Deposition control compounds for lubricating compositions

Abstract

The subject matter disclosed herein provides a lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to Formula I: wherein, independently for each molecule of the compound: R1 is an aliphatic hydrocarbyl group having 10 to 24 carbon atoms; r2 is CH3 or C2H5; and n is an integer from 3 to 8; and (c) an alkaline earth metal alkyl detergent. # imgabs0 #

Description

[0001] The disclosed technology relates to lubricating compositions for internal combustion engines such as diesel engines (such as heavy-duty diesel engines) or gasoline direct injection engines (such as those with turbocharging), and methods for lubricating such engines by supplying the lubricating compositions to the engines. The lubricating compositions disclosed herein can improve fuel economy and / or wear protection.

[0002] Lubricating compositions are used for the smooth operation of internal combustion engines. Engine oils for internal combustion engines are used, for example, to: (i) lubricate various sliding interfaces between piston rings and cylinder liners, in the bearings of crankshafts and connecting rods, and in the valve drive mechanism including cams and valve lifters; (ii) cool the engine; (iii) clean and disperse the combustion products; and / or (iv) prevent corrosion and subsequent rust. The stringent requirements for high-performance engines in recent years have meant a greater need for improved lubricants used in such engines.

[0003] There is a growing interest in improving the fuel efficiency of internal combustion engines. Vehicle manufacturers have improved fuel economy through engine design, and these improvements have taken advantage of advances in lubricating compositions that provide, for example, better oxidation stability, wear protection, and reduced friction. Specifically, operators of heavy-duty diesel vehicles have been reluctant to adopt low viscosity grades of engine oil to improve fuel economy; durability (or the ability to keep the vehicle on the road for extended periods of time and mileage) has always been and remains a major concern. Therefore, the most widely used viscosity grades for highway heavy-duty diesel vehicles are SAE 15W-40, 10W-30, and 5W-30. In recent years, there has been a continuous push to improve the fuel efficiency of heavy-duty diesel vehicles. Therefore, it is necessary to improve the fuel economy of diesel engines without compromising the durability of the engine or otherwise adversely affecting lubricant properties, including deposit and soot control and oxidation resistance and corrosion resistance. This is particularly relevant to viscosity grades lower than SAE 5W-30 viscosity grades (such as 0W-20, 0W-16, and 0W-12 viscosity grades).

[0004] In addition, with the recent changes in engine specifications, the demand for lubricants that reduce deposits has increased. For example, the Caterpillar 1N (ASTM D6750) requirement in API CK-4, CJ-4 and FA-4 requires a maximum weight defect of 286.2 for the piston after 252 hours. API FA-4 oil is blended to a high temperature high shear ("HTHS") viscosity range of 2.9 cP to 3.2 cP to help reduce greenhouse gas ("GHG") emissions. When using particulate filters and other advanced aftertreatment systems, these oils are particularly effective in maintaining the durability of emission control systems. Oils with lower HTHS viscosity ranges, such as 2.0 cP to 2.9 cP, will improve fuel economy, but still require special attention to soot deposits, because the accumulation of soot deposits can lead to higher viscosity.

[0005] The disclosed technology provides a compound that can provide deposit control in a lubricating composition while maintaining adequate viscosity.

[0006] The subject matter disclosed herein provides a lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to Formula I:

[0007]

[0008] Wherein, for each molecule of the compound independently: R 1 is an aliphatic hydrocarbon group having 10 to 24 carbon atoms; R 2 is CH3 or C2H5; and n is an integer from 3 to 8; and (c) an alkaline earth metal alkyl detergent. In certain embodiments, a deposit control additive according to Formula I as described above is provided.

[0009] The following implementations of the present subject matter are contemplated:

[0010] 1. A lubricating composition comprising: (a) an oil having a lubricating viscosity; (b)

[0011] Compounds according to formula I:

[0012]

[0013] Wherein, for each molecule of the compound independently: R 1 is an aliphatic hydrocarbon group having 10 to 24 carbon atoms; R 2 is CH3 or C2H5; and n is an integer from 3 to 8; and (c) an alkaline earth metal alkyl detergent.

[0014] 2. The lubricating composition of embodiment 1, having a high temperature high shear viscosity of 1.5 to 4.5 mPa·s, as measured at 150° C. according to ASTM D4683.

[0015] 3. The lubricating composition of embodiment 1 or embodiment 2, having a high temperature high shear viscosity of 1.5 to 3.5 mPa·s, as measured at 150° C. according to ASTM D4683.

[0016] 4. The lubricating composition according to any one of embodiments 1 to 3, wherein the alkaline earth metal alkyl detergent contributes 2 to 7 TBN to the composition as measured by ASTM D4739.

[0017] 5. The lubricating composition according to any one of embodiments 1 to 3, wherein the alkaline earth metal alkyl detergent contributes 2 to 6 TBN to the composition as measured by ASTM D4739.

[0018] 6. The lubricating composition according to any one of embodiments 1 to 3, wherein the alkaline earth metal alkyl detergent contributes 2 to 4 TBN to the composition as measured by ASTM D4739.

[0019] 7. The lubricating composition of any one of embodiments 1 to 6, having a sulfated ash content less than or equal to 1 wt. %, based on the total weight of the composition, as measured by ASTM D874.

[0020] 8. The lubricating composition according to embodiment 7, wherein the alkaline earth metal alkyl detergent contributes 6 to 7 TBN to the composition as measured by ASTM D4739.

[0021] 9. The lubricating composition of any one of embodiments 1 to 6, having a sulfated ash content less than or equal to 0.5 wt. %, based on the total weight of the composition, as measured by ASTM D874.

[0022] 10. The lubricating composition of embodiment 9, wherein the alkaline earth metal alkyl detergent contributes 2 to 3.5 TBN to the composition as measured by ASTM D4739.

[0023] 11. The lubricating composition according to any one of embodiments 1 to 10, wherein the compound according to formula I is present in the composition in an amount of 1 wt. % to 10 wt. %, based on the total weight of the composition.

[0024] 12. The lubricating composition according to any one of embodiments 1 to 11, wherein R1 To have

[0025] An aliphatic hydrocarbon group of 14 to 20 carbon atoms.

[0026] 13. The lubricating composition of any one of embodiments 1 to 12, having a TBN of 2 to 12 as measured by ASTM D2896.

[0027] 14. The lubricating composition of any one of embodiments 1 to 12, having a TBN of 2 to 8 as measured by ASTM D2896.

[0028] 15. The lubricating composition of any one of embodiments 1 to 12, having a TBN of 2 to 7 as measured by ASTM D2896.

[0029] 16. The lubricating composition of any one of embodiments 1 to 12, having a TBN of 2 to 6 as measured by ASTM D2896.

[0030] 17. The lubricating composition of any one of embodiments 1 to 16, wherein the alkaline earth metal alkyl detergent is present in the composition in an amount of less than 3.5 wt. %, based on the total weight of the composition.

[0031] 18. The lubricating composition of any one of embodiments 1 to 16, wherein the alkaline earth metal alkyl detergent is present in the composition in an amount of less than 1 wt. %, based on the total weight of the composition.

[0032] 19. The lubricating composition according to any one of embodiments 1 to 18, wherein the alkaline earth metal

[0033] The alkyl detergent comprises an alkaline earth metal, the alkaline earth metal being at least one of magnesium or calcium.

[0034] 20. The lubricating composition of any one of embodiments 1 to 19, wherein the alkaline earth metal alkyl detergent comprises a surfactant moiety which is at least one of a phenate, a salicylate, a sulfonate, a salicyl alcohol, or a salicylic acid alkoxide.

[0035] 21. The lubricating composition of any one of embodiments 1 to 20, wherein the alkaline earth metal alkyl detergent comprises a surfactant moiety which is at least one of a salicylate or a sulfonate.

[0036] 22. The lubricating composition of any one of embodiments 1 to 21, further comprising at least one additional additive comprising at least one of an antioxidant, a detergent, a dispersant, an antiwear agent, a corrosion inhibitor, a viscosity modifier, a metal passivator, a pour point depressant, a seal compatibility agent, a defoamer, an extreme pressure agent, or a friction modifier.

[0037] 23. The lubricating composition of any one of embodiments 1 to 22, having less than 200 ppm by weight of molybdenum, based on the total weight of the composition.

[0038] 24. The lubricating composition of any one of embodiments 1 to 23, having less than 120 ppm by weight of molybdenum, based on the total weight of the composition.

[0039] 25. The lubricating composition of any one of embodiments 1 to 24, further comprising at least one of a metal-based antiwear agent or an amine-based antiwear agent.

[0040] 26. The lubricating composition of any one of embodiments 1 to 25, further comprising an antiwear agent, wherein the antiwear agent contributes 300 ppm to 900 ppm by weight of phosphorus to the composition, based on the total weight of the composition.

[0041] 27. The lubricating composition of any one of embodiments 1 to 25, further comprising an antiwear agent, wherein the antiwear agent contributes 300 ppm to 800 ppm by weight of phosphorus to the composition, based on the total weight of the composition.

[0042] 28. The lubricating composition of any one of embodiments 1 to 27, having 700 ppm to 1,000 ppm by weight of zinc, based on the total weight of the composition.

[0043] 29. The lubricating composition of any one of embodiments 1 to 27, having 700 ppm to 900 ppm by weight of zinc, based on the total weight of the composition.

[0044] 30. The lubricating composition according to any one of embodiments 1 to 29, further comprising an aromatic amine, maleic anhydride, ethylene-propylene copolymer dispersant in an amount of 0.1 wt % to 5 wt %, based on the total weight of the composition.

[0045] 31. A method of lubricating a heavy duty diesel engine, the method comprising supplying a composition according to any one of embodiments 1 to 30 to the engine.

[0046] 32. A method of lubricating a compression ignition internal combustion engine having a load mass exceeding 2,700 kg, the method comprising supplying a composition according to any one of embodiments 1 to 30 to the engine.

[0047] 33. A method of lubricating the crankcase of a compression-ignition or spark-ignition engine, the method comprising supplying a composition according to any one of embodiments 1 to 30 to the crankcase.

[0048] 34. A method according to embodiment 33, wherein the spark ignition engine is a gasoline direct injection engine.

[0049] 35. The method of embodiment 34, wherein the gasoline direct injection engine comprises a turbocharger.

[0050] Various features and embodiments of the present subject matter are described below by way of non-limiting illustration.

[0051] As used herein, the term "condensation product" is intended to encompass esters, amides, imides, and other such materials that can be prepared by the condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, whether or not the condensation reaction is actually carried out to produce the product directly. Thus, for example, a particular ester can be prepared by an ester exchange reaction rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

[0052] Unless otherwise specified, the amount of each chemical component described herein does not include any solvent or diluent oil which may be customarily present in the commercial material, i.e., on a 100% active chemical basis. Unless otherwise specified, each chemical or composition mentioned herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.

[0053] As used herein, the term "alkyl" refers to a group having a carbon atom directly connected to the rest of the molecule, wherein the group includes at least a carbon atom and a hydrogen atom. If the alkyl group contains more than one carbon atom, these carbons do not have to be bonded to each other. For example, at least two carbons in the carbon can be bonded via a suitable element or group. In various embodiments, the term "alkyl" refers to a group having a carbon atom directly connected to the rest of the molecule, wherein the group is composed of carbon, hydrogen, and optionally one or more heteroatoms, provided that the heteroatom does not change the main hydrocarbon nature of the substituent. The heteroatom can bond at least two carbons in the carbon in the alkyl group and optionally no more than two non-hydrocarbon substituents. Suitable heteroatoms will be obvious to those skilled in the art, and include, for example, sulfur, nitrogen, oxygen, phosphorus and silicon. When the alkyl group contains heteroatoms, optionally, no more than two heteroatoms will be present for every ten carbon atoms in the alkyl group. Suitable non-hydrocarbon substituents will also be obvious to those skilled in the art, and include, for example, halo, hydroxyl, alkoxy, sulfhydryl, alkylthiol, nitro, nitroso and sulfinyl.

[0054] Therefore, examples of hydrocarbon groups in the context of the present technology include: (i) hydrocarbon groups selected from aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl, cycloalkadienyl) and aromatic groups; (ii) substituted hydrocarbon groups selected from hydrocarbon groups defined in (i) substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents, the non-hydrocarbon substituents selected from the group consisting of: halo, hydroxyl, alkoxy, mercapto, alkylthiol, nitro, nitroso and sulfinyl; and / or (iii) heterohydrocarbon-containing groups selected from hydrocarbon groups defined in (i) containing one or more heteroatoms in a ring or chain, provided that no more than two heteroatoms are present for every ten carbon atoms in the group, the heteroatoms being selected from sulfur, nitrogen, oxygen, phosphorus and silicon. The heterohydrocarbon-containing group may be substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents. In certain embodiments, the term "hydrocarbon group" refers to a group having a carbon atom directly connected to the rest of the molecule, wherein the group is composed of carbon atoms and hydrogen atoms.

[0055] It is known that some of the materials described herein can interact in the final formulation so that the components of the final formulation may be different from those initially added. For example, metal ions (e.g., metal ions of detergents) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed when the compositions of the present subject matter are employed in their intended use, may not be easy to describe. However, all such adjustments and reaction products are included within the scope of the present subject matter; the present subject matter includes compositions prepared by mixing the components described herein.

[0056] As used herein, the indefinite article "a" / "an" is intended to mean one or more than one / one or more than one. As used herein, the phrase "at least one / at least one" means one or more than one / one or more than one of the following terms. Therefore, "a" / "an" and "at least one / at least one" can be used interchangeably. For example, "at least one of A, B or C" means that in alternative embodiments, only one of A, B or C may be included, and any mixture of two or more of A, B and C may be included.

[0057] As used herein, the term "substantially free" means that a component does not include any intentional addition of a material that the component is "substantially free of." For example, the component may include a material that the component is "substantially free of" to no more than impurity levels that may be the result of an incomplete chemical reaction and / or an unintentional / undesirable (but perhaps unavoidable) reaction product.

