Lubricating composition containing phenolic antioxidant, calcium salicylate detergent and low active sulfur

Abstract

The invention provides a lubricating composition comprising an oil of lubricating viscosity, a phenolic antioxidant, a succinimide dispersant that is at least substantially free of boron, a detergent comprising an alkaline earth metal salicylate, and a sulfurized organic compound.

Description

Technical Field

[0001] Exemplary embodiments relate to lubricating compositions, and specific applications have been found associated with lubricating compositions containing phenolic antioxidants, detergents containing calcium salicylate, and sulfurized organic compounds with low active sulfur content. When used in engines, these lubricating compositions provide improved lubricant oxidative stability and corrosion resistance. Background Technology

[0002] Ashless additives (additives that produce little or no ash upon combustion) are commonly used in engine oil formulations to provide performance properties such as antioxidants. Basic ashless additives (such as amines) are frequently used as antioxidants. Specifically, hydrocarbon-substituted diphenylamines, such as octyl diphenylamine, dioctyl diphenylamine, and dinonyl diphenylamine, have been used. See, for example, U.S. Patent No. 10,800,992 B2 to Mosier et al. concerning “LUBRICANT COMPOSITIONS FOR DIRECT INJECTION ENGINE,” which describes lubricant compositions that may contain diarylamine antioxidants such as dioctyl diphenylamine.

[0003] Substituted diphenylamine (SDPA) antioxidants are known to inhibit engine oil oxidation. They are widely used in heavy-duty engine oil applications where oxidation stability is crucial for reducing deposits, sludge, and varnish formation, controlling viscosity increases, and thus maintaining optimal engine performance. However, in practice, hydrocarbon-substituted diphenylamines can be detrimental to corrosion and deposit testing.

[0004] Experiments have been conducted to replace substituted diphenylamines with similar compounds, such as polymeric diphenylamine. For example, U.S. Publication No. 20190127526 A of Farng et al., “ANTIOXIDANT POLYMERIC DIPHENYLAMINE COMPOSITIONS”, describes an antioxidant polymer composition comprising repeating units of diphenylamine monomers, which can be combined with base oils and common lubricant additives.

[0005] Others use combinations of antioxidants. For example, U.S. Publication No. 20220145204A1, published on May 12, 2022, by Mayhew et al., describes a lubricating composition containing an antioxidant comprising a mixture of phenolic antioxidants, amine antioxidants, and sulfurized olefins.

[0006] Dodd et al. published U.S. Publication No. 20130281334A1 on "MARINE ENGINE LUBRICATION" on October 24, 2013, describing a marine engine lubricant composition with a TBN in the range of 20 mg to 60 mg KOH / g. The composition contains 40 mmol to 90 mmol of alkyl salicylate and polyalkenyl-substituted carboxylic anhydride per kg of composition, wherein the polyalkenyl is derived from a polyolefin with a number average molecular weight Mn of 200 to 3,000.

[0007] Hartley et al., in their U.S. Publication No. 20170058228A1, published on March 2, 2017, on “LUBRICATING OIL COMPOSITIONS,” describe a lubricating oil composition comprising: an oil-soluble or oil-dispersible sulfurized fatty acid ester providing at least 0.02% by mass of sulfur to the lubricating oil composition; and an oil-soluble or oil-dispersible alkali metal or alkaline earth metal salicylate detergent providing at least 5.0 mmol of salicylate soap per kg of the lubricating oil composition.

[0008] However, such compositions typically do not provide a good combination of antioxidant properties and reduced corrosion. Achieving both corrosion resistance and oxidation control is challenging, especially when using sulfur and amine compounds. Furthermore, sulfurized olefins also present problems. For example, U.S. Patent No. 4,873,006A, entitled "COMPOSITIONSCONTAINING ACTIVE SULFUR" and published by Vinci et al. on October 10, 1989, describes the use of nitrogen-containing carboxylic acid compounds to reduce hydrogen sulfide production from active sulfur-containing compounds.

[0009] There is still a need for a lubricating composition that provides good antioxidant properties while reducing the corrosion tendency of lubrication devices. Summary of the Invention

[0010] According to one exemplary embodiment, the lubricating composition comprises an oil having a lubricating viscosity, a phenolic antioxidant, a sulfurized organic compound, a succinimide dispersant that is at least substantially free of boron, and a detergent comprising an alkaline earth metal salicylate.

[0011] In various aspects of the exemplary implementation scheme: The lubricating composition may be at least substantially free of substituted diphenylamine (SDPA) antioxidants.

[0012] The lubricating composition may be at least substantially free of amine antioxidants.

