Lubricant composition for passenger car for fuel economy

Abstract

To provide a low-viscosity lubricant composition for large-sized vehicles and passenger cars comprising an organic friction modifier exhibiting good frictional properties and improved fuel economy.SOLUTION: The lubricant composition for a passenger car internal combustion engine comprises (a) a major amount of a base oil of lubricating viscosity, (b) a nitrogen-containing dispersant, (c) an alkaline earth metal-containing detergent, and (d) a compound comprising a reaction product of (i) a nitrogen-containing reactant comprising an alkylalkanolamide, an alkylalkoxylated alkanolamide, an alkylalkanolamine, an alkylalkoxylated alkanolamine or a mixture thereof, (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups.SELECTED DRAWING: None

Description

[Background technology]

[0001] The boundary friction regime is an important consideration in the design of low-viscosity engine oils. Boundary friction occurs when the fluid film separating two surfaces becomes thinner than the height of the surface asperities. The resulting surface-to-surface contact results in undesirably high friction and poor fuel economy in the engine. Boundary friction in engines can occur at high loads, low engine speeds, and low oil viscosities. Low-viscosity engine oils make it easier to operate the engine in boundary friction regimes because the oil is thinner and the film is less robust. Because additives, not the base oil, affect the friction coefficient under boundary conditions, additives that provide a lower friction coefficient under boundary conditions provide superior fuel economy in low-viscosity engine oils.

[0002] Despite advances in lubricant formulation technology, a need exists for low viscosity engine oil lubricants suitable for both hybrid and direct injection engines that effectively improve fuel economy while maintaining or improving friction reducing properties and deposit control. The present disclosure generally relates to low viscosity heavy-duty and passenger car lubricating oil compositions (i.e., 0W or 5W SAE viscosity grades and HTHS viscosities less than 2.9 cP) containing organic friction modifiers that exhibit surprisingly good friction properties and improved fuel economy compared to friction modifiers more commonly known in the art. Summary of the Invention

[0003] According to one embodiment of the present disclosure, there is provided an internal combustion engine lubricating oil composition comprising a compound comprising: (a) a major amount of a base oil of lubricating viscosity, (b) a nitrogen-containing dispersant, (c) an alkaline earth metal-containing detergent, (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof, (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups. Also provided is a method for improving the fuel economy of fresh or used oil in an internal combustion engine comprising lubricating said engine with said lubricating oil composition. DETAILED DESCRIPTION OF THE INVENTION

[0004] To facilitate understanding of the subject matter disclosed herein, certain terms, abbreviations or other shorthand notations used herein are defined below. Any term, abbreviation or shorthand notation not defined will be understood to have the ordinary meaning used by those skilled in the art upon the filing of this application.

[0005] Definition: As used herein, the following words and expressions, if and when used, have the meanings indicated below.

[0006] By "major amount" is meant greater than 50% by weight of the composition.

[0007] "Minor amount" means less than 50% by weight of the composition, considered as the active ingredient of one or more additives, with respect to the listed additive and with respect to the total mass of all additives present in the composition.

[0008] "Active ingredient" or "active substance" refers to an excipient that is not a diluent or solvent.

[0009] All percentages reported are weight percent on an active ingredient basis (i.e., without regard to carrier or diluent oil) unless otherwise specified.

[0010] The abbreviation "ppm" means parts per million by weight, based on the total weight of the lubricating oil composition.

[0011] High temperature high shear (HTHS) viscosity at 150°C was measured according to ASTM D4683.

[0012] Kinematic viscosity at 100°C (KV 100) was measured according to ASTM D445.

[0013] Metal - The term "metal" refers to an alkali metal, an alkaline earth metal, or a mixture thereof.

[0014] The terms oil-soluble or dispersible are used throughout this specification and claims. Oil-soluble or dispersible means that the amount required to provide the desired level of activity or performance can be incorporated by dissolving, dispersing, or suspending in an oil of lubricating viscosity. Typically, this means that at least about 0.001 wt. % of the material can be incorporated into a lubricating oil composition. For further discussion of the terms oil-soluble and dispersible, particularly "stable dispersibility," see U.S. Pat. No. 4,320,019, the relevant teachings of which are expressly incorporated herein by reference.

[0015] As used herein, the term "sulfated ash" refers to non-combustible residues resulting from detergents and metallic additives in lubricating oils. Sulfated ash can be measured using ASTM Test D874.

[0016] As used herein, the term "Total Base Number" or "TBN" refers to the amount of base equivalents equivalent to milligrams of KOH in one gram of sample. Thus, a higher TBN number reflects more alkaline production and therefore greater alkalinity. TBN was measured using the ASTM D 2896 test.

[0017] Unless otherwise specified, all percentages are by weight.

[0018] Generally, the level of sulfur in the lubricating oil compositions of the present invention is about 0.7 wt.% or less, e.g., about 0.01 wt.% to about 0.70 wt.%, 0.01 wt.% to about 0.6 wt.%, 0.01 wt.% to 0.5 wt.%, 0.01 wt.% to 0.4 wt.%, 0.01 wt.% to 0.3 wt.%, 0.01 wt.% to 0.2 wt.%, or 0.01 wt.% to 0.10 wt.% sulfur, based on the total weight of the lubricating oil composition. In one embodiment, the level of sulfur in the lubricating oil compositions of the present invention is about 0.60 wt.% or less, about 0.50 wt.% or less, about 0.40 wt.% or less, about 0.30 wt.% or less, about 0.20 wt.% or less, or about 0.10 wt.% or less, based on the total weight of the lubricating oil composition.

[0019] In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.12 wt. % or less, e.g., from about 0.01 wt. % to about 0.12 wt. % based on the total weight of the lubricating oil composition. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.11 wt. % or less, e.g., from about 0.01 wt. % to about 0.11 wt. % based on the total weight of the lubricating oil composition. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.10 wt. % or less, e.g., from about 0.01 wt. % to about 0.10 wt. % based on the total weight of the lubricating oil composition. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.09 wt. % or less, e.g., from about 0.01 wt. % to about 0.09 wt. % based on the total weight of the lubricating oil composition. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.08 wt. % or less, e.g., from about 0.01 wt. % to about 0.08 wt. % based on the total weight of the lubricating oil composition. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.07 wt. % or less, e.g., from about 0.01 wt. % to about 0.07 wt. % based on the total weight of the lubricating oil composition. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.05 wt. % or less, e.g., from about 0.01 wt. % to about 0.05 wt. % based on the total weight of the lubricating oil composition. In one embodiment, the lubricating oil is substantially free of phosphorus.

[0020] In one embodiment, the lubricating oil compositions of the present invention produce sulfated ash levels of about 1.60 wt. % or less as measured by ASTM D 874, for example, from about 0.10 to about 1.60 wt. % sulfated ash as measured by ASTM D 874. In one embodiment, the lubricating oil compositions of the present invention produce sulfated ash levels of about 1.00 wt. % or less as measured by ASTM D 874, for example, from about 0.10 to about 1.00 wt. % sulfated ash as measured by ASTM D 874. In one embodiment, the lubricating oil compositions of the present invention produce sulfated ash levels of about 0.80 wt. % or less as measured by ASTM D 874, for example, from about 0.10 to about 0.80 wt. % sulfated ash as measured by ASTM D 874. In one embodiment, the sulfated ash level produced by the lubricating oil composition of the present invention is about 0.60 wt. % or less as measured by ASTM D 874, such as a sulfated ash level of about 0.10 to about 0.60 wt. % as measured by ASTM D 874.

[0021] All ASTM standards referred to herein are the most current versions as of the filing date of this application.

[0022] In one aspect, there is provided a passenger car internal combustion engine lubricating oil additive composition comprising: (a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity (Kv) of from about 2.0 to about 12 centistokes (cSt) at 100°C; (b) nitrogen-containing dispersants; (c) an alkaline earth metal-containing detergent provided in an amount of from about 0.03 to about 0.7 weight percent of the lubricating oil composition, based on the metal content thereof; (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof; (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups; (d) about 0.01 wt % to about 2.0 wt % of a compound comprising a reaction product.

[0023] Also provided is a method of improving new and used oil fuel economy in a passenger vehicle internal combustion engine comprising lubricating said engine with a lubricating oil composition comprising: (a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity (Kv) of from about 2.0 to about 12 centistokes (cSt) at 100°C; (b) nitrogen-containing dispersants; (c) an alkaline earth metal-containing detergent provided in an amount of from about 0.03 to about 0.7 weight percent of the lubricating oil composition, based on the metal content thereof; (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof; (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups; (d) about 0.01 wt % to about 2.0 wt % of a compound comprising a reaction product.