[0058] As used herein, the transitional term "comprising," which is synonymous with "comprising," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each use of "comprising" herein, it is intended that the term also encompasses the phrases "consisting essentially of" and "consisting of" as alternative embodiments, wherein "consisting of" excludes any element or step not specified, and "consisting essentially of" permits the inclusion of additional, unrecited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0059] A lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to formula I:

[0060]

[0061] Wherein, for each molecule of the compound independently: R 1 is an aliphatic hydrocarbon group having 10 to 24, such as 12 to 24, 14 to 24, 16 to 24, 18 to 24, 20 to 24, 22 to 24, 10 to 22, 12 to 22, 14 to 22, 16 to 22, 18 to 22, 20 to 22, 10 to 20, 12 to 20, 14 to 20, 16 to 20, 18 to 20, 10 to 18, 12 to 18, 14 to 18, 16 to 18, 10 to 16, 12 to 16, 14 to 16, 10 to 14, 12 to 14, or 10 to 12, carbon atoms; R 2is CH3 or C2H5; and n is an integer from 3 to 8 (such as 4 to 8, 5 to 8, 6 to 8, 7 to 8, 3 to 7, 4 to 7, 5 to 7, 6 to 7, 3 to 6, 4 to 6, 5 to 6, 3 to 5, 4 to 5, or 3 to 4); and (c) an alkaline earth metal alkyl detergent.

[0062] The lubricating compositions described herein can be used in various applications as lubricating compositions for internal combustion engines, including gasoline engines and / or spark-ignition engines, such as passenger car engines, diesel engines, or compression-ignition engines, such as heavy-duty diesel truck engines, natural gas fueled engines, such as stationary power engines, two-stroke engines, aviation piston engines and turbine engines, marine and railroad diesel engines; and hydrocarbon fuels for internal combustion engines, such as middle distillate fuels, such as jet fuel, kerosene and diesel fuel.

[0063] The lubricating composition disclosed herein comprises an oil with lubricating viscosity. Such oils may include natural oils and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrofining, unrefined oils, refined oils, re-refined oils or mixtures thereof. A more detailed description of unrefined oils, refined oils and re-refined oils is provided in WO 2008 / 147704 A1, in paragraphs

[0054] to

[0056] . A more detailed description of natural and synthetic lubricating oils is described in paragraphs

[0058] and

[0059] of WO 2008 / 147704 A1, respectively. Synthetic oils may also be produced by Fischer-Tropsch reactions, and may generally be Fischer-Tropsch hydrocarbons or waxes of hydroisomerization. In certain embodiments, oil may be prepared by Fischer-Tropsch gas-to-liquid synthesis procedures and other gas-to-liquid procedures.

[0064] Suitable oils can be produced from biological (i.e., natural) sources or by bioengineering methods. This includes naturally occurring oils such as vegetable oils and triglyceride oils that can be further refined or purified by standard methods, as well as those oils that can be derived by direct bioconversion of natural chemicals into oils or by biological formation of building block precursor molecules that can be further converted into oils by known methods.

[0065] Oils of lubricating viscosity may also be defined as defined in the "Base Stock Categories" of section 1.3 of the April 2008 edition of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils". The API guidelines are also summarized in US 7,285,516 B2 (see column 11, line 64 to column 12, line 10). In certain embodiments, the oil of lubricating viscosity may be an API Group I base oil, a Group II base oil, a Group III base oil, or a Group IV base oil (e.g., mineral oil), an ester or other synthetic oil, a Group V base oil, or any mixture thereof.

[0066] The amount of oil of lubricating viscosity present is generally the balance remaining after deducting the sum of the amounts of additives and other performance additives of the disclosed composition from 100 wt %. Exemplary amounts may include 50 wt % to 99 wt %, or 60 wt % to 98 wt %, or 70 wt % to 95 wt %, or 80 wt % to 94 wt %, or 85 wt % to 93 wt %, based on the total weight of the composition.

[0067] The lubricating composition may be in the form of a concentrate and / or in the form of a fully formulated lubricant. If the lubricating composition described herein (including the additives disclosed herein) is in the form of a concentrate (which may be combined with additional oils to form a finished lubricant in whole or in part), the ratio of these additives to the oil of lubricating viscosity and / or to the diluent oil comprises a range of 1:99 to 99:1 by weight or 80:20 to 10:90 by weight. Typically, the lubricating composition described herein comprises at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or at least 80 wt% of an oil of lubricating viscosity.

[0068] In certain embodiments, the composition has a value of 1.5 to 4.5 (such as 1.6 to 4.5, 1.7 to 4.5, 1.8 to 4.5, 1.9 to 4.5, 2 to 4.5, 2.1 to 4.5, 2.2 to 4.5, 2.3 to 4.5, 2.4 to 4.5, 2.5 to 4.5, 2.6 to 4.5, 2.7 to 4.5, 2.8 to 4.5, 2.9 to 4.5, 3 to 4.5, 3.1 to 4.5, 3.2 to 4.5, 3.3 to 4.5, 3.4 to 4.5, 3.5 to 4.5, 3.6 to 4.5, 3.7 to 4.5, 3.8 to 4.5, 3.9 to 4.5, 4 to 4.5, 4.1 to 4.5, 4.2 to 4.5, 4.3 to 4.5, 4.4 to 4.5 , 1.5 to 4.4, 1.6 to 4.4, 1.7 to 4.4, 1.8 to 4.4, 1.9 to 4.4, 2 to 4.4, 2.1 to 4.4, 2.2 to 4.4, 2.3 to 4.4, 2.4 to 4.4, 2.5 to 4.4, 2.6 to 4.4, 2.7 to 4.4, 2.8 to 4.4, 2.9 to 4.4, 3 to 4.4, 3.1 to 4.4, 3.2 to 4.4, 3.3 to 4.4, 3.4 to 4.4, 3.5 to 4.4, 3.6 to 4.4, 3.7 to 4.4, 3.8 to 4.4, 3.9 to 4.4, 4 to 4.4, 4.1 to 4.4, 4.2 to 4.4, 4.3 to 4.4, 1.5 to 4.3, 1.6 to 4.3, 1.7 to 4.3 , 1.8 to 4.3, 1.9 to 4.3, 2 to 4.3, 2.1 to 4.3, 2.2 to 4.3, 2.3 to 4.3, 2.4 to 4.3, 2.5 to 4.3, 2.6 to 4.3, 2.7 to 4.3, 2.8 to 4.3, 2.9 to 4.3, 3 to 4.3, 3.1 to 4.3, 3.2 to 4.3, 3.3 to 4.3, 3.4 to 4.3, 3.5 to 4.3, 3.6 to 4.3, 3.7 to 4.3, 3.8 to 4.3, 3.9 to 4.3, 4 to 4.3, 4.1 to 4.3, 4.2 to 4.3, 1.5 to 4.2, 1.6 to 4.2, 1.7 to 4.2, 1.8 to 4.2, 1.9 to 4.2, 2 to 4.2, 2.1 to 4.2, 2 .2 to 4.2, 2.3 to 4.2, 2.4 to 4.2, 2.5 to 4.2, 2.6 to 4.2, 2.7 to 4.2, 2.8 to 4.2, 2.9 to 4.2, 3 to 4.2, 3.1 to 4.2, 3.2 to 4.2, 3.3 to 4.2, 3.4 to 4.2, 3.5 to 4.2, 3.6 to 4.2, 3.7 to 4.2, 3.8 to 4.2, 3.9 to 4.2, 4 to 4.2, 4.1 to 4.2, 1.5 to 4.1, 1.6 to 4.1, 1.7 to 4.1, 1.8 to 4.1, 1.9 to 4.1, 2 to 4.1, 2.1 to 4.1, 2.2 to 4.1, 2.3 to 4.1, 2.4 to 4.1, 2.5 to 4.1, 2.6 to 4.1, 2.7 to 4.1, 2.8 to 4.1, 2.9 to 4.1, 3 to 4.1, 3.1 to 4.1, 3.2 to 4.1, 3.3 to 4.1, 3.4 to 4.1, 3.5 to 4.1, 3.6 to 4.1, 3.7 to 4.1, 3.8 to 4.1, 3.9 to 4.1, 4 to 4.1, 1.5 to 4, 1.6 to 4, 1.7 to 4, 1 .8 to 4, 1.9 to 4, 2 to 4, 2.1 to 4, 2.2 to 4, 2.3 to 4, 2.4 to 4, 2.5 to 4, 2.6 to 4, 2.7 to 4, 2.8 to 4, 2.9 to 4, 3 to 4, 3.1 to 4, 3.2 to 4, 3.3 to 4, 3.4 to 4, 3.5 to 4, 3.6 to 4, 3.7 to 4, 3.8 to 4, 3.9 to 4, 1.5 to 3.9, 1.6 to 3.9, 1.7 to 3.9, 1.8 to 3.9, 1.9 to 3.9, 2 to 3.9, 2.1 to 3.9, 2.2 to 3.9, 2.3 to 3.9, 2.4 to 3.9, 2.5 to 3.9, 2.6 to 3.9, 2.7 to 3.9, 2.8 to 3.9, 2.9 to 3.9, 3 to 3.9 , 3.1 to 3.9, 3.2 to 3.9, 3.3 to 3.9, 3.4 to 3.9, 3.5 to 3.9, 3.6 to 3.9, 3.7 to 3.9, 3.8 to 3.9, 1.5 to 3.8, 1.6 to 3.8, 1.7 to 3.8, 1.8 to 3.8, 1.9 to 3.8, 2 to 3.8, 2.1 to 3.8, 2.2 to 3. 8, 2.3 to 3.8, 2.4 to 3.8, 2.5 to 3.8, 2.6 to 3.8, 2.7 to 3.8, 2.8 to 3.8, 2.9 to 3.8, 3 to 3.8, 3.1 to 3.8, 3.2 to 3.8, 3.3 to 3.8, 3.4 to 3.8, 3.5 to 3.8, 3.6 to 3.8, 3.7 to 3.8, 1.5 to 3 .7, 1.6 to 3.7, 1.7 to 3.7, 1.8 to 3.7, 1.9 to 3.7, 2 to 3.7, 2.1 to 3.7, 2.2 to 3.7, 2.3 to 3.7, 2.4 to 3.7, 2.5 to 3.7, 2.6 to 3.7, 2.7 to 3.7, 2.8 to 3.7, 2.9 to 3.7, 3 to 3.7, 3.1 to 3. 7, 3.2 to 3.7, 3.3 to 3.7, 3.4 to 3.7, 3.5 to 3.7, 3.6 to 3.7, 1.5 to 3.6, 1.6 to 3.6, 1.7 to 3.6, 1.8 to 3.6, 1.9 to 3.6, 2 to 3.6, 2.1 to 3.6, 2.2 to 3.6, 2.3 to 3.6, 2.4 to 3.6, 2.5 to 3 .6, 2.6 to 3.6, 2.7 to 3.6, 2.8 to 3.6, 2.9 to 3.6, 3 to 3.6, 3.1 to 3.6, 3.2 to 3.6, 3.3 to 3.6, 3.4 to 3.6, 3.5 to 3.6, 1.5 to 3.5, 1.6 to 3.5, 1.7 to 3.5, 1.8 to 3.5, 1.9 to 3.5, 2 to 3.5, 2.1 to 3.5, 2.2 to 3.5, 2.3 to 3.5, 2.4 to 3.5, 2.5 to 3.5, 2.6 to 3.5, 2.7 to 3.5, 2.8 to 3.5, 2.9 to 3.5, 3 to 3.5, 3.1 to 3.5, 3.2 to 3.5, 3.3 to 3.5, 3.4 to 3.5, 1.5 to 3.4, 1.6 to 3 .4, 1.7 to 3.4, 1.8 to 3.4, 1.9 to 3.4, 2 to 3.4, 2.1 to 3.4, 2.2 to 3.4, 2.3 to 3.4, 2.4 to 3.4, 2.5 to 3.4, 2.6 to 3.4, 2.7 to 3.4, 2.8 to 3.4, 2.9 to 3.4, 3 to 3.4, 3.1 to 3.4, 3.2 to 3. 4, 3.3 to 3.4, 1.5 to 3.3, 1.6 to 3.3, 1.7 to 3.3, 1.8 to 3.3, 1.9 to 3.3, 2 to 3.3, 2.1 to 3.3, 2.2 to 3.3, 2.3 to 3.3, 2.4 to 3.3, 2.5 to 3.3, 2.6 to 3.3, 2.7 to 3.3, 2.8 to 3.3, 2.9 to 3 .3, 3 to 3.3, 3.1 to 3.3, 3.2 to 3.3, 1.5 to 3.2, 1.6 to 3.2, 1.7 to 3.2, 1.8 to 3.2, 1.9 to 3.2, 2 to 3.2, 2.1 to 3.2, 2.2 to 3.2, 2.3 to 3.2, 2.4 to 3.2, 2.5 to 3.2, 2.6 to 3.2, 2.7 to 3. 2, 2.8 to 3.2, 2.9 to 3.2, 3 to 3.2, 3.1 to 3.2, 1.5 to 3.1, 1.6 to 3.1, 1.7 to 3.1, 1.8 to 3.1, 1.9 to 3.1, 2 to 3.1, 2.1 to 3.1, 2.2 to 3.1, 2.3 to 3.1, 2.4 to 3.1, 2.5 to 3.1, 2.6 to 3.1 , 2.7 to 3.1, 2.8 to 3.1, 2.9 to 3.1, 3 to 3.1, 1.5 to 3, 1.6 to 3, 1.7 to 3, 1.8 to 3, 1.9 to 3, 2 to 3, 2.1 to 3, 2.2 to 3, 2.3 to 3, 2.4 to 3, 2.5 to 3, 2.6 to 3, 2.7 to 3, 2.8 to 3, 2.9 to 3, 1.5 to 2. 9, 1.6 to 2.9, 1.7 to 2.9, 1.8 to 2.9, 1.9 to 2.9, 2 to 2.9, 2.1 to 2.9, 2.2 to 2.9, 2.3 to 2.9, 2.4 to 2.9, 2.5 to 2.9, 2.6 to 2.9, 2.7 to 2.9, 2.8 to 2.9, 1.5 to 2.8, 1.6 to 2.8, 1.7 to 2 .8, 1.8 to 2.8, 1.9 to 2.8, 2 to 2.8, 2.1 to 2.8, 2.2 to 2.8, 2.3 to 2.8, 2.4 to 2.8, 2.5 to 2.8, 2.6 to 2.8, 2.7 to 2.8, 1.5 to 2.7, 1.6 to 2.7, 1.7 to 2.7, 1.8 to 2.7, 1.9 to 2.7, 2 to 2.7, 2.1 to 2.7, 2.2 to 2.7, 2.3 to 2.7, 2.4 to 2.7, 2.5 to 2.7, 2.6 to 2.7, 1.5 to 2.6, 1.6 to 2.6, 1.7 to 2.6, 1.8 to 2.6, 1.9 to 2.6, 2 to 2.6, 2.1 to 2.6, 2.2 to 2.6, 2.3 to 2.6, 2.4 to 2.6, 2.5 to 2.6, 1.5 to 2.5, 1.6 to 2.5, 1.7 to 2.5, 1.8 to 2.5, 1.9 to 2.5, 2 to 2.5, 2.1 to 2.5, 2.2 to 2.5, 2.3 to 2.5, 2.4 to 2.5, 1.5 to 2.4, 1.6 to 2.4, 1.7 to 2.4, 1.8 to 2.4, 1.9 to 2.4, 2 to 2.4, 2.1 to 2.4, 2.2 to 2.4, 2.3 to 2.4, 1.5 to 2 .3, 1.6 to 2.3, 1.7 to 2.3, 1.8 to 2.3, 1.9 to 2.3, 2 to 2.3, 2.1 to 2.3, 2.2 to 2.3, 1.5 to 2.2, 1.6 to 2.2, 1.7 to 2.2, 1.8 to 2.2, 1.9 to 2.2, 2 to 2.2, 2.1 to 2.2, 1.5 to 2.1, 1.6 to 2.1, 1.7 to 2.1, 1.8 to 2.1, 1 .9 to 2.1, 2 to 2.1, 1.5 to 2, 1.6 to 2, 1.7 to 2, 1.8 to 2, 1.9 to 2, 1.5 to 1.9, 1.6 to 1.9, 1.7 to 1.9, 1.8 to 1.9, 1.5 to 1.8, 1.6 to 1.8, 1.7 to 1.8, 1.5 to 1.7, 1.6 to 1.7, or 1.5 to 1.6) mPa·s high temperature high shear viscosity as measured at 150°C according to ASTM D4683. When referring to ASTM D4683 herein, it means version 20 published on June 10, 2020. .