[0013] The phenolic antioxidant may account for at least 0.1% by weight, or at least 0.5% by weight, or at least 1% by weight, or at least 1.5% by weight, or at least 2% by weight of the lubricating composition.

[0014] Phenolic antioxidants may account for no more than 8% by weight of the lubricating composition, or no more than 6% by weight, or no more than 5% by weight, or no more than 4% by weight, or no more than 3% by weight of the lubricating composition.

[0015] Phenolic antioxidants can be selected from hindered phenols, hindered alkylphenol esters, hindered alkoxyphenols, hindered phenolic acetates, hindered bisphenols, polyphenols, 4-tert-butylphenol-formaldehyde condensate, 4-tert-butylphenol-acetaldehyde condensate, and mixtures thereof.

[0016] Phenolic antioxidants may be selected from: mixtures of C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid; C4 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid; 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; and mixtures thereof.

[0017] Detergents may contain calcium salicylate or its salts.

[0018] The detergent may provide at least 0.04% by weight, or at least 0.08% by weight, or at most 0.4% by weight, or at most 0.3% by weight of calcium in the lubricating composition.

[0019] The lubricating composition may contain at least 0.1% by weight, or at least 0.12% by weight, or at least 0.15% by weight and / or no more than 0.3% by weight of calcium (Ca). The total calcium in the lubricating oil composition was determined by inductively coupled plasma atomic emission spectrometry according to ASTM D4951-14(2019), "Standard Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry" (hereinafter referred to as ASTM D4951).

[0020] Alkaline earth metal salicylates and lubricating compositions may be at least substantially free of magnesium. Specifically, the lubricating composition may contain no more than 0.01% by weight of magnesium.

[0021] The lubricating composition may contain at least 15, or at least 17, or at least 20, or at least 22 millimoles of alkaline earth metal detergent per kilogram of lubricating composition.

[0022] The lubricating composition may contain no more than 35, or no more than 32, or no more than 30, or no more than 25 millimoles of alkaline earth metal detergent per kilogram of lubricating composition.

[0023] The sulfurized organic compound may have an active sulfur content of no more than 8% by weight, or no more than 6% by weight, or no more than 4.0% by weight, or no more than 3.5% by weight, or no more than 3% by weight.

[0024] The sulfurized organic compound can provide a lubricating composition containing at least 0.01% by weight, or at least 0.03% by weight, or at least 0.05% by weight, or at most 0.12% by weight, or at most 0.09% by weight of sulfur.

[0025] The sulfurized organic compound may comprise at least 0.1% by weight, or at least 0.15% by weight, or at least 0.2% by weight of the lubricating composition.

[0026] The sulfurized organic compound may comprise up to 1% by weight, or up to 0.8% by weight, or up to 0.6% by weight, or up to 0.5% by weight of the lubricating composition.

[0027] The active sulfur may account for no more than 25% by weight, or no more than 22% by weight, or no more than 20% by weight, or no more than 19% by weight of the total sulfur in the sulfurized organic compound, or at least 1% by weight, or at least 1.5% by weight, or at least 6% by weight of the total sulfur in the sulfurized organic compound.

[0028] The sulfurized organic compound may have a total sulfur content of at least 0.1% by weight, or at least 1% by weight, or at least 1.5% by weight, or at least 2% by weight, or not more than 18% by weight, or not more than 15% by weight, or not more than 14.0% by weight, or not more than 12.0% by weight, or not more than 5% by weight.

[0029] The active sulfur may account for no more than 25% by weight, or no more than 22% by weight, or no more than 20% by weight, or no more than 19% by weight, or at least 1% by weight, or at least 1.5% by weight of the total sulfur in the sulfurized organic compound.

[0030] The sulfurized organic compound may provide at least 0.01% by weight, or at least 0.03% by weight, or at least 0.05% by weight, or at most 0.12% by weight, or at most 0.09% by weight of sulfur in the lubricating composition.

[0031] The sulfurized organic compound may provide active sulfur in the lubricating composition in amounts not exceeding 0.02% by weight, or not exceeding 0.018% by weight, or not exceeding 0.015% by weight, or not exceeding 0.013% by weight. The amount of active sulfur in the lubricating composition shall be determined according to ASTM D1662: “Active Sulfur in Cutting Oils”.

[0032] The sulfurized organic compound may comprise at least 0.1% by weight, or at least 0.15% by weight, or at least 0.2% by weight of the lubricating composition. The sulfurized organic compound may comprise at most 1% by weight, or at most 0.8% by weight, or at most 0.6% by weight, or at most 0.5% by weight of the lubricating composition.