[0024] In one aspect, there is provided a heavy duty diesel engine lubricating oil additive composition comprising: (a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity (Kv) of from about 2.0 to about 12 centistokes (cSt) at 100°C; (b) nitrogen-containing dispersants; (c) an alkaline earth metal-containing detergent provided in an amount of from about 0.03 to about 0.7 weight percent of the lubricating oil composition, based on the metal content thereof; (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof; (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups; (d) 0.30 wt % to about 2.0 wt % of a compound comprising a reaction product.

[0025] Also provided is a method of improving new and used oil fuel economy in a heavy duty diesel engine comprising lubricating said engine with a lubricating oil composition comprising: (a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity (Kv) of from about 2.0 to about 12 centistokes (cSt) at 100°C; (b) nitrogen-containing dispersants; (c) an alkaline earth metal-containing detergent provided in an amount of from about 0.03 to about 0.7 weight percent of the lubricating oil composition, based on the metal content thereof; (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof; (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups; (d) 0.30 wt % to about 2.0 wt % of a compound comprising a reaction product.

[0026] In certain embodiments, the present disclosure provides lubricating oil compositions suitable for reducing friction in passenger vehicle internal combustion engines, particularly spark ignition, direct injection, and / or port fuel injected engines. In certain embodiments, the engine can be coupled to a hybrid vehicle electric motor / battery system (e.g., a port fuel injected spark ignition engine coupled to a hybrid vehicle electric motor / battery system). In certain embodiments, the present disclosure provides lubricating oil compositions suitable for reducing friction in heavy duty diesel internal combustion engines.

[0027] Nitrogen-containing reactants Alkanolamides In one embodiment, the nitrogen-containing reactant is an alkyl dialkanolamide. Such alkyl dialkanolamides include, but are not limited to, diethanolamides derived from coconut oil. Typically, the alkyl groups in coconut oil include a mixture of caprylyl, capryl, lauryl, myristyl, palmityl, stearyl, oleyl, and linoleyl.

[0028] Typically, alkyl dialkanolamides are prepared by reacting carboxylic acids and esters with dialkanolamines. Alkyl dialkanolamides are derived from individual C2-C carboxylic acids such as myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. 30 They can be prepared from carboxylic acids or their methyl esters, such as decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid, or mixtures of alkyl oils derived from animal fats or vegetable oils, such as tallow, coconut oil, palm oil, palm kernel oil, and fish oil. These can be readily reacted with various dialkanolamines to produce the desired alkyl dialkanolamides. Alkyl dialkanolamides can be prepared according to methods known in the art, including, but not limited to, the processes described in U.S. Pat. Nos. 4,085,126; 4,116,986; and 8,901,328, the disclosures of which are incorporated herein by reference.

[0029] In one embodiment, the nitrogen-containing reactant is an alkyldialkanolamide having the following formula (I): [ka] wherein R contains 1 to 30 carbon atoms; preferably, R contains 6 to 22 carbon atoms; more preferably, R contains from about 8 to about 18 carbon atoms; and Q is a C1 to C4 linear or branched alkylene group. In one embodiment, R contains 17 carbon atoms. In another embodiment, R contains 11 carbon atoms.

[0030] In one embodiment, the dialkanolamide comprises a bisethoxyalkylamide, for example, the bisethoxyalkylamide has the following formula (II): [ka] wherein R contains 1 to 30 carbon atoms; preferably, R contains 6 to 22 carbon atoms; more preferably, R contains from about 8 to about 18 carbon atoms. In one embodiment, R contains 17 carbon atoms. In another embodiment, R contains 11 carbon atoms. Alkanolamines

[0031] In one embodiment, the nitrogen-containing reactant is an alkyldialkanolamine. Such alkyldialkanolamines include, but are not limited to, diethanolamines derived from coconut oil. Typically, the alkyl groups in coconut oil include a mixture of caprylyl, capryl, lauryl, myristyl, palmityl, stearyl, oleyl, and linoleyl.

[0032] In one embodiment, the nitrogen-containing reactant is an alkyldialkanolamine having the following formula (III): [ka] wherein R contains 1 to 30 carbon atoms; preferably, R contains 6 to 22 carbon atoms; more preferably, R contains from about 8 to about 18 carbon atoms; and Q is a C1 to C4 linear or branched alkylene group. In one embodiment, R contains 17 carbon atoms. In another embodiment, R contains 11 carbon atoms.

[0033] In one embodiment, the dialkanolamine comprises a bis-ethoxyalkylamine, for example, the bis-ethoxyalkylamine has the following formula (IV): [ka] wherein R contains 1 to 30 carbon atoms; preferably, R contains 6 to 22 carbon atoms; more preferably, R contains from about 8 to about 18 carbon atoms. In one embodiment, R contains 17 carbon atoms. In another embodiment, R contains 11 carbon atoms.

[0034] The alkyl groups of the dialkanolamides and dialkanolamines can have various levels of unsaturation, for example, the alkyl groups can contain double and triple bonds.

[0035] Alkyl dialkanolamines are typically commercially available from Akzo Nobel, for example, products sold under the trade names Ethomeen (registered trademark in some countries) C / 12 or Ethomeen (registered trademark in some countries) O / 12 are suitable dialkanolamines for use in the present invention.

[0036] Examples of alkylalkanolamines include, but are not limited to, the following: oleyldiethanolamine, dodecyldiethanolamine, 2-ethylhexyldiethanolamine, diethanolamine derived from coconut oil, and diethanolamine derived from beef tallow.

[0037] Alkoxylated Alkyl Alkanolamides In one embodiment, the nitrogen-containing reactant is an alkoxylated alkyl alkanolamide. The alkoxylated moieties may be ethoxylated, propoxylated, butoxylated, etc.

[0038] The alkyl portion of the alkoxylated alkyl alkanolamide is preferably a branched or straight chain alkyl or alkenyl group, or a combination thereof, containing 3 to 21 carbon atoms, more preferably 8 to 18 carbon atoms. The alkoxy portion may be an ethoxy, propoxy, or butoxy group, or a combination thereof. In a preferred embodiment, a propoxylated alkyl alkanolamide, more preferably a propoxylated alkylethanolamide, is used.

[0039] Alkoxylated alkyl alkanolamides of formula (V): [ka] In the formula, R 1 Branched or straight chain, saturated or unsaturated C3-C 21 Alkyl radicals, preferably C8-C 18 R2 is hydrogen, or a C1-C2 alkyl radical, or a combination thereof, preferably R2 is either hydrogen or a C1 alkyl radical; x is from about 1 to about 8, preferably from about 1 to about 5, and more preferably from about 1 to about 3.

[0040] Examples of useful alkoxylated alkyl alkanolamides include polyoxypropylene, polyoxybutylene, alkylethanolamides, or alkylisopropanolamides. Alkoxylated alkylethanolamides, particularly propoxylated alkylethanolamides, are preferred. The alkylethanolamide moiety is preferably an alkylmonoethanolamide, more preferably derived from lauric acid monoethanolamide, capric acid monoethanolamide, caprylic acid monoethanolamide, caprylic / capric acid monoethanolamide, decanoic acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, isostearic acid monoethanolamide, oleic acid monoethanolamide, linoleic acid monoethanolamide, octydecanoic acid monoethanolamide, 2-heptylundecanoic acid monoethanolamide, coconut oil-derived alkylmonoethanolamide, beef tallow-derived alkylmonoethanolamide, soybean oil-derived alkylmonoethanolamide, and palm kernel oil-derived alkylmonoethanolamide. Of these, caprylic, linoleic, stearic, isostearic, and those derived from soybean or coconut oil are preferred.

[0041] Preferred propoxylated fatty ethanolamides include propoxylated hydroxyethyl caprylamide, propoxylated hydroxyethyl cocamide, propoxylated hydroxyethyl linoleamide, propoxylated hydroxyethyl isostearate amide, and combinations thereof. Propoxylated hydroxyethyl cocamide is more preferred. Specific preferred materials are PPG-1 hydroxyethyl caprylamide, PPG-2 hydroxyethyl cocamide, PPG-3 hydroxyethyl linoleamide, PPG-2 hydroxyethyl isostearate amide, and combinations thereof. PPG-2 hydroxyethyl cocamide is particularly preferred.

[0042] In another embodiment, an alkoxylated alkyl isopropanolamide is used. The alkyl isopropanolamide moiety is preferably an alkyl monoisopropanolamide, and more preferably derived from lauric acid monoisopropanolamide, capric acid monoisopropanolamide, caprylic acid monoisopropanolamide, caprylic / capric acid monoisopropanolamide, decanoic acid monoisopropanolamide, myristic acid monoisopropanolamide, palmitic acid monoisopropanolamide, stearic acid monoisopropanolamide, isostearic acid monoisopropanolamide, oleic acid monoisopropanolamide, linoleic acid monoisopropanolamide, octyldecanoic acid monoisopropanolamide, 2-heptylundecanoic acid monoisopropanolamide, coconut oil-derived alkyl monoisopropanolamide, beef tallow-derived alkyl monoisopropanolamide, soybean oil-derived monoisopropanolamide, and palm kernel oil-derived alkyl monoisopropanolamide.

