Lubricant additives for performance enhancement

Abstract

This disclosure relates to booster additive packages with improved deposit, sludge, wear, TBN retention, and / or corrosion prevention properties, and to lubricating oil compositions comprising a booster additive package. The booster additive package comprises at least one oil-soluble nitrogen-containing compound and one or more detergent additives.

Description

[Technical Field]

[0001] This disclosure relates to booster additive packages for lubricating compositions, in particular to booster additive packages suitable for improving lubricant performance, including at least one of deposit, sludge, wear, TBN retention, and / or corrosion prevention, while maintaining API and / or ILSAC approval, and to lubricating compositions comprising such booster additive packages. [Background technology]

[0002] Automotive manufacturers continue to demand improvements in efficiency, fluid life, and fuel economy, and as a result, the requirements for engines, lubricants, and their components are constantly increasing. To this end, industry standards and / or automotive manufacturers require specific performance standards to ensure that today's lubricants meet the performance requirements of vehicle and engine manufacturers. For example, the American Petroleum Institute (API) and / or the International Lubricant Standardization and Approval Committee (ILSAC) provide standards established by various vehicle and engine manufacturers, technical associations, and / or trading associations such as ASTM, SAE, and / or the American Chemical Council (ACC) to ensure that today's automotive lubricants meet specific performance requirements. The API engine oil approval and certification system is a program that allows engine oils that meet specific requirements to be identified through one or more API and / or ILSAC certification marks or symbols.

[0003] Aftermarket additives have been proposed to treat existing unused or used motor oil. However, a drawback of adding additives, boosters, and / or so-called top-treatment additives to motor oil that is already API or ILSAC approved is that the combination of motor oil and additive often no longer meets the API and / or ILSAC approval standards. In other words, top-treated or supplemented motor oil is likely to be insufficient in one or more performance standards set by the industry or manufacturers. Currently, it is known that there are no such additives, boosters, or other top-treatment lubricant additives that can be added to unused or used motor oil while simultaneously maintaining API and / or ILSAC approval. [Overview of the project]

[0004] In one approach or embodiment, a booster additive package for passenger car motor oil lubrication compositions suitable for improving at least one of deposits, sludge, wear, TBN, and corrosion prevention while maintaining API and / or ILSAC approval is described herein. In one embodiment, the booster additive package comprises one or more oil-soluble nitrogen-containing compounds that provide the booster additive package with about 1000 ppm to about 8500 ppm of nitrogen, preferably about 1000 ppm to about 6000 ppm, more preferably about 1100 ppm to about 5800 ppm of nitrogen, and one or more detergent additives that provide the booster additive package with about 0.2% to about 5% by weight of soap.

[0005] In other approaches, the booster additive package described in the preceding paragraph may include one or more optional features or embodiments in any combination. These optional features or embodiments may include one or more of the following: the booster additive package is configured to maintain API SP and / or GF-6 certification when added to unused and / or used passenger car motor oil compositions; and / or the booster additive package is configured to maintain API SP and / or GF-6 certification when added to passenger car motor oil lubrication compositions, and / or the combination of passenger car motor oil lubrication compositions and booster additive packages is appropriable by the American Petroleum Institute (API) and / or the International Lubricants Standardization and Approval Committee (ILSAC); and / or at least about 90 weight percent, preferably at least about 95 weight percent, more preferably at least about 98 weight percent, most preferably 100 weight percent of detergent soap is provided by one or more detergent additives having a total base number (TBN) of about 250 mg KOH / g or more; and one or more detergent additives have a total base number (TBN) of about 280 mg KOH / g, or about 300 mg KOH / g or more, or about 320 mg KOH / g or more, or about 350 mg The total base number is greater than or equal to KOH / g, and / or one or more cleaning additives include a magnesium-containing cleaning additive, and / or one or more cleaning additives include only a magnesium-containing cleaning additive, and / or one or more cleaning additives give the booster additive package a total base number (TBN) of approximately 5 mg KOH / g to approximately 40 mg KOH / g as measured according to ASTM D2896, and / or the TBN / ounce of the booster additive package is approximately 0.5 to approximately 16 mg per ounce of the booster additive package. The KOH / g and / or about 65-100 percent of the detergent TBN is provided by one or more magnesium-containing detergent additives and / or the booster additive package contains about 1,000 ppm to about 10,000 ppm of magnesium from the magnesium-containing detergent, preferably about 1,200 ppm to about 8,000 ppm, more preferably about 1,400 ppm to about 7,800 ppm of magnesium and / or the booster additive package isThe booster additive package contains approximately 100 ppm magnesium per ounce to approximately 5000 ppm magnesium per ounce, and / or an oil-soluble nitrogen-containing compound, which contains an amine antioxidant, and / or an oil-soluble nitrogen-containing compound, which is an aromatic amine, alkylated diphenylamine, alkyl (e.g., nonyl)diphenylamine, di-alkyl (e.g., di-nonyl)diphenylamine, octyldiphenylamine, dioctyldiphenylamine, phenyl-alpha-naphthylamine, alkylated phenyl- The booster additive package contains an amine-based antioxidant selected from the group including rufa-naphthylamine, hindered non-aromatic amines, or combinations thereof, and / or an oil-soluble nitrogen-containing compound which is a di-alkyldiphenylamine-based antioxidant, preferably a di-nonyldiphenylamine-based antioxidant, and / or the booster additive package contains about 2 to about 20 weight percent of the amine-based antioxidant, and / or the booster additive package contains about 1000 ppm to about 6000 ppm of antioxidant nitrogen, and / or the booster additive package is a booster additive The detergent package contains approximately 100 ppm to approximately 3000 ppm of antioxidant nitrogen per ounce, and / or the ratio of total base number (TBN) to total soap content of the detergent is approximately 10:1 to approximately 15:1, and / or approximately 90 to approximately 100 percent of the nitrogen is provided by amine antioxidants, and / or the booster additive package further contains one or more ashless dispersants obtained by reacting a hydrocarbyl-substituted acylating agent with a nitrogen source, wherein the acylating agent is maleic anhydride, and the nitrogen source is ammonia, porcine Realkylene polyamines or combinations thereof are selected, and / or the nitrogen source is a polyalkylene polyamine selected from a mixture of polyethylene polyamines having an average of 5 nitrogen atoms, triethylenetetraamine, tetraethylenepentamine, or combinations thereof, and / or the ashless dispersant is post-treated with one or more of boron, carboxylic acids or derivatives thereof, and combinations thereof, and / or the booster additive package contains about 2 to about 20 weight percent of the ashless dispersant, and / or the booster additive packageThe booster additive package contains approximately 400 to approximately 2500 ppm of dispersant nitrogen provided by one or more ashless dispersants, and / or the booster additive package contains approximately 40 ppm to approximately 1300 ppm of dispersant nitrogen per ounce of booster additive package, and / or the booster additive package contains approximately 900 ppm to approximately 5,000 ppm of calcium from calcium-containing detergent additives, and / or the booster additive package contains approximately 90 ppm to approximately 2,500 ppm of detergent calcium per ounce of booster additive package.

[0006] Further approaches or embodiments describe lubricating compositions suitable for improving at least one of deposits, sludge, wear, TBN retention, and corrosion prevention. In aspects of this embodiment, the lubricating composition comprises (a) an unused or used passenger car motor oil lubricating composition comprising (i) a base oil of one or more lubricating viscosities, (ii) a dispersant inhibitor additive package, and (iii) optionally a viscosity index improver, and (b) any embodiment of the booster additive package described in the preceding two paragraphs.

[0007] In other approaches or embodiments, the lubrication compositions described in the preceding paragraph may include, in any combination, one or more optional features or embodiments. These optional features or embodiments may include one or more of the following: (a) the combination of the passenger car motor oil lubrication composition and (b) the booster additive package is API SP and / or GF-6 compliant, and / or the passenger car motor oil lubrication composition is an unused or used passenger car motor oil composition, and / or the combination of (a) the unused or used passenger car motor oil lubrication composition and (b) the booster additive package is compliant with the American Petroleum Institute (API) and / or the International Lubricants Standardization and Approval Committee (ILSAC), and / or the booster additive package has (a) an increase of at least about 5% in total nitrogen content relative to the passenger car motor oil lubrication composition (preferably an increase of about 5 to about 15%), and (b) an increase of at least about 20% in magnesium content relative to the passenger car motor oil lubrication composition (preferably about 20% (a) an increase of approximately 50%, (c) an increase of at least approximately 20% in magnesium soap content relative to the passenger car motor oil lubrication composition (preferably an increase of approximately 20% to approximately 50% in magnesium soap content), or (d) an amount effective in providing one or more of the above combinations, and / or the lubrication composition is provided with (a) approximately 450 ppm to approximately 550 ppm of magnesium provided from the combination of the passenger car motor oil lubrication composition and the booster additive package, (b) approximately 700 to approximately 1200 ppm of total nitrogen provided from the combination of the passenger car motor oil lubrication composition and the booster additive package, and (c) approximately 0.5 to approximately 1 ppm from the combination of the passenger car motor oil lubrication composition and the booster additive package.(d) containing 0% by weight soap content, or at least one of a combination thereof, and / or the lubricating composition exhibits higher rust prevention for up to approximately 6,000 miles of lubrication compared to a baseline lubricating composition containing a passenger car motor oil composition but without a booster additive package, as measured according to ASTM D6557, and / or the passenger car motor oil composition is either an unused passenger car motor oil composition or a used passenger car motor oil composition, and / or the used passenger car motor oil composition is at least 1,000 miles, 2,000 miles, 3,000 miles, 4,000 miles, 5,000 miles, 6,000 miles, 8,000 miles The lubrication system lubricates a combustion engine over a distance of 10,000 miles, and / or the lubrication composition comprises a booster additive package of about 1 to about 10 weight percent, preferably about 1.1 to about 8 weight percent, more preferably about 1.2 to about 6.5 weight percent, most preferably about 1.2 to about 6.3 weight percent, and / or the dispersant inhibitor package comprises one or more of the following: dispersants, detergents, anti-wear additives, antioxidants, friction modifiers, pour point dispersants, seal swelling agents, or a combination thereof.

[0008] Further approaches or embodiments describe methods for providing corrosion protection to valve train components of a passenger car engine. In aspects of this embodiment, the method involves lubricating the valve train components of a passenger car engine with any embodiment of the lubrication composition described in this summary, the valve train components maintaining a higher level of corrosion protection for up to 6,000 miles of lubrication compared to a lubrication composition that includes a passenger car motor oil composition but does not include a booster additive package.

[0009] In other approaches or embodiments, the method described in the preceding paragraph may include one or more optional features, steps, or embodiments in any combination. These optional features, steps, or embodiments may include one or more of the following: rust prevention is determined using ASTM D6557, and / or the lubricating composition is a used lubricating composition that has lubricated a combustion engine for at least 1,000 miles, 2,000 miles, 3,000 miles, 4,000 miles, 5,000 miles, 6,000 miles, 8,000 miles, or 10,000 miles.

[0010] Further approaches or embodiments describe further methods for providing corrosion protection to valve train components of a passenger car engine using a lubricating composition. In one embodiment, the method comprises providing a passenger car motor oil lubricating composition comprising one or more detergent additives that provide up to about 0.5 weight percent of soap to the passenger car motor oil lubricating composition, and one or more oil-soluble nitrogen-containing compounds that provide up to about 600 ppm of dispersant nitrogen to the passenger car motor oil lubricating composition, and adding a booster additive package to the passenger car motor oil lubricating composition to form a lubricating composition, wherein the lubricating composition maintains a higher level of corrosion protection to valve train components than a lubricating composition that includes the passenger car motor oil lubricating composition but does not include the booster additive package.