[0069] In certain embodiments, the alkaline earth metal alkyl detergent contributes 2 to 7 (such as 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 7, 4 to 6, 4 to 5, 5 to 7, 5 to 6, or 6 to 7) TBN as measured by ASTM D4739. The acronym "TBN" refers to Total Base Number, as known to those skilled in the art. When referring to ASTM D4739 herein, it means Version 11 published on February 7, 2018.

[0070] In certain embodiments, the composition has a sulfated ash content of less than or equal to 1 wt % (such as less than or equal to 0.9 wt %, 0.8 wt %, 0.7 wt %, 0.6 wt %, 0.5 wt %, 0.4 wt %, 0.3 wt %, 0.2 wt % or 0.1 wt %), based on the total weight of the composition, as measured by ASTM D874. When ASTM D874 is referred to herein, it means Version 13a published on June 1, 2018. In certain embodiments, such as when the composition has a sulfated ash content of less than or equal to 1 wt %, based on the total weight of the composition, the alkaline earth metal alkyl detergent contributes 6 to 7 TBN to the composition, such as measured by ASTM D4739. In certain embodiments, such as when the composition has a sulfated ash content of less than or equal to 0.5 wt %, based on the total weight of the composition, the alkaline earth metal alkyl detergent contributes 2 to 3.5 TBN to the composition, such as measured by ASTM D4739.

[0071] In certain embodiments, the compound according to Formula I is present at 1 to 10 wt % (such as 2 to 10 wt %, 3 to 10 wt %, 4 to 10 wt %, 5 to 10 wt %, 6 to 10 wt %, 7 to 10 wt %, 8 to 10 wt %, 9 to 10 wt %, 1 to 9 wt %, 2 to 9 wt %, 3 to 9 wt %, 4 to 9 wt %, 5 to 9 wt %, 6 to 9 wt %, 7 to 9 wt %, 8 to 9 wt %, 1 to 8 wt %, 2 to 8 wt %, 3 to 8 wt %, 4 to 8 wt %, % to 5 wt %, 2 wt % to 5 wt %, 3 wt % to 5 wt %, 4 wt % to 5 wt %, 1 wt % to 4 wt %, 2 wt % to 4 wt %, 3 wt % to 4 wt %, 1 wt % to 3 wt %, 2 wt % to 3 wt %, or 1 wt % to 2 wt %) is present in the composition.

[0072] In certain embodiments, the composition has 2 to 12 (such as 3 to 12, 4 to 12, 5 to 12, 6 to 12, 7 to 12, 8 to 12, 9 to 12, 10 to 12, 11 to 12, 2 to 11, 3 to 11, 4 to 11, 5 to 11, 6 to 11, 7 to 11, 8 to 11, 9 to 11, 10 to 11, 2 to 10, 3 to 10, 4 to 10, 5 to 10, 6 to 10, or 2 to 3) TBN as measured by ASTM D2896.

