Diesel engine lubricating composition and method of use

Abstract

The present disclosure provides a diesel engine lubricating composition and a method of lubricating a diesel engine by supplying the engine with the lubricating composition disclosed herein. The lubricating composition disclosed herein comprises 0.3 to 1.1 wt. % total sulfated ash, a kinematic viscosity at 100°C of less than 8.3 cSt, 0.6 to 2.1 wt. % total alkaline earth metal soaps, and an HTHS of less than 2.7 mPa·s as measured in accordance with ASTM D4683. The lubricating composition can be used to improve one or more of fuel economy and wear protection in diesel engines, particularly heavy-duty diesel engines.

Description

[Technical Field]

[0001] The present disclosure provides diesel engine lubricating compositions and methods of lubricating a diesel engine by supplying the engine with the lubricating compositions disclosed herein. The lubricating compositions disclosed herein may be used in diesel engines, including particularly heavy-duty diesel engines, to improve one or more of fuel economy and wear protection. [Background technology]

[0002] Lubricating oil compositions are used for the smooth operation of internal combustion engines. Engine oils for internal combustion engines serve, among other things, to (i) lubricate the various sliding interfaces between piston rings and cylinder liners, crankshaft and connecting rod bearings, and valve drive mechanisms including cams and valve lifters, (ii) cool the engine, (iii) clean and disperse combustion products, and (iv) prevent corrosion and the resulting rust formation. The stringent requirements for modern high-performance engines mean greater demands on the lubricants used in such engines.

[0003] There has been growing interest in improving the fuel efficiency of internal combustion engines. Vehicle manufacturers have improved fuel economy through improvements in engine design and by taking advantage of advances in lubricants that offer better oxidation stability, wear protection, and reduced friction. Operators of heavy-duty diesel vehicles have been hesitant to adopt lower viscosity grades of engine oil to improve fuel economy. Durability, i.e., the ability to maintain a vehicle on the road for extended periods and mileage, has been and remains a primary concern. Therefore, the most widely used viscosity grades for on-highway heavy-duty diesel vehicles have been SAE 15W-40, 10W-30, and 5W-30. In recent years, there has been a strong demand for improving the fuel economy of heavy-duty diesel vehicles. Therefore, there is a need to improve diesel engine fuel economy without compromising engine durability or adversely affecting lubricant performance, including deposit and soot control and oxidation and corrosion resistance. This is particularly relevant for viscosity grades lighter than the SAE 5W-30 viscosity grade, particularly the 0W-20, 0W-16, and 0W-12 viscosity grades.

[0004] Therefore, there is an interest in developing lubricating compositions that can be used in diesel engines that can operate under severe conditions and loads while reducing soot and soot-related wear effects, as well as cleanliness, deposits, and better fuel economy. Summary of the Invention [Means for solving the problem]

[0005] The present disclosure relates to diesel engine lubricating compositions for internal combustion engines (typically compression ignition engines) having at least one of reduced soot, improved fuel economy, reduced deposit formation, reduced wear, and improved cleanliness.

[0006] The lubricating composition includes an oil of lubricating viscosity having greater than 50 weight percent (sometimes referred to as "wt. %) of a Group III base oil, a Group IV base oil, a Group V base oil, or a mixture thereof. The composition further includes a first PIB succinimide dispersant derived from a PIB having an Mn of 1800 to 2500 and a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600, with the proviso that at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is boron-free. The composition further includes an alkaline earth metal salicylate detergent, such as calcium salicylate, an alkaline earth metal sulfonate, the alkaline earth metal sulfonate being present to provide the composition with 0.1 wt. % to 1.2 wt. % alkaline earth metal soap, and a phosphorus antiwear agent present in an amount to provide the lubricating composition with 300 to 900 ppm phosphorus.

[0007] The lubricating composition may have a sulfated ash content of 0.3 to 1.1 wt. %, a kinematic viscosity at 100°C of less than 8.3 cSt, 0.6 wt. % to 2.1 wt. % total alkaline earth metal soaps, and an HTHS of less than 2.7 mPa·s measured in accordance with ASTM D4683. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure provides a diesel engine lubricating composition and a method for using the same. The lubricating composition includes an oil of lubricating viscosity having greater than 50 weight percent of a Group III base oil, a Group IV base oil, a Group V base oil, or a mixture thereof; a first PIB succinimide dispersant derived from a PIB having an Mn of 1800 to 2500; and a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600, wherein at least one of the first and second PIB succinimide dispersants is boron-free. The composition also includes an alkaline earth metal salicylate detergent, an alkaline earth metal sulfonate detergent present in an amount to provide the lubricating composition with 0.1 to 1.2 weight percent alkaline earth metal soap, and a phosphorus antiwear agent present in an amount to provide the lubricating composition with 300 to 900 ppm phosphorus. The lubricating compositions disclosed herein further comprise a total sulfated ash content of 0.3 to 0.9 wt. % or 0.3 to 1.1 wt. %, a total alkaline earth metal soap content of 0.6 to 2.1 wt. %, and an HTHS of less than 2.7 mPa·s as measured in accordance with ASTM D4683. Oil of lubricating viscosity

[0009] The lubricating compositions disclosed herein contain an oil of lubricating viscosity. Such oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined oils, refined oils, rerefined oils, or mixtures thereof. A more detailed description of unrefined, refined, and rerefined oils is provided in paragraphs

[0054] to

[0056] of WO 2008 / 147704 (a similar disclosure is provided in U.S. Patent Application No. 2010 / 197536, see paragraphs

[0072] to

[0073] ). A more detailed description of natural and synthetic lubricating oils is provided in paragraphs

[0058] to

[0059] of WO 2008 / 147704 (a similar disclosure is provided in U.S. Patent Application No. 2010 / 197536, see paragraphs

[0075] to

[0076] ). Synthetic oils may also be produced by the Fischer-Tropsch reaction and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils may be prepared by Fischer-Tropsch gas-to-liquid synthesis procedures as well as other gas-to-liquid oils.

[0010] Oils of lubricating viscosity may also be defined as set forth in Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, April 2008 Edition, Section 1.3, Subheading 1.3, "Base Stock Categories." The API guidelines are also summarized in U.S. Patent No. 7,285,516 (see column 11, line 64 to column 12, line 10).

[0011] Group IV base oils (also known as polyalphaolefins, or PAOs) are known in the art and are prepared by the oligomerization or polymerization of linear alphaolefins. PAOs are characteristically water-white oils with excellent low temperature viscometric properties (as measured) as well as high viscosity indices. Typical PAOs suitable for use in internal combustion engines include those with a viscosity of 3 to 10 m / s. 2Polyalphaolefins such as PAO-4 and PAO-6 having a kinematic viscosity of about 4 m / s, respectively. 2 / sec and 6m 2 / seconds.

[0012] In addition to the traditional Group III and Group IV base oils, low levels of some Group V base oils, particularly Group V ester base oils, may be present. Ester-based fluids include esters of monocarboxylic acids and monohydric alcohols; di-esters of diols and monocarboxylic acids and di-esters of dicarboxylic acids and monohydric alcohols; polyol esters of monocarboxylic acids and polyesters of monohydric alcohols and polycarboxylic acids; and mixtures thereof. Esters can be broadly classified into two categories: synthetic and natural.

[0013] Synthetic esters may include esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, and alkenyl malonic acid) with any of a variety of monohydric alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and 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, diecocyl 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. Other synthetic esters include those made from C5-C12 monocarboxylic acids and polyols and polyol ethers, such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Esters can also be monoesters of monocarboxylic acids and monohydric alcohols.

[0014] Natural (or bio-derived) esters refer to materials derived from renewable biological resources, organisms, or entities, as opposed to materials derived from petroleum or equivalent sources. Natural esters include fatty acid triglycerides, hydrolyzed or partially hydrolyzed triglycerides, or transesterified triglyceride esters, such as fatty acid methyl esters (FAMEs). Suitable triglycerides include, but are not limited to, palm oil, soybean oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and related materials. Other triglyceride sources include, but are not limited to, algae, tallow, and zooplankton. Methods for producing biolubricants from natural triglycerides are described, for example, in U.S. Patent Application Publication No. 2011 / 0009300(A1).

[0015] In one embodiment, the lubricant composition of this disclosure contains 0.1 to 10 weight percent ester-based fluid, or 0.25 to 5 weight percent, or 0.1 to 2 weight percent ester-based fluid. In one embodiment, the lubricant composition contains 5 weight percent or less ester-based fluid, 2.5 weight percent or less, or 1 weight percent or less ester-based fluid. In one embodiment, the lubricant composition is free or substantially free of intentionally added ester-based fluid, i.e., contains less than 0.2 weight percent ester-based fluid.

[0016] In one embodiment, the oil of lubricating viscosity may be a base oil comprising an API Group I-IV oil, an ester, or a synthetic oil, or a mixture thereof. In one embodiment, the oil of lubricating viscosity may be an API Group II, Group III, or Group IV oil, an ester, or a synthetic oil, or a mixture thereof. In some embodiments, the oil of lubricating viscosity comprises at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 95 wt%, or at least 100 wt% Group III or Group IV base oil, or a mixture of Group III and Group IV base oils.

[0017] The amount of oil of lubricating viscosity present is typically the remainder remaining after subtracting from 100% by weight the sum of the amounts of additives and other performance additives in the disclosed composition.

[0018] The lubricating compositions may be in the form of concentrates and / or fully formulated lubricants. When the lubricating compositions described herein (including the additives disclosed herein) are in the form of concentrates that can be combined with additional oils to form, in whole or in part, a finished lubricant, the ratio of these additives to oil of lubricating viscosity and / or diluent oil ranges from 1:99 to 99:1 by weight, or from 80:20 to 10:90 by weight. Typically, the lubricating compositions described herein contain at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight of oil of lubricating viscosity.

[0019] In some embodiments, the oil of lubricating viscosity is 2.4 ml 2 / sec~6.4m 2 In some embodiments, the kinematic viscosity may be 3.8 m / s. 2 / sec~5.0m 2 / sec, or 5.2m 2 / sec ~5.8m 2 / sec, or 6.0 m 2 / sec~6.5m 2 In another embodiment, the kinematic viscosity of the base oil is 4.5 m / s. 2 / sec or 4.3m 2 / sec or 4.2m 2 / second. Polyisobutenyl (PIB) succinimide dispersant

[0020] The lubricating compositions of the present disclosure further comprise a first polyisobutenyl succinimide dispersant and a second polyisobutenyl succinimide dispersant. References herein to a polyisobutylene succinimide dispersant refer to both the first polyisobutenyl succinimide dispersant as well as the second polyisobutenyl succinimide dispersant. The difference is that the first polyisobutenyl succinimide dispersant is derived from a polyisobutenyl moiety having a higher number average molecular weight (Mn) than the PIB of the second polyisobutenyl succinimide dispersant.