[0043] An alkoxylated alkyldialkanolamide of formula (VI): [ka] In the formula, R 1 is branched or straight chain, saturated or unsaturated C3-C 21 Alkyl radicals, preferably C8-C 18 alkyl radicals, or combinations thereof; R 2 is hydrogen, or a C1-C2 alkyl radical or a combination thereof, preferably R 2 is hydrogen or a C1 alkyl radical; x is from about 1 to about 8, preferably from about 1 to about 5, and more preferably from about 1 to about 3.

[0044] Examples of useful alkoxylated alkyl dialkanolamides include polyoxypropylene, polyoxybutylene, alkyl diethanolamides, or alkyl diisopropanolamides. Alkoxylated alkyl diethanolamides, particularly propoxylated alkyl diethanolamides, are preferred. The alkyl diethanolamide moiety is preferably an alkyl diethanolamide, more preferably derived from lauric acid diethanolamide, capric acid diethanolamide, caprylic acid diethanolamide, caprylic / capric acid diethanolamide, decanoic acid diethanolamide, myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, isostearic acid diethanolamide, oleic acid diethanolamide, linoleic acid diethanolamide, octydecane diethanolamide, 2-heptylundecanoic acid diethanolamide, coconut oil-derived alkyl diethanolamide, beef tallow-derived alkyl diethanolamide, soybean oil-derived alkyl diethanolamide, or palm kernel oil-derived alkyl diethanolamide. Of these, caprylic, linoleic, stearic, isostearic, and those derived from soybean or coconut oil are preferred.

[0045] Preferred propoxylated aliphatic diethanolamides include propoxylated bisethoxycaprylamide, propoxylated bisethoxycocamide, propoxylated bisethoxylinoleamide, propoxylated bisethoxyisostearamide, and combinations thereof. Propoxylated bisethoxycocamide is more preferred. Specific preferred materials are PPG-1 bisethoxycaprylamide, PPG-2 bisethoxycocamide, PPG-3 bisethoxylinoleamide, PPG-2 bisethoxyisostearamide, and combinations thereof. PPG-2 bisethoxycocamide is particularly preferred.

[0046] In another embodiment, an alkoxylated alkyldiisopropanolamide is used. The alkylisopropanolamide moiety is preferably an alkylalkyldiisopropanolamide, and more preferably derived from lauric diisopropanolamide, capric diisopropanolamide, caprylic diisopropanolamide, caprylic / capric diisopropanolamide, decanoic diisopropanolamide, myristic diisopropanolamide, palmitic diisopropanolamide, stearic diisopropanolamide, isostearic diisopropanolamide, oleic diisopropanolamide, linoleic diisopropanolamide, octyldecanoic diisopropanolamide, 2-heptylundecanoic diisopropanolamide, coconut oil-derived alkyldiisopropanolamide, beef tallow-derived alkyldiisopropanolamide, soybean oil-derived diisopropanolamide, and palm kernel oil-derived alkyldiisopropanolamide. Alkoxylated Alkyl Alkanolamines

[0047] In one embodiment, the nitrogen-containing reactant is an alkylalkanolamine having one of the following formulas (VII or VIII): [ka] In the formula, R 1 is branched or straight chain, saturated or unsaturated, C3 to C 21 Alkyl radicals, preferably C8-C 18 alkyl radicals, or combinations thereof; R 2 is hydrogen, or a C1-C2 alkyl radical or a combination thereof, preferably R 2 is hydrogen or a C1 alkyl radical; x is from about 1 to about 8, preferably from about 1 to about 5, and more preferably from about 1 to about 3.

[0048] In one embodiment, the nitrogen-containing reactant is an alkylmonoalkanolamine or alkyldialkanolamine. Such alkylmonoalkanolamines and alkyldialkanolamines include, but are not limited to, monoethanolamine derived from coconut oil or cocomonoethanolamine derived from coconut oil, diethanolamine, myristic diethanolamine laurate, monoethanolamine laurate, diethanolamine laurate, and monoisopropanolamine laurate. Typically, the alkyl groups in coconut oil include a mixture of caprylic, capric, lauric, myristic, palmitic, stearic, oleic, and linoleic acids.

[0049] Typically, alkylmonoalkanolamines and alkyldialkanolamines are commercially available from Akzo Nobel.

[0050] Examples of alkylalkanolamines include, but are not limited to, the following:

[0051] Oleyldiethanolamine, diethanolamine derived from coconut oil, diethanolamine derived from beef tallow, etc.

[0052] Useful examples of alkoxylated alkyldialkanolamines include polyoxypropylene, polyoxybutylene, alkyldiethanolamine, or alkyldiisopropanolamine. Alkoxylated alkyldiethanolamines, particularly propoxylated alkyldiethanolamines, are preferred. The alkyldiethanolamine moiety is preferably an alkyldiethanolamine, more preferably derived from lauric acid diethanolamine, capric acid diethanolamine, caprylic acid diethanolamine, caprylic / capric acid diethanolamine, decanoic acid diethanolamine, myristic acid diethanolamine, palmitic acid diethanolamine, stearic acid diethanolamine, isostearic acid diethanolamine, oleic acid diethanolamine, linoleic acid diethanolamine, octydecanoic acid diethanolamine, 2-heptylundecanoic acid diethanolamine, coconut oil-derived alkyldiethanolamine, beef tallow-derived alkyldiethanolamine, soybean oil-derived alkyldiethanolamine, and palm kernel oil-derived alkyldiethanolamine. Of these, caprylic, linoleic, stearic, isostearic, and those derived from soybean or coconut oil are preferred.

[0053] Preferred propoxylated aliphatic diethanolamines include propoxylated bisethoxycaprylamine, propoxylated bisethoxycocamine, propoxylated bisethoxylinolamine, propoxylated bisethoxyisostearamine, and combinations thereof. Propoxylated bisethoxycocamine is more preferred. Specific preferred materials are PPG-1 bisethoxycaprylamine, PPG-2 bisethoxycocamine, PPG-3 bisethoxylinolamine, PPG-2 bisethoxyisostearamine, and combinations thereof. PPG-2 bisethoxycocamine is particularly preferred.

[0054] In another embodiment, an alkoxylated alkyldiisopropanolamine is used. The alkylisopropanolamine moiety is preferably an alkyldiisopropanolamine, and more preferably derived from diisopropanolamine laurate, diisopropanolamine caprate, diisopropanolamine caprylate, diisopropanolamine caprylate / caprate, diisopropanolamine decanoate, diisopropanolamine myristate, diisopropanolamine palmitate, diisopropanolamine stearate, diisopropanolamine isostearate, diisopropanolamine oleate, diisopropanolamine linoleate, diisopropanolamine octyldecanoate, diisopropanolamine 2-heptylundecanoate, alkyldiisopropanolamine derived from coconut oil, alkyldiisopropanolamine derived from beef tallow, diisopropanolamine derived from soybean oil, and alkyldiisopropanolamine derived from palm kernel oil.

[0055] The nitrogen-containing reactants can be prepared by methods known in the art. Alkyl alkanolamides and alkyl alkanolamines can be prepared according to U.S. Patent No. 4,085,126; U.S. Patent No. 7,479,473 and other methods known in the art; or can be purchased from Akzo Nobel.

[0056] Boron Source Suitable boron compounds include boron oxide or any of the various forms of boric acid, including metaboric acid (HBO), orthoboric acid (HBO), and tetraboric acid (HBO). 1-6Alkyl borate salts such as alkyl borates can be used. Thus, suitable alkyl borates include mono-, di-, and tri-methyl borates; mono-, di-, and tri-ethyl borates; mono-, di-, and tri-propyl borates, and mono-, di-, and tri-butyl borates, and mixtures thereof. A particularly preferred boron compound is boric acid, especially orthoboric acid. These can be purchased from suppliers such as Aldrich or Fisher Scientific.

[0057] Hydrocarbyl Polyol Reactant In one embodiment, the hydrocarbyl polyol reactant comprises a hydrocarbyl polyol component, the derivatives of which, excluding esters, have at least three hydroxyl groups. More preferably, the hydrocarbyl polyol component has the following formula (IX): [ka] In the formula, n is 0 or an integer of 1 to 5. Preferably, n is 0 or 1.