[0073] In certain embodiments, the alkaline earth metal alkyl detergent may be present in the composition in an amount less than 3.5 wt%, such as less than 3.4 wt%, 3.3 wt%, 3.2 wt%, 3.1 wt%, 3 wt%, 2.9 wt%, 2.8 wt%, 2.7 wt%, 2.6 wt%, 2.5 wt%, 2.4 wt%, 2.3 wt%, 2.2 wt%, 2.1 wt%, 2. wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, or 0.1 wt%, based on the total weight of the composition. In certain embodiments, the alkaline earth metal alkyl detergent is present in an amount of greater than 0 wt % to 3.5 wt % (such as 0.1 wt % to 3.5 wt %, 0.2 wt % to 3.5 wt %, 0.3 wt % to 3.5 wt %, 0.4 wt % to 3.5 wt %, 0.5 wt % to 3.5 wt %, 0.6 wt % to 3.5 wt %, 0.7 wt % to 3.5 wt %, 0.8 wt % to 3.5 wt %, 0.9 wt % to 3.5 wt %, 1 wt % to 3.5 wt %, 1.5 wt % to 3.5 wt %, 2.5 wt % to 3.5 wt %, 3.5 wt % to 3.5 wt %, 4.5 wt % to 3.5 wt %, 5. % to 3.5 wt %, 1.1 % to 3.5 wt %, 1.2 % to 3.5 wt %, 1.3 % to 3.5 wt %, 1.4 % to 3.5 wt %, 1.5 % to 3.5 wt %, 1.6 % to 3.5 wt %, 1.7 % to 3.5 wt %, 1.8 % to 3.5 wt %, 1.9 % to 3.5 wt %, 2 % to 3.5 wt %, 2.1 % to 3.5 wt %, 2.2 % to 3.5 wt %, 2. 3 wt % to 3.5 wt %, 2.4 wt % to 3.5 wt %, 2.5 wt % to 3.5 wt %, 2.6 wt % to 3.5 wt %, 2.7 wt % to 3.5 wt %, 2.8 wt % to 3.5 wt %, 2.9 wt % to 3.5 wt %, 3 wt % to 3.5 wt %, 3.1 wt % to 3.5 wt %, 3.2 wt % to 3.5 wt %, 3.3 wt % to 3.5 wt %, 3.4 wt % to 3.5 wt %, 3.4 wt % to 3.5 wt %, 3.0 wt % to 3.4 wt %, 3.1 wt % to 3.5 wt %, 3.2 wt % to 3.5 wt %, 3.3 wt % to 3.5 wt %, 3.4 wt % to 3.5 wt %, 3.5 wt % to 3.4 wt %, 3.0 wt % to 3.5 ... %, 0.1 wt % to 3.4 wt %, 0.2 wt % to 3.4 wt %, 0.3 wt % to 3.4 wt %, 0.4 wt % to 3.4 wt %, 0.5 wt % to 3.4 wt %, 0.6 wt % to 3.4 wt %, 0.7 wt % to 3.4 wt %, 0.8 wt % to 3.4 wt %, 0.9 wt % to 3.4 wt %, 1 wt % to 3.4 wt %, 1.1 wt % to 3.4 wt %, 1.2 wt % to 3.4 wt %, 1.3 wt % to 3.4 wt %.4 wt %, 1.4 wt % to 3.4 wt %, 1.5 wt % to 3.4 wt %, 1.6 wt % to 3.4 wt %, 1.7 wt % to 3.4 wt %, 1.8 wt % to 3.4 wt %, 1.9 wt % to 3.4 wt %, 2 wt % to 3.4 wt %, 2.1 wt % to 3.4 wt %, 2.2 wt % to 3.4 wt %, 2.3 wt % to 3.4 wt %, 2.4 wt % to 3.4 wt %, 2.5 wt % to 3.4 wt %, 2.6 wt % to 3.4 wt %, 2.7 wt % to 3.4 wt %, 2.8 wt % to 3.4 wt %, 2.9 wt % to 3.4 wt %, 3.1 wt % to 3.4 wt %, 3.2 wt % to 3.4 wt %, %, 3.2 wt% to 3.4 wt%, 3.3 wt% to 3.4 wt%, greater than 0 wt% to 3.3 wt%, 0.1 wt% to 3.3 wt%, 0.2 wt% to 3.3 wt%, 0.3 wt% to 3.3 wt%, 0.4 wt% to 3.3 wt%, 0.5 wt% to 3.3 wt%, 0.6 wt% to 3.3 wt%, 0.7 wt% to 3.3 wt%, 0.8 wt% to 3.3 wt%, 0.9 wt% to 3.3 wt%, 1 wt% to 3.3 wt%, 1.1 wt% to 3.3 wt%, 1.2 wt% to 3.3 wt%, 1.3 wt% to 3.3 wt%, 1.4 wt% to 3.3 wt%, 1.5 wt% to 3.3 wt%. 3 wt %, 1.6 wt % to 3.3 wt %, 1.7 wt % to 3.3 wt %, 1.8 wt % to 3.3 wt %, 1.9 wt % to 3.3 wt %, 2 wt % to 3.3 wt %, 2.1 wt % to 3.3 wt %, 2.2 wt % to 3.3 wt %, 2.3 wt % to 3.3 wt %, 2.4 wt % to 3.3 wt %, 2.5 wt % to 3.3 wt %, 2.6 wt % to 3.3 wt %, 2.7 wt % to 3.3 wt %, 2.8 wt % to 3.3 wt %, 2.9 wt % to 3.3 wt %, 3 wt % to 3.3 wt %, 3.1 wt % to 3.3 wt %, 3.2 wt % to 3.3 wt %, and 3.2 wt % to 3.2 wt %, or more than 0 wt %. %, 0.1 wt % to 3.2 wt %, 0.2 wt % to 3.2 wt %, 0.3 wt % to 3.2 wt %, 0.4 wt % to 3.2 wt %, 0.5 wt % to 3.2 wt %, 0.6 wt % to 3.2 wt %, 0.7 wt % to 3.2 wt %, 0.8 wt % to 3.2 wt %, 0.9 wt % to 3.2 wt %, 1 wt % to 3.2 wt %, 1.1 wt % to 3.2 wt %, 1.2 wt % to 3.2 wt %, 1.3 wt % to 3.2 wt %, 1.4 wt % to 3.2 wt %, 1.5 wt % to 3.2 wt %, 1.6 wt % to 3.2 wt %, 1.7 wt % to 3.2 wt %, 1.8 wt % to 3.2 wt %.%, 1.9 wt % to 3.2 wt %, 2 wt % to 3.2 wt %, 2.1 wt % to 3.2 wt %, 2.2 wt % to 3.2 wt %, 2.3 wt % to 3.2 wt %, 2.4 wt % to 3.2 wt %, 2.5 wt % to 3.2 wt %, 2.6 wt % to 3.2 wt %, 2.7 wt % to 3.2 wt %, 2.8 wt % to 3.2 wt %, 2.9 wt % to 3.2 wt %, 3 wt % to 3.2 wt %, 3.1 wt % to 3.2 wt %, greater than 0 wt % to 3.1 wt %, 0.1 wt % to 3.1 wt %, 0.2 wt % to 3.1 wt %, 0.3 wt % to 3.1 wt %, 0.4 wt % to 3.1 %, 0.5 wt % to 3.1 wt %, 0.6 wt % to 3.1 wt %, 0.7 wt % to 3.1 wt %, 0.8 wt % to 3.1 wt %, 0.9 wt % to 3.1 wt %, 1 wt % to 3.1 wt %, 1.1 wt % to 3.1 wt %, 1.2 wt % to 3.1 wt %, 1.3 wt % to 3.1 wt %, 1.4 wt % to 3.1 wt %, 1.5 wt % to 3.1 wt %, 1.6 wt % to 3.1 wt %, 1.7 wt % to 3.1 wt %, 1.8 wt % to 3.1 wt %, 1.9 wt % to 3.1 wt %, 2 wt % to 3.1 wt %, 2.1 wt % to 3.1 wt %, 2.2 wt % to 3.1 wt %. %, 2.3 wt % to 3.1 wt %, 2.4 wt % to 3.1 wt %, 2.5 wt % to 3.1 wt %, 2.6 wt % to 3.1 wt %, 2.7 wt % to 3.1 wt %, 2.8 wt % to 3.1 wt %, 2.9 wt % to 3.1 wt %, 3 wt % to 3.1 wt %, greater than 0 wt % to 3 wt %, 0.1 wt % to 3 wt %, 0.2 wt % to 3 wt %, 0.3 wt % to 3 wt %, 0.4 wt % to 3 wt %, 0.5 wt % to 3 wt %, 0.6 wt % to 3 wt %, 0.7 wt % to 3 wt %, 0.8 wt % to 3 wt %, 0.9 wt % to 3 wt %, 1 wt % to 3 wt %, 1.1 wt % 3 wt %, 1.2 wt % to 3 wt %, 1.3 wt % to 3 wt %, 1.4 wt % to 3 wt %, 1.5 wt % to 3 wt %, 1.6 wt % to 3 wt %, 1.7 wt % to 3 wt %, 1.8 wt % to 3 wt %, 1.9 wt % to 3 wt %, 2 wt % to 3 wt %, 2.1 wt % to 3 wt %, 2.2 wt % to 3 wt %, 2.3 wt % to 3 wt %, 2.4 wt % to 3 wt %, 2.5 wt % to 3 wt %, 2.6 wt % to 3 wt %, 2.7 wt % to 3 wt %, 2.8 wt % to 3 wt %, 2.9 wt % to 3 wt %, 0.1 wt % to 2.9 wt %, 0.2 wt % to 2.9 wt %, 0.3 wt % to 2.9 wt %, 0.4 wt % to 3.9 wt %, 0.6 wt % to 3.9 wt %, 0.7 wt % to 3.9 wt %, 0.8 wt % to 3.9 wt %, 0.9 wt % to 3.9 wt %, 0.1 wt % to 3.9 wt %, 0.9 wt % to 3.9 wt %.% to 2.9 wt %, 0.2 wt % to 2.9 wt %, 0.3 wt % to 2.9 wt %, 0.4 wt % to 2.9 wt %, 0.5 wt % to 2.9 wt %, 0.6 wt % to 2.9 wt %, 0.7 wt % to 2.9 wt %, 0.8 wt % to 2.9 wt %, 0.9 wt % to 2.9 wt %, 1 wt % to 2.9 wt %, 1.1 wt % to 2.9 wt %, 1.2 wt % to 2.9 wt %, 1.3 wt % to 2.9 wt %, 1.4 wt % to 2.9 wt %, 1.5 wt % to 2.9 wt %, 1.6 wt % to 2.9 wt %, 1.7 wt % to 2.9 wt %, 1.8 wt % to 2.9 wt %, 1.9 wt % to 2.9 wt %, 2 % to 2.9 wt%, 2.1 wt% to 2.9 wt%, 2.2 wt% to 2.9 wt%, 2.3 wt% to 2.9 wt%, 2.4 wt% to 2.9 wt%, 2.5 wt% to 2.9 wt%, 2.6 wt% to 2.9 wt%, 2.7 wt% to 2.9 wt%, 2.8 wt% to 2.9 wt%, greater than 0 wt% to 2.8 wt%, 0.1 wt% to 2.8 wt%, 0.2 wt% to 2.8 wt%, 0.3 wt% to 2.8 wt%, 0.4 wt% to 2.8 wt%, 0.5 wt% to 2.8 wt%, 0.6 wt% to 2.8 wt%, 0.7 wt% to 2.8 wt%, 0.8 wt% to 2.8 wt%, 0. .9 wt % to 2.8 wt %, 1 wt % to 2.8 wt %, 1.1 wt % to 2.8 wt %, 1.2 wt % to 2.8 wt %, 1.3 wt % to 2.8 wt %, 1.4 wt % to 2.8 wt %, 1.5 wt % to 2.8 wt %, 1.6 wt % to 2.8 wt %, 1.7 wt % to 2.8 wt %, 1.8 wt % to 2.8 wt %, 1.9 wt % to 2.8 wt %, 2 wt % to 2.8 wt %, 2.1 wt % to 2.8 wt %, 2.2 wt % to 2.8 wt %, 2.3 wt % to 2.8 wt %, 2.4 wt % to 2.8 wt %, 2.5 wt % to 2.8 wt %, 2.6 wt % to 2.8 wt %, 2. 7 wt % to 2.8 wt %, greater than 0 wt % to 2.7 wt %, 0.1 wt % to 2.7 wt %, 0.2 wt % to 2.7 wt %, 0.3 wt % to 2.7 wt %, 0.4 wt % to 2.7 wt %, 0.5 wt % to 2.7 wt %, 0.6 wt % to 2.7 wt %, 0.7 wt % to 2.7 wt %, 0.8 wt % to 2.7 wt %, 0.9 wt % to 2.7 wt %, 1 wt % to 2.7 wt %, 1.1 wt % to 2.7 wt %, 1.2 wt % to 2.7 wt %, 1.3 wt % to 2.7 wt %, 1.4 wt % to 2.7 wt %, 1.5 wt % to 2.7 wt %, 1.6 wt % to 2.7 wt %, 1.% to 2.6 wt %, 0.1 wt % to 2.6 wt %, 0.2 wt % to 2.6 wt %, 0.3 wt % to 2.6 wt %, 0.4 wt % to 2.6 wt %, 0.5 wt % to 2.6 wt %, 0.6 wt % to 2.6 wt %, 0.7 wt % to 2.6 wt %, 0.8 wt % to 2.6 wt %, 0.9 wt ...9 wt % to 2.6 wt %, 0.9 wt % to 2.6 wt %, 0.1 wt .8 wt % to 2.6 wt %, 0.9 wt % to 2.6 wt %, 1 wt % to 2.6 wt %, 1.1 wt % to 2.6 wt %, 1.2 wt % to 2.6 wt %, 1.3 wt % to 2.6 wt %, 1.4 wt % to 2.6 wt %, 1.5 wt % to 2.6 wt %, 1.6 wt % to 2.6 wt %, 1.7 wt % to 2.6 wt %, 1.8 wt % to 2.6 wt %, 1.9 wt % to 2.6 wt %, 2 wt % to 2.6 wt %, 2.1 wt % to 2.6 wt %, 2.2 wt % to 2.6 wt %, 2.3 wt % to 2.6 wt %, 2.4 wt % to 2.6 wt %, 2.5 wt % to 2.6 wt %, more than 0 wt % to 2.5 wt %, 0.1 wt % to 2.5 wt %, 0.2 wt % to 2.5 wt %, 0.3 wt % to 2.5 wt %, 0.4 wt % to 2.5 wt %, 0.5 wt % to 2.5 wt %, 0.6 wt % to 2.5 wt %, 0.7 wt % to 2.5 wt %, 0.8 wt % to 2.5 wt %, 0.9 wt % to 2.5 wt %, 1 wt % to 2.5 wt %, 1.1 wt % to 2.5 wt %, 1.2 wt % to 2.5 wt %, 1.3 wt % to 2.5 wt %, 1.4 wt % to 2.5 wt %, 1.5 wt % to 2.5 wt %, 1.6 wt % to 2.5 wt %, 1.7 wt % to 2.5 wt %, 1 .8 wt % to 2.5 wt %, 1.9 wt % to 2.5 wt %, 2 wt % to 2.5 wt %, 2.1 wt % to 2.5 wt %, 2.2 wt % to 2.5 wt %, 2.3 wt % to 2.5 wt %, 2.4 wt % to 2.5 wt %, greater than 0 wt % to 2.4 wt %, 0.1 wt % to 2.4 wt %, 0.2 wt % to 2.4 wt %, 0.3 wt % to 2.4 wt %, 0.4 wt % to 2.4 wt %, 0.5 wt % to 2.4 wt %, 0.6 wt % to 2.4 wt %, 0.7 wt % to 2.4 wt %, 0.8 wt % to 2.4 wt %, 0.9 wt % to 2.4 wt %, 1 wt % to 2.4 wt %, 1.1 wt % to 2.4 wt %, 1.2 wt % to 2.4 wt %, 1.3 wt % to 2.4 wt %, 1.4 wt % to 2.4 wt %, 1.5 wt % to 2.4 wt %, 1.6 wt % to 2.4 wt %, 1.7 wt % to 2.4 wt %, 1.8 wt % to 2.4 wt %, 1.9 wt % to 2.4 wt %, 2 wt % to 2.4 wt %, 2.1 wt % to 2.4 wt %, 2.2 wt % to 2.4 wt %, 2.3 wt % to 2.4 wt %, greater than 0 wt % to 2.3 wt %, 0.1 wt % to 2.3 wt %, 0.2 wt % to 2.3 wt %, 0.3 wt % to 2.3 wt %, 0.4 wt % to 2.3 wt %, 0 %. 0.5 wt % to 2.3 wt %, 0.6 wt % to 2.3 wt %, 0.7 wt % to 2.3 wt %, 0.8 wt % to 2.3 wt %, 0.9 wt % to 2.3 wt %, 1 wt % to 2.3 wt %, 1.1 wt % to 2.3 wt %, 1.2 wt % to 2.3 wt %, 1.3 wt % to 2.3 wt %, 1.4 wt % to 2.3 wt %, 1.5 wt % to 2.3 wt %, 1.6 wt % to 2.3 wt %, 1.7 wt % to 2.3 wt %, 1.8 wt % to 2.3 wt %, 1.9 wt % to 2.3 wt %, 2 wt % to 2.3 wt %, 2.1 wt % to 2.3 wt %, 2.2 wt % to 2.3 wt %, more than 0 wt % to 2.2 wt %, 0.1 wt % to 2.2 wt %, 0.2 wt % to 2.2 wt %, 0.3 wt % to 2.2 wt %, 0.4 wt % to 2.2 wt %, 0.5 wt % to 2.2 wt %, 0.6 wt % to 2.2 wt %, 0.7 wt % to 2.2 wt %, 0.8 wt % to 2.2 wt %, 0.9 wt % to 2.2 wt %, 1 wt % to 2.2 wt %, 1.1 wt % to 2.2 wt %, 1.2 wt % to 2.2 wt %, 1.3 wt % to 2.2 wt %, 1.4 wt % to 2.2 wt %, 1.5 wt % to 2.2 wt %, 1.6 wt % to 2.2 wt %, 1.7 wt % to 2.2 wt %, 1 .8 wt % to 2.2 wt %, 1.9 wt % to 2.2 wt %, 2 wt % to 2.2 wt %, 2.1 wt % to 2.2 wt %, greater than 0 wt % to 2.1 wt %, 0.1 wt % to 2.1 wt %, 0.2 wt % to 2.1 wt %, 0.3 wt % to 2.1 wt %, 0.4 wt % to 2.1 wt %, 0.5 wt % to 2.1 wt %, 0.6 wt % to 2.1 wt %, 0.7 wt % to 2.1 wt %, 0.8 wt % to 2.1 wt %, 0.9 wt % to 2.1 wt %, 1 wt % to 2.1 wt %, 1.1 wt % to 2.1 wt %, 1.2 wt % to 2.1 wt %, 1.3 wt % to 2.1 wt %, 1.4 wt % to 2.1 wt %, 1.5 wt % to 2.1 wt %, 1.6 wt % to 2.1 wt %, 1.7 wt % to 2.1 wt %, 1.8 wt % to 2.1 wt %, 1.9 wt % to 2.1 wt %, 2 wt % to 2.1 wt %, greater than 0 wt % to 2 wt %, 0.1 wt % to 2 wt %, 0.2 wt % to 2 wt %, 0.3 wt % to 2 wt %, 0.4 wt % to 2 wt %, 0.5 wt % to 2 wt %, 0.6 wt % to 2 wt %, 0.7 wt % to 2 wt %, 0.8 wt % to 2 wt %, 0.9 wt % to 2 wt %, 1.1 wt % to 2 wt %, 1.2 wt % to 2 wt %, 1. 3 wt % to 2 wt %, 1.4 wt % to 2 wt %, 1.5 wt % to 2 wt %, 1.6 wt % to 2 wt %, 1.7 wt % to 2 wt %, 1.8 wt % to 2 wt %, 1.9 wt % to 2 wt %, greater than 0 wt % to 1.9 wt %, 0.1 wt % to 1.9 wt %, 0.2 wt % to 1.9 wt %, 0.3 wt % to 1.9 wt %, 0.4 wt % to 1.9 wt %, 0.5 wt % to 1.9 wt %, 0.6 wt % to 1.9 wt %, 0.7 wt % to 1.9 wt %, 0.8 wt % to 1.9 wt %, 0.9 wt % to 1.9 wt %, 1.1 wt % to 1.9 wt %, 1.2 wt % to 1.9 wt %, 1.3 wt % to 1.9 wt %, 1.4 wt % to 1.9 wt %, 1.5 wt % to 1.9 wt %, 1.6 wt % to 1.9 wt %, 1.7 wt % to 1 2 wt % to 1.9 wt %, 1.3 wt % to 1.9 wt %, 1.4 wt % to 1.9 wt %, 1.5 wt % to 1.9 wt %, 1.6 wt % to 1.9 wt %, 1.7 wt % to 1.9 wt %, 1.8 wt % to 1.9 wt %, greater than 0 wt % to 1.8 wt %, 0.1 wt % to 1.8 wt %, 0.2 wt % to 1.8 wt %, 0.3 wt % to 1.8 wt %, 0.4 wt % to 1.8 wt %, 0.5 wt % to 1.8 wt %, 0.6 wt % to 1.8 wt %, 0.7 wt % to 1.8 wt %, 0.8 wt % to 1.8 wt %, 0.9 wt % to 1.8 wt %, 1.1 wt % to 1.8 wt %, 1. 1 wt % to 1.8 wt %, 1.2 wt % to 1.8 wt %, 1.3 wt % to 1.8 wt %, 1.4 wt % to 1.8 wt %, 1.5 wt % to 1.8 wt %, 1.6 wt % to 1.8 wt %, 1.7 wt % to 1.8 wt %, greater than 0 wt % to 1.7 wt %, 0.1 wt % to 1.7 wt %, 0.2 wt % to 1.7 wt %, 0.3 wt % to 1.7 wt %, 0.4 wt % to 1.7 wt %, 0.5 wt % to 1.7 wt %, 0.6 wt % to 1.7 wt %, 0.7 wt % to 1.7 wt %, 0.8 wt % to 1.7 wt %, 0.9 wt % to 1.7 wt %, 1.7 wt % to 1.7 wt %, 1.8 wt % to 1.8 wt %, 1.9 wt % to 1.8 wt %, 2.1 wt % to 1.7 wt %, 1.2 wt % to 1.7 wt %, 1.3 wt % to 1.7 wt %, 1.4 wt % to 1.7 wt %, 1.5 wt % to 1.7 wt %, 1.6 wt % to 1.7 wt %, greater than 0 wt % to 1.6 wt %, 0.1 wt % to 1.6 wt %, 0.2 wt % to 1.6 wt %, 0.3 wt % to 1.6 wt %, 0.4 wt % to 1.6 wt %, 0.5 wt % to 1.6 wt %, 0.6 wt % to 1.6 wt %, 0.7 wt % to 1.6 wt %, 0.8 wt % to 1.6 wt %, 0.9 wt % to 1.6 wt %, 1 wt % to 1.6 wt %, 1.1 wt % to 1.6 wt %, 1. 2 wt % to 1.6 wt %, 1.3 wt % to 1.6 wt %, 1.4 wt % to 1.6 wt %, 1.5 wt % to 1.6 wt %, greater than 0 wt % to 1.5 wt %, 0.1 wt % to 1.5 wt %, 0.2 wt % to 1.5 wt %, 0.3 wt % to 1.5 wt %, 0.4 wt % to 1.5 wt %, 0.5 wt % to 1.5 wt %, 0.6 wt % to 1.5 wt %, 0.7 wt % to 1.5 wt %, 0.8 wt % to 1.5 wt %, 0.9 wt % to 1.5 wt %, 1 wt % to 1.5 wt %, 1.1 wt % to 1.5 wt %, 1.2 wt % to 1.5 wt %, 1.3 wt % to 1.5 wt %, 1. 4 wt % to 1.5 wt %, greater than 0 wt % to 1.4 wt %, 0.1 wt % to 1.4 wt %, 0.2 wt % to 1.4 wt %, 0.3 wt % to 1.4 wt %, 0.4 wt % to 1.4 wt %, 0.5 wt % to 1.4 wt %, 0.6 wt % to 1.4 wt %, 0.7 wt % to 1.4 wt %, 0.8 wt % to 1.4 wt %, 0.9 wt % to 1.4 wt %, 1 wt % to 1.4 wt %, 1.1 wt % to 1.4 wt %, 1.2 wt % to 1.4 wt %, 1.3 wt % to 1.4 wt %, greater than 0 wt % to 1.3 wt %, 0.1 wt % to 1.3 wt %, 0.2 wt % to 1.3 wt %, 0. 3 wt % to 1.3 wt %, 0.4 wt % to 1.3 wt %, 0.5 wt % to 1.3 wt %, 0.6 wt % to 1.3 wt %, 0.7 wt % to 1.3 wt %, 0.8 wt % to 1.3 wt %, 0.9 wt % to 1.3 wt %, 1 wt % to 1.3 wt %, 1.1 wt % to 1.3 wt %, 1.2 wt % to 1.3 wt %, greater than 0 wt % to 1.2 wt %, 0.1 wt % to 1.2 wt %, 0.2 wt % to 1.2 wt %, 0.3 wt % to 1.2 wt %, 0.4 wt % to 1.2 wt %, 0.5 wt % to 1.2 wt %, 0.6 wt % to 1.2 wt %, 0.7 wt % to 1.2 wt %, 0.8 wt % to 1.2 wt %, 0.9 wt % to 1.2 wt %, 1 wt % to 1.2 wt %, 1.1 wt % to 1.2 wt %, greater than 0 wt % to 1.1 wt %, 0.1 wt % to 1.1 wt %, 0.2 wt % to 1.1 wt %, 0.3 wt % to 1.1 wt %, 0.4 wt % to 1.1 wt %, 0.5 wt % to 1.1 wt %, 0.6 wt % to 1.1 wt %, 0.7 wt % to 1.1 wt %, 0.8 wt % to 1.1 wt %, 0.9 wt % to 1.1 wt %, 1 wt % to 1.1 wt %, greater than 0 wt % to 1 wt %, 0.1 wt % to 1 wt %, 0.2 wt % to 1 wt %, 0.3 wt % to 1 wt %, 0.4 wt % to 1 wt %, 0.5 wt % to 1 wt %, 0.6 wt % to 1 wt %, 0.7 wt % to 1 wt %, 0.8 wt % to 1 wt %, 0.9 wt % to 1 wt %, greater than 0 wt % to 0.9 wt %, 0.1 wt % to 0.9 wt %, 0.2 wt % to 0.9 wt %, 0.3 wt % to 0.9 wt %, 0.4 wt % to 0.9 wt %, 0.5 wt % to 0.9 wt %, 0.6 wt % to 0.9 wt %, 0.7 wt % to 0.9 wt %, 0.8 wt % to 0.9 wt %, greater than 0 wt % to 0.8 wt %, 0.1 wt % to 0.9 wt %. 8 wt%, 0.2 wt% to 0.8 wt%, 0.3 wt% to 0.8 wt%, 0.4 wt% to 0.8 wt%, 0.5 wt% to 0.8 wt%, 0.6 wt% to 0.8 wt%, 0.7 wt% to 0.8 wt%, greater than 0 wt% to 0.7 wt%, 0.1 wt% to 0.7 wt%, 0.2 wt% to 0.7 wt%, 0.3 wt% to 0.7 wt%, 0.4 wt% to 0.7 wt%, 0.5 wt% to 0.7 wt%, 0.6 wt% to 0.7 wt%, greater than 0 wt% to 0.6 wt%, 0.1 wt% to 0.6 wt%, 0.2 wt% to 0.6 wt%, 0.3 wt% to 0 .6 wt %, 0.4 wt % to 0.6 wt %, 0.5 wt % to 0.6 wt %, greater than 0 wt % to 0.5 wt %, 0.1 wt % to 0.5 wt %, 0.2 wt % to 0.5 wt %, 0.3 wt % to 0.5 wt %, 0.4 wt % to 0.5 wt %, greater than 0 wt % to 0.4 wt %, 0.1 wt % to 0.4 wt %, 0.2 wt % to 0.4 wt %, 0.3 wt % to 0.4 wt %, greater than 0 wt % to 0.3 wt %, 0.1 wt % to 0.3 wt %, 0.2 wt % to 0.3 wt %, greater than 0 wt % to 0.2 wt %, 0.1 wt % to 0.2, or greater than 0 wt % to 0.1 wt %) is present in the composition. In certain embodiments, the alkaline earth metal alkyl detergent comprises an alkaline earth metal, the alkaline earth metal being at least one of magnesium or calcium. In certain embodiments, the alkaline earth metal alkyl detergent comprises a surfactant portion, the surfactant portion being at least one of a phenate, a salicylate, a sulfonate, a salicyl alcohol, or a salicylate alcohol. In certain embodiments, the alkaline earth metal alkyl detergent comprises a surfactant portion, the surfactant portion being at least one of a salicylate or a sulfonate. .