[0021] The first polyisobutenyl succinimide and / or second polyisobutenyl succinimide dispersants can each be prepared (or, as used herein, "derived") from a polyisobutylene ("PIB") succinimide dispersant, which is either a "conventional" PIB or a high vinylidene PIB. The difference between conventional polyolefins and high vinylidene polyolefins can be explained by reference to the production of PIB. In a conventional PIB production method, isobutylene is polymerized in the presence of AlCl to produce a mixture of polymers containing primarily tri-substituted olefin (III) and tetra-substituted olefin (IV) end groups, with only a very small amount (e.g., less than 20 percent) of chains containing terminal vinylidene groups (I). In another method, isobutylene is polymerized in the presence of a BF catalyst to produce a mixture of polymers containing primarily (e.g., at least 70 percent) terminal vinylidene groups, with smaller amounts of tetra-substituted end groups and other structures. Materials made by alternative methods, sometimes referred to as "high vinylidene PIB," are also described in U.S. Patent No. 6,165,235, which is incorporated herein by reference in its entirety. In one embodiment, the polyisobutylene-derived dispersant is a conventional polyisobutylene-derived dispersant. In another embodiment, the polyisobutylene-derived dispersant is a high vinylidene succinimide dispersant or a medium vinylidene succinimide dispersant. Polyisobutylene-derived dispersants as used herein are generally known in the art.

[0022] Polyisobutylene-derived acylating agents may be prepared / obtained / obtainable from reaction with maleic anhydride via an "ene" or "thermal" reaction (also known as direct alkylation). The "ene" reaction mechanism and general reaction conditions are summarized in "Maleic Anhydride," pp. 147-149, edited by B.C. Trivedi and B.C. Culbertson, published by Plenum Press (1982). Polyisobutylene-derived dispersants prepared by a process involving an "ene" reaction include dispersants having carbocyclic rings present in less than 50 mole percent, or 0-30 mole percent, or 0-20 mole percent, or 0 mole percent of the dispersant molecules. The "ene" reaction may have a reaction temperature of 180°C to less than 300°C, or 200°C to 250°C, or 200°C to 220°C.

[0023] Polyisobutylene-derived acylating agents may also be obtained / obtainable from chlorine-assisted processes (often involving Diels-Alder chemistry, leading to the formation of carbocyclic bonds). Processes are known to those skilled in the art. Chlorine-assisted processes may produce acylating agents with carbocyclic rings present in 50 mole % or more, or 60-100 mole % of the molecules. Both thermal and chlorine-assisted processes are described in more detail in U.S. Pat. No. 7,615,521, columns 4-5, and Preparative Examples A and B.

[0024] The polyisobutylene-derived acylating agent may further be prepared / obtained / obtainable from a free radical process in which the acylating agent reacts with polyisobutylene in the presence of a free radical initiator. This type of free radical process is well known in the art and may be carried out in the presence of an additional alpha-olefin.

[0025] Polyisobutylene-derived acylating agents can be obtained by reacting polyisobutylene with an acylating agent (i.e., an ethylenically unsaturated carbonyl compound) to form an acylated polyisobutylene, which can then be further functionalized with an amine or alcohol to form a suitable dispersant. Suitable acylating agents include maleic anhydride or its reactive equivalents (e.g., acid or ester) (i.e., succinic acid) and their reactive equivalents. In one embodiment, polyisobutylene can be reacted with maleic anhydride to form an acylated product at a conversion of 1 to 2. In one embodiment, monosuccinic acid is reacted with an amine such that the target product comprises a mixture in which all of the anhydrides present in the acylating agent are converted to imides.

[0026] The polyisobutylene derived dispersant may have a carbonyl to nitrogen ratio (CO:N ratio) of from 5:1 to 1:10, from 2:1 to 1:10, or from 2:1 to 1:5, or from 2:1 to 1:2. In one embodiment, the dispersant may have a CO:N ratio of from 2:1 to 1:10, or from 2:1 to 1:5, or from 2:1 to 1:2, or from 1:1.4 to 1:0.6.

[0027] The polyisobutylene succinimide dispersants of the present disclosure can be prepared by reacting an acylated PIB with a suitable amine compound, including one or more hydrocarbyl amines, amino alcohols, polyether amines, or combinations thereof.

[0028] In one embodiment, the hydrocarbyl amine component may include at least one aliphatic amine containing at least one amino group capable of condensing with the acyl group to provide a pendant group and at least one additional group containing at least one nitrogen, oxygen, or sulfur atom. Suitable aliphatic amines include polyethylene polyamines (e.g., tetraethylene pentamine (TEPA), triethylene tetraamine (TETA), pentaethylene hexamine (PEHA), and polyamine bottoms), N,N-dimethylaminopropylamine (DMAPA), N-(aminopropyl)morpholine, N,N-diisostearylaminopropylamine, ethanolamine, and combinations thereof.

[0029] In one embodiment, the hydrocarbyl amine component may comprise at least one aromatic amine comprising at least one amino group capable of condensing with the acyl group to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom, the aromatic amine being selected from the group consisting of: (i) nitro-substituted anilines; (ii) amines comprising two aromatic moieties linked by a -C(O)NR-, -C(O)O-, -O-, N=N-, or -SO2- group, where R is hydrogen or hydrocarbyl and one of the aromatic moieties bears the condensable amino group; (iii) aminoquinolines; (iv) aminobenzimidazoles; (v) N,N-dialkylphenylenediamines; (vi) aminodiphenylamines (also N,N-phenyldiamines); and (vii) ring-substituted benzylamines.

[0030] In one embodiment, the polyetheramine compound may comprise an amine-terminated polyether compound. The amine-terminated polyether compound may comprise units derived from ethylene oxide, propylene oxide, propylene oxide, or some combination thereof. Suitable polyether compounds include the Jeffamine® series of polyetheramines available from Huntsman.

[0031] In one embodiment, a first polyisobutylene succinimide dispersant may be prepared by the thermal direct alkylation process described herein. In another embodiment, a second polyisobutylene succinimide dispersant may be prepared by the thermal direct alkylation process described herein.

[0032] The polyisobutylene-derived dispersants described herein can be further described as having a TBN. In one embodiment, the first polyisobutylene succinimide dispersant has a TBN of 15-25. In another embodiment, the first polyisobutylene succinimide dispersant has a TBN of 15-20. In one embodiment, the second polyisobutylene succinimide dispersant has a TBN of 20-35. In another embodiment, the second polyisobutylene succinimide dispersant has a TBN of 25-30. In one embodiment, the second polyisobutylene succinimide dispersant has a TBN of 27-28.

[0033] In one embodiment, the first polyisobutylene succinimide dispersant is derived from a PIB having a number average molecular weight in the range of 1720 to 2200. In another embodiment, the first polyisobutylene succinimide dispersant is derived from a PIB having a number average molecular weight in the range of 1800 to 2100. In one embodiment, the first polyisobutylene succinimide dispersant is derived from a PIB having a number average molecular weight in the range of 1850 to 2150.

[0034] In one embodiment, the second polyisobutylene succinimide dispersant is derived from a PIB having a number average molecular weight in the range of 750 to 1600. In another embodiment, the second polyisobutylene succinimide dispersant is derived from a PIB having a number average molecular weight in the range of 1000 to 1600. In one embodiment, the second polyisobutylene succinimide dispersant is derived from a PIB having a number average molecular weight in the range of 1200 to 1600. In one embodiment, the second polyisobutylene succinimide dispersant is derived from a PIB having a number average molecular weight in the range of 800 to 1150. In another embodiment, the second polyisobutylene succinimide dispersant is derived from a PIB having a number average molecular weight in the range of 900 to 1100.

[0035] In one embodiment, the first polyisobutylene succinimide dispersant may be present in the lubricating composition in an amount of from 0.5 wt% to 10 wt%. In another embodiment, the first polyisobutylene succinimide dispersant may be present in the lubricating composition in an amount of from 0.8 wt% to 6 wt%. In one embodiment, the first polyisobutylene succinimide dispersant may be present in the lubricating composition in an amount of from 1 wt% to 5 wt%. In one embodiment, the first polyisobutylene succinimide dispersant may be present in the lubricating composition in an amount of from 1.1 wt% to 2.2 wt%.

[0036] In one embodiment, the second polyisobutylene succinimide dispersant is present in the lubricating composition in an amount from 1 wt% to 5 wt%. In another embodiment, the second polyisobutylene succinimide dispersant is present in the lubricating composition in an amount from 1.5 wt% to 4.8 wt%. In another embodiment, the second polyisobutylene succinimide dispersant is present in the lubricating composition in an amount from 1.8 wt% to 4.6 wt%. In another embodiment, the second polyisobutylene succinimide dispersant is present in the lubricating composition in an amount from 1.9 wt% to 3.3 wt%.

[0037] In one embodiment, the first polyisobutylene succinimide dispersant may comprise a mixture of two or more dispersants, each of which falls within the ranges including, but not limited to, the PIB Mn, TBN, and treat rate of the first polyisobutylene succinimide dispersant as disclosed herein. In another embodiment, the first polyisobutylene succinimide dispersant may comprise a mixture of two dispersants, each of which falls within the ranges including, but not limited to, the PIB Mn, TBN, and treat rate of the first polyisobutylene succinimide dispersant as disclosed herein.

[0038] In some embodiments, the second polyisobutylene succinimide dispersant may comprise a mixture of two or more dispersants, each falling within the ranges including, but not limited to, the PIB Mn, TBN, and treat rate of the second polyisobutylene succinimide dispersant as disclosed herein. In another embodiment, the second polyisobutylene succinimide dispersant comprises 1% to 5% by weight of a PIB succinimide dispersant derived from a PIB having an Mn of 900-1100, and 1% to 5% by weight of a PIB succinimide dispersant derived from a PIB having an Mn of 1200-1600.

[0039] The lubricating compositions of the present disclosure further provide that at least one of the first polyisobutylene succinimide dispersant and the second polyisobutylene succinimide dispersant is boron-free. In one embodiment, the first polyisobutylene succinimide dispersant is boron-free and the second polyisobutylene succinimide dispersant is boronated. In another embodiment, the first polyisobutylene succinimide dispersant is boronated and the second polyisobutylene succinimide dispersant is boron-free.

[0040] In preparing boron-containing polyisobutylene succinimide dispersants, the first polyisobutylene-derived succinimide dispersant or the second polyisobutylene-derived succinimide dispersant described herein may be post-treated by conventional methods, including reaction with a boron compound, to produce the boron-containing polyisobutylene succinimide dispersant. Suitable boron compounds that can be used to borate polyisobutylene-derived dispersants include one or more of the various agents selected from the group consisting of various forms of boric acid (including metaboric acid, HBO, orthoboric acid, HBO, and tetraboric acid, HBO), boron oxide, boron trioxide, and alkyl borates. In one embodiment, the boronating agent is boric acid, which can be used alone or in combination with other boronating agents. Methods for preparing borated dispersants are known in the art. The boronated dispersants can be prepared so that they contain 0.1% to 2.5% by weight boron, or 0.1% to 2.0% by weight boron, or 0.2 to 1.5% by weight boron, or 0.3 to 1.0% by weight boron.