[0058] Examples of hydrocarbyl polyols that can be used in the present invention include compounds of formulae (X) and (XI) below: [ka]

[0059] Method for making lubricating oil additive compositions

[0060] The lubricating oil additive composition is prepared by charging a nitrogen-containing reactant with an aromatic solvent into a vessel. Preferably, the nitrogen reactant is a bisethoxyalkylamine (also known as an alkyldiethanolamine) or a bisethoxyalkylamide. A boron source, such as boric acid, is then added to the vessel. The mixture is refluxed until the water is substantially removed and the reaction is complete. A hydrocarbyl polyol having at least three hydroxyl groups, such as glycerol or pentaerythritol, is then added to the mixture.

[0061] In one embodiment, a hydrocarbyl polyol having at least three hydroxyl groups is added to a vessel simultaneously with a boron source, and the mixture is then refluxed for two hours.

[0062] Preferably, the ratio of nitrogen-containing reactant, boron reactant source, and glycerol is about 1:0.2:0.2 to 1:2.5:2.5. More preferably, the ratio is about 1:0.2:0.2 to 1:1.5:1.5. Even more preferably, the ratio is about 1:0.4:0.4 to 1:1:1. Most preferably, the ratio is about 1:0.5:0.5 to 1:0.75:0.75.

[0063] Oil of lubricating viscosity

[0064] An oil of lubricating viscosity (sometimes called a "base stock" or "base oil") is the primary liquid component of a lubricant into which additives and possibly other oils are blended to produce, for example, the finished lubricant (or lubricant composition). Base oils are useful for making concentrates and for making lubricating oil compositions therefrom, and can be selected from natural and synthetic lubricating oils and combinations thereof.

[0065] Natural oils include animal and vegetable oils, liquid petroleum oils, and solvent-processed and mineral-processed lubricating oils of the paraffinic, naphthenic, and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

[0066] Synthetic lubricating oils include hydrocarbon oils such as polymeric and copolymeric olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, alkylated naphthalenes); polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogs, and homologs.

[0067] Another suitable class of synthetic lubricating oils includes the esters of carboxylic acids (e.g., malonic acid, alkylmalonic acids, alkenylmalonic acids, succinic acid, alkylsuccinic and alkenylsuccinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, diecosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

[0068] Esters useful as synthetic oils also include C5-C 12 Included are those made from monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

[0069] Base oils may be derived from Fischer-Tropsch synthesized hydrocarbons. Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing to be useful as base oils. For example, the hydrocarbons may be hydroisomerized; hydrocracking and hydroisomerized; dewaxed; or hydroisomerized and dewaxed using methods known to those skilled in the art.

[0070] Unrefined, refined, and re-refined oils can be used in the lubricating oil compositions of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from retorting operations, petroleum oil obtained directly from distillation, or ester oil obtained directly from an esterification process and used without further treatment are unrefined oils. Refined oils are similar to unrefined oils, except that they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration, and percolation, are known to those skilled in the art.

[0071] Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils that have already been used. Such re-refined oils are also known as reclaimed or reprocessed oils and are often treated by techniques to remove used additives and oil breakdown products.

[0072] Thus, the base oils that can be used to make the present lubricating oil compositions can be selected from any of Groups I to V of base oils as specified in the American Petroleum Institute (API) Base Oil Compatibility Guidelines (API Publication 1509). Such base oil groups are summarized in Table 1 below: [Table 1]

[0073] Suitable base oils for use herein are any type corresponding to API Group II, Group III, Group IV, and Group V oils and combinations thereof, preferably Group III-V oils due to their exceptional volatility, stability, viscosity, and cleanliness characteristics.

[0074] The oil of lubricating viscosity for use in the lubricating oil compositions of the present disclosure, also referred to as base oil, is typically present in a major amount, e.g., greater than 50 wt.%, preferably greater than about 70 wt.%, more preferably about 80 to about 99.5 wt.%, and most preferably about 85 to about 98 wt.%, based on the total weight of the composition. As used herein, the term "base oil" should be understood to mean a base stock or blend of base stocks that are lubricant components produced by a single manufacturer to the same specifications (independent of source or location of manufacturer); meet the same manufacturer's specifications; and are recognized by a unique formula, product identification number, or both. Base oils for use herein may be any now-known or later-discovered oil of lubricating viscosity used in formulating lubricating oil compositions for any such application, e.g., functional fluids such as engine oils, marine cylinder oils, hydraulic oils, gear oils, and transmission oils. Additionally, base oils for use herein may contain viscosity index improvers, e.g., polymeric alkyl methacrylates; olefin-based copolymers, e.g., ethylene-propylene copolymers or styrene-butadiene copolymers; and mixtures thereof. The topology of the viscosity modifier includes, but is not limited to, linear, branched, hyperbranched, star, or comb topologies.

[0075] As one skilled in the art will readily appreciate, the viscosity of the base oil will depend on the application. Thus, the viscosity of base oils for use herein will typically range from about 2 to about 2000 centistokes (cSt) at 100 degrees Celsius (C.). Generally, base oils used as engine oils individually have a kinematic viscosity range of from about 2 cSt to about 30 cSt at 100°C, preferably from about 3 cSt to about 16 cSt, and most preferably from about 4 cSt to about 12 cSt, and are selected or blended depending on the desired end use and additives in the finished oil to obtain a lubricating oil composition having a desired grade of engine oil, for example, an SAE viscosity grade such as 0W, 0W-8, 0W-12, 0W-16, 0W-20, 0W-26, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40, etc.

[0076] The lubricating oil composition has a viscosity index of at least 135 (e.g., 135-400, or 135-250), at least 150 (e.g., 150-400, 150-250), at least 165 (e.g., 165-400, or 165-250), at least 190 (e.g., 190-400, or 190-250), or at least 200 (e.g., 200-400, or 200-250). If the viscosity index of the lubricating oil composition is less than 135, it may be difficult to improve fuel efficiency while maintaining the HTHS viscosity at 150°C. If the viscosity index of the lubricating oil composition is greater than 400, evaporation characteristics may be reduced, and defects may occur due to insufficient solubility of additives and matching characteristics with sealing materials.

[0077] The lubricating oil composition has a high temperature shear (HTHS) viscosity at 150°C of 3.5 cP or less (e.g., 1.0 to 3.5 cP), 3.3 cP or less (e.g., 1.0 to 3.3 cP), 3.0 cP or less (e.g., 1.3 to 3.0 cP), 2.6 cP or less (e.g., 1.3 to 2.6 cP), 2.3 cP or less (e.g., 1.0 to 2.3 cP, or 1.3 to 2.3 cP), 2.0 cP or less (e.g., 1.0 to 2.0 cP, or 1.3 to 2.0 cP), etc., or 1.7 cP or less (e.g., 1.0 to 1.7 cP, or 1.3 to 1.7 cP).

[0078] The lubricating oil composition has a viscosity of 3 to 12 mm at 100°C. 2 / s (e.g., 3 to 6.9 mm 2 / s, 3.5~6.9mm 2 / s, or 4 to 6.9 mm 2 / s).

[0079] Suitably, the lubricating oil composition may have a total base number (TBN) of from 4 to 15 mg KOH / g (e.g., from 5 to 12 mg KOH / g, from 6 to 12 mg KOH / g, or from 8 to 12 mg KOH / g).

[0080] In one embodiment, the lubricating oil compositions of this disclosure may further comprise an organo-molybdenum compound.

[0081] Organomolybdenum Compounds Organomolybdenum compounds contain at least molybdenum, carbon, and hydrogen atoms, but may also contain sulfur, phosphorus, nitrogen, and / or oxygen atoms. Suitable organomolybdenum compounds include molybdenum dithiocarbamates, molybdenum dithiophosphates, and various organomolybdenum complexes, such as molybdenum carboxylates, molybdenum esters, molybdenum amines, and molybdenum amides, which can be obtained by reacting molybdenum oxide or ammonium molybdate with fats, glycerides, fatty acids, or fatty acid derivatives (e.g., esters, amines, amides). The term "fatty" refers to a carbon chain having 10 to 22 carbon atoms, typically a linear carbon chain.

[0082] Molybdenum dithiocarbamate (MoDTC) is an organo-molybdenum compound represented by the following formula (XII): [ka] In the formula, R 1 , R 2 , R 3 , and R 4 are each independently a straight-chain or branched alkyl group having 4 to 18 carbon atoms (for example, 8 to 13 carbon atoms). Molybdenum dithiophosphate (MoDTP) is an organo-molybdenum compound represented by the following formula (XIII): [ka] In the formula, R 5 , R 6 , R 7 , and R 8 are each independently a straight-chain or branched alkyl group having 4 to 18 carbon atoms (for example, 8 to 13 carbon atoms). In one embodiment, the molybdenum amine is a molybdenum-succinimide complex. Suitable molybdenum-succinimide complexes are described, for example, in U.S. Patent No. 8,076,275. These complexes are prepared by a process comprising reacting an acidic molybdenum compound with an alkyl or alkenyl succinimide of a polyamine of formula (XIV) or (XV), or a mixture thereof: [ka] where R is C 24 ~C 350 (For example, C 70 ~C 128 ) alkyl or alkenyl group; R' is a straight or branched chain alkylene group having 2 to 3 carbon atoms; x is 1 to 11; and y is 1 to 10. The molybdenum compound used to prepare the molybdenum-succinimide complex is an acidic molybdenum compound or a salt of an acidic molybdenum compound. "Acidic" means that the molybdenum compound reacts with a basic nitrogen compound as measured by ASTM D664 or D2896. Typically, acidic molybdenum compounds are hexavalent. Representative examples of suitable molybdenum compounds include molybdenum trioxide, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, as well as molybdenum salts such as hydrogen salts (e.g., sodium hydrogen molybdate), MoOCl4, MoO2Br2, and Mo2O3Cl6.