[0074] In certain embodiments, the composition comprises less than 200 ppm by weight (such as less than 190 ppm, 180 ppm, less than 170 ppm, less than 160 ppm, less than 150 ppm, less than 140 ppm, less than 130 ppm, less than 120 ppm, less than 110 ppm, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm) of magnesium based on the total weight of the composition. In certain embodiments, the composition may be substantially free of magnesium-containing materials. In certain embodiments, the composition will not include any intentionally added magnesium-containing materials.

[0075] In certain embodiments, the composition further comprises 0.1% to 5% by weight (such as 0.5% to 5% by weight, 1% to 5% by weight, 1.5% to 5% by weight, 2% to 5% by weight, 2.5% to 5% by weight, 3% to 5% by weight, 3.5% to 5% by weight, 4% to 5% by weight, 4.5% to 5% by weight, 0.1% to 4.5% by weight, 0.5% to 4.5% by weight, 1% to 4.5% by weight, 2% to 5% by weight, 2% to 5% by weight, 3% to 5% by weight, 3.5% to 5% by weight, 4% to 5% by weight, 4.5% to 5% by weight, 0.1% to 4.5% by weight, 0.5% to 4.5% by weight, 1% to 4.5% by weight, 1.5 wt % to 4.5 wt %, 2 wt % to 4.5 wt %, 2.5 wt % to 4.5 wt %, 3 wt % to 4.5 wt %, 3.5 wt % to 4.5 wt %, 4 wt % to 4.5 wt %, 0.1 wt % to 4 wt %, 0.5 wt % to 4 wt %, 1 wt % to 4 wt %, 1.5 wt % to 4 wt %, 2 wt % to 4 wt %, 2.5 wt % to 4 wt %, 3 wt % to 4 wt %, 3.5 wt % to 4 wt %, 0.1 wt % to 3.5 wt % %, 0.5 wt % to 3.5 wt %, 1 wt % to 3.5 wt %, 1.5 wt % to 3.5 wt %, 2 wt % to 3.5 wt %, 2.5 wt % to 3.5 wt %, 3 wt % to 3.5 wt %, 0.1 wt % to 3 wt %, 0.5 wt % to 3 wt %, 1 wt % to 3 wt %, 1.5 wt % to 3 wt %, 2 wt % to 3 wt %, 2.5 wt % to 3 wt %, 0.1 wt % to 2.5 wt %, 0.5 wt % to 2.5 wt %, 1 wt % to 2 %. 0.1 wt % to 0.5 wt %, 0.5 wt % to 2 wt %, 1 wt % to 2 wt %, 1.5 wt % to 2 wt %, 0.1 wt % to 1.5 wt %, 0.5 wt % to 1.5 wt %, 1 wt % to 1.5 wt %, 0.1 wt % to 1 wt %, 0.5 wt % to 1 wt %, or 0.1 wt % to 0.5 wt %) of aromatic amines, maleic anhydride, ethylene-propylene copolymer dispersants in an amount of .5 wt %, 1.5 wt % to 2.5 wt %, 2 wt % to 2.5 wt %, 0.1 wt % to 2 wt %, 0.5 wt % to 2 wt %, 1 wt % to 2 wt %, 1.5 wt % to 2 wt %, 0.1 wt % to 1.5 wt %, 0.5 wt % to 1.5 wt %, 1 wt % to 1.5 wt %, 0.1 wt % to 1 wt %, 0.5 wt % to 1 wt %, or 0.1 wt % to 0.5 wt %).

[0076] In certain embodiments, the composition further comprises at least one additional additive comprising at least one of an antioxidant, a detergent (other than the alkaline earth metal alkyl detergents described herein), a dispersant, an antiwear agent, a corrosion inhibitor, a viscosity modifier (other than the DVM described above), a metal deactivator, a pour point depressant, a seal compatibility agent, a defoamer, an extreme pressure agent, or a friction modifier.

[0077] Any suitable antioxidant may be used, as will be understood by those of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable antioxidants. Antioxidants include phenolic antioxidants, which may include butyl-substituted phenols containing 2 or 3 tert-butyl groups. The para position may also be occupied by a hydrocarbon group, a lipid-containing group, or a group bridging two aromatic rings. Antioxidants also include aromatic amines, such as nonylated diphenylamine or alkylated phenylnaphthylamine. Other antioxidants include sulfided olefins, titanium compounds, and molybdenum compounds. For example, US 4,285,822 discloses lubricating oil compositions containing molybdenum-containing and sulfur-containing compositions. US2006 / 0217271 A1 discloses a variety of titanium compounds, including titanium alkoxides and titanated dispersants, which may also impart improvements in sediment control and filterability. Other titanium compounds include titanium carboxylates, such as titanium neodecanoate. If a titanium compound is present, its amount may be such as those providing 15 to 1000 or 25 to 200 parts per million of titanium. Typical amounts of antioxidants will of course depend on the specific antioxidants and their respective potencies, but exemplary total amounts may be 0.01 wt % to 5 wt % (such as 0.15 wt % to 4.5 wt %, or 0.2 wt % to 4 wt %) based on the total weight of the composition. In addition, more than one antioxidant may be present, and certain combinations of these antioxidants may be synergistic in terms of their combined overall effect.

[0078] In addition to the above-mentioned alkaline earth metal alkyl detergents, any other suitable detergents can be used, as will be understood by those of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable additional detergents. In certain embodiments, the detergent may include a high-basicity metal detergent. High-basicity detergents are generally homogeneous Newtonian systems, and their metal content exceeds the amount present for neutralization according to the stoichiometric amount of metal and detergent anions. The amount of excess metal is generally expressed as a metal ratio, i.e., the ratio of the total equivalent of the metal to the equivalent of the acidic organic compound. High-basic substances are prepared by reacting an acidic substance (such as carbon dioxide) with an acidic organic compound, an inert reaction medium (such as mineral oil), a stoichiometric excess of a metal base, and a promoter (such as phenol or alcohol). The acidic organic material will generally have a sufficient number of carbon atoms to provide oil solubility.

[0079] Overbased detergents may be characterized by TBN (ASTM D4739), the amount of strong acid required to neutralize the basicity of all materials, in mg KOH / gram of sample. Since overbased detergents are typically supplied with diluent oil, for the purposes of this document, the TBN will be recalculated to an oil-free basis by dividing by the portion of detergent that is not oil (as supplied). Some suitable detergents may have a TBN of 100 to 800, or 150 to 750, or 400 to 700.

[0080] Metal compounds suitable for preparing basic metal salts are generally any Group 1 or Group 2 metal compounds (CAS version of the periodic table). Examples include alkali metals such as sodium, potassium, lithium, copper, magnesium, calcium, barium, zinc, and cadmium. In certain embodiments, the metal is sodium, magnesium, or calcium; or calcium or magnesium; or calcium. The anion portion of the salt can be hydroxide, oxide, carbonate, borate, or nitrate.

[0081] In certain embodiments, the lubricant may contain an overbased sulfonate detergent. Suitable sulfonic acids include sulfonic acids and thiosulfonic acids, including mononuclear or polynuclear aromatic or cycloaliphatic compounds. Certain oil-soluble sulfonates may be prepared from R 2 -T-(SO3 - ) a or R 3 -(SO3 - ) b represents, wherein a and b are each at least one; T is a cyclic nucleus, such as benzene or toluene; R 2 is an aliphatic group, such as an alkyl group, an alkenyl group, an alkoxy group or an alkoxyalkyl group; (R 2 )-T usually contains a total of at least 15 carbon atoms; R 3 is an aliphatic hydrocarbon group usually containing at least 15 carbon atoms. 2 and R 3 Other inorganic or organic substituents may also be present. In certain embodiments, the sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in paragraphs

[0026] to

[0037] of US 2005 / 0065045 A1. In some embodiments, 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 in the 2, 3, or 4 positions of the linear chain, and in some cases predominantly in the 2 position.