[0011] In further embodiments, the method for providing the rust prevention described in the preceding paragraph may include one or more optional features, steps, or embodiments in any combination. These optional features, steps, or embodiments may include one or more of the following: a lubricating composition as described in any embodiment as described in this summary, and / or a combination of (a) a passenger car motor oil lubricating composition and (b) a booster additive package, API The combination of (a) a passenger car motor oil lubrication composition and (b) a booster additive package is approved by the American Petroleum Institute (API) and / or the International Lubricants Standardization and Approval Committee (ILSAC), and / or the booster additive package is added in an amount effective to provide (a) an increase of at least about 5% in total nitrogen content relative to the passenger car motor oil lubrication composition (preferably an increase of about 5 to about 15%), (b) an increase of at least about 20% in magnesium content relative to the passenger car motor oil lubrication composition (preferably an increase of about 20 to about 50%), (c) an increase of at least about 20% in magnesium soap content relative to the passenger car motor oil lubrication composition (preferably an increase of about 20 to about 50% in magnesium soap content), or (d) a combination thereof.

[0012] In a further approach or embodiment, a method for lubricating an engine crankcase using a lubricating composition is described herein. In an embodiment, the method includes providing a passenger car motor oil lubricating composition comprising one or more detergent additives providing up to about 0.5 weight percent soap and one or more oil-soluble nitrogen-containing compounds providing up to about 600 ppm dispersant nitrogen; adding a booster additive package to the passenger car motor oil lubricating composition to form a lubricating composition; and lubricating an engine crankcase with the lubricating composition.

[0013] In further approaches or embodiments, the methods described in the preceding paragraph may include one or more optional features, steps, or embodiments in any combination. These optional features, steps, or embodiments may include one or more of the following: a lubricating composition as described in any embodiment of this summary, and / or a combination of (a) a passenger car motor oil lubricating composition and (b) a booster additive package, API The combination of (a) a passenger car motor oil lubrication composition and (b) a booster additive package is approved by the American Petroleum Institute (API) and / or the International Lubricants Standardization and Approval Committee (ILSAC), and / or the additive booster package is added in an amount effective to provide (a) an increase of at least about 5% in total nitrogen content (preferably an increase of about 5 to about 15%) relative to the passenger car motor oil lubrication composition, (b) an increase of at least about 20% in magnesium content (preferably an increase of about 20 to about 50%) relative to the passenger car motor oil lubrication composition, (c) an increase of at least about 20% in magnesium soap content (preferably an increase of about 20 to about 50%) relative to the passenger car motor oil lubrication composition, or (d) one or more of these combinations, and / or the lubrication composition exhibits higher rust prevention for up to about 6,000 miles of lubrication according to ASTM D6557 compared to a baseline lubrication composition containing the passenger car motor oil composition but without the booster additive package. [Brief explanation of the drawing]

[0014] [Figure 1] This is a graph of rust prevention over a maximum of 6,000 miles, measured according to ASTM D6557, comparing conventional GF-6 motor oil with enhanced GF-6 motor oil, which still maintains its certification. [Modes for carrying out the invention]

[0015] This disclosure relates to an auxiliary or concentrate in the form of a booster additive package for motor oil or lubricant, a final lubricant comprising such concentrate or booster additive package as a top treatment for passenger car motor oil, and a method for lubricating or improving the performance of motor oil, which includes at least one of improved deposit, sludge, wear, TBN retention, and / or rust prevention. Surprisingly, when the auxiliary or booster additive package of this specification is used as a top treatment for passenger car motor oil to form a final lubricant, it not only provides improved performance but also maintains API and / or ILSAC certification requirements, and in particular maintains API SP and / or GF-6 certification.

[0016] As shown in the following examples and Figure 1, the booster additive packages of this specification, when topped with passenger car motor oil at a concentration of about 0.5 to about 2 weight percent (preferably about 0.8 to about 1.8 weight percent as a top treatment) to form a final lubricant including the top treatment, provided higher initial rust prevention and maintained a higher level of rust prevention for a longer period compared to untreated conventional GF-6 motor oil. When used herein, rust prevention was evaluated using the ASTM D6557 ball rust test.

[0017] More specifically, the booster additive packages described herein are configured as top-treatment aids or additives for API or ILSAC approved passenger car motor oils to enhance or increase one or more of the following: nitrogen, calcium, total base number (TBN), and / or soap content, to form a final lubricant that maintains approval requirements. As used herein, final lubricant (or final lubrication composition) refers to a blend comprising a composition combining passenger car motor oil (or passenger car motor oil lubrication composition) and the booster additive packages described herein. Passenger car motor oil (or passenger car motor oil lubrication composition) refers to a lubricant comprising a base oil of lubrication viscosity, a dispersant inhibitor additive package, and an optional viscosity index improver (and not a booster additive package). As further described below, a booster additive package comprises at least an oil-soluble nitrogen-containing compound, a detergent additive, and a process oil / base oil of lubrication viscosity.

[0018] In one embodiment, the auxiliary or booster additive package of this specification comprises at least (i) one or more oil-soluble nitrogen-containing compounds that provide the booster additive package with about 1000 ppm to about 8500 ppm of nitrogen (preferably about 1000 ppm to about 6000 ppm, more preferably about 1100 ppm to about 5800 ppm of nitrogen), and (ii) one or more detergent additives that provide the booster additive package with about 0.2 mass percent to about 5 mass percent of soap (preferably about 0.4 to about 4 mass percent of overbasic soap, more preferably about 0.4 to about 3 mass percent of overbasic magnesium-containing soap). The auxiliary or booster additive package of this specification is configured, when added to unused and / or used passenger car motor oil compositions forming the final lubricant, to maintain API and / or ILSAC certifications such as SP and / or GF-6 certification. In other words, when the booster additive package described herein is added to a passenger car motor oil lubrication composition, the combination of the passenger car motor oil lubrication composition and the booster additive package is still appropriable by the American Petroleum Institute (API) and / or the International Lubricants Standardization and Approval Committee (ILSAC).

[0019] oil-soluble nitrogen-containing compounds The booster additive package is generally in the form of a concentrate, which contains one or more oil-soluble nitrogen-containing compounds configured to provide a selected amount of nitrogen to the concentrate, among other components, and to selectively increase the nitrogen content of the passenger car motor oil in the final lubricant specified herein. As described above, the selected oil-soluble nitrogen-containing compound is in an amount that provides the booster additive package with about 1000 ppm to about 8500 ppm of nitrogen, preferably about 1000 ppm to about 6000 ppm, more preferably about 1100 ppm to about 5800 ppm of nitrogen. In other embodiments, the oil-soluble nitrogen-containing compound in the booster is in an amount that provides about 100 ppm to about 4500 ppm of nitrogen per ounce of booster (in other approaches, about 100 ppm to about 3000 ppm of nitrogen per ounce of booster, or about 110 ppm to about 2900 ppm of nitrogen per ounce of booster).

[0020] The amount of oil-soluble nitrogen-containing compound in the booster is configured to increase the total nitrogen content of the final lubricant (e.g., PCMO and booster) by at least about 5 percent compared to the untreated passenger car motor oil lubrication composition (preferably increasing the total nitrogen content by about 5 to about 15 percent). In embodiments, the oil-soluble nitrogen-containing compound may be an antioxidant, a dispersant, or a combination thereof. Preferably, the oil-soluble nitrogen-containing compound is one or more amine-based antioxidants, and more preferably, the nitrogen content of the booster is provided solely by one or more amine-based antioxidants.

[0021] Antioxidant Nitrogen: In one embodiment, the nitrogen content of the booster additive package is provided by one or more antioxidants, more preferably one or more amine antioxidants. For example, the booster additive package or concentrate herein may contain about 2 to about 20 weight percent (in other approaches, about 2 to about 18 weight percent, or about 3 to about 15 weight percent) of one or more amine antioxidants to provide the above nitrogen content of the booster. In one approach, the booster additive package herein can increase the amount of amine antioxidant in the final lubricant (e.g., PMCO + booster) by about 10 to about 30 percent compared to the amine antioxidant content of untreated passenger car motor oil.

[0022] In some approaches or embodiments, suitable amine antioxidants may include, but are not limited to, antioxidants selected from aromatic amines, alkylated diphenylamines, alkyl (e.g., nonyl) diphenylamines, di-alkyl (e.g., di-nonyl) diphenylamines, octyldiphenylamine, di-octyldiphenylamine, phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, hindered non-aromatic amines, or combinations thereof. Preferably, the oil-soluble nitrogen-containing component is di-alkyl diphenylamine, more preferably di-nonyl diphenylamine. In one approach, the only nitrogen source in the booster additive package herein is the amine antioxidant, and in such an approach, it may contain about 1000 to about 6000 ppm of antioxidant nitrogen per ounce of booster, or in other approaches, about 100 to about 3000 ppm of antioxidant nitrogen.

[0023] Once top-treated, the total amount of antioxidant in the final lubricant composition of the present specification (e.g., PCMO + booster) can be an amount that provides up to about 400 ppm antioxidant nitrogen, or up to about 350 ppm antioxidant nitrogen, or up to about 325 ppm antioxidant nitrogen, or up to about 315 ppm antioxidant nitrogen. In other approaches, the total amount of antioxidant nitrogen in the lubricant composition can provide from about 200 to about 400 ppm antioxidant nitrogen, from about 250 to about 350 ppm antioxidant nitrogen, from about 300 to about 325 ppm antioxidant nitrogen. Such total nitrogen can be provided by from about 100 to about 300 ppm amine nitrogen in passenger car motor oil and from about 50 to about 80 ppm amine nitrogen from the booster concentrate. In other approaches, the final lubricant composition of the present specification can contain up to about 1 weight percent amine antioxidant, or from about 0.1 to about 1.0 weight percent amine antioxidant, in other approaches, from about 0.5 to about 1.0 weight percent, or from about 0.5 to about 0.95 weight percent, of amine antioxidant provided from both passenger car motor oil and booster (about 70 to about 80 weight percent amine antioxidant from PMCO and about 20 to about 30 weight percent from the booster).

[0024] In some approaches or embodiments, the amine antioxidant can be one or more aromatic amine antioxidants and can include, but is not limited to, diarylamines having the following formula

[0025]

Chemical formula

[0026] Examples of diarylamines that may be used include, but are not limited to, diphenylamine; various alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, monobutyldiphenylamine, dibutyldiphenylamine, monooctyldiphenylamine, dioctyldiphenylamine, monononyldiphenylamine, dinonyldiphenylamine, monotetradecyldiphenylamine, ditetradecyldiphenylamine, phenyl-alpha-naphthylamine, monooctylphenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, monoheptyldiphenylamine, diheptyldiphenylamine, p-oriented styrene-diphenylamine, mixed butyloctyldiphenylamine, and mixed octylstyryldiphenylamine.

[0027] In other approaches, suitable antioxidants may include aromatic amine antioxidants. Examples of phenolic antioxidants include N,N'-di-sec-butylphenylene-diamine, 4-isopropylaminodiphenylamine, phenyl-alpha-naphthylamine, phenyl-alpha-naphthylamine, and cyclic alkylated diphenylamines.

