148] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense, well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) and aromatic, aliphatic and alicyclic substituted aromatic substituents, as well as cyclic substituents in which a ring is completed through another portion of the molecule (e.g., two substituents taken together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy) that do not alter the predominantly hydrocarbon substituent in the context of this disclosure; (3) hetero substituents, i.e., substituents that, while having predominantly hydrocarbon character in the context of this disclosure, contain other than carbon in the ring or chain or are otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and encompass such substituents as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than 2, or as a further example, only one non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group, and in some embodiments, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0149] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0150] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be straight 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, heteroaralkylcarbonylaminoalkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic -SO 2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Some non-limiting examples of substituted alkyl include carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO 2 -amino)alkyl), aminoalkyl, amidoalkyl, (alicyclic)alkyl, or haloalkyl.

[0151] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be linear or branched. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. An alkenyl group can be 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, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO 2 -, alicyclic-SO 2 - or aryl-SO 2 -], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, cycloaliphatic oxy, heterocycloaliphatic oxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Some non-limiting examples of substituted alkenyls include cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO 2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (alicyclic)alkenyl, or haloalkenyl.

[0152] As used herein, an "alkynyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. The alkynyl group may be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. An alkynyl group may be substituted with one or more substituents, such as, for example, aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or cycloaliphatic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or cycloaliphatic finyl], sulfonyl [e.g., aliphatic -SO 2 -, Aliphatic amino-SO 2 - or alicyclic -SO 2 -], amido [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, arylaminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamido, alkoxycarbonyl, alkylcarbonyloxy, alicyclic, heteroalicyclic, aryl, heteroaryl, acyl [e.g., (alicyclic)carbonyl or (heteroalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heteroalicyclic)oxy, or (heteroaryl)alkoxy.

[0153] As used herein, an "amino" group refers to an -NR X R Y In the formula, R X and R Y Each of is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaralkyl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is not limited to -NR X - Represented by R X is as defined above.

[0154] 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.

[0155] 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.

[0156] As used herein, a "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or combinations thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fused ring systems having 2 to 3 rings. For example, benzo-fused groups include benzo fused to one or two 4-8 membered heterocyclic aliphatic moieties (e.g., indolisyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzthiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzthiazolyl, puryl, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthyridyl.

[0157] Monocyclic heteroaryls include, but are not limited to, furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridyl, pyridazyl, pyrimidyl, pyrazolyl, pyrazyl, or 1,3,5-triazyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0158] 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.

[0159] As used herein, the term "treat rate" refers to the weight percentage of a component in a lubricating and cooling fluid.

[0160] The weight average molecular weight (Mw) and number average molecular weight (Mn) may be determined using a gel permeation chromatography (GPC) instrument from Waters or similar instrumentation and Waters Empower Software or similar software. The GPC instrument may be provided with a Waters separation module and a Waters refractive index detector (or similar optional instrumentation). GPC operating conditions may include a guard column, four Agilent PLgel columns (length 300×7.5 mm, particle size 5μ, and pore size range 100-10000 Å), and a column temperature of about 40° C. Non-stabilized HPLC grade tetrahydrofuran (THF) may 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 distribution in the range of 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 prepared 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 further provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland and D.D. Ly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is incorporated herein by reference. EXAMPLES

[0161] A better understanding of the present disclosure and its many advantages can be made clear with the following examples. The following examples are illustrative and are not intended to be limiting in scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise stated or apparent from the context of the following examples and discussion throughout this disclosure, all percentages, ratios, and parts described in this disclosure are by weight.

[0162] Comparative Example 1 The lubricating compositions were evaluated for sequence IVB engine performance according to ASTM D8350. Testing generally involves 24,000 32-second cycles over approximately 200 hours, with each cycle including four stages, including two steady-state stages with a transition ramp stage between them, as described in the ASTM test method. The average intake lifter wear volume and end-of-test oil iron concentration were measured. Passing performance was determined by removing 2.7 mm of intake lifter. 3 and an average volume loss of less than 400 ppm at the end of the test.