[0041] In some embodiments, either the first boronated polyisobutylene succinimide dispersant or the second boronated polyisobutylene succinimide dispersant is present in an amount to provide at least 25 ppm, or at least 50 ppm, or at least 75 ppm of boron to the lubricating composition. In other embodiments, either the first boronated polyisobutylene succinimide dispersant or the second boronated polyisobutylene succinimide dispersant is present in an amount to provide from 25 ppm to 400 ppm of boron to the lubricating composition. In other embodiments, either the first boronated polyisobutylene succinimide dispersant or the second boronated polyisobutylene succinimide dispersant is present in an amount to provide from 25 ppm to 400 ppm, or from 50 ppm to 200 ppm, or from 75 ppm to 150 ppm, or from 78 ppm to 100 ppm of boron to the lubricating composition. Detergent

[0042] The lubricating compositions of the present disclosure further comprise an alkaline earth metal salicylate detergent and at least one alkaline earth metal sulfonate detergent as described herein. Metal-containing detergents are well known in the art. They generally consist of metal salts of acidic organic substrates, particularly alkali and alkaline earth metals. Metal-containing detergents may be neutral, i.e., stoichiometric salts of metal and substrate, also known as neutral soaps or soaps, or overbased.

[0043] Metal-overbased detergents, also called overbased detergents, metal-containing overbased detergents, or superbased salts, are characterized by a metal content in excess of that required for stoichiometric neutralization of the metal and the particular acidic organic compound (i.e., the substrate with which the metal reacts). Overbased detergents may include one or more of sulfonates, salicylates, non-sulfur-containing phenates, sulfur-containing phenates, and mixtures thereof.

[0044] The amount of excess metal relative to the substrate is usually expressed as a metal ratio. The term "metal ratio" is used in the prior art and herein to define the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in the salt that would be expected to result from the reaction between a hydrocarbyl-substituted organic acid, i.e., a hydrocarbyl-substituted phenol or mixture thereof to be overbased, and a basic metal compound according to the known chemical reactivity and stoichiometry of the two reactants. Thus, in a normal or neutral salt (i.e., a soap), the metal ratio is 1, while in an overbased salt, the metal ratio is greater than 1, particularly greater than 1.3. Overbased metal detergents can have a metal ratio of 5 to 30, or a metal ratio of 7 to 22, or a metal ratio of 11 to 18, or a metal ratio of at least 11.

[0045] Metal-containing detergents may also include "hybrid" detergents formed from mixed surfactant systems containing phenate and / or sulfonate components, such as phenate-salicylate, sulfonate-phenate, sulfonate-salicylate, and sulfonate-phenate-salicylate, as described, for example, in U.S. Patent Nos. 6,429,178, 6,429,179, 6,153,565, and 6,281,179. For example, when a hybrid sulfonate / salicylate detergent is used, the hybrid detergent is considered equivalent to the amounts of separate salicylate and sulfonate detergents incorporating similar amounts of salicylate and sulfonate soaps, respectively. Overbased phenates and salicylates typically have a total base number of 180 to 450 TBN. Overbased sulfonates typically have a total base number of from 250 to 800, or from 300 to 600. Overbased detergents are known in the art.

[0046] Alkylphenols are often used as components in and / or as building blocks of overbased detergents. Alkylphenols can be used to prepare phenate, salicylate, salixarate, or saligenin detergents, or mixtures thereof. Suitable alkylphenols can include para-substituted hydrocarbylphenols. The hydrocarbyl group can be a linear or branched aliphatic group of 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms. In one embodiment, the alkylphenol overbased detergent is prepared from an alkylphenol or mixture thereof that is free or substantially free (i.e., contains less than 0.1 weight percent) of p-dodecylphenol. In one embodiment, the lubricating composition contains less than 0.3 weight percent alkylphenol, less than 0.1 weight percent alkylphenol, or less than 0.05 weight percent alkylphenol. In one embodiment, the alkylphenol detergent is a salicylate. alkaline earth metal salicylates

[0047] Salicylate detergents and overbased salicylate detergents can be prepared in at least two different ways. Carbonylation (also called carboxylation) of p-alkylphenols is described in many references, including U.S. Pat. No. 8,399,388. Carbonylation can be followed by overbasing to form overbased salicylate detergents. Suitable p-alkylphenols include those having linear and / or branched hydrocarbyl groups of 1 to 60 carbon atoms, 4 to 34 carbon atoms, 14 to 24 carbon atoms, and combinations thereof. Salicylate detergents may also be prepared by alkylation of salicylic acid followed by overbasing, as described in U.S. Pat. No. 7,009,072. Salicylate detergents prepared in this manner may be prepared from linear and / or branched alkylating agents (usually 1-olefins) containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms. In one embodiment, the overbased detergent is a salicylate detergent. In one embodiment, the salicylate detergent is free of unreacted p-alkylphenol (i.e., contains less than 0.1 weight percent). In one embodiment, the salicylate detergent is prepared by alkylation of salicylic acid.

[0048] In one embodiment, the alkaline earth metal salicylate detergent has a TBN (KOH / g) of 200 to 575, or 200 to 500. In another embodiment, the alkaline earth metal salicylate detergent has a TBN (KOH / g) of 250 to 350. In one embodiment, the alkaline earth metal salicylate detergent has a metal ratio of 2 to 7, or 2 to 4, or 2.5 to 3.5. In one embodiment, the alkaline earth metal salicylate detergent is present in the lubricating composition in an amount of 0.1 to 5 wt %. In another embodiment, the alkaline earth metal salicylate detergent is present in the lubricating composition in an amount of 0.2 to 3 wt %. In one embodiment, the alkaline earth metal salicylate detergent is present in the lubricating composition in an amount of 0.5 to 3 wt %. In one embodiment, the alkaline earth metal salicylate detergent is present in the lubricating composition in an amount of 0.8 to 2.5 wt %. In one embodiment, the calcium alkaline earth metal detergent is present in the lubricating composition in an amount of from 0.9 to 2.3 wt %.

[0049] In one embodiment, the alkaline earth metal salicylate detergent may be calcium salicylate, magnesium salicylate, or a combination thereof. In one embodiment, the alkaline earth metal salicylate is calcium salicylate. In one embodiment, the alkaline earth metal salicylate is magnesium salicylate. The calcium salicylate may be present in an amount to provide 150 to 1500 ppm of calcium to the lubricant composition, or 250 to 1100 ppm of calcium to the composition. The magnesium salicylate may be present in an amount to provide 100 to 2000 ppm of magnesium to the lubricant composition, or 250 to 1750 ppm of magnesium to the lubricant composition, or 300 to 1550 ppm of magnesium to the lubricant composition. Alkaline Earth Metal Sulfonate Detergents

[0050] The alkaline earth metal sulfonate may be a neutral sulfonate salt (metal ratio less than 1.3), a low overbased detergent (metal ratio between 1.5 and 6), or a high overbased detergent (metal ratio of at least 8), or any combination thereof, such that at least 0.1 weight percent of alkaline earth metal soap is present in the lubricant composition.

[0051] The alkaline earth metal sulfonate detergent may be a linear alkylbenzene sulfonate detergent as described in paragraphs

[0026] to

[0037] of U.S. Patent Application Publication No. 2005 / 065045 (issued as U.S. Patent No. 7,407,919). Linear alkylbenzene sulfonate detergents may be particularly useful for helping improve fuel economy. The linear alkyl group may be attached to the benzene ring at any position along the linear chain of the alkyl group, but is often attached at the 2-, 3-, or 4-position of the linear chain, and in some cases is attached primarily at the 2-position, resulting in a linear alkylbenzene sulfonate detergent.

[0052] In one embodiment, the alkaline earth metal sulfonate detergent of this disclosure is selected from calcium sulfonate detergents and magnesium sulfonate detergents. In another embodiment, the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent. In one embodiment, the calcium sulfonate detergent has a TBN of less than 250 on an oil-free basis. In another embodiment, the calcium sulfonate detergent has a TBN of less than 200, or less than 150, or less than 80. In one embodiment, the calcium sulfonate detergent has a TBN of 50 to 90. In one embodiment, the calcium sulfonate has a TBN of 120 to 250 mg KOH / g and a metal ratio of 1.5 to 5.

[0053] In one embodiment, the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent present in the lubricating composition in an amount from 0.1 wt % to 2.0 wt %. In another embodiment, the calcium sulfonate detergent is present in the lubricating composition in an amount from 0.3 wt % to 1.5 wt %.

[0054] In one embodiment, the alkaline earth metal sulfonate detergent is a magnesium sulfonate detergent. The magnesium sulfonate may have a TBN (mg KOH / g) of 300 to 800 on an oil-free basis. In some embodiments, the magnesium sulfonate may have a TBN (mg KOH / g) of 400 to 750. In other embodiments, the magnesium sulfonate may have a TBN (mg KOH / g) of 250 to 350. In other embodiments, the magnesium sulfonate may have a TBN (mg KOH / g) of 350 to 375. In one embodiment, the magnesium sulfonate may have a metal ratio of 8 to 30, 10 to 25, or 12 to 18.

[0055] In one embodiment, the magnesium sulfonate detergent is present in the lubricating composition in an amount from 0.05 to 0.5 wt %, or from 0.05 to 0.2, hi another embodiment, the magnesium sulfonate detergent is present in the lubricating composition in an amount from 0.06 to 0.1 wt %, or from 0.06 to 0.2 wt %.

[0056] In one embodiment, the alkaline earth metal sulfonate may be a combination of at least one neutral or low overbased alkaline earth metal sulfonate (i.e., metal ratio less than 6) and at least one high overbased alkaline earth metal sulfonate (metal ratio of at least 8).

[0057] The alkaline earth metal detergent used herein may be a sodium, calcium, or magnesium salt of sulfonate, or a mixture thereof. In one embodiment, the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent, a magnesium sulfonate detergent, or a mixture thereof. In one embodiment, one or more of the calcium sulfonate detergent and the magnesium sulfonate detergent are overbased. In one embodiment, the alkaline earth metal detergent is an overbased calcium sulfonate detergent. In another embodiment, the alkaline earth metal detergent is an overbased magnesium sulfonate detergent. In yet another embodiment, the alkaline earth metal detergent is a mixture of an overbased calcium sulfonate detergent and an overbased magnesium sulfonate detergent. In one embodiment, the alkaline earth metal sulfonate detergent is a mixture of 0.6 wt % to 1.5 wt % of a calcium sulfonate detergent having a TBN (mg KOH / g) from 50 to 200 and 0.04 wt % to 0.1 wt % of an overbased magnesium sulfonate detergent having a TBN (mg KOH / g) from 400 to 800.