[0033] The sulfurized organic compound can be selected from oligomeric polysulfides, alkyl polysulfides, sulfurized esters, sulfurized alicyclic dialkyl esters, sulfurized alicyclic dienyl esters, and mixtures thereof.

[0034] The sulfurized organic compound can be selected from oligomeric polysulfides of formula I: R 1 —S x ―[(C(R') v H 2-v ) n —S x ] p —R 2 Formula I, Where R 1 and R 2 Each is independently a C2-C20 alkyl group, such as C3 or C4 or higher alkyl groups, or C16 or lower alkyl groups; each R' is independently a C1-C20 alkyl group, or C6 or lower alkyl groups; each n is independently at least 1, or at least 2, or at most 8, such as 3-5, like 3 or 4; p is independently at least 1, or at least 2, or at most 8; each v is 0-2, such as v is 0; and each x is independently at least 1.

[0035] The oligomeric polysulfides or mixtures thereof may have a total sulfur content of at least 5% by weight and / or up to 45% by weight and an active sulfur content of at least 0.5% by weight and / or up to 10% by weight.

[0036] Sulfurized organic compounds may include alkyl polysulfides or mixtures thereof.

[0037] Alkyl polysulfides may have formula II: R 1 —S x —R 2 , where R 1 and R 2Each is independently a C2-C20 alkyl or C3-C8 alkyl, such as a C4 alkyl; and each x is independently at least 1.

[0038] Alkyl polysulfides or mixtures thereof may have a total sulfur content of at least 5% by weight and / or up to 20% by weight and an active sulfur content of at least 0.5% by weight and / or up to 45% by weight.

[0039] Sulfurized organic compounds can include sulfurized fatty acid esters of fatty alcohols.

[0040] Sulfurized fatty acid esters of fatty alcohols may include sulfurized triglycerides.

[0041] Thioglycerides or mixtures thereof may have the general structure of Formula III:

[0042] Formula III, Where R 3 R 4 and R 5 Each of the following is independently a C8 or higher alkyl or alkenyl group, or a C10 or higher alkyl or alkenyl group, or at most a C30 or at most a C24 alkyl or alkenyl group; and Where R 3 R 4 and R 5 At least one of them is attached to the sulfur atom of the sulfur-containing portion or the middle end of the alkyl group.

[0043] The triglycerides or mixtures thereof may have a total sulfur content of at least 5% by weight and / or at most 15% by weight and an active sulfur content of less than 5% by weight.

[0044] Sulfated triglycerides or mixtures thereof may be sulfated triglycerides in the general form shown in Formula IV:

[0045] Formula IV, Where R 6 It is a straight-chain or branched alkyl or alkenyl group with C4 or higher, C6 or higher, C8 or higher, C10 or higher, or up to C50; R 7 R 8 R 9 R 10 R 11 and R 12 Each of them is independently a C2 to C8 alkyl or alkenyl group; and each x is independently at least 1.

[0046] According to ASTM D1552, the sulfurized triglycerides of formula (IV) may have a total sulfur content of at least 5% by weight, or at least 7% by weight, or at most 15% by weight, or at most 12% by weight.

[0047] According to ASTM D1662, the sulfurized triglycerides of formula (IV) may have an active sulfur content of less than 5% by weight, or less than 4% by weight, or at least 3% by weight.

[0048] Sulfurized organic compounds may include at least one of alicyclic dialkyl esters and alicyclic dienyl esters.

[0049] At least one of alicyclic dialkyl esters and alicyclic dienyl esters may have the general formula V: , Formula V, Where R 13 and R 14 Each of them is independently a C2 or higher alkyl or alkenyl group; and x is at least 1.

[0050] At least one of the alicyclic dialkyl esters and alicyclic dienyl esters may have a total sulfur content of at least 5% by weight and / or at most 15% by weight and an active sulfur content of at least 1% by weight and / or at most 5% by weight.

[0051] The succinimide dispersant may comprise at least 0.2% by weight, or at least 0.5% by weight, or at least 1.0% by weight, or at most 7.0% by weight, or at most 6.0% by weight of the lubricating composition.

[0052] Succinimide dispersants can provide no more than 0.1% by weight of nitrogen in the lubricating composition.

[0053] The oil having a lubricating viscosity may comprise at least 70% by weight of the lubricating composition, or at most 94% by weight of the lubricating composition.

[0054] The lubricating composition may also include at least one of the following: anti-wear agent, corrosion inhibitor, viscosity modifier, pour point depressant, defoamer, extreme pressure agent, friction modifier, and combinations thereof.

[0055] Based on the total weight of the lubricating composition, the anti-wear agent can provide 300ppm-850ppm of phosphorus by weight to the lubricating composition.