[0028] As described above, the booster additive package may contain about 2 to about 20 weight percent of amine-based antioxidants, providing about 1000 to about 6000 ppm of antioxidant nitrogen per booster, or in other approaches, about 100 ppm to about 3000 ppm of antioxidant nitrogen per ounce of booster. In other approaches, the final lubricant (including both passenger car motor oil and the booster additive package) may contain about 0.5 to about 5 weight percent of total antioxidants, and the booster additive package provides an increase in amine-based antioxidants as described above. Preferably, about 90 to about 100% by weight of nitrogen in the booster is provided by amine-based antioxidants.

[0029] Nitrogen from Dispersants: The booster additive packages described herein may also optionally include dispersant additives that provide additional oil-soluble nitrogen-containing compounds. If included in the booster, the dispersant may be obtained by reacting a hydrocarbyl-substituted acylating agent with a nitrogen source and may be an ashless dispersant such as one or more hydrocarbyl-substituted succinimide dispersants. If included, the booster may further contain an additional 400–2500 ppm of dispersant nitrogen in the booster, or by other approaches, about 40–1300 ppm of dispersant nitrogen per ounce of booster. Preferably, one or more dispersant additives in the booster may include a polyisobutylene succinimide dispersant derived from a highly reactive polyisobutylene having a number average molecular weight of at least about 2,000, preferably a polyisobutylene succinimide dispersant derived from a highly reactive polyisobutylene having a number average molecular weight of about 2,000 to about 5,000, about 2,000 to about 3,000, or about 2,000 to about 2,600.

[0030] Dispersants are often known as ashless dispersants because they do not contain ash-forming metals before being mixed into a lubricant composition and do not typically contribute to any ash when added to the lubricant. Ashless dispersants are characterized by polar groups being bonded to hydrocarbon chains with relatively high molecular weights. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. An example of a nitrogen-substituted long-chain alkenyl succinimide is polyisobutylene succinimide, in which the number-average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000, or preferably up to about 5,000, or up to about 3,000, as measured by GPC. Succinimide dispersants and their preparations are disclosed, for example, in U.S. Patent No. 7,897,696 and U.S. Patent No. 4,234,435, which are incorporated herein by reference. Alkenyl substituents can be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines (typically poly(ethyleneamines)).

[0031] In the approach, preferred amines for the dispersant may be selected from polyamines and hydroxylamines. Examples of polyamines that may be used include, but are not limited to, higher homologues such as diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and pentaethylamine hexamine (PEHA). In some approaches, so-called heavy polyamines may be used, which are polyalkylene-polyamine mixtures containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers with broader branching than conventional polyamine mixtures. Heavy polyamines preferably contain polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule.

[0032] In some embodiments, polyisobutylene (PIB), if included, is a preferred reactant for forming a dispersant and may have a terminal double bond content of more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, or more than 90 mol%. Such PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number-average molecular weight in the range of about 800 to about 5000 as determined by GPC are preferred for use in embodiments of this disclosure. Conventional PIBs typically have a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0033] HR-PIBs having a number-average molecular weight in the range of about 900 to about 3,000, preferably about 2,000 to about 3,000, as determined by GPC, may be preferred. Such HR-PIBs are commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinating catalyst such as boron trifluoride, as described in U.S. Patent No. 4,152,499 and / or U.S. Patent No. 5,739,355. When used in the aforementioned thermal ene reaction, HR-PIBs may result in a higher conversion rate in the reaction and less precipitate formation due to their increased reactivity. A preferred method is described in U.S. Patent No. 7,897,696. In one embodiment, the disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride, "PIBSA". PIBSA may have an average succinic acid moiety of about 1.0 to about 2.0 per polymer.

[0034] In some approaches, the dispersants in the booster additive packages herein may not involve any post-treatment, such as post-treatment with boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. In other approaches, the dispersants in the booster additive packages, if included, may be post-treated by conventional methods involving reaction with any of a variety of agents, and / or the dispersants in the passenger car motor oil lubrication composition may be post-treated. Furthermore, at least one of the dispersants in the passenger car motor oil may be post-treated. Suitable post-treatment agents include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. (See, for example, U.S. Patents 7,645,726, 7,214,649, 8,048,831, and 5,241,003, which are incorporated herein by reference in their entirety.)

[0035] When boron is used for post-treatment, the boron compound used as the post-treatment reagent can be selected from boron oxide, boron halides, boric acid, and esters of boric acid, in amounts that provide boron at an atomic proportion of about 0.1 per mole of nitrogen composition to about 20 per atomic proportion of nitrogen used. The boron-treated dispersant may contain boron at a concentration of about 0.05% to about 2.0% by weight, or, in other approaches, about 0.05% to about 0.7% by weight, based on the total weight of the boro-oxidation dispersant.

[0036] In other approaches, and where used, carboxylic acids may also be used as work-up reagents and may be saturated or unsaturated mono-, di-, or polycarboxylic acids. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, and naphthalidic acid (e.g., 1,8-naphthalidic acid). Anhydrides may also be used as work-up reagents and can be selected from the group consisting of mono-unsaturated anhydrides (e.g., maleic anhydride), alkyl or alkylene-substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride), and aromatic carboxylic anhydrides (including naphthalic anhydride, e.g., 1,8-naphthalic anhydride).

[0037] In one embodiment, and when used, the process for post-treating the dispersant comprises first forming a succinimide product as described above, and then further reacting the succinimide product with a post-treatment agent such as a boron compound such as boric acid. In some cases, the dispersants herein may be post-treated with more than one post-treatment agent. For example, the dispersant may be post-treated with a boron compound such as boric acid, and may also be post-treated with anhydrides such as maleic anhydride and / or 1,8-naphthalic anhydride.

[0038] Where included, the booster additive package herein may contain about 2 to about 20 weight percent of a dispersant (preferably untreated) to provide the booster with the above-mentioned levels of optional additional nitrogen. The final lubricant of this application (again PCMO and booster) may contain a total of about 1 to about 5 weight percent of dispersants provided from the dispersant in the booster additive package and the dispersant in the passenger car motor oil, which may be a blend of untreated dispersant (provided from the booster and passenger car motor oil) and a treated dispersant provided from the passenger car motor oil. In some embodiments, the final lubricant herein may contain about 75 to about 85 weight percent of dispersant from PMCO and about 15 to about 25 weight percent of dispersant from the booster.

[0039] In other embodiments, the total amount of dispersant in the final lubricant may be sufficient to provide up to about 15 weight percent (preferably about 2 to about 10 weight percent) of the final lubrication composition from both the passenger car motor oil and the booster, and one or more of the dispersants (preferably from the passenger car motor oil rather than the booster) may be post-treated to provide at least about 40 ppm and up to 500 ppm of boron (preferably about 100 to about 200 ppm of boron) to the lubrication composition. In other approaches, the dispersant may be used in the final lubrication composition in amounts of about 0.1 weight percent to about 15 weight percent, or about 0.1 weight percent to about 10 weight percent, about 0.1 weight percent to about 8 weight percent, or about 1 weight percent to about 10 weight percent, or about 1 weight percent to about 8 weight percent, or about 1 weight percent to about 6 weight percent, based on the final weight of the lubricating oil composition.

[0040] Cleaning agent additive The booster additive package also contains one or more detergent additives in an amount that provides the booster additive package with about 0.2 to about 5 weight percent of soap (in other approaches, about 0.3 to about 4 weight percent or about 0.4 to about 3 weight percent of soap). In one approach, at least about 90 weight percent of the detergent soap, preferably at least about 95 weight percent of the detergent soap, more preferably at least about 98 weight percent, and most preferably 100 weight percent, is provided by one or more overbasic detergent additives having a total base number (TBN) of about 250 mg KOH / g or more (preferably about 250 to about 500 mg KOH / g) with TBN determined according to ASTM D2896.

[0041] In one approach or embodiment, one or more detergent additives in the booster additive package include a magnesium-containing detergent additive, more preferably a sulfonate-based calcium-providing detergent. In another approach, the booster additive package includes only a magnesium-containing detergent additive, preferably only a magnesium sulfonate-based detergent having the high TBN content described above. These selected detergent additives have a total base number (TBN) of booster measured according to ASTM D2896 of at least about 5 mg KOH / g, at least about 10 mg KOH / g, at least about 520 mg KOH / g, or at least about 30 mg KOH / g, and in another approach or embodiment, the detergents herein provide a TBN of about 40 mg KOH / g or less in the booster additive package. In yet another approach, the detergent additive provides a TBN per ounce of booster of about 0.5 to about 16 mg KOH / g per ounce of booster additive package. The booster additive package may optionally contain other detergent additives (e.g., calcium-containing detergent additives), but about 65 to about 100% (preferably 80 to about 100%, more preferably about 90 to about 100%) of the above-mentioned detergent TBN is provided by one or more overbasic magnesium-containing detergent additives.

[0042] In other embodiments, the booster additive package according to this specification contains up to about 10,000 ppm of magnesium from a magnesium-containing detergent, up to about 8,000 ppm of magnesium from a magnesium-containing detergent, or up to about 7,800 ppm of magnesium from a magnesium-containing detergent, and / or the booster additive package contains at least about 1,000 ppm of magnesium from a magnesium-containing detergent, at least about 1,200 ppm of magnesium from the magnesium-containing detergent, or at least about 1,400 ppm of magnesium, or any range in between. In another approach, the booster additive package contains about 100 ppm of magnesium per ounce of the booster additive package to about 5,000 ppm of magnesium per ounce of the booster additive package.

[0043] The booster additive package and its selected detergent additive are configured to increase the magnesium content of a passenger car motor oil lubrication composition, and preferably to increase the overbasic soap content. That is, the booster additive package is configured to be added to a passenger car motor oil composition to form a final lubricant (e.g., PMCO Plus Booster) having higher levels of magnesium and / or overbasic soap compared to the magnesium and soap content of an untreated passenger car motor oil lubrication composition. In an approach or embodiment, the booster additive package herein increases the magnesium content by at least about 20% (preferably an increase of about 20 to about 50%) compared to an untreated passenger car motor oil lubrication composition, and / or increases the overbasic or magnesium soap content by at least about 20% (preferably an increase of about 20 to about 50%) compared to a passenger car motor oil lubrication composition.

[0044] In other embodiments, the final lubrication composition herein (i.e., both the passenger car motor oil lubrication composition and the booster additive package as a top treatment thereof) has a total magnesium content of about 400 ppm to about 1000 ppm provided from the combination of the passenger car motor oil lubrication composition and the booster additive package, and / or a total soap content (e.g., overbasic or magnesium soap content) of about 0.1 to about 0.2 weight percent provided from the combination of the passenger car motor oil lubrication composition and the booster additive package. In embodiments, about 75 to about 85 weight percent of the final lubricant is a magnesium-containing detergent from PMCO, and about 15 to about 25 weight percent is a magnesium-containing detergent from the booster.

[0045] Suitable detergents and methods for preparing them are described in more detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited herein, which are incorporated herein by reference. The booster additive packages herein may contain about 1 to about 10 weight percent of individual and / or total detergent additives, or in other approaches, about 1.5 to about 8 weight percent, insofar as the detergent additives satisfy the magnesium, sulfonate, and / or soap content described herein. Similarly, as a top treatment, the final lubrication composition herein (again, a combination of passenger car motor oil and booster additive package) comprising about 0.5 to about 2 weight percent of the booster additive package herein may comprise about 0.1 to about 5 weight percent of individual and / or total detergent additives (including detergents provided by the booster and detergents provided by the lubricant), in other approaches about 0.15 to about 3 weight percent, and in yet other approaches about 0.15 to 2.6 weight percent of individual and / or total detergent additives (from both the booster and the lubricant), provided that the detergent additives meet the calcium, sulfonate, and / or soap content described herein.