[0082] Another high-base material is a high-base phenate detergent. Phenol suitable for preparing phenate detergents can be prepared from (R 1 ) a -Ar-(OH) b Indicates that R 1 is an aliphatic hydrocarbon group of 4 to 400, or 6 to 80, or 6 to 30, or 8 to 25, or 8 to 15 carbon atoms; Ar is an aromatic group, such as benzene, toluene or naphthalene; a and b are each at least one, and the sum of a and b is up to the number of replaceable hydrogens on the aromatic nucleus of Ar, such as 1 to 4 or 1 to 2. For each phenol compound, there is usually a 1 The groups provide an average of at least 8 aliphatic carbon atoms. Phenate detergents are also sometimes provided as sulfur-bridged materials.

[0083] Alkylphenols are commonly used as ingredients in overbased detergents and / or as structural units for overbased detergents. Alkylphenols can be used to prepare phenates, salicylates, salicylate alkoxides or salicin detergents or mixtures thereof. Suitable alkylphenols can include para-substituted hydrocarbylphenols. The hydrocarbyl group can be a straight or branched aliphatic group having 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 certain embodiments, the alkylphenol overbased detergent is prepared from an alkylphenol or a mixture thereof that is free of or substantially free of p-dodecylphenol. In certain embodiments, the lubricating composition of the present invention contains less than 0.3% by weight of alkylphenol, less than 0.1% by weight of alkylphenol or less than 0.05% by weight of alkylphenol.

[0084] In certain embodiments, the overbased material is an overbased salicyl alcohol detergent. An overbased salicyl alcohol detergent is typically an overbased magnesium salt based on a salicyl alcohol derivative. A general example of such a salicyl alcohol derivative can be represented by the following formula:

[0085]

[0086] wherein X is -CHO or -CH2OH, Y is -CH2- or -CH2OCH2-, and the -CHO group typically contains at least 10 mole % of the X group and the Y group; M is hydrogen, ammonium, or a metal ion of one valence (i.e., if M is multivalent, one of the valences is satisfied by the structure shown, and the other valences are satisfied by other species such as anions or by another instance of the same structure), R1 is a hydrocarbyl group having 1 to 60 carbon atoms, m is 0 to 10, and each p is independently 0, 1, 2, or 3, provided that at least one aromatic ring contains R 1 Substituents and all R 1 The total number of carbon atoms in the group is at least 7. When m is 1 or greater, one of the X groups may be hydrogen. In certain embodiments, M is a Mg ion in one valence state or a mixture of Mg and hydrogen. Salicyl alcohol detergents are disclosed in more detail in US 6,310,009B1, with particular reference to its synthesis method (column 8 and example 1) and preferred amounts of various species of X and Y (column 6).

[0087] Salixarate detergents are overbased materials that may be represented by a compound comprising at least one unit of formula (A) and / or formula (B) and each end of a compound having an end group of formula (C) and / or (D):

[0088]

[0089] Such groups are linked via a divalent bridging group A which may be identical or different. In formulae (A) to (D), R3 is hydrogen, a hydrocarbon group, or a metal ion in a valence state; R 2 is a hydroxyl group or a hydrocarbon group, and j is 0, 1 or 2; R 6 is hydrogen, a hydrocarbyl group or a heterosubstituted hydrocarbyl group; or R 4 is a hydroxyl group, and R 5 and R 7 are independently hydrogen, a hydrocarbyl group or a heterosubstituted hydrocarbyl group, or R 5 and R 7 Both are hydroxyl groups, and R 4 is hydrogen, a hydrocarbyl group or a heterosubstituted hydrocarbyl group; provided that R 4 , R 5 , R 6 and R 7 At least one of the units (A) or (C) is a hydrocarbon group containing at least 8 carbon atoms; and wherein the molecule contains, on average, at least one of the units (A) or (C) and at least one of the units (B) or (D), and the ratio of the total number of units (A) and (C) to the total number of units (B) and (D) in the composition is 0.1:1 to 2:1. The divalent bridging group "A" may be the same or different at each occurrence, including -CH2- and -CH2OCH2-, either of which may be derived from formaldehyde or a formaldehyde equivalent (e.g., paraformaldehyde, formalin). Salicylic acid alkoxide derivatives and methods for their preparation are described in more detail in US 6,200,936 B1 and WO 01 / 56968A1. It is believed that salicylic acid alkoxide derivatives have a structure that is significantly linear rather than macrocyclic, but both structures are intended to be covered by the term "salicylic acid alkoxide".

[0090] Glyoxylate detergents are similar overbased materials based on anionic groups which, in certain embodiments, may have the following structure:

[0091]

[0092] Wherein each R is independently an alkyl group containing at least 4 or at least 8 carbon atoms, provided that the total number of carbon atoms in all such R groups is at least 12, or at least 16, or at least 24. Alternatively, each R can be an olefin polymer substituent. The acidic material for preparing the overbased glyoxylate detergent is a condensation product of a hydroxy aromatic material (such as a hydrocarbyl-substituted phenol) and a carboxylic acid reactant (such as glyoxylic acid or another ω-oxoalkanoic acid). Overbased glyoxylate detergents and methods for their preparation are disclosed in more detail in US 6,310,011 B1.

[0093] The high-based detergent can also be a high-based salicylate, such as an alkali metal salt or alkaline earth metal salt of a substituted salicylic acid. Salicylic acid can be hydrocarbyl substituted, wherein each substituent contains an average of at least 8 carbon atoms / substituent and 1 to 3 substituents / molecule. The substituent can be a polyolefin substituent. In certain embodiments, the hydrocarbyl substituent contains 7 to 300 carbon atoms and can be an alkyl group with a molecular weight of 150 to 2000. High-based salicylate detergents and methods for their preparation are disclosed in US 4,719,023 and US 3,372,116. Salicylate detergents and overbased salicylate detergents can be prepared in at least two different ways. Carbonylation (also known as carboxylation) of p-alkylphenol is described in many references (including US 8,399,388 B2). Carbonylation can be followed by overbasing to form an overbased salicylate detergent. Suitable p-alkylphenols include those with straight and / or branched hydrocarbon groups having 1 to 60 carbon atoms. Salicylate detergents can also be prepared by alkylation of salicylic acid, followed by overbasing, as described in US 7,009,072 B2. Salicylate detergents prepared in this manner can be prepared by straight 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 certain embodiments, the high alkalinity detergent of the present invention is a salicylate detergent. In certain embodiments, the salicylate detergent of the present invention may be substantially free of or free of unreacted p-alkylphenol. In certain embodiments, the salicylate detergent of the present invention is prepared by alkylation of salicylic acid.

[0094] Other overbased detergents may include overbased detergents having a Mannich base structure, such as disclosed in US 6,569,818 B2.

[0095] In certain embodiments, the hydrocarbyl substituents on the hydroxy-substituted aromatic rings of the above detergents (e.g., phenates, salicyl alcohols, salicyl alcohol salts, glyoxylates, or salicylates) are free or substantially free of C 12 Aliphatic hydrocarbyl groups. In some embodiments, such hydrocarbyl substituents contain at least 14 or at least 18 carbon atoms.

[0096] Any suitable dispersant may be used, as will be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable dispersants. In certain embodiments, the dispersant may be a succinimide dispersant. In certain embodiments, the succinimide dispersant may be present in the lubricating composition in an amount of 0.25 wt % to 5 wt % (such as 0.25 wt % to 4.5 wt %, 0.25 wt % to 4.25 wt %, 0.5 wt % to 4 wt %, 1 wt % to 3.5 wt %, 0.35 wt % to 1.8 wt %, 0.5 wt % to 1.5 wt %, or 1 wt % to 1.45 wt %), based on the total weight of the composition. Suitable succinimide dispersants include, but are not limited to, N-substituted long chain alkenyl succinimides having a variety of chemical structures, such as

[0097]

[0098] Each R 1 are independently alkyl groups, such as polyisobutylene groups, and R 1 The group may have a number average molecular weight (M) of 1,000 to 3,500. n ). 2 The group is an alkylene group, such as an ethylene (C2H4) group. 1 M n Alternatively, it may be 1500 to 3000, or 2800 to 2500. Such molecules may be derived from the reaction of an olefinic acylating agent with a polyamine, and in addition to the simple imide structure shown above, a variety of linkages between the two moieties are possible, including a variety of amides and quaternary ammonium salts. In the above structure, the amine portion is shown as an alkylene polyamine, but other aliphatic and aromatic monoamines and polyamines may also be used. Similarly, R 1 A variety of linkage modes of the group to the imide structure are possible, including various cyclic linkages. The ratio of the carbonyl group of the acylating agent to the nitrogen atom of the amine can be 1:0.5 to 1:3, and in other cases 1:1 to 1:2.75 or 1:1.5 to 1:2.5. Succinimide dispersants are more fully described in US 4,234,435, US 3,172,892 and EP 0 355 895 B1. Succinimides prepared by the so-called conventional (or chloro) route and by thermal or direct alkylation or "ene" routes are included, as disclosed in the patent literature cited above. Succinimide dispersants prepared by different routes can be characterized by differences in detailed structure, whereby R is linked 1 The dispersant may also be post-treated with various reagents such as a borated agent (eg, boric acid) to prepare a borated dispersant.

[0099] The TBN of the dispersant will depend on the amount of amine functionality contained therein, and may be from 10 to 60, or from 12 to 50, or from 15 to 40, or from 20 to 35, or from 30 to 35. Other embodiments may include from 10 mg KOH / g to 30 mg KOH / g, or from 12 mg KOH / g to 25 mg KOH / g, or from 20 mg KOH / g to 60 mg KOH / g, or from 30 mg KOH / g to 50 mg KOH / g (all calculated on an oil-free basis).

[0100] The succinimide dispersants can also be post-treated by reaction with any of a variety of agents. Among the various agents are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References to such treatments are listed in detail in US 4,654,403.

[0101] In certain embodiments, the dispersant may be or include a dispersant viscosity modifier (because a substance may have both dispersant and viscosity modifier properties, for example, as described below, an olefin polymer may be used to impart viscosity modifier properties, and the reacted amine may provide nitrogen or other polar functional groups that may impart dispersant properties). In certain embodiments, the dispersant viscosity modifier may include an olefin polymer that has been modified by the addition of a polar moiety. In certain embodiments, the dispersant viscosity modifier may include an ashless condensation reaction product of an olefin polymer having a grafted carboxylic acid (or equivalent) functional group and a monoamine or polyamine, the monoamine or polyamine may have a single primary amino group. If the olefin polymer is an ethylene / propylene copolymer, the polyamine is not poly(ethylene amine). Various dispersant viscosity modifiers have been used for the lubrication of heavy-duty diesel engines, where they serve to disperse the soot produced by the combustion of diesel fuel. Gasoline (spark ignition) engines do not typically produce soot, so such dispersant viscosity modifiers may not be used in gasoline engines to disperse soot. The use of dispersant viscosity modifier of the present invention in a smokeless engine environment allows to reduce the amount of conventional dispersants (such as succinimide dispersants), while maintaining dispersant performance and allowing greater flexibility in the formulation of lubricant compositions to meet performance targets. In certain embodiments, olefin polymers are ethylene-alpha-olefin copolymers. The formation of functionalized ethylene-alpha-olefin copolymers is well known in the art, such as described in US 7,790,661 B2 the 2nd column, the 48th row to the 10th column, those in the 38th row. Other detailed descriptions of similar functionalized ethylene-alpha-olefin copolymers are found in WO 2006 / 015130A1, US 4,863,623, US 6,107,257, US 6,107,258, US 6,117,825 and US 7,790,661 B2. In certain embodiments, the functionalized ethylene-α-olefin copolymers may include those described in US 4,863,623 (see column 2, line 15 to column 3, line 52) or WO 2006 / 015130A1 (paragraphs

[0008] and paragraphs

[0065] to

[0073] ).

[0102] Olefin polymers are functionalized by modifying the polymers by the addition of polar moieties. In certain embodiments, the functionalized copolymer is the reaction product of an olefin polymer grafted with an acylating agent. In certain embodiments, the acylating agent may be an olefinically unsaturated acylating agent. Suitable acylating agents are typically α,β-unsaturated compounds having at least one olefinic bond (before the reaction) and at least one, for example two, carboxylic acid (or its anhydride) groups or polar groups that can be converted into the carboxyl groups by oxidation or hydrolysis. The acylating agent is grafted onto the olefin polymer to obtain two carboxylic acid functional groups. Examples of suitable acylating agents include maleic anhydride, chloromaleic anhydride, itaconic anhydride, or reactive equivalents thereof, for example, corresponding dicarboxylic acids such as maleic acid, fumaric acid, cinnamic acid, (meth) acrylic acid, esters of these compounds, and acyl chlorides of these compounds.

[0103] In certain embodiments, the functionalized ethylene-α-olefin copolymers include olefin copolymers grafted with acyl groups further functionalized with polyether compounds terminated with hydrocarbyl amines, hydrocarbyl alcohol groups, amino groups, or hydroxyl groups, and mixtures thereof.

[0104] In certain embodiments, the hydrocarbyl amine may be selected from aromatic amines, aliphatic amines, and mixtures thereof. In certain embodiments, the hydrocarbyl amine component may 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, wherein the aromatic amine is selected from the group consisting of: (i) nitro-substituted aniline; (ii) an amine comprising two aromatic moieties linked by a -(C=O)NR- group, a -C=O- group, an -O- group, an -N=N- group, or a -CH2- group, wherein R is hydrogen or a hydrocarbyl group, and one of the aromatic moieties carries the condensable amino group; (iii) aminoquinoline; (iv) aminobenzimidazole; (v) N,N-dialkylphenylenediamine; (vi) aminodiphenylamine (also known as N-phenylphenylenediamine); (vii) ring-substituted benzylamine; and (viii) methylene-bound dimers of aminodiphenylamine.