[0058] The detergents of the disclosed lubricating compositions may include alkaline earth metals provided by the detergent. In one embodiment, the calcium salicylate detergent is present in an amount providing 150 to 1500 ppm, or 250 to 1100 ppm, or 300 to 800 ppm of calcium to the lubricating composition. In embodiments where the alkaline earth metal detergent includes a calcium sulfonate detergent, the calcium sulfonate detergent may be present in an amount providing 100 to 1000 ppm, 150 to 800 ppm, or 250 to 650 ppm of calcium to the lubricating composition. In embodiments where the alkaline earth metal detergent includes a magnesium sulfonate detergent, the magnesium sulfonate detergent may be present in an amount providing 50 to 500 ppm, 100 to 425 ppm, or 150 to 350 ppm of magnesium to the lubricating composition. In some embodiments, the alkaline earth metal detergent comprises a calcium sulfonate detergent, and the total amount of calcium contributed to the lubricating composition from the calcium salicylate detergent and the calcium sulfonate detergent is from 800 to 2500, 900 to 1800, or 950 to 1450 ppm of calcium based on the lubricating composition.

[0059] The metal-containing detergent contributes sulfated ash to the lubricating composition. Sulfated ash content can be determined by ASTM D874. In one embodiment, the alkaline earth metal salicylate detergent and alkaline earth metal detergent contribute to the lubricating composition a total sulfated ash content of 0.25 to 0.95 weight percent. In other embodiments, the alkaline earth salicylate detergent is present in an amount that contributes about 0.05 to 0.5 weight percent, or 0.1 to 0.35 weight percent, of sulfated ash to the lubricating composition. In other embodiments, the alkaline earth metal detergent is present in an amount that contributes 0.05 to 0.75, or 0.1 to 0.6 weight percent, of sulfated ash to the lubricating composition.

[0060] In addition to ash and TBN, the overbased detergent contributes detergent soap (also called neutral detergent salt) to the lubricating composition. The substrate metal salt soap may act as a surfactant in the lubricating composition. In one embodiment, the alkaline earth metal sulfonate detergent is present in an amount that provides the lubricating composition with 0.1 wt. % to 1.5 wt. %, or 0.15 wt. % to 1.2 wt. %, or 0.2 wt. % to 0.9 wt. % of sulfonate soap. In one embodiment, the alkaline earth metal salicylate detergent is present in an amount that provides the lubricating composition with 0.3 wt. % to 1.4 wt. %, or 0.35 wt. % to 1.2 wt. %, or 0.4 wt. % to 1.0 wt. % of salicylate soap. In one embodiment, the alkaline earth metal soap may be calcium, magnesium, or any mixture thereof. In one embodiment, the alkaline earth metal sulfonate soap is present in an amount from 0.2% to 0.8% by weight of the lubricant composition, and the alkaline earth metal salicylate soap is present in an amount from 0.3% to 1.0% by weight of the lubricant composition. The sum of all alkaline earth metal detergent soaps may be present in an amount from 0.6% to 2.1% by weight, or from 0.7% to 1.4% by weight of the lubricant composition. Anti-wear agent

[0061] The lubricating compositions of the present disclosure further comprise one or more phosphorus-containing antiwear agents.

[0062] Phosphorus-containing antiwear agents are well known to those skilled in the art and include metal dialkyl (dithio)phosphates, hydrocarbyl phosphites, hydrocarbyl phosphines, hydrocarbyl phosphonates, alkyl phosphate esters, amine or ammonium (alkyl) phosphates, and combinations thereof.

[0063] In one embodiment, the phosphorus-containing antiwear agent may be a metal dialkyldithiophosphate, which may include zinc dialkyldithiophosphate. Such zinc salts are often referred to as zinc dialkyldithiophosphate (ZDDP) or simply zinc dithiophosphate (ZDP). They are well known and readily available to those skilled in the art of lubricant formulation. Additional zinc dialkyldithiophosphates may be described as primary zinc dialkyldithiophosphates or secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in their preparation. In some embodiments, the composition may include a primary zinc dialkyldithiophosphate. In some embodiments, the composition includes a secondary zinc dialkyldithiophosphate. In some embodiments, the composition includes a mixture of primary and secondary zinc dialkyldithiophosphates. In some embodiments, component (b) is a mixture of a primary zinc dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate, where the ratio (by weight) of the primary zinc dialkyldithiophosphate to the secondary zinc dialkyldithiophosphate is at least 1:1, or even at least 1:1.2, or even at least 1:1.5 or 1:2, or 1:10.

[0064] Examples of suitable metal dialkyldithiophosphates include metal salts of the formula: [ka] In the formula, R 1 and R 2 are independently hydrocarbyl groups containing 3 to 24 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, and M is a metal having a valence n, typically including zinc, copper, iron, cobalt, antimony, manganese, and combinations thereof. 1 and R 2 is a secondary aliphatic hydrocarbyl group containing 3 to 8 carbon atoms and M is zinc.

[0065] In one embodiment, the phosphorus-containing antiwear agent may be a zinc-free phosphorus compound. The zinc-free phosphorus-based antiwear agent may contain sulfur or may be sulfur-free. The sulfur-free phosphorus-containing antiwear agent may include a hydrocarbyl phosphite, a hydrocarbyl phosphine, a hydrocarbyl phosphonate, an alkyl phosphate ester, an amine or ammonium phosphate salt, or a mixture thereof.

[0066] In one embodiment, the phosphorus-containing antiwear agent is present in the lubricating composition in an amount to provide the lubricating composition with from 300 ppm to 900 ppm of phosphorus. In one embodiment, the antiwear agent is ZDDP and is present in the composition in an amount to provide the lubricating composition with from 400 ppm to 850 ppm, or from 450 ppm to 800 ppm, or from 500 ppm to 800 ppm, or from 550 ppm to 780 ppm, or from 650 ppm to 780 ppm of phosphorus.

[0067] In one embodiment, the phosphorus-containing antiwear agent is present in an amount from 0.2 to 2 wt %, or from 0.3 to 1.3 wt %, or from 0.5 to 0.95 wt % of the lubricant composition. Other Performance Additives

[0068] The lubricating compositions may be prepared by mixing an oil of lubricating viscosity, a first PIB succinimide dispersant, a second succinimide dispersant, a calcium salicylate detergent, an alkaline earth metal detergent, a phosphorus antiwear agent, and optionally one or more performance additives (as described herein below).

[0069] Other performance additives include at least one of metal deactivators, viscosity modifiers, friction modifiers, antiwear agents, corrosion inhibitors, extreme pressure agents, antioxidants, antifoam agents, demulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil contains one or more of these performance additives.

[0070] In further embodiments, the lubricating composition includes an antioxidant, wherein the antioxidant comprises a phenolic or aminic antioxidant, or a mixture thereof. The antioxidant may include a diarylamine, an alkylated diarylamine, a hindered phenol, or a mixture thereof. When present, each antioxidant is independently present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt % of the lubricating composition.

[0071] The diarylamine or alkylated diarylamine may be phenyl-α-naphthylamine (PANA), alkylated diphenylamine, or alkylated phenylnaphthylamine, or a mixture thereof. Alkylated diphenylamines include di-nonylated diphenylamine, nonyldiphenylamine, octyldiphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyldiphenylamine, and mixtures thereof. In one embodiment, the diphenylamine may include nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, or a mixture thereof. In another embodiment, the alkylated diphenylamine may include nonyldiphenylamine or dinonyldiphenylamine. Alkylated diarylamines include octyl, dioctyl, nonyl, dinonyl, decyl, or didecylphenylnaphthylamine.

[0072] Hindered phenol antioxidants often contain secondary and / or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group (typically a linear or branched alkyl) and / or a bridging group connecting to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, such as Irganox® L-135 from Ciba. Suitable hindered phenol esters include hydrocarbyl esters of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid, such as hydrocarbyl esters containing 3 to 18 carbon atoms, or 4 to 12 carbon atoms, or 6 to 10 carbon atoms. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistries can be found in U.S. Patent No. 6,559,105.

[0073] In one embodiment, the lubricating composition contains a friction modifier, which may be selected from long-chain fatty acid derivatives of amines, long-chain fatty esters, or derivatives of long-chain fatty epoxides; fatty imidazolines; amine salts of alkyl phosphates; fatty alkyl tartrates; fatty alkyl tartrate imides; fatty alkyl tartrate amides; fatty glycolates; fatty glycolamides; and combinations thereof.

[0074] As used herein, the term "fatty alkyl" or "fatty" in reference to friction modifiers means a carbon chain, typically a straight carbon chain, having 10 to 24 carbon atoms, which may be saturated or unsaturated.

[0075] Examples of suitable friction modifiers include long-chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines, such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrate imides; fatty alkyl tartrate amides; fatty phosphonates; fatty phosphites; boronated phospholipids, boronated fatty epoxides; glycerol esters; boronated glycerol esters; fatty amines; alkoxylated fatty amines; boronated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines, including tertiary hydroxy fatty amines; hydroxyalkylamides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylenepolyamines; or reaction products of fatty carboxylic acids with guanidine, aminoguanidine, urea, or thiourea, and salts thereof.

[0076] Friction modifiers can also include materials such as sulfurized fatty compounds and olefins, molybdenum compounds such as molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salt molybdate compounds, and molybdenum post-treated succinimide dispersants. The molybdenum dithiocarbamates may be mononuclear, dinuclear, or trinuclear complexes. Suitable molybdenum compounds may exist as Mo(IV) complexes, Mo(V) complexes, Mo(VI) complexes, or combinations thereof, and include commercially available materials such as Sakura-lube 525 from Adeka Co. Ltd. and Molyvan © 855 from Vanderbilt Chemicals LLC.

[0077] In another embodiment, the friction modifier may be a long chain fatty acid ester. In another embodiment, the long chain fatty acid ester may be a monoester, and in another embodiment, the long chain fatty acid ester may be a triglyceride. Suitable triglycerides include vegetable oils such as soybean oil or sunflower oil.

[0078] The ashless friction modifier may be present in the lubricating composition in an amount of from 0.01 to 2.5 wt %, or from 0.1 to 0.5 wt %, or from 0.3 to 2.0 wt %, or from 0.5 to 0.9 wt %.

[0079] The lubricating composition optionally further comprises at least one antiwear agent other than the phosphorus-containing antiwear agent described above. Examples of suitable antiwear agents include titanium compounds, tartrate esters, tartrate imides, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. In one embodiment, the antiwear agent can comprise a tartrate or tartrate imide, such as those disclosed in International Publication No. 2006 / 044411 or Canadian Patent No. 1183125. The tartrate or tartrate imide may contain alkyl-ester groups, where the total number of carbon atoms on the alkyl group is at least 8. In one embodiment, the antiwear agent can comprise a citrate, such as those disclosed in U.S. Patent Application No. 2005 / 0198894.