[0046] As described above, in some approaches, the detergent system of the booster additive package provides selected amounts of magnesium soap, sulfonate soap, and / or overbasic soap, as well as selected TBN levels of these detergent metals. The booster additive package contains at least about 0.2 weight percent of soap, preferably about 0.2 to about 5 weight percent of soap, more preferably about 0.2 to about 5 weight percent of overbasic magnesium-based soap (or other amounts as described above). In other approaches, the ratio of the total detergent base number (TBN) of the booster additive package to the total detergent soap content in the booster additive package is at least about 10:1, at least about 12:1, or at least about 14:1, and in other approaches, about 10:1 to about 15:1. Preferably, the soap content of the booster additive package is mainly overbasic magnesium-based soap. Therefore, the above ratio of detergent TBN to detergent soap in the booster additive package is the ratio of detergent TBN to overbasic / magnesium-based detergent soap in the booster additive package.

[0047] In general, suitable detergents in boosters or lubricants according to this specification (that meet the requirements for the calcium content, TBN content, magnesium content, and / or soap content described herein) may include linear or branched alkali or alkaline earth metal salts, e.g., calcium, sodium, or magnesium, of petroleum sulfonic acid and long-chain mono- or di-alkylaryl sulfonic acid whose aryl group is benzyl, tolyl, and xylyl, and / or various phenates or derivatives of phenates. Examples of suitable detergents include, in addition to the required amount of sulfonate soap described above, the following low-basic / neutral and over-basic variations of detergents: calcium carbonate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkylphenol, calcium sulfur-bonded alkylphenol compounds, calcium methylene crosslinked phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixalate, magnesium Magnesium salicylate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkylphenol, magnesium sulfur-bonded alkylphenol compound, magnesium methylene crosslinked phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixalate, sodium salicalate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkylphenol, sodium sulfur-bonded alkylphenol compound, or sodium methylene crosslinked phenol.

[0048] As can be understood, overbasic detergent additives are well known in the art and may be alkali metal or alkaline earth metal overbasic detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a base and carbon dioxide gas. The base is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0049] The term "overbasic" refers to metal salts in which the amount of metal present exceeds the stoichiometric amount, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates. Such salts may have a conversion level greater than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert an acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR (metal ratio), is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. For standard or neutral salts, MR is 1, and for overbasic salts, MR is greater than 1. They are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0050] As used herein, the term "TBN" is used to express the total base number in units of mg KOH / g, measured by the method of ASTM D2896. Detergents may be neutral or overbasic. For example, the low-basic or neutral detergents herein may have a total base number (TBN) of up to about 250 mg KOH / g, as described above. Overbasic detergents provided herein for passenger car motor oil and / or final lubricants may have a total base number (TBN) of about 250 mg KOH / g or more, or about 300 mg KOH / g or more, or about 350 mg KOH / g or more, or about 375 mg KOH / g or more, or about 400 mg KOH / g or more, and generally less than about 500 mg KOH / g. The overbasic cleaning agent 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.

[0051] Examples of suitable overbasic detergents (subject to other limitations on detergents as described above) include, but are not limited to, overbasic calcium phenates, overbasic calcium sulfur-containing phenates, overbasic calcium sulfonates, overbasic calcium calixalates, overbasic calcium salixalates, overbasic calcium salicylates, overbasic calcium carboxylic acids, overbasic calcium phosphates, overbasic calcium mono- and / or di-thiophosphates, overbasic calcium alkylphenols, overbasic calcium sulfur-bonded alkylphenol compounds, overbasic calcium methylene crosslinked phenols, overbasic magnesium phenates, overbasic magnesium sulfur-containing phenates, overbasic magnesium sulfonates, overbasic magnesium calixalates, overbasic magnesium salixalates, overbasic magnesium salicylates, overbasic magnesium carboxylic acids, overbasic magnesium phosphates, overbasic magnesium mono- and / or di-thiophosphates, overbasic magnesium alkylphenols, overbasic magnesium sulfur-bonded alkylphenol compounds, or overbasic magnesium methylene crosslinked phenols.

[0052] As described above, the booster additive package is preferably configured to increase the magnesium content in the final lubricant by at least about 20% (preferably an increase of about 20 to about 50%) compared to the magnesium content provided by the passenger car motor, and / or increase the overbasic or magnesium soap content by at least about 20% (preferably an increase of about 20 to about 50%) compared to the passenger car motor oil lubricant composition.

[0053] The booster additive packages herein also have a high level of sulfonate soap content and / or a high level of overbasic soap content, in particular having at least about 75 percent such soap, and in other approaches having at least about 80 percent such soap, at least about 85 percent sulfonate soap, at least about 90 percent such soap, at least about 95 percent such soap, at least about 98 percent such soap, at least about 99 percent such soap, or about 100 percent such soap (or any range in between).

[0054] Soap content generally refers to the amount of neutral organic salts and reflects the cleaning ability, or detoxifying power, and dirt-lifting ability of a detergent. The soap content of a lubricant can be determined by ASTM D3712. Further considerations regarding the determination of soap content can be found in the relevant sections of FUELS AND LUBRICANT SHANDBOOK, TECHNOLOGY, PROPERTIES, PERFORMANCE, AND TESTING, George Totten, editor, ASTM International, 2003, incorporated herein by reference.

[0055] Base oil or base oil blend: The booster additive packages described herein may contain the above-mentioned additives in combination with a large portion of the process oil or base oil. The process oil or base oil used in the passenger car motor oil described herein may be an oil with lubricating viscosity and may be selected from any of the API Group I to V base oils as defined in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. Both the booster additive packages and the final lubrication composition containing the booster may have a KV100 of about 10 to about 15 cSt (ASTM D445). The five base oil groups are generally shown in Table 1 below.

[0056] [Table 1]

[0057] Groups I, II, and III are mineral oil process raw materials. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinic unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but can also be natural oils such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but due to the rigorous processing these fluids undergo, their physical properties become very similar to those of some true synthetics such as PAO. Therefore, oils derived from Group III base oils can be referred to as synthetic fluids in industry. Group II+ may include high viscosity index Group II.

[0058] The base oil blends used in the disclosed lubricating oil compositions may be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrotapping, hydrofinishing, unrefined oils, refined oils, and re-refined oils, as well as mixtures thereof.

[0059] Unrefined oils are derived from natural, mineral, or synthetic sources that undergo little to no further refining. Refined oils are similar to unrefined oils except that they have been treated with one or more refining steps that may result in an improvement in one or more properties. Examples of preferred refining techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, and osmosis. Oils refined to a quality suitable for consumption may or may not be useful. Edible oils are sometimes called white oils. In some embodiments, lubricating oil compositions do not contain edible oils or white oils.

[0060] Refined oil is also known as recycled oil or reprocessed oil. These oils are obtained in the same way as refined oil using the same or similar processes. Often, these oils are further treated by techniques that target the removal of spent additives and oil degradation products.

[0061] 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, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricants, such as liquid petroleum, and paraffinic, naphthenic, or mixed paraffinic-naphthenic type solvent-treated or acid-treated mineral lubricants. Such oils may be partially or completely hydrogenated if desired. Oils derived from coal or shale may also be useful.

[0062] Useful synthetic lubricants include hydrocarbon oils, for example, polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer); trimers or oligomers of poly(1-hexene), poly(1-octene), and 1-decene, for example, poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0063] Other synthetic lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl esters of decanephosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure and other gas-liquid oils.

[0064] In another embodiment, the main amount of base oil contained in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and any combination of two or more of the aforementioned, but the main amount of base oil is other than base oil resulting from the provision of additive components or viscosity index improvers in the composition.

[0065] The amount of oil with lubricating viscosity present may be the difference remaining after subtracting the total amount of performance additives, including viscosity index improvers and / or pour point depressants and / or other top-treatment additives, from 100% by weight. For example, the amount of oil with lubricating viscosity that may be present in the final fluid may be the main amount, e.g., more than about 50% by weight, more than about 60% by weight, more than about 70% by weight, more than about 80% by weight, more than about 85% by weight, or more than about 90% by weight.

[0066] In some approaches or embodiments, the base oil systems of this specification comprise one or more base oils from groups I to V and may have a KV100 of about 2 to about 20 cSt, in other approaches about 5 to about 15 cSt, about 8 to about 15 cSt, and in yet other approaches about 10 to about 15 cSt.

[0067] Where used herein, the terms “oil composition,” “lubricating composition,” “lubricating oil composition,” “lubricating oil,” “lubricant composition,” “lubricant,” and “lubricant” are considered synonymous and fully interchangeable, and refer to passenger car motor oil lubrication products comprising a primary amount of base oil components, plus small amounts of detergents and other optional components, preferably API GF-6. A booster additive package is a concentrate configured to be top-treated with passenger car motor oil to produce a final lubricant. Thus, the final lubricant or final lubrication composition comprises a combination of passenger car motor oil and a booster additive package.

[0068] Optional additives: The booster additive packages and / or passenger car motor oil lubrication compositions described herein may also include several optional additives, combined with the detergent and dispersant systems described above, as necessary to meet performance requirements. These optional additives are described in the following paragraphs.

[0069] Dispersants: Lubricating oil compositions may optionally contain one or more other dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain metals that form ash before being mixed into the lubricating oil composition and do not typically contribute to ash when added to the lubricant. Ashless dispersants are characterized by polar groups being bonded to hydrocarbon chains with relatively high molecular weights. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. An example of an N-substituted long-chain alkenyl succinimide is polyisobutylene succinimide, in which the number-average molecular weight of the polyisobutylene substituents is in the range of about 350 to about 50,000, or about 5,000, or about 3,000, when measured by GPC. Succinimide dispersants and their preparations are disclosed, for example, in U.S. Patent No. 7,897,696 or No. 4,234,435. Alkenyl substituents can be prepared from polymerizable monomers containing about 2 to about 16 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines (typically poly(ethyleneamine)).

[0070] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, higher homologues such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylamine hexamine (PEHA).

[0071] A suitable heavy polyamine is a polyalkylene-polyamine mixture containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers having a broader branching range than conventional polyamine mixtures. The heavy polyamine preferably contains polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. The heavy polyamine contains more than 28% by weight (e.g., more than 32% by weight) of total nitrogen and 120 to 160 grams of primary amine groups per equivalent weight.

[0072] In some approaches, preferred polyamines are commonly known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the main components of the polyamine, usually less than 80%.

[0073] Typically, PAMs contain 8.7–8.9 milliequivalents of primary amine per gram (115–112 gram equivalents per primary amine equivalent) and a total nitrogen content of approximately 33–34% by weight. Heavier cuts of PAM oligomers, which are substantially TEPA-free and contain very small amounts of PEHA, but mainly contain oligomers with more than six nitrogen atoms and broader branching, can produce dispersants with improved dispersibility.