[0105] As will be appreciated by one of ordinary skill in the art, any suitable corrosion inhibitor may be used.

[0106] Other performance additives such as corrosion inhibitors, including those described in WO 2006 / 047486 A1, octyl octanamide, condensation products of dodecenyl succinic acid or anhydride and fatty acids such as oleic acid with polyamines may be present in the lubricating compositions described herein. In certain embodiments, the corrosion inhibitors include (Registered trademark of The Dow Chemical Company) corrosion inhibitor. The corrosion inhibitor may be a homopolymer or a copolymer of propylene oxide. Corrosion inhibitors are described in more detail in a product brochure published by The Dow Chemical Company (Form No. 118-01453-0702 AMS, entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications").

[0107] The lubricating composition described herein may also include: a metal deactivator, the metal deactivator including a derivative of benzotriazole (typically tolyltriazole), a dithiothiadiazole derivative, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole and / or 2-alkyldithiobenzothiazole; a foam inhibitor, the foam inhibitor including a copolymer of ethyl acrylate and 2-ethylhexyl acrylate, and / or a copolymer of ethyl acrylate and 2-ethylhexyl acrylate and vinyl acetate; a demulsifier, the demulsifier including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide and / or (ethylene oxide / propylene oxide) polymer; and a pour point depressant including an ester of maleic anhydride-styrene, polymethacrylate, polyacrylate and / or polyacrylamide.

[0108] Instead of the above optional dispersants (such as dispersant viscosity modifiers) or in addition thereto, any other suitable viscosity modifiers may be used, as will be understood by those of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable viscosity modifiers. Oils with lubricating viscosity will generally be selected to provide, among other properties, appropriate viscosity (kinematic viscosity and / or high temperature high shear viscosity) and viscosity index. Most modern engine lubricants are multi-grade lubricants containing viscosity index modifiers to provide suitable viscosity at both low and high temperatures, i.e., viscosity modifiers, rather than dispersant viscosity modifiers as described above, i.e., supplementary viscosity modifiers. Although viscosity modifiers are sometimes considered to be part of base oils, they may be considered to be independent components, which are selected within the capabilities of those of ordinary skill in the art.

[0109] The viscosity modifier may be a polymeric material, which may be a hydrocarbon-based polymer typically having a number average molecular weight of 25,000 to 500,000, such as 50,000 to 300,000, or 50,000 to 200,000.

[0110] Hydrocarbon polymers can be used as viscosity index modifiers. Examples include C2 to C 30Olefins, such as homopolymers and polymers of two or more monomers of C2 to C8 olefins, including both alpha olefins and internal olefins, which may be linear or branched, aliphatic, aromatic, alkyl aromatic or cycloaliphatic. Examples include ethylene-propylene copolymers, commonly referred to as OCPs, which are prepared by copolymerizing ethylene and propylene by known methods.

[0111] Hydrogenated styrene-conjugated diene copolymers or hydrogenated conjugated diene polymers are other types of viscosity modifiers. These polymers include polymers that are hydrogenated or partially hydrogenated homopolymers, and also include random, tapered, star and block copolymers. The term "styrene" includes various substituted styrenes. Conjugated dienes can contain four to six carbon atoms, and can include, for example, piperylene, 2,3-dimethyl-1,3-butadiene, chloroprene, isoprene and 1,3-butadiene. The mixture of such conjugated dienes is suitable. The styrene content of these copolymers can be 20% to 70% by weight or 40% to 60% by weight, and the aliphatic conjugated diene content can be 30% to 80% by weight or 40% to 60% by weight. These copolymers can be prepared by methods well known in the art, and are usually hydrogenated to remove a considerable portion of their olefinic double bonds.

[0112] The copolymerization of styrene and maleic anhydride in the presence of a free radical initiator and then 4-18 The esters obtained by esterifying the copolymers with a mixture of alcohols are also suitable as viscosity modifying additives in motor oils. Similarly, poly(meth)acrylates (PMAs) can be used as viscosity modifiers. As used herein, the term "(meth)acrylate" and its cognates refer to methacrylates or acrylates, which will be readily understood. These materials are generally prepared from a mixture of (meth)acrylate monomers having different alkyl groups, which can be straight or branched groups containing 1 to 18 carbon atoms.

[0113] Some viscosity modifiers can be multi-arm polymers. These can include polymers containing (meth)acrylates, which include multiple arms containing at least 20, or at least 50, or at least 100, or at least 200, or at least 350, or at least 500, or at least 1000 carbon atoms, which are connected to a multivalent organic moiety. Therefore, the multi-arm polymer can be characterized by a "star-shaped" polymer, a "comb-shaped" polymer, or a polymer otherwise having multiple arms or side chains as described herein.

[0114] The amount of viscosity modifier component (other than the dispersant viscosity modifiers described above) may be 0.02 wt % to 5 wt % (such as 0.1 wt % to 2 wt %, or 0.2 wt % to 1 wt %, or 0.3 wt % to 0.6 wt %) based on the total weight of the composition.

[0115] Any suitable metal passivating agent may be used, as will be appreciated by one of ordinary skill in the art.

[0116] Any suitable pour point depressant may be used, as will be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable pour point depressants. Suitable pour point depressants may include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates and / or polyacrylamides.

[0117] Any suitable seal compatibility agent may be used, as will be appreciated by one of ordinary skill in the art.

[0118] Any suitable defoamer may be used, as will be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable defoamers. Suitable defoamers may include copolymers of polysiloxanes, ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers include fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers.

[0119] Any suitable extreme pressure agent may be used, as will be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable extreme pressure agents. Extreme pressure (EP) agents soluble in oil include sulfur-containing and chlorinated sulfur-containing EP agents, dithiothiadiazole or CS2 derivatives of dispersants (typically succinimide dispersants), chlorinated hydrocarbon EP agents, and derivatives of phosphorus EP agents. Examples of such EP agents include chlorinated waxes; sulfurized olefins (such as sulfurized isobutylene), hydrocarbon-substituted 2,5-dithiothio-1,3,4-thiadiazoles or oligomers thereof, organic sulfides and polysulfides (such as dibenzyl disulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide), sulfurized methyl oleate, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons, such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters, such as di- and tri-hydrocarbon phosphites, for example phosphorous phosphite; dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, amylphenyl phosphite; diamylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene-substituted phenol phosphites; metal thiocarbamates, such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts or derivatives of alkyl and dialkyl phosphoric acids, including, for example, amine salts of the product of the reaction of dialkyldithiophosphoric acids with propylene oxide and subsequent further reaction with P2O5; and mixtures thereof (as described in US 3,197,405).

[0120] Any suitable friction modifier may be used, as will be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable friction modifiers. Friction modifiers that may be suitable for use in exemplary lubricating compositions include fatty acid derivatives, such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines, and amine salts of alkylphosphoric acids. Friction modifiers are those that generally do not produce any sulfated ash under the conditions of ASTM D 874. If the additive does not contribute metal content to the lubricant composition, it is referred to as "metal-free". As used herein, the term "fatty alkyl" or "fat" with respect to friction modifiers means a carbon chain having 8 to 30 carbon atoms, typically a straight carbon chain. In certain embodiments, the ashless friction modifier may be represented by the following formula:

[0121]

[0122] Wherein, D and D' are independently selected from -O-, -NH, -NR 23 , by combining the D and D' groups and forming R between the two -C=O groups 21 -N- group to form an imide group; E is selected from -R 24 -OR 25 -、-CH2、-CHR 26 , -CR 26 R 27 、-C(OH)(CO2R 22 )、-C(CO2R 22 )2 and -CHOR 28 ; where R 24 and R 25 Independently selected from -CH2, -CHR 26 , -CR 26 R 27 、-C(OH)(CO2R 22 ) and -CHOR 28 ; q is 0 to 10, provided that when q is 1, E is not -CH2, and when n is 2, both E are not -CH2; p is 0 or 1; R 21 is independently hydrogen or a hydrocarbyl group optionally containing 1 to 150 carbon atoms, provided that when R 21 When it is hydrogen, p is 0, and q is greater than or equal to 1; R 22 is a hydrocarbon group usually containing 1 to 150 carbon atoms; R 23 , R 24 , R 25 , R 26 and R 27 are independently a hydrocarbon group; and R 28is hydrogen or a hydrocarbyl group, optionally containing 1 to 150 carbon atoms, or 4 to 32 carbon atoms, or 8 to 24 carbon atoms. In certain embodiments, the hydrocarbyl group R 23 , R 24 and R 25 The alkyl group may be straight-chain or predominantly straight-chain.

[0123] In certain embodiments, the ashless friction modifier is a fatty ester, amide or imide of various hydroxy-carboxylic acids, such as tartaric acid, malic acid, lactic acid, glycolic acid and mandelic acid. Examples of suitable materials include di(2-ethylhexyl) tartrate (e.g., di(2-ethylhexyl) tartrate), di(C8-C 10 ) ester, tartaric acid di(C 12-15 ) esters, dioleoyl tartarate, oleoyl triamide and oleoyl maleimide.

[0124] In certain embodiments, the ashless friction modifier may be selected from 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 alkyl phosphoric acids; fatty alkyl tartaric acid esters; fatty alkyl tartarimides; fatty alkyl tartaramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerides; borated glycerides; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxy and polyhydroxy fatty amines, including tertiary hydroxy fatty amines; hydroxyalkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or reaction products from fatty carboxylic acids with guanidine, aminoguanidine, urea or thiourea and their salts.

[0125] Suitable friction modifiers may also encompass materials such as sulphurized fatty compounds and olefins, sunflower oil or soybean oil monoesters of polyols and aliphatic carboxylic acids.

[0126] In certain embodiments, the friction modifier may be a long chain fatty acid ester. In certain embodiments, the long chain fatty acid ester may be a monoester, and in another embodiment the long chain fatty acid ester may be a triglyceride. In certain embodiments, the ashless friction modifier is one or more of an ester, amide or imide of an alpha-hydroxycarbonyl compound, and mixtures thereof.

[0127] The ashless friction modifier may be present in the lubricating composition in an amount from 0.01 wt % to 6 wt %, or from 0.05 wt % to 4 wt %, or from 0.1 wt % to 2 wt %, or from 0.01 wt % to 1.1 wt %, or from 0.1 wt % to 0.5 wt %, or from 0.2 wt % to 0.4 wt %, based on the total weight of the composition.

[0128] In certain embodiments, based on the total weight of the composition, the composition comprises less than 200ppm by weight (such as less than 190ppm, 180ppm, less than 170ppm, less than 160ppm, less than 150ppm, less than 140ppm, less than 130ppm, less than 120ppm, less than 110ppm, less than 100ppm, less than 90ppm, less than 80ppm, less than 70ppm, less than 60ppm, less than 50ppm, less than 40ppm, less than 30ppm, less than 20ppm or less than 10ppm) of platinum. In certain embodiments, the composition may be substantially free of platinum-containing materials. In certain embodiments, the composition will not include any intentionally added platinum-containing materials. Any suitable platinum-containing material can be used, as will be understood by those of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable platinum-containing materials (also referred to as platinum compounds). Platinum compounds as lubricant additives are known in the art and can be used for various functions, such as antiwear agents, friction modifiers and antioxidants. It is known to use molybdenum- and sulfur-containing compositions as antiwear agents and antioxidants in lubricating oil compositions. Such materials may be molybdenum dithiocarbamates. For example, US 4,285,822 discloses a lubricating oil composition containing a molybdenum- and sulfur-containing composition prepared by (1) combining a polar solvent, an acidic molybdenum compound, and an oil-soluble basic nitrogen compound to form a molybdenum-containing complex and (2) contacting the complex with carbon disulfide to form a molybdenum- and sulfur-containing composition. Other molybdenum-containing materials include dihydrocarbyl dithiophosphate molybdenum. Other molybdenum-containing materials include molybdenum-amine compounds as described in US 6,329,327 B1; organic molybdenum compounds prepared by reaction of a molybdenum source, a fatty oil, and a diamine as described in US 6,914,037 B2; trinuclear molybdenum-sulfur complexes as described in US 6,232,276 B2. In certain embodiments, the platinum compound is a platinum dithiocarbamate complex, a platinum dithiocarbamate dimer complex, or a trinuclear platinum compound.

[0129] In certain embodiments, the lubricant formulation contains an amount of platinum-containing material to provide the lubricant with 40 to 1200 parts per million by weight of platinum, or alternatively 50 to 250, 50 to 500, 60 to 200, 300 to 1000, or 400 to 800 parts per million by weight. The actual amount of platinum-containing material will depend in part on the nature and formula weight of the anion or complexing agent associated with the platinum, in a manner that can be easily calculated. In certain embodiments, the molybdenum-containing compound is present in the lubricating composition in an amount of 0 wt % to 1.1 wt %, or 0.01 wt % to 0.5 wt %, or 0.03 wt % to 0.35 wt %, or 0.02 wt % to 0.2 wt %, or 0.07 wt % to 0.18 wt %, or 0.04 wt % to 0.18 wt %, based on the total weight of the lubricating composition.