[0056] Viscosity modifiers may include dispersant viscosity modifiers comprising at least one of the following: reaction products of olefin polymers containing carboxylic acid functional groups with 3-nitroaniline; and amine-functionalized aromatic maleic anhydride-styrene copolymers.

[0057] The dispersant and viscosity modifier may account for at least 0.01% by weight, or at least 0.1% by weight, or at least 2% by weight, or no more than 8% by weight, or no more than 7% by weight of the lubricating composition.

[0058] Viscosity modifiers may include hydrogenated styrene- b -At least one of butadiene copolymer resin viscosity modifiers and olefin copolymer resin viscosity modifiers.

[0059] In the lubricating composition, based on the total weight of the lubricating composition, molybdenum may not exceed 800 ppm, or 400 ppm, or 150 ppm, or 100 ppm, or 80 ppm, or 50 ppm, or 20 ppm.

[0060] For example, the TBN of a lubricating composition, as determined according to ASTM D2896-21 "Standard Test Method for Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration", may not exceed 10, 9, or 8.

[0061] The lubricating composition may be free of polyisobutylene succinic anhydride (PIBSA).

[0062] The lubricating composition may have an oxidation induction time of at least 120 minutes, or at least 130 minutes, or at least 135 minutes, as determined according to CEC L-85-99, “Oxidative Stability of Lubricants by PDSC (Pressure Differential Scanning Calorimetry)”.

[0063] The lubricating composition according to any of the above aspects can be used to lubricate engines, such as internal combustion engines or heavy-duty diesel engines.

[0064] In another embodiment, a method for improving oxidation stability in an engine may include supplying the lubricating composition described in any of the foregoing aspects to the engine.

[0065] In this method, the oxidation induction time of the lubricating composition, as determined according to CEC L-85-99, can be at least 65 minutes.

[0066] According to another exemplary embodiment, the lubricating composition comprises an oil having a lubricating viscosity; a sulfurized organic compound sufficient to provide at least 0.1% by weight of sulfur in the lubricating composition; at least 0.1% by weight of a phenolic antioxidant; at least 0.1% by weight of a succinimide dispersant that is at least substantially free of boron; and a calcium salicylate detergent present in an amount sufficient to provide at least 0.02% by weight of Ca, or at least 0.04% by weight, or at least 0.1% by weight, or at most 0.3% by weight, or at most 0.2% by weight, or at most 0.15% by weight of Ca to the lubricating composition. The lubricating composition contains no more than 0.04% by weight of active sulfur and no more than 0.01% by weight of magnesium.

[0067] In another aspect of the exemplary embodiment, a method for improving the oxidative stability of lubricating oil in an engine includes supplying the aforementioned lubricating composition to the engine. Detailed Implementation

[0068] Exemplary embodiments relate to lubricating compositions and methods of lubricating mechanical devices. The compositions provide improved oxidative stability of lubricating oils in mechanical devices while minimizing corrosion of conductive metals.

[0069] As used herein, TBN is measured according to ASTM D2896-21, "Standard Test Method for Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration," ASTM International, WestConshohocken, PA, 2015, hereinafter D2896.

[0070] The exemplary lubricating composition has a total TBN of at least 5 or at least 7. The TBN may not exceed 10, or 9, or 8. A succinimid dispersant may contribute to the total TBN of the lubricating composition. For example, a succinimid dispersant may have a total TBN of at least 12, or at least 15, or at most 20.

[0071] An exemplary lubricating composition comprises: a) Oils with lubricating viscosity; b) Phenolic antioxidants, namely one or more phenolic antioxidants; c) Succinimid dispersants, i.e., one or more succinimid dispersants; d) Detergents, namely one or more detergents, including alkaline earth metal salts of salicylic acid; e) a sulfurized organic compound, namely one or more sulfurized organic compounds, selected to provide a lubricating composition having a low active sulfur content; and f) Optionally, one or more other performance additives, such as anti-wear agents, corrosion inhibitors, viscosity modifiers, pour point depressants, defoamers, extreme pressure agents, friction modifiers, viscosity modifiers and / or combinations thereof.

[0072] The exemplary succinimide dispersant and lubricating composition, as a whole, are at least substantially boron-free or boron-free. As used herein, "substantially boron-free" means that the lubricating composition contains no more than 50 ppm of boron by weight, for example, no more than 25 ppm of boron by weight. As used herein, "boron-free" means taking into account trace amounts of boron or contamination with low or unintended levels of boron; for example, the lubricating composition may contain no more than 15 ppm of boron by weight, or no more than 10 ppm of boron by weight, or no more than 5 ppm of boron by weight, or as little as 0 ppm of boron by weight (i.e., an undetectable amount). In an exemplary embodiment, this can be achieved using an unboronized succinimide dispersant. Theoretically, the percentage by weight of boron can be estimated based on the amount of boron known to be present in each component of the lubricating composition. However, this amount can be accurately determined by spectrometry according to ASTM D4951-09, "Standard Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry".