[0080] Another type of additive includes oil-soluble titanium compounds, such as those disclosed in U.S. Patent No. 7,727,943 and U.S. Patent Application Publication No. 2006 / 0014651. The oil-soluble titanium compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or two or more of these functions. In one embodiment, the oil-soluble titanium compound is a titanium(IV) alkoxide. The titanium alkoxide is formed from a monohydric alcohol, a polyol, or a mixture thereof. The monohydric alkoxide may have 2 to 16, or 3 to 10, carbon atoms. In one embodiment, the titanium alkoxide is titanium(IV) isopropoxide. In one embodiment, the titanium alkoxide is titanium(IV) 2-ethylhexoxide. In one embodiment, the titanium compound comprises an alkoxide of a vicinal 1,2-diol or polyol. In one embodiment, the 1,2-vicinal diol comprises a fatty acid monoester of glycerol, and often the fatty acid is oleic acid.

[0081] In one embodiment, the oil-soluble titanium compound is a titanium carboxylate. In a further embodiment, the titanium(IV) carboxylate is titanium neodecanoate.

[0082] Oil-soluble extreme pressure (EP) agents include sulfur- and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2 derivatives of dispersants (typically succinimide dispersants), derivatives of chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; sulfurized olefins (e.g., sulfurized isobutylene); hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or its oligomers; organic sulfides and polysulfides (e.g., dibenzyl disulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpenes, and sulfurized Diels-Alder adducts); phosphorus sulfurized hydrocarbons, such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbon and trihydrocarbon phosphites. Included are phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenol phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptyl-phenol dioic acid; amine salts or derivatives of alkyl and dialkylphosphoric acids, such as the amine salt of the reaction product of a dialkyldithiophosphoric acid with propylene oxide, which is subsequently further reacted with P2O5, and mixtures thereof (as described in U.S. Pat. No. 3,197,405).

[0083] Antifoaming agents that may be useful in the present compositions include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers.

[0084] Polymeric viscosity index improvers, also known as viscosity modifiers (VMs) or dispersant viscosity modifiers (DVMs), can be useful in the compositions disclosed herein. Dispersant viscosity modifiers can generally be understood to be functionalized, i.e., derivatized, forms of polymers similar to polymeric viscosity modifiers. The polymeric viscosity modifier may be an olefin (co)polymer, poly(meth)acrylate (PMA), or a mixture thereof. In one embodiment, the polymeric viscosity modifier is an olefin (co)polymer or a dispersant viscosity modifier derived therefrom.

[0085] The olefin polymer may be derived from isobutylene or isoprene. In one embodiment, the olefin polymer is prepared from ethylene and a higher olefin in the range of C3 to C10 alpha-monoolefins, for example, the olefin polymer may be prepared from ethylene and propylene.

[0086] Useful olefin polymers, especially ethylene-α-olefin copolymers, have number average molecular weights in the range of 4500 to 500,000, for example, 5000 to 100,000, or 7500 to 60,000, or 8000 to 45,000.

[0087] The formation of functionalized ethylene-α-olefin copolymers is well known in the art, and is described, for example, in U.S. Pat. No. 7,790,661, column 2, line 48 to column 10, line 38. Additional detailed descriptions of similar functionalized ethylene-α-olefin copolymers can be found in WO 2006 / 015130 or U.S. Pat. Nos. 4,863,623, 6,107,257, 6,107,258, 6,117,825, and 7,790,661. In one embodiment, the functionalized ethylene-α-olefin copolymer may include those described in U.S. Pat. No. 4,863,623 (see column 2, line 15 to column 3, line 52) or WO 2006 / 015130 (see page 2, paragraph

[0008] ; preparation examples are described in paragraphs

[0065] to

[0073] ).

[0088] In one embodiment, the lubricating composition comprises a dispersant viscosity modifier (DVM). The DVM may comprise an olefin polymer modified by the addition of a polar moiety.

[0089] Olefin polymers are functionalized by modifying the polymer with the addition of polar moieties. In one useful embodiment, the functionalized copolymer is the reaction product of an olefin polymer grafted with an acylating agent. In one embodiment, the acylating agent can be an ethylenically unsaturated acylating agent. Useful acylating agents are typically α,β-unsaturated compounds having at least one ethylenic bond (before reaction) and at least one, e.g., two, carboxylic acid (or anhydride thereof) groups or polar groups convertible to such carboxylic groups by oxidation or hydrolysis. The acylating agent is grafted onto the olefin polymer to provide two carboxylic acid functional groups. Examples of useful acylating agents include maleic anhydride, chloromaleic anhydride, itaconic anhydride, or their reactive equivalents, e.g., the corresponding dicarboxylic acids such as maleic acid, fumaric acid, cinnamic acid, (meth)acrylic acid, etc., esters of these compounds, and acid chlorides of these compounds.

[0090] In one embodiment, the functionalized ethylene-α-olefin copolymer comprises an olefin copolymer grafted with acyl groups, which are further functionalized with hydrocarbyl amines, hydrocarbyl alcohol groups, amino- or hydroxy-terminated polyether compounds, and mixtures thereof.

[0091] In one embodiment, the hydrocarbyl amine can be selected from aromatic amines, aliphatic amines, and mixtures thereof. In one embodiment, the hydrocarbyl amine component can include at least one aromatic amine containing at least one amino group capable of condensing with the acyl group to provide a pendant group and at least one additional group containing at least one nitrogen, oxygen, or sulfur atom, the aromatic amine being selected from the group consisting of (i) nitro-substituted anilines, (ii) amines containing two aromatic moieties linked by a C(O)NR-, -C(O)O-, -O-, N=N-, or -SO2- group (where R is hydrogen or hydrocarbyl and one of the aromatic moieties bears the condensable amino group), (iii) aminoquinolines, (iv) aminobenzimidazoles, (v) N,N-dialkylphenylenediamines, (vi) aminodiphenylamines (also N-phenylphenylenediamines), and (vii) ring-substituted benzylamines, and (viii) methylene-linked dimers of aminodiphenylamines.

[0092] In one embodiment, the lubricating composition may include a poly(meth)acrylate polymer viscosity modifier. As used herein, the term "(meth)acrylate" and its cognates refer to either methacrylate or acrylate, as will be readily understood.

[0093] In one embodiment, the poly(meth)acrylate polymer is prepared from a monomer mixture containing (meth)acrylate monomers having alkyl groups of various lengths. The (meth)acrylate monomers may contain alkyl groups that are straight-chain or branched-chain groups. The alkyl groups may contain 1 to 24 carbon atoms, for example, 1 to 20 carbon atoms.

[0094] In one embodiment, the poly(meth)acrylate polymer includes a dispersant monomer. The dispersant monomer can be copolymerized with the (meth)acrylate monomer and can include a monomer containing one or more heteroatoms in addition to the carbonyl group of the (meth)acrylate. The dispersant monomer can contain a nitrogen-containing group, an oxygen-containing group, or a mixture thereof.

[0095] The dispersant monomer may be present in an amount up to 5 mole percent of the monomer composition of the (meth)acrylate polymer. In one embodiment, the poly(meth)acrylate is present in an amount from 0 to 5 mole percent, 0.5 to 4 mole percent, or 0.8 to 3 mole percent of the polymer composition. In one embodiment, the poly(meth)acrylate is free or substantially free of dispersant monomer.

[0096] In one embodiment, the poly(meth)acrylate polymer (P) is a block or tapered block copolymer comprising at least one polymer block (Bi) that is insoluble or substantially insoluble in the base oil and a second polymer block (B2) that is soluble or substantially soluble in the base oil.

[0097] In one embodiment, the poly(meth)acrylate polymer may have a structure selected from linear, branched, hyperbranched, crosslinked, star (also called "radial"), or a combination thereof. Star or radial refers to a multi-arm polymer. Such polymers include (meth)acrylate-containing polymers containing three or more arms or branches, and in some embodiments, contain at least about 20, or at least 50, 100, 200, 350, 500, or 1000 carbon atoms. The arms are generally attached to a polyvalent organic moiety that acts as a "core" or "coupling agent." Multi-arm polymers may also be referred to as radial or star polymers, or even "comb" polymers, or polymers having multiple arms or branches as described herein.

[0098] The linear poly(meth)acrylate, random, block, or otherwise, may have a weight average molecular weight (Mw) of 1,000 to 400,000 Daltons, 1,000 to 150,000 Daltons, or 15,000 to 100,000 Daltons. In one embodiment, the poly(meth)acrylate may be a linear block copolymer having a Mw of 5,000 to 40,000 Daltons, or 10,000 to 30,000 Daltons. Radial, crosslinked, or star copolymers can be derived from linear random or diblock copolymers having the above molecular weights. Star polymers may have a weight average molecular weight of 10,000 to 1,500,000 Daltons, or 40,000 to 1,000,000 Daltons, or 300,000 to 850,000 Daltons.

[0099] Another class of polymeric viscosity modifiers are styrene-diene (SD) copolymers, such as styrene isoprene (SI) and styrene butadiene (SBR). Styrene-diene copolymers may be linear or radial (star) and generally contain one or more discrete blocks of styrene bound to one or more discrete blocks of hydrogenated diene.

[0100] The lubricating composition may comprise from 0.05% to 2%, or from 0.08% to 1.2%, or from 0.1 to 0.8% by weight of one or more polymeric viscosity modifiers and / or dispersant viscosity modifiers.

[0101] Pour point depressants that may be useful in the compositions disclosed herein include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates, or polyacrylamides.

[0102] Demulsifiers include trialkyl phosphates and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.

[0103] Metal deactivators include derivatives of benzotriazole (typically tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole. Metal deactivators may also be described as corrosion inhibitors.

[0104] Seal swell agents include sulfolene derivatives Exxon Necton-37™ (FN 1380) and Exxon Mineral Seal Oil™ (FN 3200).

[0105] The lubricating composition may further comprise one or more dispersants different from the first PIB succinimide dispersant and second PIB succinimide dispersant dispersants of the compositions disclosed herein, including succinimide dispersants, Mannich dispersants, polyolefin succinate esters, amides, or ester-amides, or mixtures thereof, different from those of the described compositions.

[0106] The additional dispersant may be a PIB succinimide, similar to the dispersant of the described composition, derived from polyisobutylene having a number average molecular weight of 800 to 2600 daltons. The additional dispersant may be present to enhance soot treatment or as an ashless source of TBN. The soot dispersant may be functionalized with an aromatic (poly)amine. Dispersants used as TBN boosters typically have a high TBN, such as greater than 80 mg KOH / g, greater than 95 mg KOH / g, or even greater than 110 mg KOH / g.