[0083] Succinimides that can be used to prepare molybdenum-succinimide complexes are disclosed in numerous references and are known in the art. Certain basic types of succinimides and related materials encompassed by the technical term "succinimide" are taught in U.S. Patent Nos. 3,172,892; 3,219,666; and 3,272,746. The term "succinimide" is understood in the art to encompass many of the amide, imide, and amidine species that may be formed. However, the primary product is succinimide, and the term is generally accepted to refer to the product of the reaction of an alkyl- or alkenyl-substituted succinic acid or anhydride with a nitrogen-containing compound. Preferred succinimides are those prepared by reacting polyisobutenyl succinic anhydride of about 70 to 128 carbon atoms with a polyalkylene polyamine selected from triethylenetetramine, tetraethylenepentamine, and mixtures thereof.

[0084] The molybdenum-succinimide complex can be post-treated with a sulfur source at an appropriate pressure and a temperature not exceeding 120°C to provide a molybdenum sulfide-succinimide complex. The sulfurization step can be carried out for about 0.5 to 5 hours (e.g., 0.5 to 2 hours). Suitable sources of sulfur include elemental sulfur, hydrogen sulfide, diphosphorus pentasulfide, and sulfur compounds of the formula R2S. xand R is hydrocarbyl (e.g., C1-C 10 alkyl), organic polysulfides where x is at least 3, C1-C 10 These include mercaptans, inorganic sulfides and polysulfides, thioacetamides, and thioureas.

[0085] The molybdenum-succinimide complex is used in an amount to provide at least 50 ppm (e.g., 50 to 1500 ppm), at least 100 ppm (e.g., 100 to 1500 ppm), or at least 200 ppm (e.g., 200 to 1500 ppm, 200 to 1100 ppm, 250 to 1500 ppm, 250 to 1100 ppm, or 300 to 1000 ppm) of molybdenum to the lubricating oil composition.

[0086] In one embodiment, the lubricating oil composition of this disclosure may further comprise an antiwear agent. In a particular embodiment, the antiwear agent may be a zinc dithiophosphate (ZnDTP) compound.

[0087] Anti-wear agent The lubricating oil compositions disclosed herein may contain antiwear agents capable of reducing friction and excessive wear. Non-limiting examples of suitable antiwear agents include zinc dithiophosphates, metal (e.g., Pb, Sb, Mo, etc.) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamates, metal (e.g., Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphate esters, phosphites, amine salts of phosphate esters or thiophosphate esters, reaction products of dicyclopentadiene and thiophosphoric acid, and combinations thereof. The amount of antiwear agent may vary from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %, based on the total weight of the lubricating oil composition.

[0088] In certain embodiments, the antiwear agent comprises a metal dihydrocarbyl dithiophosphate, such as a zinc dialkyldithiophosphate compound. The metal of the metal dihydrocarbyl dithiophosphate may be an alkali metal or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the metal dihydrocarbyl dithiophosphate has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0089] The amount of metal dihydrocarbyl dithiophosphate, including zinc dialkyl dithiophosphate, in the lubricating oil compositions disclosed herein is measured by its phosphorus content. In some embodiments, the lubricating oil compositions disclosed herein have a phosphorus content of from about 0.01 wt % to about 0.12 wt %, from about 0.01 wt % to about 0.10 wt %, from about 0.01 wt % to about 0.08 wt %, from about 0.01 wt % to about 0.05 wt %, or less than 0.08 wt %, based on the total weight of the lubricating oil composition.

[0090] In certain embodiments, the lubricating oil composition is substantially free of phosphorus.In certain embodiments, the lubricating oil composition is substantially free of zinc-containing compounds.

[0091] Metal dihydrocarbyl dithiophosphate salts can be prepared according to known methods, typically by reacting one or more alcohol and phenolic compounds with P2S5 to first form a dihydrocarbyl dithiophosphate (DDPA), and then neutralizing the formed DDPA with a metal compound such as the metal oxide, hydroxide, or carbonate. In some embodiments, DDPA can be made by reacting a mixture of primary and secondary alcohols with P2S5. In another embodiment, two or more dihydrocarbyl dithiophosphates can be prepared, where the hydrocarbyl groups on one are entirely secondary and the hydrocarbyl groups on the other are entirely primary. Zinc salts can be prepared from the dihydrocarbyl dithiophosphates by reaction with a zinc compound. In some embodiments, basic or neutral zinc compounds are used. In another embodiment, zinc oxides, hydroxides, or carbonates are used.

[0092] In some embodiments, the oil-soluble zinc dialkyldithiophosphate can be produced from a dialkyldithiophosphoric acid represented by formula (XVI): [ka]

[0093] In the formula, R 3 and R 4 are, independently of each other, straight-chain or branched alkyl or straight-chain or branched substituted alkyl. In some embodiments, the alkyl group has from about 3 to about 30 carbon atoms or from about 3 to about 8 carbon atoms.

[0094] The dialkyldithiophosphoric acid of formula (XVI) is 3 OH and R 4 OH can be prepared by reacting with P2S5, R 3 and R 4 is as defined above. In some embodiments, R 3 and R 4 In another embodiment, R 3and R 4 In a further embodiment, R 3 OH and R 4 OH reacts simultaneously with P2S5. In yet another embodiment, R 3 OH and R 4 OH reacts sequentially with P2S5.

[0095] Mixtures of hydroxyl alkyl compounds can also be used. These hydroxyl alkyl compounds need not be monohydroxy alkyl compounds. In some embodiments, the dialkyl dithiophosphates are prepared from mono-, di-, tri-, tetra-, and other polyhydroxy alkyl compounds, or mixtures of two or more of the foregoing. In another embodiment, the zinc dialkyl dithiophosphate derived exclusively from primary alkyl alcohols is derived from a single primary alcohol. In a further embodiment, the single primary alcohol is 2-ethylhexanol. In certain embodiments, the zinc dialkyl dithiophosphate is derived exclusively from secondary alkyl alcohols. In a further embodiment, the mixture of secondary alcohols is a mixture of 2-butanol and 4-methyl-2-pentanol.

[0096] The phosphorus pentasulfide reactant used in the dialkyldithiophosphoric acid-forming step may contain a certain amount of one or more of P2S3, P4S3, P4S7, or P4S9. Such compositions may also contain small amounts of free sulfur. In certain embodiments, the phosphorus pentasulfide reactant is substantially free of P2S3, P4S3, P4S7, or P4S9. In certain embodiments, the phosphorus pentasulfide reactant is substantially free of free sulfur.

[0097] In certain embodiments, the lubricating oil composition comprises a zinc dithiophosphate (ZnDTP) compound, in certain embodiments, the ZnDTP is selected from the group consisting of a primary ZnDTP, a secondary ZnDTP, or a combination thereof.

[0098] Detergent Mixture The detergent mixture comprises at least one calcium-containing detergent and may optionally comprise at least one magnesium-containing detergent.

[0099] Typical detergents are anionic materials containing a long-chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of the detergent is usually derived from an organic acid such as a sulfur acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof. The counterion is usually an alkaline earth or alkali metal.

[0100] Salts containing substantially stoichiometric amounts of metal are described as neutral salts and have a total base number (TBN) of 0 to 80 mg KOH / g. Many compositions are overbased, containing large amounts of metal base, achieved by reacting excess metal compounds (e.g., metal hydroxides or oxides) with an abundance of acid gas (e.g., carbon dioxide). Useful detergents may be neutral, weakly overbased, or highly overbased.

[0101] It is desirable that at least a portion of the detergent used in the detergent mixture be overbased. Overbased detergents neutralize acidic impurities produced in the combustion process, allowing them to become trapped in the oil. Typically, the overbased material has a ratio of metal ions to the anionic portion of the detergent, on an equivalents basis, of 1.05:1 to 50:1 (e.g., 4:1 to 25:1). The resulting detergent is typically an overbased detergent with a TBN of 150 mg KOH / g or greater (e.g., 250 to 450 mg KOH / g or greater). Mixtures of detergents with different TBNs can be used.