[0130] In certain embodiments, the composition further comprises an antiwear agent, wherein the antiwear agent contributes 300 ppm to 900 ppm by weight (such as 350 ppm to 900 ppm, 400 ppm to 900 ppm, 450 ppm to 900 ppm, 500 ppm to 900 ppm, 550 ppm to 900 ppm, 600 ppm to 900 ppm, 650 ppm to 900 ppm, 700 ppm to 900 ppm, 750 ppm to 900 ppm, 800 ppm to 900 ppm, 850 ppm to 900 ppm, 300 ppm to 850 ppm, 350 ppm to 850 ppm, 400ppm to 850ppm, 450ppm to 850ppm, 500ppm to 850ppm, 550ppm to 850ppm, 600ppm to 850ppm, 650ppm to 850ppm, 700ppm to 850ppm, 750ppm to 850ppm, 800ppm to 850ppm, 300ppm to 800ppm, 350ppm to 800ppm, 400ppm to 800ppm, 450ppm to 800ppm, 500ppm to 800ppm, 550ppm to 800ppm, 600ppm to 800ppm, 650ppm to 800ppm, 700ppm to 80 0ppm, 750ppm to 800ppm, 300ppm to 750ppm, 350ppm to 750ppm, 400ppm to 750ppm, 450ppm to 750ppm, 500ppm to 750ppm, 550ppm to 750ppm, 600ppm to 750ppm, 650ppm to 750ppm, 700ppm to 750ppm, 300ppm to 700ppm, 350ppm to 700ppm, 400ppm to 700ppm, 450ppm to 700ppm, 500ppm to 700ppm, 550ppm to 700ppm, 600ppm to 700ppm, 650ppm to 750ppm ppm to 700ppm, 300ppm to 650ppm, 350ppm to 650ppm, 400ppm to 650ppm, 450ppm to 650ppm, 500ppm to 650ppm, 550ppm to 650ppm, 600ppm to 650ppm, 300ppm to 600ppm, 350ppm to 600ppm, 400ppm to 600ppm, 450ppm to 600ppm, 500ppm to 600ppm, 550ppm to 600ppm, 300ppm to 550ppm, 350ppm to 550ppm, 400ppm to 550ppm, 450ppm to 550ppm,ppm to 550ppm, 300ppm to 500ppm, 350ppm to 500ppm, 400ppm to 500ppm, 450ppm to 500ppm, 300ppm to 450ppm, 350ppm to 450ppm, 400ppm to 450ppm, 300ppm to 400ppm, 350ppm to 400ppm, or 300ppm to 350ppm).

[0131] Any suitable antiwear agent can be used, as will be understood by those of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable antiwear agents. Examples of antiwear agents include phosphorus-containing antiwear / extreme pressure agents (such as metal thiophosphates), phosphates and their salts, phosphorus-containing carboxylic acids, phosphorus-containing esters, phosphorus-containing ethers, phosphorus-containing amides and phosphites. In certain embodiments, the phosphorus antiwear agent may be present in an amount of 0.01 to 0.2 wt %, or 0.015 to 0.15 wt %, or 0.02 to 0.1 wt %, or 0.025 to 0.08 wt %, or 0.01 to 0.05 wt % phosphorus delivered to the total lubricating composition. In certain embodiments, the antiwear agent is zinc dialkyl dithiophosphate.

[0132] Zinc dialkyl dithiophosphates may be described as primary zinc dialkyl dithiophosphates or secondary zinc dialkyl dithiophosphates, depending on the structure of the alcohol used in their preparation. In certain embodiments, the lubricating compositions described herein may include primary zinc dialkyl dithiophosphates. In certain embodiments, the lubricating compositions described herein may include secondary zinc dialkyl dithiophosphates. In certain embodiments, the lubricating compositions described herein may include a mixture of primary zinc dialkyl dithiophosphates and secondary zinc dialkyl dithiophosphates, optionally wherein the ratio (by weight) of primary zinc dialkyl dithiophosphates to secondary zinc dialkyl dithiophosphates is at least 1:1, or at least 1:1.2, or at least 1:1.5, or at least 1:2, or at least 1:10. In certain embodiments, the lubricating compositions described herein may include a mixture of primary zinc dialkyl dithiophosphates and secondary zinc dialkyl dithiophosphates, the secondary zinc dialkyl dithiophosphate being at least 50% by weight (such as at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 90% by weight) of the primary zinc dialkyl dithiophosphates. In certain embodiments, the lubricating compositions described herein are substantially free of, or free of, primary dialkyl zinc dithiophosphates.

[0133] Other substances that may be present include tartrates, tartrate amides and tartrimides. Examples include oleyl tartrimide (imide formed by oleylamine and tartaric acid) and oleyl diester (from, for example, mixed C12-16 alcohol). Other related substances that may be suitable generally include esters, amides and imides of other hydroxycarboxylic acids, including hydroxypolycarboxylic acids, for example, such as tartaric acid, citric acid, lactic acid, glycolic acid, hydroxypropionic acid, hydroxyglutaric acid and acids of their mixtures. These substances can also impart additional functions to lubricants in addition to anti-wear properties. These substances are described in more detail in US 2006 / 0079413A1 and WO 2010 / 077630 A1. If present, such derivatives of hydroxycarboxylic acids (or compounds derived from hydroxycarboxylic acids) can generally be present in the lubricating composition in an amount of 0.1% to 5% by weight or 0.2% to 3% by weight or greater than 0.2% to 3% by weight.

[0134] In certain embodiments, the composition comprises 700 to 1,000 ppm by weight, such as 750 to 1,000 ppm, 800 to 1,000 ppm, 850 to 1,000 ppm, 900 to 1,000 ppm, 950 to 1,000 ppm, 700 to 950 ppm, 750 to 950 ppm, 800 to 950 ppm, 850 to 950 ppm, 900 to 950 ppm, 700 to 900 ppm, 750 to 900 ppm, 800 to 900 ppm, 850 to 900 ppm, 700 to 850 ppm, 750 to 850 ppm, 800 to 850 ppm, 700 to 800 ppm, 750 to 800 ppm, or 700 to 750 ppm, based on the total weight of the composition.

[0135] A method of lubricating a heavy duty diesel engine, the method comprising supplying a lubricating composition as described herein to the engine.

[0136] A method of lubricating a compression ignition internal combustion engine having a loaded mass in excess of 2,700 kg, the method comprising supplying to the engine a lubricating composition as described herein.

[0137] A method of lubricating the crankcase of a compression ignition or spark ignition engine, the method comprising supplying a lubricating composition as described herein to the crankcase. In certain embodiments, the spark ignition engine may be a gasoline direct injection engine. In certain embodiments, the gasoline direct injection engine includes a turbocharger.

[0138] Without limitation, the lubricating composition as described herein may have a composition as disclosed in Table 1:

[0139] Table 1

[0140] A B C Deposit control additive of formula I 0.5–8 1–7 2.5-–7 Detergent 0.1–2 0.2–1.5 0.25–1.25 Dispersant Viscosity Modifier 0–1.5 0.3–1.5 0.5–1.25 Dispersants 0.25–5 0.5–4 1–3.5 Antioxidants 0.5–6 1–5 2–4 Antiwear Agents 0.1–5 0.25–4 0.5–3 Friction modifier 0.01–6 0.05–4 0.1–2 Viscosity modifier 0 to 5 0 to 4 0 to 3.5 Any other performance additives 0 to 10 0 to 8 0 to 6 Oil of lubricating viscosity Margin to 100% Margin to 100% Margin to 100%

[0141] The subject matter disclosed herein can be better understood with reference to the following examples, which are only used to further illustrate the subject matter disclosed herein. The exemplary embodiments should not be interpreted as limiting the subject matter in any way.

[0142] A series of engine lubricants suitable for heavy duty diesel engines having low HTHS (2.4) were prepared in a Group III base oil of lubricating viscosity containing the additives described herein, including a deposit control additive according to Formula I, a polymeric viscosity modifier, an ashless succinimide dispersant, an overbased detergent, an antioxidant, a zinc dialkyl dithiophosphate (ZDDP), and other performance additives in the amounts (weight percent based on total lubricant weight) shown in Table 2:

[0143] Table 2

[0144]

[0145] 1 According to ASTM D4739, TBN=300

[0146] 2 According to ASTM D4739, TBN = 170

[0147] 3 According to ASTM D4739, TBN = 690

[0148] 4 Reaction products of olefin polymers containing carboxylic acid functional groups and 3-nitroaniline

[0149] 5 Amine functionalized aromatic maleic anhydride-styrene copolymer

[0150] 6 Succinimide dispersants derived from polyisobutylene

[0151] 7 Combination of phenolic and arylamine antioxidants

[0152] 8 Combinations of primary and secondary ZDDPs derived from C3 and C6 alcohols 9 Other additives include defoamers, pour point depressants, extreme pressure agents and metal deactivators

[0153] Table 3 shows the results of certain tests performed on the lubricants of Examples 1 to 4:

[0154] Table 3

[0155]

[0156] A series of engine lubricants suitable for use in passenger car diesel engines having low HTHS (2.5) were prepared in a Group III base oil of lubricating viscosity containing the additives described herein, including a deposit control additive according to Formula I, a polymeric viscosity modifier, an ashless succinimide dispersant, an overbased detergent, an antioxidant, a zinc dialkyl dithiophosphate (ZDDP), and other performance additives in the amounts (weight percent based on total lubricant weight) shown in Table 4:

[0157] Table 4

[0158]

[0159]

[0160] 1 According to ASTM D4739, TBN=300

[0161] 2 Example F from US2017 / 0026794 A1 (US Patent / Publication No.) 3 According to ASTM D4739, TBN = 690

[0162] 4 Styrene / butadiene block copolymer

[0163] 6 Borated succinimide dispersants derived from polyisobutylene

[0164] 7 Combination of phenolic and arylamine antioxidants

[0165] 8 Combinations of primary and secondary ZDDPs derived from C3 and C6 alcohols

[0166] 9 Other additives include defoamers, pour point depressants, alkylene sulfides and metal deactivators

[0167] The lubricating compositions of Examples 5 to 7 were tested in a plate coker heated to 325°C, with an oil bath temperature of 105°C and a sparging / baking cycle of 120 seconds / 45 seconds. The airflow was 350 ml / min, the spindle speed was 1000 rpm and the test lasted 4 hours. The oil was splashed onto an aluminum plate. The plate weight was recorded before and after exposure and the difference was recorded as the deposit gain. The results obtained are summarized in Table 5.

[0168] Table 5

[0169] Example 5 Example 6 Example 7 Sediment gain (mg) 14.8 11.7 7.9

[0170] Unless in the examples or otherwise clearly indicated or the context requires, all numerical values ​​of the amount of substance, reaction conditions, molecular weight, number of carbon atoms, etc. specified in this specification should be understood to be modified by the word "about". As used herein, the term "about" means that the value of a given amount is within ± 20% of the specified value. In other embodiments, the value is within ± 15% of the specified value. In other embodiments, the value is within ± 10% of the specified value. In other embodiments, the value is within ± 5% of the specified value. In other embodiments, the value is within ± 2.5% of the specified value. In other embodiments, the value is within ± 1% of the specified value. In other embodiments, the value is within the range of the clearly described values ​​that will be understood by those of ordinary skill in the art based on the disclosure provided herein, with a composition substantially similar to the literal amount described herein.

[0171] It should be understood that the upper and lower limits of the amounts, ranges, and ratios described herein can be independently combined, and any amount within the disclosed range is considered to provide a minimum or maximum value of a narrower range in an alternative embodiment (of course, the minimum amount of the range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts of each element of the subject matter disclosed herein can be used together with the ranges or amounts of any other element.

[0172] While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter disclosed herein, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the scope of the subject matter. In this regard, the scope of the present invention is limited solely by the following claims.

Claims

1. A lubricating composition, comprising: a. Oil of lubricating viscosity; b. Compounds according to formula I: in, For each molecule of the compound independently: R 1 is an aliphatic hydrocarbon group having 10 to 24 carbon atoms; R 2 is CH3 or C2H5; and n is an integer from 3 to 8; and c. Alkaline earth metal alkyl detergents. 2 . The lubricating composition of claim 1 , having a high temperature high shear viscosity of 1.5 to 4.5 mPa·s, as measured at 150° C. according to ASTM D4683.

3. The lubricating composition of claim 1 or claim 2, wherein the alkaline earth metal alkyl detergent contributes 2 to 7 TBN to the composition as measured by ASTM D4739.

4. The lubricating composition of any one of claims 1 to 3, having a sulfated ash content less than or equal to 1 wt. %, based on the total weight of the composition, as measured by ASTM D874.

5. The lubricating composition of claim 4, wherein the alkaline earth metal alkyl detergent contributes 6 to 7 TBN to the composition as measured by ASTM D4739.

6. The lubricating composition according to any one of claims 1 to 5, wherein the compound according to formula I is present in the composition in an amount of 1% to 10% by weight, based on the total weight of the composition.

7. The lubricating composition of any one of claims 1 to 6, having a TBN of 2 to 12 as measured by ASTM D2896.

8. The lubricating composition of any one of claims 1 to 7, wherein the alkaline earth metal alkyl detergent is present in the composition in an amount of less than 3.5 wt. %, based on the total weight of the composition.

9. The lubricating composition according to any one of claims 1 to 8, wherein the alkaline earth metal alkyl detergent comprises an alkaline earth metal, the alkaline earth metal being at least one of magnesium or calcium.

10. The lubricating composition of any one of claims 1 to 9, wherein the alkaline earth metal alkyl detergent comprises a surfactant portion, the surfactant portion being at least one of a phenate, a salicylate, a sulfonate, a salicyl alcohol, or a salicylic acid alkoxide.

11. The lubricating composition of any one of claims 1 to 10, having less than 200 ppm by weight of molybdenum, based on the total weight of the composition.

12. The lubricating composition according to any one of claims 1 to 11, further comprising an antiwear agent, wherein the antiwear agent contributes 300 ppm to 900 ppm by weight of phosphorus to the composition, based on the total weight of the composition.

13. The lubricating composition of any one of claims 1 to 12, having 700 ppm to 1,000 ppm by weight of zinc, based on the total weight of the composition.

14. The lubricating composition according to any one of claims 1 to 13, further comprising an aromatic amine, maleic anhydride, ethylene-propylene copolymer dispersant in an amount of 0.1 wt% to 5 wt%, based on the total weight of the composition.

15. A method of lubricating a heavy duty diesel engine, the method comprising supplying a composition according to any one of claims 1 to 14 to the engine.

16. A method of lubricating a compression ignition internal combustion engine having a load mass in excess of 2,700 kg, the method comprising supplying a composition according to any one of claims 1 to 14 to the engine.

17. A method of lubricating the crankcase of a compression ignition or spark ignition engine, the method comprising supplying a composition according to any one of claims 1 to 14 to the crankcase.

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