[0074] In embodiments, the disclosure further includes at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or about 5,000, or about 3,000, as determined by GPC. Polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0075] In some embodiments, polyisobutylene, if present, may have a terminal double bond content of more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, or more than 90 mol%. Such PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number-average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for use in the embodiments of this disclosure. Conventional PIBs typically have a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0076] HR-PIB having a number-average molecular weight in the range of approximately 900 to 3000, as determined by GPC, may be preferred. Such HR-PIBs are commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinating catalyst such as boron trifluoride, as described in U.S. Patent No. 4,152,499 by Boerzel et al. and U.S. Patent No. 5,739,355 by Gateau et al. When HR-PIB is used in the above-mentioned thermal ene reaction, it may result in a higher conversion rate and less precipitate formation during the reaction due to increased reactivity. A preferred method is described in U.S. Patent No. 7,897,696.

[0077] In one embodiment, the disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride, "PIBSA". PIBSA may have an average succinic acid moiety of about 1.0 to about 2.0 per polymer.

[0078] The percentage of active ingredients in alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0079] The conversion percentage of polyolefins is calculated from the active ingredient percentage using the formulas in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0080] Unless otherwise stated, all percentages are weight percentages, and all molecular weights are number-average molecular weights determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (with a number-average molecular weight of 180 to approximately 18,000 as a calibration standard).

[0081] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted onto an ethylene-propylene copolymer.

[0082] A suitable class of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically from ethylene-propylene dispersants that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with functionalized OCPs is described and / or commercially available in U.S. Patents No. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383.

[0083] One class of suitable dispersants may also be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in detail by U.S. Patent No. 3,634,515.

[0084] A suitable class of dispersants may also be high molecular weight esters or semi-esteramides. Suitable dispersants may also be post-treated by conventional methods with any of a variety of agents. These include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patents 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entirety.

[0085] In addition to the post-treatment of carbonates and boric acid, each compound may be post-treated or further post-treated by 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 by: inorganic phosphoric acid or anhydride (e.g., U.S. Patents No. 3,403,102 and No. 4,648,980), organophosphorus compounds (e.g., U.S. Patent No. 3,502,677), phosphorus pentasulfide, boron compounds as already described above (e.g., U.S. Patents No. 3,178,663 and No. 4,652,387), carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patents No. 3,708,522 and No. 4,9 (Patent No. 48,386), epoxides, polyepoxyates, or thioepoxides (e.g., U.S. Patents No. 3,859,318 and 5,026,495), aldehydes or ketones (e.g., U.S. Patent No. 3,458,530), carbon disulfide (e.g., U.S. Patent No. 3,256,185), glycidol (e.g., U.S. Patent No. 4,617,137), urea, thiourea, or guanidine (e.g., U.S. Patents No. 3,312,619 and 3,865,813, and British Patent No. 1,065) ,595), organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and UK Patent No. 2,140,811), alkenyl cyanides (e.g., U.S. Patents No. 3,278,550 and No. 3,366,569), diketenes (e.g., U.S. Patent No. 3,546,243), diisocyanates (e.g., U.S. Patent No. 3,573,205), alkansultones (e.g., U.S. Patent No. 3,749,695), 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675) U.S. Patent No. 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. Patent No. 4,612,132, 4,647,(Patents No. 390, No. 4,648,886, No. 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and UK Patent No. 2,140,811), hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522), lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patents No. 4,614,603 and No. 4,666,460), cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and UK Patent No. 2,440,811), hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522), lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patents No. 4,614,603 and 4,666,460), cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Patent Nos. 4,663,062 and 4,666,459), hydroxyaliphatic carboxylic acids (e.g., U.S. Patents Nos. 4,482,464, 4,521,318 and 4,713,189), oxidizing agents (e.g., U.S. Patent No. 4,379,064), combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Patent No. 3,185,647), combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Patents Nos. 3,390,086 and 3,470,098), hydrazine and disulfide Combinations of carbon (e.g., U.S. Patent No. 3,519,564), combinations of aldehydes and phenols (e.g., U.S. Patents No. 3,649,229, 5,030,249, and 5,039,307), combinations of aldehydes and O-diesters of dithiophosphate (e.g., U.S. Patent No. 3,865,740), combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Patent No. 4,554,086), combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenol (e.g., U.S. Patent No. 4,636,(e.g., U.S. Patent No. 322), combinations of hydroxyaliphatic carboxylic acids and subsequent aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064), combinations of formaldehyde and phenol and subsequent glycolic acid (e.g., U.S. Patent No. 4,699,724), combinations of hydroxyaliphatic carboxylic acids or oxalic acid and subsequent diisocyanates (e.g., U.S. Patent No. 4,713,191), combinations of inorganic acids or anhydrides of phosphorus or their partial or whole sulfur analogs and boron compounds (e.g., U.S. Patent No. 4,857,21 (4) Combinations of organic diacids, followed by unsaturated fatty acids, followed by nitroso aromatic amines, optionally followed by boron compounds, and subsequently glycolating agents (e.g., U.S. Patent No. 4,973,412), combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278), combinations of aldehydes and triazoles, followed by boron compounds (e.g., U.S. Patent No. 4,981,492), and combinations of cyclic lactones and boron compounds (e.g., U.S. Patents No. 4,963,275 and 4,971,711). In this specification, the patents mentioned above are incorporated herein in their entirety.

[0086] A suitable dispersant may have a TBN of approximately 5 to 30 TBN when measured in a dispersant sample containing approximately 50% diluted oil, and may be a dispersant of approximately 10 to 65 mg KOH / g on an oil-free basis. TBN is measured by the method of ASTM D2896.

[0087] In further embodiments, the optional dispersion additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, 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 when measured by GPC using polystyrene as the calibration standard.

[0088] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0089] [ka] In the formula, each R and R' is independently a divalent C1-C6 alkylene linker, each R1 and R2 independently forms a 5-membered or 6-membered ring by being fused with one or more aromatic or non-aromatic rings, either with hydrogen, a C1-C6 alkyl group, or the nitrogen atom to which they are bonded, and n is an integer from 0 to 8. Another approach is to select polyalkylene polyamines from the group consisting of mixtures of polyethylene polyamines having an average of 5-7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0090] If present, the dispersant 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. Other amounts of dispersant that may be used may be about 0.1% to about 15% by weight, or about 0.1% to about 10% by weight, about 0.1% to about 8% by weight, or about 1% to about 10% by weight, or about 1% to about 8% by weight, or 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.

[0091] Antioxidants: The lubricating oil compositions described herein may optionally contain one or more antioxidants. Known antioxidant compounds include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfur terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

[0092] Hindered phenol antioxidants may contain secondary butyl groups and / or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group and / or a crosslinking group bonded to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, but may include, for example, Irganox® L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain about 1 to about 18 carbon atoms, or about 2 to about 12 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester, but may include Ethanox® 4716 available from Albemarle Corporation.

[0093] Useful antioxidants may include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, so that each antioxidant may be present in an amount sufficient to provide up to about 5% by weight, based on the final weight of the lubricating oil composition. In embodiments, the antioxidant may be a mixture of about 0.3 to about 1.5% by weight of diarylamine and about 0.4 to about 2.5% by weight of high molecular weight phenol, based on the final weight of the lubricating oil composition.

[0094] 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 may be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0095] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable or animal oils and typically contain about 4 to about 22 carbon atoms. Suitable examples of fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as α-olefins.

[0096] In another alternative embodiment, the antioxidant composition also contains a molybdenum-containing antioxidant in addition to the phenolic and / or amine antioxidants discussed above. When a combination of these three antioxidants is used, the treatment rate ratio of the phenol, amine, and molybdenum-containing components is preferably (0-3):(0-3):(0-3).

[0097] One or more antioxidants may be present in the lubricating oil composition in an amount ranging from about 0% to about 20% by weight, or from about 0.1% to about 10% by weight, or from about 1% to about 5% by weight.

[0098] Anti-wear agents: The lubricating oil compositions described herein may optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphate esters or salts thereof; phosphate 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) disulfide; and mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are fully described in European Patent No. 612839. The metal in the dialkyldithiophosphate salt may be alkali metals, alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful anti-wear agent may be zinc dialkyldithiophosphate.

[0099] Further examples of suitable abrasion resistant agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphates (e.g., dibutylphosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. Tartarates or tartrimides may contain alkyl ester groups, and the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the abrasion resistant agent may include citrates.

[0100] The anti-wear agent may be present in the range of about 0% to about 15% by weight, or about 0.01% to about 10% by weight, or about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0101] Boron-containing compounds: The lubricating oil compositions described herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borate fatty amines, borate epoxides, borate detergents, and borate dispersants such as succinimide borate dispersants, as disclosed in U.S. Patent No. 5,883,057. If present, the boron-containing compound may be used in an amount sufficient to provide up to about 8% by weight, about 0.01% to about 7% by weight, about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0102] Detergents: The lubricating oil composition may optionally further contain one or more neutral detergents, low-basic detergents, or over-basic detergents, and mixtures thereof. Suitable detergent bases include phenates, sulfur-containing phenates, sulfonates, calixalates, salixalates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphates, alkylphenols, sulfur-linked alkylphenol compounds, or methylene-crosslinked phenols. Suitable detergents and methods for preparing them are described in detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited therein.

[0103] The detergent base may, but is not limited to, alkali metals or alkaline earth metals such as 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 include alkali metal salts or alkaline earth metal salts of petroleum sulfonic acid and long-chain mono- or di-alkylaryl sulfonic acid whose aryl group is benzyl, tolyl, or xylyl. Examples of suitable cleaning agents include, but are not limited to, calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylate, calcium phosphate, mono- and / or di-thiophosphate calcium, calcium alkylphenol, calcium sulfur-linked alkylphenol compounds, calcium methylene crosslinked phenol, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixalate, magnesium salixalate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, mono- and / or di-thiophosphate magnesium, magnesium alkylphenol, magnesium sulfur-linked alkylphenol compounds, magnesium methylene crosslinked phenol, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixalate, sodium salixalate, sodium salicylate, sodium carboxylate, sodium phosphate, mono- and / or di-thiophosphate sodium, sodium alkylphenol, sodium sulfur-linked alkylphenol compounds, or sodium methylene crosslinked phenol.

[0104] Overbasic detergent additives are well known in the art and may be alkaline or alkaline earth metal overbasic detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a base and carbon dioxide gas. The base is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0105] The term "overbasic" refers to metal salts such as sulfonates, carboxylates, and phenates in which the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level greater than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert an acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR (metal ratio), is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbasic salts, the MR is greater than 1. They are commonly referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0106] The overbasic detergent in the lubricating oil composition may have a total base number (TBN) of approximately 200 mg KOH / g or more, or, as further examples, approximately 250 mg KOH / g or more, or approximately 350 mg KOH / g or more, or approximately 375 mg KOH / g or more, or approximately 400 mg KOH / g or more. The TBN is measured by the method of ASTM D2896.

[0107] Suitable examples of perbasic detergents include, but are not limited to, perbasic calcium phenate, perbasic calcium sulfur-containing phenate, perbasic calcium sulfonate, perbasic calcium calixalate, perbasic calcium salixalate, perbasic calcium salicylate, perbasic calcium carboxylic acid, perbasic calcium phosphate, perbasic calcium mono- and / or di-thiophosphate, perbasic calcium alkylphenol, perbasic calcium sulfur-bonded alkylphenol compound, perbasic calcium methylene crosslinked phenol, perbasic magnesium phenate, perbasic magnesium sulfur-containing phenate, perbasic magnesium sulfonate, perbasic magnesium calixalate, perbasic magnesium salixalate, perbasic magnesium salicylate, perbasic magnesium carboxylic acid, perbasic magnesium phosphate, perbasic magnesium mono- and / or di-thiophosphate, perbasic magnesium alkylphenol, perbasic magnesium sulfur-bonded alkylphenol compound, or perbasic magnesium methylene crosslinked phenol.