[0102] Suitable detergents include metal salts of sulfonates, phenates, carboxylates, phosphates, and salicylates.

[0103] Sulfonates can be prepared from sulfonic acids obtained by the sulfonation of alkyl-substituted aromatic hydrocarbons, such as those typically obtained by petroleum fractionation or the alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives. Alkylation can be carried out in the presence of a catalyst using alkylating agents having from about 3 to more than 70 carbon atoms. Alkaryl sulfonates typically contain from about 9 to 80 or more carbon atoms (e.g., from about 16 to 60 carbon atoms) per alkyl-substituted aromatic moiety.

[0104] Phenates can be prepared by reacting an alkaline earth metal hydroxide or oxide (e.g., CaO, Ca(OH), MgO, or Mg(OH)) with an alkylphenol or sulfurized alkylphenol. Useful alkyl groups include linear or branched C1-C 30 (For example, C4~C 20 ) alkyl groups, or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecylphenol, and the like. It should be noted that the starting alkylphenol may contain multiple alkyl substituents, each independently linear or branched. When non-sulfurized alkylphenols are used, the sulfurized product can be obtained by methods known in the art. These methods involve heating a mixture of an alkylphenol and a sulfurizing agent (e.g., elemental sulfur, sulfur halides such as sulfur dichloride, etc.), and then reacting the sulfurized phenol with an alkaline earth metal base.

[0105] Salicylates can be prepared by reacting a basic metal compound with at least one carboxylic acid and removing water from the reaction product. Detergents made from salicylic acid are a type of detergent prepared from carboxylic acids. Useful salicylates include long-chain alkyl salicylates. One useful family of compositions is represented by the following formula (XVI): [ka] In the formula, R″ is C1 to C 30 (For example, C 13 ~C 30 ) alkyl group; n is an integer from 1 to 4; and M is an alkaline earth metal (eg, Ca or Mg).

[0106] Hydrocarbyl-substituted salicylic acids can be prepared from phenols by the Kolbe reaction (see U.S. Pat. No. 3,595,791). Metal salts of hydrocarbyl-substituted salicylic acids can be prepared by metathesis of the metal salt in a polar solvent such as water or alcohol.

[0107] Alkaline earth metal phosphates are also used as detergents and are known in the art.

[0108] Preferred calcium-containing detergents include calcium sulfonates, calcium phenates, and calcium salicylates, especially calcium sulfonates, calcium salicylates, and mixtures thereof.

[0109] Preferred magnesium-containing detergents include magnesium sulfonates, magnesium phenates, and magnesium salicylates, especially magnesium sulfonates.

[0110] Viscosity modifier Viscosity modifiers function to impart high and low temperature operability to lubricating oils. The viscosity modifiers used may have that sole function or may be multifunctional. Multifunctional viscosity modifiers that also function as dispersants are also known. Suitable viscosity modifiers include polyisobutylene, copolymers of ethylene, propylene, and higher alpha olefins, polymethacrylates, polyalkyl methacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acids and vinyl compounds, copolymers of styrene and acrylic acid esters, and partially hydrogenated copolymers of styrene / isoprene, styrene / butadiene, and isoprene / butadiene, as well as partially hydrogenated homopolymers of butadiene and isoprene and isoprene / divinylbenzene. In one embodiment, the viscosity modifier is a polyalkyl methacrylate. The viscosity modifier topology includes, but is not limited to, linear, branched, hyperbranched, star, or comb topologies. The viscosity modifier may be non-dispersant or dispersant. In one embodiment, the viscosity modifier is a dispersant polymethacrylate.

[0111] Suitable viscosity modifiers have a permanent shear stability index (PSSI) of 30 or less (e.g., 10 or less, 5 or less, or 2 or less). PSSI is a measure of the shear-induced irreversible decrease in oil viscosity caused by the additive. PSSI is measured in accordance with ASTM D6022. The lubricating oil compositions of this disclosure exhibit stay-in-grade capability. Retention of kinematic viscosity at 100°C within a single SAE viscosity grade classification by new oil and its sheared version is evidence of the oil's stay-in-grade capability.

[0112] The viscosity modifier can be used in an amount of 0.5 to 15.0 wt % (e.g., 0.5 to 10 wt %, 0.5 to 5 wt %, 1.0 to 15 wt %, 1.0 to 10 wt %, or 1.0 to 5 wt %), based on the total weight of the lubricating oil composition.

[0113] Additional lubricant additives The lubricating oil compositions of the present disclosure may also contain other conventional additives capable of imparting or improving any desirable properties of the lubricating oil composition in which the additive is dispersed or dissolved. Any additive known to those skilled in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives are described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer (1996); and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Inc. (2003), both of which are incorporated herein by reference. For example, the lubricating oil compositions may be blended with antioxidants, rust inhibitors, dehazers, demulsifiers, metal deactivators, friction modifiers, pour point depressants, antifoam agents, cosolvents, corrosion inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents, and the like, and mixtures thereof. A variety of additives are known and commercially available. These additives, or their analogous compounds, can be used to prepare the lubricating oil compositions of the present disclosure by conventional blending procedures.

[0114] In preparing lubricating oil formulations, it is common practice to introduce the additives in the form of a 10 to 80 wt. % active ingredient concentrate in a hydrocarbon oil, e.g., mineral lubricating oil, or other suitable solvent.

[0115] Typically, these concentrates can be diluted with 3 to 100 parts by weight, e.g., 5 to 40 parts by weight, of lubricating oil per part by weight of the additive package to form a finished lubricant, e.g., crankcase motor oil. The purpose of the concentrate, of course, is to make the handling of the various materials less difficult and easier to handle and to facilitate solution or dispersion in the final blend.

[0116] When used, each of the foregoing additives is used in a functionally effective amount to impart the desired characteristics to the lubricant. Thus, for example, if an additive is a friction modifier, a functionally effective amount of the friction modifier would be an amount sufficient to impart the desired friction modifying characteristics to the lubricant.

[0117] Generally, the concentration of each additive, if used, in the lubricating oil composition may range from about 0.001 to about 20% by weight, from about 0.01 to about 15% by weight, from about 0.1 to about 10% by weight, from about 0.005 to about 5% by weight, or from about 0.1 to about 2.5% by weight, based on the total weight of the lubricating oil composition. Furthermore, the total amount of additives in the lubricating oil composition may range from about 0.001 to about 20% by weight, from about 0.01 to about 10% by weight, or from about 0.1 to about 5% by weight, based on the total weight of the lubricating oil composition.

[0118] The internal combustion engine may or may not be equipped with an exhaust gas recirculation system. The internal combustion engine may be fitted with an emission control system or a turbocharger. Examples of emission control systems include systems that use a diesel particulate filter (DPF), a gasoline particulate filter (GPF), a three-way catalyst (TWC), or a selective catalytic reduction (SCR).

[0119] In one embodiment, the internal combustion engine may be a diesel-fueled engine (typically a heavy-duty diesel engine), a gasoline-fueled engine, a natural gas-fueled engine, a mixed gasoline / alcohol-fueled engine, or a hydrogen-fueled internal combustion engine. In one embodiment, the internal combustion engine may be a diesel-fueled engine, and in another embodiment, it may be a gasoline-fueled engine. In one embodiment, the internal combustion engine may be a heavy-duty diesel engine. In one embodiment, the internal combustion engine may be a gasoline engine, such as a gasoline direct injection engine (GDI engine). GDI engines produce high levels of soot, which causes corrosive wear. The organic-type friction modifiers of the present disclosure exhibit superior friction-reducing performance compared to other types of friction modifiers, such as MDOT.

[0120] The following examples are presented to illustrate embodiments of the present disclosure, but are not intended to limit the disclosure to the specific embodiments described. Unless otherwise indicated, all parts and percentages are by weight. All numerical values ​​are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the present disclosure. The specific details described in each example should not be construed as necessary features of the present disclosure.

[0121] It should be understood that various modifications may be made to the embodiments disclosed herein. Accordingly, the above description should not be construed as limiting, but merely as exemplifications of preferred embodiments. For example, the functions described above and implemented as the best mode for operating the disclosure are for illustrative purposes only. Other arrangements and methods may be devised by those skilled in the art without departing from the scope and spirit of the present disclosure. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the claims appended hereto.

[0122] example The following examples are for illustrative purposes only and are not intended to limit the scope of the disclosure in any way.

[0123] Example A Example A is a mixed borate ester of bisethoxycocamide and glycerol, prepared according to Example 3 of US Pat. No. 9,371,499.

[0124] Comparative example A Comparative Example A is molybdenum dithiocarbamate (SAKURA-LUBE (registered trademark in some countries) 515; Adeka Corporation).

[0125] Comparative example B Comparative Example B is a borated glycerol monooleate friction modifier.