[0163] The comparative lubricating compositions evaluated for this example were formulated in a 0W-8 viscosity grade and contained overbased calcium and magnesium sulfonate detergents, the indicated amounts of molybdenum from molybdenum dithiocarbamate to provide the fluid relationships in Table 3 below, and a similar base additive package including dispersants, antiwear additives, antioxidants, antifoam agents, friction modifiers, and about 0.05 wt. % of a polymeric pour point depressant (a copolymer of alkyl methacrylate and vinylpyrrolidone) in a Group III base oil to achieve a KV100 of about 5 cSt (ASTM D445).

[0164] [Table 3]

[0165] [Table 4]

[0166] As shown in Table 4, Comparative Lubricant 1 passed Sequence IVB testing but did not contain any molybdenum from the molybdenum dithiocarbamate additive and therefore would be expected to fail the JASO M365 Motor Friction Test. Comparative Lubricant 2, with 820 ppm molybdenum from the molybdenum dithiocarbamate additive, would be expected to pass the JASO M365 Motor Friction Test but failed Sequence IVB performance given the high level of molybdenum.

[0167] Example 1 Lubricating compositions of the present invention were evaluated for Sequence IVB engine performance according to ASTM D8350 as described in Comparative Example 1. The lubricating compositions of the present invention evaluated for this example were formulated in a 0W-8 viscosity grade and contained overbased calcium and magnesium sulfonate detergents, the indicated amounts of molybdenum from molybdenum dithiocarbamate to provide the fluid relationships in Table 5 below, and an additive package similar to that of Comparative Example 1, including dispersants, antiwear additives, antioxidants, antifoam agents, friction modifiers, and about 0.05 wt. % of a polymeric pour point depressant (a copolymer of alkyl methacrylate and vinylpyrrolidone) in a Group III base oil to achieve a KV100 of about 5 cSt (ASTM D445).

[0168] [Table 5]

[0169] [Table 6]

[0170] As shown in Table 6, Lubricant 1 of the present invention, having an increased amount of detergent TBN provided by magnesium sulfonate when combined with a high level of molybdenum that passed the motor friction test, also achieved passing Sequence IVB performance at the same time.

[0171] Comparative Example 2 Additional comparative lubricating compositions were evaluated for Sequence IVB engine performance when containing the high levels of molybdenum required to pass the motor friction test according to ASTM D8350, as described in Comparative Example 1. The comparative lubricating compositions evaluated for this example were formulated in a 0W-8 viscosity grade and contained overbased calcium and magnesium sulfonate detergents, the indicated amounts of molybdenum from molybdenum dithiocarbamate to provide the fluid relationships in Table 7 below, and an additive package similar to that of Comparative Example 1, including dispersants, antiwear additives, antioxidants, antifoam agents, friction modifiers in a Group III base oil to achieve a KV100 of about 5 cSt (ASTM D445).

[0172] Comparative Lubricants 3 and 5 also contained about 0.2 weight percent of a polymeric pour point depressant (a copolymer of an alkyl methacrylate and vinylpyrrolidone), and Comparative Lubricant 4 contained about 0.05 weight percent of a polymeric pour point depressant (a copolymer of an alkyl methacrylate and vinylpyrrolidone), but then contained 0.6 weight percent of a phenolic antioxidant.

[0173] [Table 7]

[0174] [Table 8]

[0175] As shown in Table 8, this comparative example fluid is expected to pass the JASO M365 motor-driven friction test due to the high molybdenum content from the molybdenum dithiocarbamate additive, but none of these comparative lubricants was able to achieve passing performance in the Sequence IVB test without the correct balance of magnesium detergent TBN relative to the other lubricant components.

[0176] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list excludes other similar items that may be substituted for or added to the items in the list.

[0177] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0178] 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.

[0179] It is further to be understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but any range of such values.

[0180] It is further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is further understood that any range between the endpoint values ​​within the broad range is also contemplated herein. Thus, a range of 1 to 4 also means a range of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0181] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and therefore can be combined with any other lower or upper limit of a range or specific amount / value for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0182] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or that cannot be currently anticipated by the applicants or others skilled in the art. It is therefore intended that the appended claims as filed, and the appended claims as they may be amended, cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 1. An engine lubricating oil composition providing improved low temperature valve train wear according to ASTM D8350, Sequence IVB engine test, comprising: one or more base oils of lubricating viscosity; 300 to 1000 ppm molybdenum from an oil-soluble molybdenum compound; one or more metal-containing detergents providing a TBN of greater than 5 to the lubricating oil composition, the TBN being measured using ASTM D4739; one or more metal-containing detergents, at least one of which comprises an overbased magnesium-containing detergent providing the lubricating oil composition with a TBN of greater than 2, wherein the TBN is measured using ASTM D4739; and less than 0.2 wt. % of a polymeric pour point depressant; The engine lubricating oil composition, wherein the lubricating oil composition has a viscosity grade according to SAE J 300 of 0W-8, 0W-12, 0W-16, or 0W-20.