[0107] The additional dispersant may be present in an amount of from 0.05 to 2%, or from 0.1 to 1.1%, or from 0.2 to 0.8% by weight of the lubricant composition. Industrial Application

[0108] The lubricating compositions disclosed herein are suitable for use in diesel engines. Diesel engines are classified by their Gross Vehicle Weight Rating (GVWR). The GVWR includes the maximum rated weight of the vehicle, including passengers, and cargo. The GVWR applies to the truck or trailer, but not to the two combined, which is a separate rating called the Gross Combined Weight Rating (GCWR). The GVWRs for various classes of diesel engines are shown in the table below. [Table 1]

[0109] Light vehicles are classified into classes 1 to 3. Class 2A vehicles are typically referred to as "light" vehicles, while Class 2B vehicles are often referred to as "light heavy" vehicles.

[0110] Medium-sized vehicles are those classified as classes 4 to 6. Large-sized vehicles are those classified as classes 7 and 8.

[0111] There are clear differences between vehicle classes as they relate to operating conditions. Size differences mean that more highly classified vehicles have engines that experience significantly different operating conditions, such as load, oil temperature, duty cycle, and engine speed. Heavy-duty diesel engines are designed to maximize torque for hauling payloads with maximum fuel economy, while passenger cars (lower-class vehicles) are designed for commuting and acceleration with maximum fuel economy. The design objectives of engines for hauling versus commutation result in differences in hardware design and in the stresses placed on lubricants intended to protect and lubricate the engine. Another clear design difference is the operating revolutions per minute (RPM) at which each engine operates for hauling versus commutation. Heavy-duty diesel engines, such as a typical 12-13 liter truck engine, typically do not exceed 2200 rpm, while passenger car engines can reach 4500 rpm.

[0112] In one embodiment, the internal combustion engine is a heavy duty diesel compression ignition (or spark assisted compression ignition) internal combustion engine.

[0113] The sulfur content of the lubricating composition may be 1 wt. % or less, or 0.8 wt. % or less, or 0.5 wt. % or less, or 0.3 wt. % or less. In one embodiment, the sulfur content may range from 0.001 wt. % to 0.5 wt. %, or from 0.01 wt. % to 0.3 wt. %. The phosphorus content may be 0.2 wt. % or less, or 0.12 wt. % or less, or 0.1 wt. % or less, or 0.085 wt. % or less, or 0.08 wt. % or less, or even 0.06 wt. % or less, or 0.055 wt. % or less, or 0.05 wt. % or less. In one embodiment, the phosphorus content may be 0.04 wt. % to 0.12 wt. %. In one embodiment, the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total sulfated ash content may be from 0.3% to 1.2%, or from 0.5% to 1.1% by weight of the lubricating composition.

[0114] In one embodiment, the sulfated ash content may be 0.2 to 1.2 wt. % of the lubricating composition. The lubricating compositions disclosed herein may have a sulfated ash content of 0.2 to 1.2 wt. %, or 0.3 to 1.1 wt. %, or 0.4 to 0.8 wt. %.

[0115] As used herein, TBN values ​​are (total base numbers) as measured by the methodology set forth in ASTM D4739 (Buffers).

[0116] The lubricating composition may be characterized as having a total base number (TBN) content of at least 3, or at least 4, or at least 5 mg KOH / g.

[0117] The lubricating composition may be characterized as having a total base number (TBN) content of 5 to 10 mg KOH / g, or 5 to 8.5 mg KOH / g.

[0118] The lubricating compositions disclosed herein have a viscosity of 2.5 to 8.3, or 3.5 to 6.5 cSt (mm) at 100°C as measured by ASTM D-445. 2 / sec) and 15-30 cSt (mm 2 In another embodiment, the lubricating composition has a kinematic viscosity of 2.5 to 6.5 or 3 to 5.5 cSt (mm 2 / sec) and 15 to 25 cSt (mm 2 / sec) kinematic viscosity.

[0119] The lubricating compositions disclosed herein have a high temperature, high shear viscosity (HTHS) of less than 2.6 mPa·s, or less than 2.5 mPa·s, or less than 2.3 mPa·s, or less than 2.1 mPa·s, as measured by ASTM D4683 at 150° C. In another embodiment, the HTHS of the lubricating composition is from 1.4 to 2.5 mPa·s, or from 1.6 to 2.1 mPa·s, or from 1.8 to 2.1 mPa·s, or from 1.9 to 2.0 mPa·s.

[0120] The lubricating composition may have an SAE viscosity grade of 0W-Y, where Y may be 12, 16, or 20. In one embodiment, the lubricating composition has an SAE viscosity grade of 0W-12.

[0121] The internal combustion engines disclosed herein may have steel surfaces on the cylinder bore, cylinder block, or piston rings.

[0122] The internal combustion engine may have a steel or aluminum alloy or aluminum composite surface.

[0123] Typically, compression ignition internal combustion engines have a maximum payload mass in excess of 3,500 kg.

[0124] The present disclosure further relates to a method of lubricating a diesel engine by supplying to the diesel engine any one of the lubricating compositions disclosed herein. In one embodiment, the method comprises lubricating a diesel engine by supplying to the engine a lubricating composition comprising: an oil of lubricating viscosity having greater than 50 weight percent of a Group III base oil, a Group IV base oil, or a mixture thereof; a first PIB succinimide dispersant derived from a PIB of 1800 to 2500 Mn; and a second PIB succinimide dispersant derived from a PIB having an Mn less than 1600, wherein at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is boron-free; and the composition further comprises a calcium salicylate detergent; an alkaline earth metal sulfonate detergent present in an amount to provide the lubricating composition with 0.3 wt. % to 2.1 wt. % alkaline earth metal soap; and a phosphorus antiwear agent present in an amount to provide the lubricating composition with 300 to 900 ppm phosphorus. and HTHS less than 2.7 mPa·s as measured in accordance with D4683.

[0125] Another embodiment provides the use of any one of the lubricating compositions disclosed herein to improve at least one of wear protection and fuel economy in a compression ignition internal combustion engine (typically a heavy duty diesel internal combustion engine).

[0126] In various embodiments, the lubricating compositions disclosed herein may have compositions as set forth in the following tables. [Table 2]

[0127] The following examples provide illustrations of the described compositions. These examples are non-exhaustive and are not intended to limit the scope of the invention. [Example]

[0128] A series of 0W-12 engine lubricants in Group III base oils of lubricating viscosity were prepared containing the additives listed above as well as conventional additives including polymeric viscosity modifiers, corrosion inhibitors, pour point depressants, and other performance additives such as the following (Table 1): Elements are included to indicate the relative equivalence of the compositions. [Table 3] 1. All treatment rates listed are oil-free unless otherwise stated. 2. Polyisobutenyl succinimide dispersant (TBN 54 mg KOH / g) prepared from 2300 Mn low vinylidene PIB by the chlorine Diels-Alder method 3. Boronated analogs of the above dispersants (1% boron by weight) 4. PIB succinimide aromatic amine soot dispersant 5. Polyisobutenyl succinimide dispersant prepared from high vinylidene 2000 Mn PIB by thermal ene alkylation (TBN 26 mg KOH / g) Polyisobutenyl succinimide dispersant (TBN 25 mg KOH / g) prepared from PIB with 6.980 Mn 7. Polyisobutenyl succinimide dispersant prepared from high vinylidene 1550 Mn PIB by thermal ene alkylation (TBN 17 mg KOH / g) 8. Overbased calcium alkylbenzene sulfonate (TBN 520 mg KOH / g, 48% substrate) 9. Calcium overbased alkyl salicylate detergent (TBN 300 mg KOH / g, metal ratio 2.8) 10. Low TBN calcium alkylbenzene sulfonate detergent (TBN 170 mg KOH / g, 84% substrate, metal ratio 2.7) 11. Combination of diarylamine, hindered phenol, and sulfurized olefin. 12. Combination of low Mn (10 kDa) and high Mn (60 kDa) substituted ethylene-propylene copolymers functionalized with aromatic amines 13. Premix of oleyl tartarimide (44 wt%), boronating agent, basic nitrogen, and compatibilizer (0.46 wt% boron, TBN 17 mg KOH / g) 14. Sulfur-bridged molybdenum(V) dimer, dithiocarbamate complex (commercially available as Sakuralube 525 from Adeka) 15. Other additives include pour point depressants, antifoam agents, and low levels of corrosion inhibitors and compatibilizers.

[0129] The lubricant examples in Table 1 are evaluated for fuel economy improvement and ability to prevent / reduce wear. The results are summarized (Table 2) along with other chemical and physical properties related to performance. Fuel economy improvement is measured according to the Volvo D13TC fuel economy test, in which improvement is determined relative to a preselected reference oil. Example 8 (EX8) was selected as the reference oil for these data.

[0130] Wear resistance (also called durability) was determined with a high frequency reciprocating rig (HFRR) available from PCS Instruments. The HFRR conditions for evaluation were a load of 500 g, a duration of 75 minutes, a stroke of 1000 micrometers, a frequency of 20 Hertz, and a temperature of 105° C. Wear and contact potentials are then measured. [Table 4]

[0131] The results obtained demonstrate that the lubricant composition can provide improved fuel economy while maintaining and even improving wear control.

[0132] The lubricant compositions described herein further provide cleanliness, deposit control, and oxidation control in suitable bench tests. Deposit performance can be measured according to the Thermo-Oxidation Engine Oil Simulation Test (TEOST 33) as set forth in ASTM D6335. The TEOST 33 test result indicates the number of milligrams of deposits after the engine oil is operated at high temperature. A lower TEOST 33 result indicates improved resistance to deposit formation. The lubricating compositions can be tested for deposit control in a panel coker heated to 325°C with a sump temperature of 105°C and a 120-second / 45-second splash / bake cycle. The air flow is 350 ml / min, the spindle speed is 1000 rpm, and the test lasts for 4 hours. The oil is sprayed onto an aluminum panel and then optically evaluated by computer. Performance ranges from 0% (black panel) to 100% (clean panel).

[0133] The fuel economy of the disclosed lubricating compositions can be tested and may have improvements according to any one of the M111 fuel economy test (CEC L-54-96), the Daimler OM501LA fuel economy test, the NEDC MB fuel economy test, and the ILSAC Sequence VI engine test. Friction performance can also be evaluated in any of several high frequency reciprocating rig (HFRR) bench tests, such as ASTM D6079.

[0134] Unless otherwise stated herein, references to treat rates or amounts of components present in the lubricating compositions disclosed herein are quoted on an oil-free basis, i.e., based on the amount of active material.

[0135] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character, including one or more double bonds. Examples of hydrocarbyl groups include hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic-substituted aromatic substituents, as well as cyclic substituents in which the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups that do not alter the predominantly hydrocarbon character of the substituent in the context of this invention (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, i.e., substituents that have a predominantly hydrocarbon character in the context of this invention but contain other than carbon in a ring or chain otherwise composed of carbon atoms, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. In general, no more than two, or no more than one non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group; alternatively, there can be no non-hydrocarbon substituents in the hydrocarbyl group.