[0108] Overbasic phenate calcium detergents, when measured by the method of ASTM D2896, have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g. When such detergent compositions are formed in an inert diluent, such as process oil, usually mineral oil, the total base number reflects the basicity of the overall composition, including the diluent and any other materials that may be included in the detergent composition (e.g., accelerators).

[0109] The overbasic detergent may have a metal-to-base ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in the engine or other automotive parts such as the transmission or gears. The detergent may be present in the lubricating composition in amounts of about 0% to about 10% by weight, or about 0.1% to about 8% by weight, or about 1% to about 4% by weight, or more than about 4% to about 8% by weight.

[0110] Extreme pressure agents: The lubricating oil compositions described herein may also optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyltetrasulfide, methyl sulfide esters of oleic acid, alkylphenol sulfides, dipentene sulfides, terpenes sulfides, and Diels-Alder sulfide adducts; phosphorus sulfide hydrocarbons such as reaction products of phosphorus sulfide with terpentine or methyl oleate; phosphate esters such as dihydrocarbyl and trihydrocarbyl phosphite, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, and pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium heptylphenol dioate; amine salts of alkyl and dialkyl phosphates, e.g., amine salts of reaction products of dialkyldithiophosphate and propylene oxide; and mixtures thereof.

[0111] Friction modifiers: The lubricating oil compositions described herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, 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.

[0112] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. Hydrocarbyl groups may consist of carbon and a heteroatom such as hydrogen or sulfur or oxygen. Hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a mono-ester, di-ester, or (tri)glyceride. Friction modifiers may be long-chain fatty amides, long-chain fatty esters, long-chain fatty epoxide derivatives, or long-chain imidazolines.

[0113] Other suitable friction modifiers may include organic, ashless (metal-free), and nitrogen-free organic friction modifiers. Such friction modifiers may contain esters formed by reacting a carboxylic acid and an anhydride with an alkanol, and may generally contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0114] Amineral friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or mixtures thereof, and may contain about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated etheramines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or mixtures thereof. These may contain about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated etheramines.

[0115] Amines and amides may be used on their own or as adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in whole.

[0116] The friction modifier may be optionally present in a range such as approximately 0% to 10% by weight, approximately 0.01% to 8% by weight, or approximately 0.1% to 4% by weight.

[0117] Molybdenum-containing components: The lubricating oil compositions described herein may also optionally contain one or more molybdenum-containing compounds. Oil-soluble molybdenum compounds may have the functional properties of anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Examples of oil-soluble molybdenum compounds include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Examples of molybdenum sulfide include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be a molybdenum dithiocarbamate.

[0118] Suitable examples of molybdenum compounds that can be used include Molyvan® 822, Molyvan® A, Molyvan® 2000, and Molyvan® 855 from RTVanderbilt Co., Ltd., as well as commercially available materials and mixtures thereof sold under trademark names such as Adeka Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 from Adeka Corporation. Suitable molybdenum components are described in U.S. Patent No. 5,650,381, U.S. Reissue Patent No. 37,363(E1), U.S. Reissue Patent No. 38,929(E1), and U.S. Reissue Patent No. 40,595(E1), which are incorporated herein by reference in their entirety.

[0119] Additionally, the molybdenum compounds may be acidic molybdenum compounds. These include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, compositions can provide molybdenum by molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Patents 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 International Publication No. 94 / 06897, the aforementioned patent documents are incorporated herein by reference in their entirety.

[0120] Another class of suitable organomolybdenum compounds is trinuclear molybdenum compounds, for example, those of the formula Mo3S k L n Q z The compounds and mixtures thereof are, in the formula, S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to make the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron-donating compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5, including non-stoichiometric values. In all ligand organic groups, there may be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms. Additional preferred molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0121] Oil-soluble molybdenum compounds may be present in amounts sufficient to provide molybdenum in concentrations of approximately 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, 1 ppm to 550 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm.

[0122] Transition metal-containing compounds: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a metalloid. Examples of transition metals include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, and tungsten. Examples of preferred metalloids include, but are not limited to, boron, silicon, antimony, and tellurium.

[0123] In embodiments, oil-soluble transition metal-containing compounds may function as anti-wear agents, friction modifiers, antioxidants, deposit control additives, or one or more of these functions. In embodiments, oil-soluble transition metal-containing compounds may be oil-soluble titanium compounds such as titanium(IV) alkoxides. Titanium-containing compounds that may be used in or for the preparation of oil-soluble materials in the art of this disclosure include, but are not limited to, various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, e.g., titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, e.g., titanium phenate; titanium carboxylates, e.g., titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV) (triethanolamine) isopropoxide. Other forms of titanium included in the disclosed technology include titanium phosphates such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or reaction products of titanium compounds that form salts, such as oil-soluble salts, with various acidic materials. Therefore, titanium compounds can be derived, in particular, from organic acids, alcohols, and glycols. Ti compounds may also exist in dimer or oligomeric forms containing a Ti-O-Ti structure. Such titanium materials are commercially available or readily prepared by appropriate synthetic techniques evident to those skilled in the art. Depending on the specific compound, they may exist as solids or liquids at room temperature. They may also be provided in solution form in a suitable inert solvent.

[0124] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such a material may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or reacted with any of several materials, such as (a) a polyamine-based succinimide / amide dispersant having a free, condensable -NH functional group; (b) a component of a polyamine-based succinimide / amide dispersant, i.e., alkenyl-(or alkyl) succinic anhydride and a polyamine; or (c) a hydroxy-containing polyester dispersant prepared by the reaction of substituted succinic anhydride with a polyol, amino alcohol, polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product may be used directly to impart Ti to the lubricant or further reacted with a succinic acid dispersant as described above. As an example, to provide a titanium-modified dispersant or intermediate, 1 part (mol) of tetraisopropyl titanate may be reacted with about 2 parts (mol) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours. The resulting material (30 g) may be further reacted at 150°C for 1.5 hours with a succinimide dispersant from a mixture of polyisobutene-substituted succinic anhydride and polyethylene polyamine (127 g + diluent oil) to produce a titanium-modified succinimide dispersant.

[0125] Another titanium-containing compound is titanium alkoxide and C6-C6 25 It may be a reaction product with a carboxylic acid. The reaction product is given by the following formula:

[0126] [ka] It can be represented by the following formula, where n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing about 5 to about 24 carbon atoms, or by the following formula:

[0127] [ka] It can be expressed as follows, where m+n=4, n is in the range of 1 to 3, R4 is an alkyl moiety having 1 to 8 carbon atoms, R1 is selected from a hydrocarbyl group containing about 6 to 25 carbon atoms, R2 and R3 are the same or different and selected from a hydrocarbyl group containing 1 to 6 carbon atoms, or the titanium compound is given by the following formula:

[0128] [ka] It can be expressed as follows, where x is in the range of 0 to 3, R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms, R2 and R3 are the same or different and selected from hydrocarbyl groups containing about 1 to 6 carbon atoms, and R4 is H, C6 to C 25 Selected from the group consisting of any of the carboxylic acid moieties.

[0129] Suitable carboxylic acids include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, and neodecanoic acid.

[0130] In embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in amounts to provide about 0 to about 3000 ppm by weight of titanium, or 25 to about 1500 ppm by weight of titanium, or about 35 ppm to about 500 ppm by weight of titanium, or about 50 ppm to about 300 ppm by weight of titanium.

[0131] Viscosity Index Modifiers: The lubricating oil compositions described herein may also optionally contain one or more viscosity index modifiers. Suitable viscosity index modifiers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene polymers, styrene / maleate copolymers, styrene-butadiene copolymers, styrene-isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index modifiers may include star polymers, but a preferred example is described in U.S. Patent Application Publication No. 20120101017(A1).

[0132] The lubricating oil compositions described herein may optionally contain, in addition to or instead of viscosity index modifiers, one or more dispersant viscosity index modifiers. Suitable viscosity index modifiers include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with reaction products of acyling agents (such as maleic anhydride) and amines, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0133] The total amount of viscosity index improvers and / or dispersible viscosity index improvers may be about 0% to about 20% by weight, about 0.1% to about 15% by weight, about 0.1% to about 12% by weight, or about 0.5% to about 10% by weight of the lubricating oil composition.

[0134] Other optional additives: Other additives may be selected to perform one or more functions required of the lubricating fluid. Furthermore, one or more of the additives mentioned may be polyfunctional and may provide functions in addition to those specified herein, or other functions.

[0135] The lubricating oil compositions according to this disclosure may optionally include other performance additives. These other performance additives may be additions to the specified additives of this disclosure and / or may include one or more of the following: metal deactivators, viscosity index modifiers, detergents, ashless TBN boosters, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index modifiers, extreme pressure agents, antioxidants, foam inhibitors, deemulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a complete lubricating oil will contain one or more of these performance additives.

[0136] Suitable metal deactivators include derivatives of benzotriazole (typically toltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam inhibitors comprising copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers comprising trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants comprising esters of maleate-styrene anhydride, polymethacrylate, polyacrylate, or polyacrylamide.

[0137] Suitable foam inhibitors include silicon-based compounds such as siloxanes.

[0138] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0% to about 1% by weight, about 0.01% to about 0.5% by weight, or about 0.02% to about 0.04% by weight, based on the final weight of the lubricating oil composition.

[0139] Suitable rust inhibitors may be a single compound or a mixture of compounds having properties that inhibit corrosion of iron metal surfaces. Non-limiting examples of useful rust inhibitors as used 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 dimeric and trimeric acids such as those derived from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinates containing about 10 or more carbon atoms in the alkenyl group, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is a semi-ester of alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol such as polyglycol. The corresponding semiamides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0140] If present, the rust inhibitor can be used in an amount sufficient to provide about 0% to about 5% by weight, about 0.01% to about 3% by weight, and about 0.1% to about 2% by weight, based on the final weight of the lubricating oil composition.

[0141] Generally speaking, preferred lubricants containing cleaning metals as used herein may contain additive components within the range listed in the table below.

[0142] [Table 2]

[0143] [Table 3]

[0144] The percentages of each component listed above represent the weight percentage of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein may be blended with the base oils individually or in various partial combinations. However, it may be preferable to blend all the components simultaneously using an additive concentrate (i.e., the additive plus a diluent such as a hydrocarbon solvent). A complete lubricant conventionally contains an additive package, referred herein as a dispersant / inhibitor package or DI package, which provides the properties required in the formulation.

[0145] definition For the purposes of this disclosure, chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. In addition, the 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, MB 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 generally illustrated above or as illustrated by specific classes, subclasses, and species of the Disclosure.

[0147] Unless otherwise made clear from the text, the term “major amount” is understood to mean an amount of 50 weight percent or more of the total weight of the composition, for example, about 80 to about 98 weight percent. Also, as used herein, the term “minor amount” is understood to mean an amount of less than 50 weight percent of the total weight of the composition.