[0126] Baseline 1 Heavy duty lubricating oil compositions were prepared containing a major amount of a base oil of lubricating viscosity and the following additives to provide a finished oil having an HTHS viscosity of 3.3 cP (5W-30) at 150°C: (1) Ethylene carbonate post-treated bissuccinimide; (2) boronated bissuccinimide dispersants; (3) succinate dispersants; (4) a mixture of overbased calcium salicylate and sulfonate detergents having a calcium content of 2870 ppm; (5) secondary zinc dialkyldithiophosphate having a phosphorus content of 400 ppm; (6) 220 ppm molybdenum sulfide succinimide complex; (7) alkylated diphenylamine and hindered phenol antioxidants; (8) Dispersed hydrated potassium borate (9) antifoaming agents; (10) Non-dispersive OCP VII; and (11) Remaining Group III base oils.

[0127] Example 1 To formulation Baseline 1, 0.6 wt. % of the friction modifier of Example A was added.

[0128] Comparative Example 1 To formulation Baseline 1, 0.6 wt. % of the friction modifier of Comparative Example A was added.

[0129] Example 2 To formulation Baseline 1, 0.3 wt. % of the friction modifier of Example A was added.

[0130] Baseline 2 Heavy duty lubricating oil compositions were prepared containing a major amount of a base oil of lubricating viscosity and the following additives to provide a finished oil having an HTHS viscosity of 3.2 cP (5W-30) at 150°C: (1) Ethylene carbonate post-treated bissuccinimide; (2) boronated bissuccinimide dispersants; (3) a mixture of overbased calcium salicylate, phenate, and sulfonate detergents having a calcium content of 2730 ppm; (4) primary zinc dialkyldithiophosphate having a phosphorus content of 400 ppm; (5) 160 ppm molybdenum sulfide succinimide complex; (6) alkylated diphenylamine antioxidants; (7) dispersed hydrated potassium borate; (8) antifoaming agents; (9) Non-dispersive OCP VII; and (10) Remaining Group III base oils.

[0131] Example 3 To formulation Baseline 2, 0.6 wt. % of the friction modifier of Example A was added.

[0132] Example 4 To formulation Baseline 1, 0.6 wt. % of the friction modifier of Example A was added.

[0133] Example 5 To formulation Baseline 1, 0.6 wt. % of the friction modifier of Example A was added.

[0134] Example 6 To formulation Baseline 2, 0.6 wt. % of the friction modifier of Example A was added.

[0135] JASO DH-2F fuel economy test The JASO DH-2F fuel economy test is conducted according to the procedures disclosed in JASO M362 and summarized in Hashimoto, K., Tomizawa, K., Nakamura, Y., Hashimoto, T. et al., "The Development of Fuel Economy Test Method for Heavy-Duty Diesel Engine Oil (The First HD Engine Test Method and the New JASO DH-2F Category)," SAE Int. J. Fuels Lubr. 10(2):2017.

[0136] The standard in the (JASO M 355:2017) application manual for the average new oil ([new oil 60°C + new oil 90°C] / 2) was set to exceed 3.7% for fuel economy diesel engine oil, and the sum of the average new oil and average aged oil was set to exceed 6.8% fuel economy improvement. [Table 2] [Table 3]

[0137] Baseline 3 Passenger car lubricating oil compositions were prepared containing a major amount of a base oil of lubricating viscosity and the following additives to provide a finished oil having an SAE viscosity of 0W-8: (1) Ethylene carbonate post-treated bissuccinimide; (2) boronated bissuccinimide dispersants; (3) a mixture of calcium salicylate and magnesium sulfonate detergents providing 1410 ppm Ca and 470 ppm Mg to the formulation; (4) primary zinc dialkyldithiophosphate having a phosphorus content of 770 ppm; (5) 800 ppm MoDTC; (6) alkylated diphenylamine and hindered phenol antioxidants; (7) antifoaming agents; (8) low SSI PMA VII; and (9) Remaining Group III base oils.

[0138] Example 7 To formulation Baseline 3, 0.20 wt. % of the friction modifier of Example A was added.

[0139] Baseline 4 Passenger car lubricating oil compositions were prepared containing a major amount of a base oil of lubricating viscosity and the following additives to provide a finished oil having an SAE viscosity of 0W-8: (1) Ethylene carbonate post-treated bissuccinimide; (2) boronated bissuccinimide dispersants; (3) a mixture of calcium salicylate and magnesium sulfonate detergents providing 1410 ppm Ca and 470 ppm Mg to the formulation; (4) secondary zinc dialkyldithiophosphate having a phosphorus content of 770 ppm; (5) 800 ppm MoDTC; (6) alkylated diphenylamine and hindered phenol antioxidants; (7) antifoaming agents; (8) low SSI PMA VII; and (9) Remaining Group III base oils.

[0140] Example 8 To formulation Baseline 4, 0.20 wt. % of the friction modifier of Example A was added.

[0141] Example 9 To formulation Baseline 4, 0.10 wt. % of the friction modifier of Example A was added.

[0142] Example 10 To formulation Baseline 4, 0.50 wt. % of the friction modifier of Example A was added.

[0143] Example 11 To formulation Baseline 4, 0.10 wt. % of the friction modifier of Example A was added, and instead of the 800 ppm molybdenum from MoDTC, 800 ppm molybdenum from a molybdenum sulfide succinimide complex was added.

[0144] Example 12 To formulation Baseline 4, 0.20 wt. % of the friction modifier of Example A was added, and instead of the 800 ppm molybdenum from MoDTC, 800 ppm molybdenum from a molybdenum sulfide succinimide complex was added.

[0145] Example 13 To formulation Baseline 4, 0.50 wt. % of the friction modifier of Example A was added, and instead of the 800 ppm molybdenum from MoDTC, 800 ppm molybdenum from a molybdenum sulfide succinimide complex was added.

[0146] Example 14 To formulation Baseline 4, 0.10 wt. % of the friction modifier of Example A was added, and the 800 ppm molybdenum from MoDTC was replaced with 400 ppm molybdenum from a molybdenum sulfide succinimide complex and 400 ppm molybdenum from MoDTC.

[0147] Example 15 To formulation Baseline 4, 0.20 wt. % of the friction modifier of Example A was added, and the 800 ppm molybdenum from MoDTC was replaced with 400 ppm molybdenum from a molybdenum sulfide succinimide complex and 400 ppm molybdenum from MoDTC.

[0148] Example 16 To formulation baseline 4, 0.50 wt. % of the friction modifier of Example A was added, and the 800 ppm molybdenum from MoDTC was replaced with 400 ppm molybdenum from a molybdenum sulfide succinimide complex and 400 ppm molybdenum from MoDTC.

[0149] Example 17 To formulation Baseline 4, 0.05 wt. % of the friction modifier of Example A was added.

[0150] Example 18 To formulation Baseline 4, 0.01 wt. % of the friction modifier of Example A was added.

[0151] High Frequency Reciprocating Rig (HFRR) The HFRR test rig is an industry-recognized tribometer for measuring lubricant performance. The PCS device uses an electromagnetic vibrator to vibrate a sample (a ball) at a small amplitude while pressing it against a fixed sample (a flat disk). The amplitude and frequency of the vibration, as well as the load, are variable. The friction force between the ball and the flat, and the electrical contact resistance (ECR) are measured. The flat, fixed sample is held in a bath to which the lubricant is added and can be heated. For this test, the tribometer was set to operate at 20 Hz using a 6 mm ball on a flat sample of 52100 steel. The load was 400 g and the temperature was 70°C. In this test, a lower friction coefficient corresponds to a more effective friction modifier additive. HFRR friction performance data are shown in Table 4. [Table 4]

[0152] Therefore, it is clear that Examples 7-18 provide significantly improved friction performance.

[0153] Baseline 5 Passenger car lubricating oil compositions were prepared containing a major amount of a base oil of lubricating viscosity and the following additives to provide a finished oil having an SAE viscosity of 5W-20, no ZnDTP, and 0.15 wt. % sulfated ash: (1) Ethylene carbonate post-treated bissuccinimide; (2) boronated bissuccinimide dispersants; (3) 400 ppm calcium from an overbased calcium phenate detergent; (5) 180 ppm Mo from molybdenum sulfide succinimide complex; (6) alkylated diphenylamine antioxidants; (7) antifoaming agents; (8) OCP VII; and (9) Remaining Group II base oils.

[0154] Example 19 To formulation Baseline 5, 0.5 wt. % of the friction modifier of Example A was added.

[0155] Comparative Example 2 To formulation Baseline 5, 0.3 wt. % of the friction modifier of Comparative Example B was added.