[0136] The present disclosure should not be limited in terms of the specific embodiments described in this application, which are intended as illustrations of various aspects. It will be apparent to those skilled in the art that many modifications and variations can be made without departing from the spirit and scope of the present invention. Functionally equivalent methods and components within the scope of the present disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that the present disclosure is not limited to particular methods, reagents, compounds, or compositions, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0137] As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Nothing in this disclosure should be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. As used herein, the term "comprising" means "including, but not limited to."

[0138] Although various compositions, methods, and devices are described in terms of "comprising" (which may be interpreted to mean "including, but not limited to") various components or steps, the compositions, methods, and devices may also "consist essentially of" or "consist of" various components and steps, and such terminology should be interpreted to define essentially a closed set of elements.

[0139] With respect to the use of virtually any plural and / or singular term herein, those of skill in the art will be able to convert from plural to singular and / or from singular to plural as appropriate to the context and / or application. Various singular / plural conversions may be expressly set forth herein for clarity.

[0140] In general, it will be understood by those skilled in the art that the terms used herein, and particularly the terms used in the appended claims (e.g., the body of the appended claims), are generally intended as "open" terms (e.g., the term "comprising" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "including" should be interpreted as "including but not limited to," etc.). Where a specific number of introduced claim recitations is intended, such intention will be explicitly set forth in the claim; in the absence of such recitation, it will be further understood by those skilled in the art that no such intention exists. For example, as an aid to understanding, the following appended claims may include the use of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that introducing a claim recitation with the indefinite article "a" or "an" limits any particular claim containing such an introduced claim recitation to embodiments containing only one such recitation, even if the same claim includes the introductory phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" and / or "an" should be construed to mean "at least one" or "one or more"). The same applies to the use of definite articles used to introduce claim recitations. Additionally, even if a specific number of introduced claim recitations is explicitly recited, those skilled in the art will recognize that such recitation should be construed to mean at least the recited number (e.g., an express recitation of "two recitations" without other modifiers means at least two recitations, or more than two recitations). Furthermore, when a convention similar to "at least one of A, B, and C, etc." is used, generally such configuration is intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, systems having only A, only B, only C, both A and B, both A and C, both B and C, and / or both A, B, and C, etc.).When a convention similar to "at least one of A, B, or C, etc." is used, generally such a configuration is intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" includes, but is not limited to, systems having only A, only B, only C, both A and B, both A and C, both B and C, and / or both A, B, and C, etc.). It will be further understood by one of ordinary skill in the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, regardless of the specification, claims, or drawings, should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" would be understood to include the possibilities of "A" or "B" or "A and B."

[0141] Additionally, where features or aspects of the present disclosure may be described in terms of a Markush group, those skilled in the art will recognize that the present disclosure is also thereby described in terms of any individual element or subgroup of elements of the Markush group.

[0142] As will be understood by those skilled in the art, for any and all purposes, including with respect to providing a written description, all ranges disclosed herein encompass any and all possible subranges and combinations thereof. Any recited range can be readily recognized as fully descriptive and allowing that same range to be broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third, and upper third, etc. As will be understood by those skilled in the art, all terms such as "up to," "at least," etc., refer to ranges that are inclusive of the recited numbers and can then be broken down into subranges, as discussed above. Finally, as will be understood by those skilled in the art, ranges include each individual element. Thus, for example, a group having 1-3 wt. % refers to the group having 1, 2, or 3 wt. %. Similarly, a group having 1-5 wt. % refers to the group having 1, 2, 3, 4, or 5 wt. %, etc., including all points in between.

[0143] Furthermore, when stated ranges for treatment rates are provided, such ranges are intended to include treatment rates for individual components and / or mixtures of components. Thus, for example, a range of 1-3 wt. % contemplates that a given component may be present in the range of 1-3 wt. %, or that a mixture of similar components may be present in the range of 1-3 wt. %.

[0144] As used herein, the term "about" means that a given quantity value is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value.

[0145] Unless otherwise specified, "wt. %" as used herein shall refer to weight percent based on the total weight of the composition on an oil-free basis.

[0146] As described below, the number average molecular weights of the dispersant viscosity modifiers and viscosity modifiers are determined using known methods, such as GPC analysis using polystyrene standards. Methods for determining the molecular weight of polymers are well known. These methods are described, for example, in: (i) P. J. Flory, "Principles of Polymer Chemistry," Cornell University Press (1953), Chapter VII, pp. 266-315; or (ii) "Macromolecules, an Introduction to Polymer Science," F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp. 296-312.

[0147] While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. It is therefore to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims. The present invention provides, for example, the following items. (Item 1) A diesel engine lubricating composition comprising: an oil of lubricating viscosity having greater than 50 weight percent of a Group III base oil, a Group IV base oil, a Group V base oil, or a mixture thereof; a first PIB succinimide dispersant derived from PIB of 1800 to 2500 Mn; a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600, wherein at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is boron-free; the composition further comprising an alkaline earth metal salicylate detergent; an alkaline earth metal sulfonate detergent present in an amount to provide the lubricating composition with 0.1 wt. % to 1.2 wt. % alkaline earth metal soap; a phosphorus antiwear agent present in an amount to provide 300 to 900 ppm phosphorus in the lubricating composition; The lubricating composition has a total sulfated ash content of 0.3 to 1.1 wt. %, a kinematic viscosity at 100°C of less than 8.3 cSt, a total alkaline earth metal soap content of 0.6 wt. % to 2.1 wt. %, and an HTHS of less than 2.7 mPa·s as measured in accordance with ASTM D4683. (Item 2) 2. The composition of claim 1, wherein the first PIB succinimide dispersant has a TBN (KOH / g) of 15 to 25. (Item 3) 3. The composition of claim 1 or 2, wherein the first PIB succinimide dispersant has a TBN (KOH / g) of 15 to 20. (Item 4) 4. The composition of any one of items 1 to 3, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1750 to 2200 Mn. (Item 5) 5. The composition of any one of items 1 to 4, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1800 to 2100 Mn. (Item 6) 6. The composition of any one of items 1 to 5, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1850 to 2150 Mn. (Item 7) 7. The composition of any one of the preceding claims, wherein the first PIB succinimide dispersant is present in the lubricating composition in an amount of 0.5 wt% to 10 wt%. (Item 8) 8. The composition of any one of the preceding claims, wherein the first PIB succinimide dispersant is present in the lubricating composition in an amount of 0.8 wt% to 6 wt%. (Item 9) 9. The composition of any one of the preceding claims, wherein the first PIB succinimide dispersant is present in the lubricating composition in an amount of 1 wt% to 5 wt%. (Item 10) 10. The composition of any one of the preceding claims, wherein the first PIB succinimide dispersant is present in the lubricating composition in an amount of 1.5 wt% to 5 wt%. (Item 11) 11. The composition of any one of the preceding claims, wherein the first PIB succinimide dispersant is prepared by a thermal direct alkylation process. (Item 12) 12. The composition of any one of items 1 to 11, wherein the first PIB succinimide dispersant comprises a mixture of two dispersants. (Item 13) 13. The composition of any one of items 1 to 12, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 750 to 1600. (Item 14) 14. The composition of any one of items 1 to 13, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 1000 to 1600. (Item 15) 15. The composition of any one of items 1 to 14, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 1200 to 1600. (Item 16) Item 14. The composition of item 13, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 800 to 1150. (Item 17) 17. The composition of claim 13 or 16, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 900 to 1100. (Item 18) 18. The composition of any one of the preceding claims, wherein the second PIB succinimide dispersant is prepared by a thermal direct alkylation process. (Item 19) 19. The composition of any one of the preceding claims, wherein the second PIB succinimide dispersant is present in the lubricating composition in an amount of 1 to 5 wt%, or 1.5 to 4.8 wt%, or 1.8 to 4.6 wt%, or 1.9 to 4.6 wt%. (Item 20) 20. The composition of any one of items 1 to 13, 18 and 19, wherein the second PIB succinimide dispersant comprises 1 to 5 wt.% of a PIB succinimide dispersant derived from a PIB having a Mn of 900-1100 and 1 to 5 wt.% of a PIB succinimide dispersant derived from a PIB having a Mn of 1200-1600. (Item 21) 21. The composition of any one of items 1 to 20, wherein the second PIB succinimide dispersant has a TBN (KOH / g) of 20 to 35. (Item 22) 22. The composition of any one of the preceding claims, wherein the second PIB succinimide dispersant has a TBN (KOH / g) of 25 to 30. (Item 23) 23. The composition of any one of the preceding claims, wherein the second PIB succinimide dispersant has a TBN (KOH / g) of 27 to 28. (Item 24) 24. The composition of any one of the preceding claims, wherein the first PIB succinimide dispersant is boronated. (Item 25) 24. The composition of any one of the preceding claims, wherein the second PIB succinimide dispersant is boronated. (Item 26) 26. The composition of claim 24 or 25, wherein the first borated dispersant and second borated dispersant are independently present in an amount to provide 25 to 400 (or 50 to 200) ppm by weight of boron to the lubricating composition. (Item 27) 27. The composition of any one of items 1 to 26, wherein the alkaline earth metal salicylate detergent has a TBN (KOH / g) of 200 to 575 or 200 to 500. (Item 28) 28. The composition according to any one of items 1 to 27, wherein the alkaline earth metal salicylate is a calcium salicylate detergent having a TBN (KOH / g) of 250 to 350. (Item 29) 29. The composition of any one of the preceding claims, wherein the alkaline earth metal salicylate detergent has a metal ratio of from 2 to 7, or from 2 to 4, or from 2.5 to 3.5. (Item 30) 30. The composition according to any one of the preceding items, wherein the alkaline earth metal sulfonate detergent is selected from calcium sulfonate detergents and magnesium sulfonate detergents. (Item 31) 31. The composition according to any one of items 1 to 30, wherein the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent. (Item 32) 32. The composition of claim 31, wherein the calcium sulfonate detergent has a TBN (KOH / g) of less than 200. (Item 33) 33. The composition of claim 31 or 32, wherein the calcium sulfonate detergent has a TBN (KOH / g) of less than 150, or less than 100, or less than 80. (Item 34) 34. The composition of any one of items 31 to 33, wherein the calcium sulfonate detergent has a TBN (KOH / g) of 50 to 90. (Item 35) 35. The composition of any one of items 31 to 34, wherein the calcium sulfonate detergent is present in the lubricant composition in an amount of 0.5 wt.% to 2.0 wt.%, or 0.6 wt.% to 1.5 wt.%. (Item 36) 31. The composition of any one of items 1 to 30, wherein the alkaline earth metal sulfonate detergent is an overbased magnesium sulfonate detergent. (Item 37) 37. The composition of any one of items 1 to 29 and 36, wherein the overbased magnesium sulfonate detergent has a TBN (KOH / g) of 200 to 500, or 250 to 400, or 250 to 350, or 350 to 375. (Item 38) 38. The composition of any one of items 1 to 29, 36, and 37, wherein the overbased magnesium sulfonate detergent is present in the lubricating composition in an amount of 0.05 wt.% to 0.2 wt.%, or 0.06 wt.% to 0.1. (Item 39) 31. The composition of any one of items 1 to 30, wherein the alkaline earth metal sulfonate comprises a mixture of 0.6 wt% to 1.5 wt% of a calcium sulfonate detergent having a TBN (KOH / g) of 50 to 100 and 0.05 wt% to 0.1 wt% of an overbased magnesium sulfonate detergent having a TBN (KOH / g) of 250 to 350. (Item 40) 40. The composition of any one of items 1 to 39, wherein the total alkaline earth metal soap of the lubricating composition is 0.6 wt.% to 1.5 wt.% or 0.7 wt.% to 1.4 wt.%. (Item 41) 41. The composition of any one of the preceding claims, wherein the phosphorus antiwear agent is a zinc dialkyldithiophosphate in an amount to provide the lubricating composition with 400 ppm to 850 ppm, or 450 ppm to 800 ppm, or 500 ppm to 800 ppm, or 550 ppm to 780 ppm, or 650 ppm to 780 ppm. (Item 42) 42. The composition according to any one of items 1 to 41, wherein the total sulfated ash content is 0.3 to 0.9% by weight, or 0.4 to 0.8% by weight. (Item 43) 43. The composition according to any one of the preceding items, wherein the HTHS is less than 2.5, or less than 2.3, or less than 2.1. (Item 44) 44. The composition according to any one of items 1 to 43, wherein the HTHS is 1.4 to 2.5, or 1.6 to 2.1, or 1.8 to 2.1, or 1.9 to 2.0. (Item 45) 45. The composition of any one of items 1 to 44, further comprising an ashless friction modifier. (Item 46) 46. ​​The composition of any one of the preceding items, further comprising a dispersant other than the first PIB succinimide dispersant and the second PIB succinimide dispersant. (Item 47) 47. The composition according to any one of the preceding items, further comprising one or more additional additives selected from antioxidants, antifoaming agents, and corrosion inhibitors. (Item 48) 48. The composition according to any one of items 1 to 47, wherein the kinematic viscosity at 100°C is 2.5 to 8.3 cSt or 3.5 to 6.5 cSt. (Item 49) 49. A method for lubricating a diesel engine, comprising supplying to said engine a lubricant composition according to any one of items 1 to 48. (Item 50) 49. Use of a lubricating composition according to any one of items 1 to 48 to improve one or more of fuel economy in a diesel engine and wear protection in a diesel engine.