[0148] As used herein, the terms "hydrocarbyl group" or "hydrocarbyl" are used in their ordinary sense as is well known to those skilled in the art. Specifically, it refers to a group having carbon atoms directly bonded to the rest of the molecule and having primarily hydrocarbon properties. Examples of hydrocarbyl groups include (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl) substituents, alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic substitutions, aliphatic substitutions, and alicyclic-substituted aromatic substituents, as well as cyclic substituents where the ring is completed via another part of the molecule (e.g., two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups that do not primarily alter the hydrocarbon substituent in the context of this disclosure (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy); and (3) heterosubstituted substituents, i.e., substituents that primarily possess hydrocarbon properties in the context of this disclosure, while containing non-carbon elements in the ring or chain, or otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, there are two or fewer non-hydrocarbon substituents for every 10 carbon atoms in the hydrocarbyl group, or in further examples, just one, and in some embodiments, there may be no non-hydrocarbon substituents in the hydrocarbyl group.

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

[0150] As used herein, the “alkyl” group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 carbon atoms (e.g., 1 to 8, 1 to 6, or 1 to 4). Alkyl groups may be linear or branched. Examples of alkyl groups, but not limited to, include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. Alkyl groups are defined as groups with one or more substituents, e.g., halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaloyl, acyl [e.g., (aliphatic) carbonyl, (alicyclic) carbonyl, or (heteroalicyclic) carbonyl], nitro, cyano, amide [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino It may be substituted (i.e., optionally substituted) with hydroxylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl, amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl, alicyclic oxy, heterocycloaliphatic oxy, aryl oxy, heteroaryl oxy, aralkyl oxy, heteroaryl alkoxy, alkoxycarbonyl, alkylcarbonyl oxy, or hydroxy.Some examples of substituted alkyls, though not limited to them, include carboxyalkyls (e.g., HOOC-alkyls, alkoxycarbonylalkyls, and alkylcarbonyloxyalkyls), cyanoalkyls, hydroxyalkyls, alkoxyalkyls, acylalkyls, aralkyls, (alkoxyaryl)alkyls, (sulfonylamino)alkyls (e.g., (alkyl-SO2-amino)alkyls), aminoalkyls, amidealkyls, (alicyclic)alkyls, or haloalkyls.

[0151] As used herein, the “alkenyl” group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like alkyl groups, alkenyl groups can be linear or branched. Examples of alkenyl groups, but not limited to, include allyl, isoprenyl, 2-butenyl, and 2-hexenyl. The alkenyl group may have one or more substituents, e.g., halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaloyl, acyl [e.g., (aliphatic) carbonyl, (alicyclic) carbonyl, or (heteroalicyclic) carbonyl], nitro, cyano, amide [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbon These can be optionally substituted with [nyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO2-, alicyclic-SO2-, or aryl-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl, alicyclic oxy, heteroalicyclic oxy, aryl oxy, heteroaryl oxy, aralkyl oxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyl oxy, or hydroxy. Some examples of substituted alkenyls, though not limited to them, include cyanoalkenyls, alkoxyalkenyls, acylalkenyls, hydroxyalkenyls, aralkenyls, (alkoxyaryl)alkenyls, (sulfonylamino)alkenyls (e.g., (alkyl-SO2-amino)alkenyls), aminoalkenyls, amidealkenyls, (alicyclic)alkenyls, or haloalkenyls.

[0152] As used herein, the term "alkynyl" 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 can be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. The alkynyl group can be optionally substituted with one or more substituents such as aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or alicyclic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or alicyclic sulfinyl], sulfonyl [e.g., aliphatic -SO2-, aliphatic amino -SO2-, or alicyclic -SO2-], amide [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, arylaminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamide, alkoxycarbonyl, alkylcarbonyloxy, alicyclic, heterocycloalicyclic, aryl, heteroaryl, acyl [e.g., (alicyclic)carbonyl or (heterocycloalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heterocycloalicyclic)oxy, or (heteroaryl)alkoxy.

[0153] As used herein, the term "amino" refers to -NR X R Y wherein R X and R YEach of these 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. If the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is -NR X It is represented by -. X This has the same meaning as defined above.

[0154] As used herein, the “cycloalkyl” group refers to a saturated carbocyclic, monocyclic, or bicyclic (fused or crosslinked) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, Cuville, 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, the "heterocycloalkyl" group refers to a 3- to 10-membered monocyclic or bicyclic (fused or bridged) saturated ring structure (e.g., a 5- to 10-membered monocyclic or bicyclic), where one or more ring atoms are heteroatoms (e.g., N, O, S, or a combination thereof). Examples of heterocycloalkyl groups include piperidyl, piperadyl, tetrahydropyranyl, tetrahydrofuryl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidyl, isoxazolidyl, morpholinyl, thiomorpholyl, octahydrobenzofuryl, octahydroclomenyl, octahydrothioclomenyl, 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, the “heteroaryl” group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or a combination thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fusion ring systems having 2 to 3 rings. For example, benzo-fusion groups include benzos fused with one or two 4 to 8-membered heterocyclic aliphatic moieties (e.g., indolidyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryls 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, prill, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalil, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthilidyl.

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

[0158] Examples of bicyclic heteroaryls include indolidyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolidinyl, isoindolyl, indolyl, benzo[b]furyl, bexo[b]thiophenyl, indazolyl, benzimimidazyl, benzthiazolyl, prinyl, 4H-quinolidyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, 1,8-naphthilidyl, or pteridyl. Bicyclic heteroaryls are numbered according to standard chemical nomenclature.

[0159] As used herein, the term “processing rate” refers to the weight percentage of the components in the final lubricant or passenger car motor oil and / or booster.

[0160] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) may be determined using a Waters gel permeation chromatography (GPC) instrument or similar instrument, along with 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 instrument). GPC operating conditions may include a guard column, four Agilent PLgel columns (300 × 7.5 mm in length, 5 μm in particle size, and pore sizes ranging from 100 to 10000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) may be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument may be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards having a narrow molecular weight distribution ranging from 960 to 1,568,000 g / mol. Calibration curves can be extrapolated for samples with a mass of less than 500 g / mol. The sample and PMMA standard can be dissolved in THF and prepared at a concentration of 0.1–0.5% by weight, and can be used without filtration. GPC measurement is also described in U.S. Patent No. 5,266,223, incorporated herein by reference. The GPC method provides additional molecular weight distribution information; see, for example, "Modern Size Exclusion Liquid Chromatography" by W.W. Yau, J.J. Kirkland and D.D.B. Ly, John Wiley and Sons, New York, 1979, incorporated herein by reference. [Examples]

[0161] A better understanding of this disclosure and its many advantages can be made apparent by the following examples. The following examples are illustrative and not limiting in any way to their scope or intent. 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 made apparent in the context of the discussion through the following examples, all percentages, ratios, and parts described in this disclosure are by weight.

[0162] Example 1 The baseline comparison (unenhanced) and the final lubrication composition of the present invention (e.g., passenger car motor oil + booster) were evaluated for rust prevention according to ASTM D6557. The evaluation was performed using a 2017 Ford F150 with a 3.5L Ecoboost V6 drive, with a total of 6,000 miles of Quad 4 drive cycles (SAE 2017-01-2298). Oil was sampled every 600 miles and evaluated using the ASTM D6557 ball rust test. The baseline comparison lubricant containing GF-6 lubricant was compared to the final lubricant of the present invention, which contained a baseline lubricant with a booster additive packing providing an additional 0.2 wt% amine antioxidant (di-nonyldiphenylamine) and an additional 0.1 wt% overbasic (400 TBN) magnesium sulfonate detergent.

[0163] The ball rust test results are shown in Figure 1, demonstrating that the enhanced lubricant of the present invention (round) provides higher initial rust prevention and a higher level of rust prevention over a 6,000-mile evaluation using used lubricant, compared to the untreated GF-6 baseline lubricant (diamond).

[0164] Where used herein and in the appended claims, the singular forms “a,” “an,” and “the” include multiple references unless explicitly and clearly limited to one. For example, a reference to “antioxidants” includes two or more different antioxidants. Where used herein, the term “includes” and its grammatical variations are intended to be non-limiting so as not to exclude other similar items that may be substituted for or added to the items in the list.

[0165] For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers representing quantities, percentages, or proportions, and other numerical values ​​used herein and in the claims should be understood in all cases as being modified by the term “approximately.” Therefore, unless otherwise indicated, the numerical parameters described herein and in the appended claims are approximations that may vary depending on the desired characteristics sought by this disclosure. Each numerical parameter should be interpreted at least in terms of the number of significant figures reported and by applying common rounding techniques, not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims.

[0166] It should be understood that each component, compound, substituent, or parameter disclosed herein is disclosed for use alone or in combination with any one or more other components, compounds, substituents, or parameters disclosed herein.

[0167] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosure range having the same number of significant figures. Therefore, for example, the range 1 to 4 should be interpreted as a clear disclosure of any range of such values, not just the values ​​1, 2, 3, and 4.

[0168] It should be further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Therefore, this 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 should also be further understood that any range between endpoint values ​​within a broad range is also considered herein. Therefore, the range 1-4 also means ranges such as 1-3, 1-2, 2-4, 2-3, etc.

[0169] Furthermore, any specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in the description or examples should be interpreted as disclosures of either a lower or upper limit of a range, and can therefore be combined with any other lower or upper limit or specific amounts / values ​​in the range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0170] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may emerge that are not currently anticipated or can not be anticipated by the applicants or others skilled in the art. Therefore, the attached claims, as filed and as may be amended, are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A booster additive package for a passenger car motor oil lubrication composition suitable for improving at least one of deposits, sludge, wear, TBN, and corrosion resistance, The booster additive package contains one or more oil-soluble nitrogen-containing compounds that provide approximately 1000 ppm to approximately 8500 ppm of nitrogen, preferably approximately 1000 ppm to approximately 6000 ppm, more preferably approximately 1100 ppm to approximately 5800 ppm of nitrogen. A booster additive package comprising one or more detergent additives that provide the booster additive package with soap in an amount of approximately 0.2% to approximately 5% by weight.

2. The booster additive package according to claim 1, wherein the booster additive package is configured to maintain API SP and / or GF-6 certification when added to unused and / or used passenger car motor oil compositions.

3. The booster additive package according to claim 1 or 2, wherein when the booster additive package is added to a passenger car motor oil lubrication composition, the combination of the passenger car motor oil lubrication composition and the booster additive package is appropriable by the American Petroleum Institute (API) and / or the International Lubricant Standardization and Approval Committee (ILSAC).

4. A booster additive package according to any one of claims 1 to 3, wherein at least about 90 percent by weight of the detergent soap, preferably at least about 95 percent by weight, more preferably at least about 98 percent by weight, and most preferably 100 percent by weight of the detergent soap is provided by one or more detergent additives having a total base number (TBN) of about 250 mg KOH / g or more.

5. The booster additive package according to any one of claims 1 to 4, wherein one or more of the cleaning agent additives have a total base number of approximately 280 mg KOH / g or more, approximately 300 mg KOH / g or more, approximately 320 mg KOH / g or more, or approximately 350 mg KOH / g or more.

6. The booster additive package according to any one of claims 1 to 5, wherein one or more of the cleaning agent additives include a magnesium-containing cleaning agent additive.

7. The booster additive package according to any one of claims 1 to 6, wherein the one or more cleaning agent additives comprise only a magnesium-containing cleaning agent additive.

8. The booster additive package according to any one of claims 1 to 7, wherein one or more cleaning additives impart a total base number (TBN) of about 5 mg KOH / g to about 40 mg KOH / g to the booster additive package as measured according to ASTM D2896, and / or the TBN / ounce of the booster additive package is about 0.5 to about 16 mg KOH / g per ounce of the booster additive package.

9. The booster additive package according to claim 8, wherein approximately 65 to 100 percent of the cleaning agent TBN is provided by one or more magnesium-containing cleaning agent additives.