[0156] Baseline 6 A passenger car lubricating oil composition was prepared containing a major amount of a base oil of lubricating viscosity and the following additives to provide a finished oil having an SAE viscosity of 5W-20 and 0.40 wt. % sulfated ash: (1) Ethylene carbonate post-treated bissuccinimide; (2) boronated bissuccinimide dispersants; (3) 400 ppm calcium from an overbased calcium phenate detergent; (4) 770 ppm phosphorus in secondary ZnDTP; (5) 180 ppm Mo from molybdenum sulfide succinimide complex; (6) alkylated diphenylamine antioxidants; (7) antifoaming agents; (8) OCP VII; and (9) Remaining Group II base oils.

[0157] Example 20 To formulation Baseline 6, 0.5 wt. % of the friction modifier of Example A was added.

[0158] Comparative Example 2 To formulation Baseline 6, 0.3 wt. % of the friction modifier of Comparative Example B was added.

[0159] Baseline 7 A passenger car lubricating oil composition was prepared containing a major amount of a base oil of lubricating viscosity and the following additives to provide a finished oil having an SAE viscosity of 5W-20 and 1.0 wt. % sulfated ash: (1) Ethylene carbonate post-treated bissuccinimide; (2) boronated bissuccinimide dispersants; (3) 2190 ppm calcium from overbased calcium phenate and calcium salicylate detergents; (4) 770 ppm phosphorus in secondary ZnDTP; (5) 180 ppm Mo from molybdenum sulfide succinimide complex; (6) alkylated diphenylamine antioxidants; (7) antifoaming agents; (8) OCP VII; and (9) Remaining Group II base oils.

[0160] Example 18 To formulation Baseline 7, 0.5 wt. % of the friction modifier of Example A was added.

[0161] Comparative Example 3 To formulation Baseline 7, 0.3 wt. % of the friction modifier of Comparative Example B was added.

[0162] Mini Traction Machine (MTM) The above compositions were tested for friction performance in an MTM bench test. The MTM was manufactured by PCS Instruments and operates with a ball (0.75-inch diameter 8620 steel ball) loaded against a rotating disk (52100 steel). Conditions used are a load of approximately 10-30 Newtons, a speed of approximately 10-2000 mm / s, and a temperature of approximately 125-150°C. In this bench test, friction performance is measured as the total area under the second Stribeck curve generated. The smaller the total area, the better the friction performance. The results are shown in Table 5. [Table 5] The data in Table 5 clearly demonstrate that examples of the present disclosure reduce friction and therefore improve fuel economy in internal combustion engines.

Claims

1. A passenger vehicle internal combustion engine lubricating oil composition comprising: (a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity (Kv) of about 2.0 to about 12 centistokes (cSt) at 100°C; (b) a nitrogen-containing dispersant; and (c) an alkaline earth metal-containing detergent provided in an amount of from about 0.03 to about 0.7 wt. % based on the metal content of the lubricating oil composition; (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof; (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups (d) from about 0.01 wt % to about 2.0 wt % of a compound comprising the reaction product.

2. 2. The lubricating oil composition of claim 1, wherein the nitrogen-containing reactant is an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof, including a bis-ethoxy alkylamine or a bis-ethoxy alkylamide.

3. 3. The lubricating oil composition of claim 2, wherein the alkyl group in the bisethoxyalkylamine comprises oleyl, dodecyl, or 2-ethylhexyl.

4. 3. The lubricating oil composition of claim 2, wherein the alkyl group in the bisethoxyalkylamide is derived from coconut oil.

5. 2. The lubricating oil composition of claim 1, wherein the boron source is boric acid.

6. 2. The lubricating oil composition of claim 1, wherein the hydrocarbyl polyol comprises glycerol or pentaerythritol.

7. 2. The lubricating oil composition of claim 1, wherein the lubricating oil composition has a HTHS viscosity in the range of about 1.3 to about 3.5 cP at 150°C.

8. 2. The lubricating oil composition of claim 1, wherein the alkaline earth metal detergent is selected from the group consisting of calcium or magnesium-containing salicylates, carboxylates, phenates, sulfonates, or combinations thereof.

9. 10. The lubricating oil composition of claim 1, wherein the lubricating oil composition further comprises an organomolybdenum compound.

10. 10. The lubricating oil composition of claim 1, further comprising a ZnDTP compound.

11. 10. The lubricating oil composition of claim 1, wherein the lubricating oil composition has a phosphorus content of less than 0.08 wt. %.

12. 10. The lubricating oil composition of claim 1, wherein the lubricating oil composition has a sulfated ash level of less than 1.6 wt%, less than 1.3 wt%, less than 1.0 wt%, less than 0.8 wt%, less than 0.6 wt%, or less than 0.3 wt%.

13. 1. A method for improving new and used oil fuel economy in a passenger vehicle internal combustion engine comprising lubricating said engine with a lubricating oil composition comprising: (a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity (Kv) of about 2.0 to about 12 centistokes (cSt) at 100°C; (b) a nitrogen-containing dispersant; and (c) an alkaline earth metal-containing detergent provided in an amount of from about 0.03 to about 0.7 wt. % based on the metal content of the lubricating oil composition; (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof; (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups (d) about 0.01% to about 2.0% by weight of a compound comprising the reaction product.

14. 14. The method of claim 13, wherein the internal combustion engine is selected from a direct fuel injection spark ignition engine and a port fuel injection spark ignition engine coupled to an electric motor / battery system of a hybrid vehicle.

15. 14. The method of claim 13, wherein the engine is equipped with a gasoline particulate filter.

16. 1. A heavy-duty diesel internal combustion engine lubricating oil additive composition comprising: (a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity (Kv) of about 2.0 to about 12 centistokes (cSt) at 100°C; (b) a nitrogen-containing dispersant; and (c) an alkaline earth metal-containing detergent provided in an amount of from about 0.03 to about 0.7 wt. % based on the metal content of the lubricating oil composition; (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof; (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups (d) 0.30 wt % to about 2.0 wt % of a compound comprising the reaction product.

17. 17. The lubricating oil composition of claim 16, wherein the nitrogen-containing reactant is an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine or mixtures thereof, including a bis-ethoxy alkylamine or a bis-ethoxy alkylamide.

18. 18. The lubricating oil composition of claim 17, wherein the alkyl group in the bisethoxyalkylamine comprises oleyl, dodecyl, or 2-ethylhexyl.

19. 18. The lubricating oil composition of claim 17, wherein the alkyl group in the bisethoxyalkylamide is derived from coconut oil.

20. 17. The lubricating oil composition of claim 16, wherein the boron source is boric acid.

21. 17. The lubricating oil composition of claim 16, wherein the hydrocarbyl polyol comprises glycerol or pentaerythritol.

22. 17. The lubricating oil composition of claim 16, wherein the lubricating oil composition has a HTHS viscosity in the range of about 2.5 to about 3.5 cP at 150°C.

23. 17. The lubricating oil composition of claim 16, wherein the alkaline earth metal detergent is selected from the group consisting of calcium or magnesium containing salicylates, carboxylates, phenates, sulfonates, or combinations thereof.

24. 17. The lubricating oil composition of claim 16, wherein the lubricating oil composition further comprises an organomolybdenum compound.

25. 17. The lubricating oil composition of claim 16, further comprising a ZnDTP compound.

26. 17. The lubricating oil composition of claim 16, wherein the lubricating oil composition has a phosphorus content of less than 0.08 wt. %.

27. 17. The lubricating oil composition of claim 16, wherein the lubricating oil composition is substantially free of phosphorus-containing additives.

28. 17. The lubricating oil composition of claim 16, wherein the lubricating oil composition is substantially free of zinc-containing additives.

29. 17. The lubricating oil composition of claim 16, wherein the lubricating oil composition has a sulfated ash level of less than 1.6 wt%, less than 1.3 wt%, less than 1.0 wt%, less than 0.8 wt%, less than 0.6 wt%, or less than 0.3 wt%.

30. 1. A method for improving new and used oil fuel economy in a heavy duty diesel internal combustion engine comprising lubricating said engine with a lubricating oil additive composition comprising: (a) a major amount of a base oil of lubricating viscosity having a kinematic viscosity (Kv) of about 2.0 to about 12 centistokes (cSt) at 100°C; (b) a nitrogen-containing dispersant; and (c) an alkaline earth metal-containing detergent provided in an amount of from about 0.03 to about 0.7 wt. % based on the metal content of the lubricating oil composition; (i) a nitrogen-containing reactant comprising an alkyl alkanolamide, an alkyl alkoxylated alkanolamide, an alkyl alkanolamine, an alkyl alkoxylated alkanolamine, or mixtures thereof; (ii) a boron source, and (iii) a hydrocarbyl polyol having at least three hydroxyl groups (d) 0.30% to about 2.0% by weight of a compound comprising the reaction product.

31. 31. The method of claim 30, wherein the engine is equipped with a diesel particulate filter.

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