Claims

1. A diesel engine lubricating composition comprising: an oil of lubricating viscosity having greater than 50 weight percent of a Group III base oil, a Group IV base oil, a Group V base oil, or a mixture thereof; a first PIB succinimide dispersant derived from an 1800-2500 Mn PIB, said first PIB succinimide dispersant being present in said lubricating composition in an amount of 1.1 wt % to 2.2 wt %; a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600, wherein at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is boron-free; the composition further comprising an alkaline earth metal salicylate detergent; an alkaline earth metal sulfonate detergent present in an amount to provide the lubricating composition with 0.1 wt % to 1.2 wt % alkaline earth metal soap; a phosphorus antiwear agent present in an amount to provide 300 to 900 ppm phosphorus in the lubricating composition; 1. The lubricating composition has a total sulfated ash content of 0.3 to 1.1 wt. %, a kinematic viscosity at 100°C of less than 8.3 cSt, a total alkaline earth metal soap content of 0.6 wt. % to 2.1 wt. %, and a HTHS of less than 2.7 mPa s as measured in accordance with ASTM D4683.

2. 10. The composition of claim 1, wherein the first PIB succinimide dispersant has a TBN (KOH / g) of 15 to 25.

3. 3. The composition of claim 1 or 2, wherein the first PIB succinimide dispersant has a TBN (KOH / g) of 15 to 20.

4. 4. The composition of any one of claims 1 to 3, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1750 to 2200 Mn.

5. 5. The composition of any one of claims 1 to 4, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1800 to 2100 Mn.

6. 6. The composition of any one of claims 1 to 5, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1850 to 2150 Mn.

7. The composition of any one of claims 1 to 6, wherein the first PIB succinimide dispersant is prepared by a thermal direct alkylation process.

8. The composition of any one of claims 1 to 7, wherein the first PIB succinimide dispersant comprises a mixture of two dispersants.

9. The composition of any one of claims 1 to 8, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 750 to 1600.

10. 10. The composition of any one of claims 1 to 9, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 1000 to 1600.

11. The composition of any one of claims 1 to 10, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 1200 to 1600.

12. 10. The composition of claim 9, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 800 to 1150.

13. 13. The composition of claim 9 or 12, wherein the second PIB succinimide dispersant is derived from a PIB having a number average molecular weight of 900 to 1100.

14. The composition of any one of claims 1 to 13, wherein the second PIB succinimide dispersant is prepared by a thermal direct alkylation process.

15. 15. The composition of any one of claims 1 to 14, wherein the second PIB succinimide dispersant is present in the lubricating composition in an amount from 1 to 5 wt%, or from 1.5 to 4.8 wt%, or from 1.8 to 4.6 wt%, or from 1.9 to 4.6 wt%.

16. 16. The composition of any one of claims 1-9, 14 and 15, wherein the second PIB succinimide dispersant comprises 1 to 5 wt% of a PIB succinimide dispersant derived from a PIB having a Mn of 900-1100 and 1 to 5 wt% of a PIB succinimide dispersant derived from a PIB having a Mn of 1200-1600.

17. 17. The composition of any one of claims 1 to 16, wherein the second PIB succinimide dispersant has a TBN (KOH / g) of 20 to 35.

18. 18. The composition of any one of claims 1 to 17, wherein the second PIB succinimide dispersant has a TBN (KOH / g) of 25 to 30.

19. 19. The composition of any one of claims 1 to 18, wherein the second PIB succinimide dispersant has a TBN (KOH / g) of 27 to 28.

20. 20. The composition of any one of claims 1 to 19, wherein the first PIB succinimide dispersant is boronated.

21. 20. The composition of any one of claims 1 to 19, wherein the second PIB succinimide dispersant is boronated.

22. 22. The composition of claim 20 or 21, wherein the first borated dispersant and second borated dispersant are independently present in amounts to provide 25 to 400 (or 50 to 200) ppm by weight of boron to the lubricating composition.

23. A composition according to any preceding claim, wherein the alkaline earth metal salicylate detergent has a TBN (KOH / g) of 200 to 575 or 200 to 500.

24. A composition according to any preceding claim, wherein the alkaline earth metal salicylate is a calcium salicylate detergent having a TBN (KOH / g) of 250 to 350.

25. The composition of any preceding claim, wherein the alkaline earth metal salicylate detergent has a metal ratio of from 2 to 7, or from 2 to 4, or from 2.5 to 3.

5.

26. A composition according to any preceding claim, wherein the alkaline earth metal sulphonate detergent is selected from calcium sulphonate detergents and magnesium sulphonate detergents.

27. A composition according to any preceding claim, wherein the alkaline earth metal sulphonate detergent is a calcium sulphonate detergent.

28. 28. The composition of claim 27, wherein the calcium sulfonate detergent has a TBN (KOH / g) of less than 200.

29. 29. The composition of claim 27 or 28, wherein the calcium sulfonate detergent has a TBN (KOH / g) of less than 150, or less than 100, or less than 80.

30. The composition of any one of claims 27 to 29, wherein the calcium sulfonate detergent has a TBN (KOH / g) of 50 to 90.

31. 31. The composition of any one of claims 27 to 30, wherein the calcium sulfonate detergent is present in the lubricant composition in an amount from 0.5 wt % to 2.0 wt %, or from 0.6 wt % to 1.5 wt %.

32. A composition according to any preceding claim, wherein the alkaline earth metal sulphonate detergent is an overbased magnesium sulphonate detergent.

33. 33. The composition of claim 32, wherein the overbased magnesium sulfonate detergent has a TBN (KOH / g) of 200 to 500, or 250 to 400, or 250 to 350, or 350 to 375.

34. 34. The composition of claim 32 or 33, wherein the overbased magnesium sulfonate detergent is present in the lubricating composition in an amount from 0.05 wt % to 0.2 wt %, or from 0.06 wt % to 0.1 wt %.

35. 27. A composition according to any preceding claim, wherein the alkaline earth metal sulfonate comprises a mixture of 0.6 to 1.5 wt % of a calcium sulfonate detergent having a TBN (KOH / g) of 50 to 100 and 0.05 to 0.1 wt % of an overbased magnesium sulfonate detergent having a TBN (KOH / g) of 250 to 350.

36. 36. The composition of any one of claims 1 to 35, wherein the total alkaline earth metal soaps of the lubricating composition is from 0.6 wt% to 1.5 wt% or from 0.7 wt% to 1.4 wt%.

37. 37. The composition of any one of claims 1 to 36, wherein the phosphorus antiwear agent is a zinc dialkyldithiophosphate in an amount to provide the lubricating composition with from 400 ppm to 850 ppm, or from 450 ppm to 800 ppm, or from 500 ppm to 800 ppm, or from 550 ppm to 780 ppm, or from 650 ppm to 780 ppm.

38. 38. The composition of any one of the preceding claims, wherein the total sulfated ash content is from 0.3 to 0.9 wt%, or from 0.4 to 0.8 wt%.

39. 39. The composition of any one of claims 1 to 38, wherein the HTHS is less than 2.5, or less than 2.3, or less than 2.

1.

40. 39. The composition of any one of the preceding claims, wherein the HTHS is from 1.4 to 2.5, or from 1.6 to 2.1, or from 1.8 to 2.1, or from 1.9 to 2.

0.

41. The composition of any one of claims 1 to 40, further comprising an ashless friction modifier.

42. 42. The composition of any one of claims 1 to 41, further comprising a dispersant other than the first PIB succinimide dispersant and the second PIB succinimide dispersant.

43. 43. The composition of any one of claims 1 to 42, further comprising one or more additional additives selected from antioxidants, antifoaming agents, and corrosion inhibitors.

44. 44. The composition of any one of claims 1 to 43, wherein the kinematic viscosity at 100°C is from 2.5 to 8.3 cSt or from 3.5 to 6.5 cSt.

45. A method of lubricating a diesel engine, comprising supplying to said engine a lubricant composition according to any one of claims 1 to 44.

46. Use of a lubricating composition according to any one of claims 1 to 44 to improve one or more of fuel economy in a diesel engine and wear protection in a diesel engine.

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