10. The booster additive package according to any one of claims 1 to 9, wherein the booster additive package contains about 1,000 ppm to about 10,000 ppm of magnesium from a magnesium-containing detergent, preferably about 1,200 ppm to about 8,000 ppm, more preferably about 1,400 ppm to about 7,800 ppm of magnesium, and / or the booster additive package contains about 100 ppm of magnesium to about 5,000 ppm of magnesium per ounce of the booster additive package.

11. The booster additive package according to any one of claims 1 to 10, wherein the oil-soluble nitrogen-containing compound comprises an amine-based antioxidant.

12. The booster additive package according to any one of claims 1 to 11, wherein the oil-soluble nitrogen-containing compound is an amine-based antioxidant selected from the group including aromatic amines, alkylated diphenylamines, alkyl (e.g., nonyl)diphenylamines, dialkyl (e.g., dinonyl)diphenylamines, octyldiphenylamines, dioctyldiphenylamines, phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, or combinations thereof.

13. The booster additive package according to any one of claims 1 to 12, wherein the oil-soluble nitrogen-containing compound is a dialkyldiphenylamine antioxidant, preferably a dinonyldiphenylamine antioxidant.

14. The booster additive package according to any one of claims 1 to 13, wherein the booster additive package comprises about 2 to about 20 weight percent of the amine-based antioxidant.

15. The booster additive package according to any one of claims 1 to 14, wherein the booster additive package comprises one or more amine-based antioxidants providing about 1,000 ppm to about 6,000 ppm of antioxidant nitrogen, and / or the booster additive package has about 100 ppm to about 3,000 ppm of antioxidant nitrogen per ounce of the booster additive package.

16. A booster additive package according to any one of claims 1 to 15, wherein the ratio of the total base number (TBN) of the detergent to the total soap content of the detergent is about 10:1 to about 15:

1.

17. The booster additive package according to any one of claims 1 to 16, wherein about 90 to about 100 percent of the nitrogen is provided by an amine-based antioxidant.

18. The booster additive package according to claim 11, further comprising one or more ashless dispersants obtained by reacting a hydrocarbyl-substituted acylating agent with a nitrogen source.

19. The booster additive package according to claim 18, wherein the acylating agent is maleic anhydride, and the nitrogen source is selected from ammonia, polyalkylene polyamine, or a combination thereof.

20. The booster additive package according to claim 18, wherein the nitrogen source is a polyalkylene polyamine selected from a mixture of polyethylene polyamines having an average of five nitrogen atoms, triethylenetetraamine, tetraethylenepentamine, or a combination thereof.

21. The booster additive package according to any one of claims 18 to 20, wherein the ashless dispersant is post-treated with one or more of boron, carboxylic acids or their derivatives, and combinations thereof.

22. The booster additive package according to any one of claims 18 to 21, wherein the booster additive package comprises about 2 to about 20 weight percent of the ashless dispersant.

23. The booster additive package according to any one of claims 18 to 22, wherein the booster additive package comprises about 400 to about 2500 ppm of dispersant nitrogen provided by the one or more ashless dispersants, and / or the booster additive package comprises about 40 ppm to about 1300 ppm of dispersant nitrogen per ounce of the booster additive package.

24. The booster additive package according to claim 1, wherein the booster additive package further comprises a calcium-containing detergent additive.

25. The booster additive package according to claim 24, wherein the booster additive package further comprises about 900 ppm to about 5,000 ppm of calcium from the calcium-containing detergent additive, and / or the booster additive package comprises about 90 ppm to about 2,500 ppm of detergent calcium per ounce of the booster additive package.

26. A lubricating composition suitable for improving at least one of the following: deposits, sludge, wear, TBN retention, and corrosion prevention, (a) an unused or used passenger car motor oil lubricant composition comprising (i) one or more base oils of lubricating viscosity, (ii) a dispersant inhibitor additive package, and (iii) optionally a viscosity index improver. (b) A lubricating composition comprising the booster additive package according to any one of claims 1 to 25.

27. The lubrication composition according to claim 26, wherein the combination of (a) the passenger car motor oil lubrication composition and (b) the booster additive package is API SP and / or GF-6 compliant, and / or the passenger car motor oil lubrication composition is an unused passenger car motor oil composition or a used passenger car motor oil composition.

28. The lubricating composition according to any one of claims 26 or 27, wherein the combination of (a) the unused or used passenger car motor oil lubricating composition and (b) the booster additive package is approved by the American Petroleum Institute (API) and / or the International Lubricant Standardization Approval Committee (ILSAC).

29. The lubrication composition according to any one of claims 26 to 28, wherein the booster additive package is added in an amount effective to provide (a) an increase in the total nitrogen content of the passenger car motor oil lubrication composition by at least about 5% (preferably an increase of about 5 to about 15%), (b) an increase in the magnesium content of the passenger car motor oil lubrication composition by at least about 20% (preferably an increase of about 20 to about 50%), (c) an increase in the magnesium soap content of the passenger car motor oil lubrication composition by at least about 20% (preferably an increase of about 20 to about 50%), or (d) a combination thereof.

30. A lubrication composition according to any one of claims 26 to 29, comprising: (a) about 450 ppm to about 550 ppm of magnesium provided from the combination of the passenger car motor oil lubrication composition and the booster additive package; (b) about 700 to about 1200 ppm of total nitrogen provided from the combination of the passenger car motor oil lubrication composition and the booster additive package; (c) about 0.5 to about 1.0 weight percent of soap content from the combination of the passenger car motor oil lubrication composition and the booster additive package; or (d) at least one of the combinations thereof.

31. The lubrication composition according to any one of claims 26 to 30, wherein the lubrication composition exhibits higher rust prevention for up to approximately 6,000 miles of lubrication, as measured according to ASTM D6557, compared to a baseline lubrication composition that includes the passenger car motor oil composition but does not include the booster additive package, and / or the passenger car motor oil composition is either an unused passenger car motor oil composition or a used passenger car motor oil composition.

32. The lubricating composition according to any one of claims 26 to 31, wherein the used passenger car motor oil composition lubricates a combustion engine for at least 1,000 miles, 2,000 miles, 3,000 miles, 4,000 miles, 5,000 miles, 6,000 miles, 8,000 miles, or 10,000 miles.

33. The lubricating composition according to any one of claims 26 to 32, wherein the lubricating composition comprises about 1 to about 10 weight percent of the booster additive package, preferably about 1.1 to about 8 weight percent, more preferably about 1.2 to about 6.5 weight percent, and most preferably about 1.2 to about 6.3 weight percent of the booster additive package.

34. The lubricating composition according to claims 26 to 33, wherein the dispersant inhibitor package comprises one or more of the following: a dispersant, a cleaning agent, an anti-wear additive, an antioxidant, a friction modifier, a pour point dispersant, a seal swelling agent, or a combination thereof.

35. A method for providing corrosion resistance to valve train components of a passenger car engine, The present invention includes lubricating the valve train components of the passenger car engine with the lubricating composition described in any one of claims 26 to 34, A method wherein the valve train components maintain a higher level of corrosion protection for up to 6,000 miles of lubrication compared to a lubrication composition that includes the passenger car motor oil composition but does not include the booster additive package.

36. The method according to claim 35, wherein the rust prevention is determined using ASTM D6557.

37. The method according to claim 36, wherein the lubricating composition is a used lubricating composition that has lubricated a combustion engine for at least 1,000 miles, 2,000 miles, 3,000 miles, 4,000 miles, 5,000 miles, 6,000 miles, 8,000 miles, or 10,000 miles.

38. A method for providing rust prevention to valve train components of a passenger car engine using a lubricating composition, To provide a passenger car motor oil lubrication composition comprising one or more detergent additives that provide up to about 0.5 weight percent of soap to the passenger car motor oil lubrication composition, and one or more oil-soluble nitrogen-containing compounds that provide up to about 600 ppm of dispersant nitrogen to the passenger car motor oil lubrication composition, This includes adding a booster additive package to the passenger car motor oil lubrication composition to form the lubrication composition, A method wherein the lubricating composition maintains a higher level of corrosion protection for the valve train components than a lubricating composition that includes the passenger car motor oil lubricating composition but does not include the booster additive package.

39. A method for providing rust prevention according to claim 38, wherein the lubricating composition is described in any one of claims 26 to 34.

40. A method for providing rust prevention according to any one of claims 38 to 39, wherein the booster additive package is as described in any one of claims 1 to 25.

41. A method for providing rust prevention according to any one of claims 38 to 40, wherein the combination of (a) the passenger car motor oil lubrication composition and (b) the booster additive package is API SP and / or GF-6 compatible.

42. A method for providing rust prevention according to any one of claims 38 to 41, wherein the combination of (a) the passenger car motor oil lubrication composition and (b) the booster additive package is approved by the American Petroleum Institute (API) and / or the International Lubricants Standardization Approval Committee (ILSAC).

43. A method for providing rust prevention according to any one of claims 38 to 42, wherein the booster additive package is added in an amount effective to provide (a) an increase in the total nitrogen content of the passenger car motor oil lubrication composition by at least about 5% (preferably an increase of about 5 to about 15%), (b) an increase in the magnesium content of the passenger car motor oil lubrication composition by at least about 20% (preferably an increase of about 20 to about 50%), (c) an increase in the magnesium soap content of the passenger car motor oil lubrication composition by at least about 20% (preferably an increase of about 20 to about 50%), or (d) a combination thereof.

44. A method for lubricating an engine crankcase using a lubricating composition, To provide a passenger car motor oil lubrication composition comprising one or more detergent additives that provide up to approximately 0.5 weight percent of soap, and one or more oil-soluble nitrogen-containing compounds that provide up to approximately 600 ppm of dispersant nitrogen, The booster additive package is added to the passenger car motor oil lubricant composition to form the lubricant composition, A method comprising lubricating the engine crankcase with the lubricating composition.

45. The method for lubricating an engine crankcase according to claim 44, wherein the lubricating composition is described in any one of claims 26 to 34.

46. A method for lubricating an engine crankcase according to any one of claims 44 to 45, wherein the booster additive package is according to any one of claims 1 to 25.

47. A method for lubricating an engine crankcase according to any one of claims 44 to 46, wherein the combination of (a) the passenger car motor oil lubrication composition and (b) the booster additive package is API SP and / or GF-6 compliant.

48. A method for lubricating an engine crankcase according to any one of claims 44 to 47, wherein the combination of (a) the passenger car motor oil lubrication composition and (b) the booster additive package is approved by the American Petroleum Institute (API) and / or the International Lubricant Standardization Approval Committee (ILSAC).

49. A method for lubricating an engine crankcase according to any one of claims 44 to 48, wherein the booster additive package is added in an amount effective to provide (a) an increase of at least about 5% in the total nitrogen content of the passenger car motor oil lubrication composition (preferably an increase of about 5 to about 15%), (b) an increase of at least about 20% in the magnesium content of the passenger car motor oil lubrication composition (preferably an increase of about 20 to about 50%), (c) an increase of at least about 20% in the magnesium soap content of the passenger car motor oil lubrication composition (preferably an increase of about 20 to about 50%), or (d) a combination thereof.

50. A method for lubricating an engine crankcase according to any one of claims 44 to 49, wherein the lubricating composition exhibits higher corrosion resistance for lubrication up to approximately 6,000 miles in accordance with ASTM D6557 compared to a baseline lubricating composition that includes the passenger car motor oil composition but does not include the booster additive package.

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