2. 2. The engine lubricating oil composition of claim 1, wherein the one or more overbased magnesium-containing detergents comprise a magnesium sulfonate.

3. 10. The engine lubricating oil composition of claim 1, wherein the lubricating oil composition further comprises a calcium-containing detergent.

4. 2. The engine lubricating oil composition of claim 1, wherein the one or more overbased magnesium-containing detergents have a total base number (TBN) of at least 250 mg KOH / g.

5. 2. The engine lubricating oil composition of claim 1, wherein the polymeric pour point depressant is a poly(meth)acrylate based pour point depressant.

6. 6. The engine lubricating oil composition of claim 5, wherein the polymeric pour point depressant is a poly(meth)acrylate copolymer having monomer units comprising: (i) one or more monomer units selected from C1 to C16 (meth)acrylates; and (2) vinylpyrrolidone monomer units.

7. 6. The engine lubricating oil composition of claim 5, wherein the amount of poly(meth)acrylate pour point depressant in the engine lubricating oil composition is less than 0.1 weight percent.

8. 10. The engine lubricating oil composition of claim 1, wherein the lubricating oil composition lubricates a hybrid gasoline-electric engine.

9. 9. The engine lubricating oil composition of claim 8, wherein the hybrid gasoline-electric engine comprises a 2.0 liter or smaller gasoline engine.

10. The lubricating oil composition has a viscosity of 2.7 mm when measured according to the Sequence IVB engine test of ASTM D8350. 3 2. The engine lubricating oil composition of claim 1, which exhibits an average intake lifter volume loss of less than or equal to 100 ppm and a maximum end of test iron content of less than or equal to 400 ppm.

11. 1. A method of lubricating a hybrid gasoline-electric engine to achieve improved low temperature valve train wear according to ASTM D8350, Sequence IVB engine test, comprising: lubricating a hybrid electric-gasoline engine with a lubricating oil composition having a viscosity grade of 0W-8, 0W-12, 0W-16, or 0W-20 according to SAE J 300; 14. The method of claim 13, wherein the lubricating oil composition comprises one or more base oils of lubricating viscosity; 300 to 1000 ppm of molybdenum from an oil-soluble molybdenum compound; one or more metal-containing detergents providing the lubricating oil composition with a TBN greater than 5, the TBN being measured using ASTM D4739, and at least one of the one or more metal-containing detergents comprises an overbased magnesium-containing detergent providing the lubricating oil composition with a TBN greater than 2, the TBN being measured using ASTM D4739; and less than 0.2 wt % of a polymeric pour point depressant.

12. 12. The method of claim 11, wherein the one or more overbased magnesium-containing detergents comprise a magnesium sulfonate and / or the lubricating oil composition further comprises a calcium-containing detergent.

13. 12. The method of claim 11, wherein the one or more overbased magnesium-containing detergents have a total base number (TBN) of at least 250 mg KOH / g and / or 40% to 100% of the detergent TBN is provided by overbased magnesium sulfonate.

14. 12. The method of claim 11, wherein the polymeric pour point depressant is a poly(meth)acrylate based pour point depressant, and / or the polymeric pour point depressant is a poly(meth)acrylate copolymer having monomer units comprising: (i) one or more monomer units selected from C1 to C16 (meth)acrylates and (ii) vinylpyrrolidone monomer units, and / or the amount of the polymeric pour point depressant in the lubricating oil composition is less than 0.1 weight percent.

15. The hybrid gasoline-electric engine comprises a 2.0 liter or smaller gasoline engine, and / or the lubricating oil composition has a 2.7 mm 3 12. The method of claim 11, wherein the method exhibits an average intake lifter volume loss of no more than 100% and a maximum end of test iron content of no more than 400 ppm.

16. 8. The engine lubricating oil composition of claim 1 or 7, wherein the weight ratio of magnesium to molybdenum in said lubricating oil composition is 0.8:1 or less.

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