[0073] The total amount of magnesium (Mg) in the lubricating composition may be determined by atomic absorption spectrometry according to ASTM D4628-16, "Standard Test Method for Analysis of Barium, Calcium, Magnesium, and Zinc in Unused Lubricating Oils by Atomic Absorption Spectrometry," and this total amount may not exceed 0.02% by weight, or 0.01% by weight, or 0.005% by weight, or 0.001% by weight, or 0.0001% by weight, or 0% by weight.

[0074] The total nitrogen content of the lubricating composition can be determined according to ASTM D3228-20, "Standard Test Method for Total Nitrogen in Lubricating Oils and Fuel Oils by Modified Kjeldahl Method", and the total nitrogen content can be at least 0.05% by weight, or at least 0.07% by weight, or at most 0.2% by weight, or at most 0.15% by weight.

[0075] The lubricating composition may have a concentration of at least 2 cSt (or mm). 2 The kinematic viscosity (KV_100) at 100°C, or at least 10 cSt, or at least 12 cSt, or at most 25 cSt, or at most 20 cSt, as measured by ASTM D445-21e1 "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)" (hereinafter referred to as "D445"). The lubricating composition may be liquid at ambient temperature (15°C–30°C), i.e., not a gel or semi-solid.

[0076] a) Oil with lubricating viscosity

[0077] The lubricating composition contains an oil having a lubricating viscosity. Suitable oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrorefining, unrefined oils, refined oils, refined oils or mixtures thereof.

[0078] Oils with lubricating viscosity can also be defined according to the provisions of Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, Section 1.3, Subheading 1.3, "Base Stock Categories," of the April 2008 edition of Appendix E. The API guidelines are also outlined in U.S. Patent No. 7,285,516. The five groups of base oils are as follows: Group I (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group II (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group III (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group IV (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group V (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group VI (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group VII (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group VIII (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group VI (sulfur content >0.03% by weight and / or <90% by weight of saturated oils, viscosity index 80-120); Group VII (sulfur content >0.03% by weight and / or <90% by < 0.03% by weight, and > 90% by weight of saturated material, viscosity index 80-120; Category III (sulfur content) < 0.03% by weight, and > 90% by weight of saturated material, viscosity index > 120); Class IV (all polyalphaolefins (PAOs)); and Class V (all other oils not included in Class I, II, III, or IV). Exemplary oils having lubricating viscosity include API Class I, II, III, IV, V oils, or mixtures thereof. In some embodiments, the oil having lubricating viscosity is API Class I, II, III, or IV oil, or mixtures thereof. In some embodiments, the oil having lubricating viscosity is API Class I, II, or III oil, or mixtures thereof. In one embodiment, the oil having lubricating viscosity may be API Class II, III mineral oil, Class IV synthetic oil, or mixtures thereof. In some embodiments, at least 5% by weight, or at least 10% by weight, or at least 20% by weight, or at least 40% by weight of the lubricating composition is polyalphaolefin (Class IV). Oils with lubricating viscosity have been defined from other classes (subclasses) of their selection, including API Group II+ base oils, which are Group II base oils with a viscosity index ≥110 and <120, and API Group III+ base oils with a viscosity index ≥130, as described in SAE publication "Design Practice: Passenger Car Automatic Transmissions," 4th Edition, AE-29, 2012, pp. 12-19. In one embodiment, Group II and / or Group III base oils are used.

[0079] Unrefined oils, refined oils, and re-refined oils, as well as natural and synthetic oils, are described, for example, in U.S. Publication No. 2010 / 0197536 A1. Synthetic oils can also be produced via the Fischer-Tropsch reaction and are typically produced by hydroisomerizing Fischer-Tropsch hydrocarbons or waxes. Oils can be prepared via Fischer-Tropsch gas-to-liquid synthesis processes and other gas-to-liquid processes.

[0080] Unrefined oils are oils that are typically obtained directly from natural or synthetic sources without (or with minimal) further purification.

[0081] Refined oils are similar to unrefined oils, except that they have undergone further processing in one or more purification steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, double distillation, acid or alkali extraction, filtration, percolation, etc.

[0082] Refined oils are also known as recycled oils or reprocessed oils, and are obtained by methods similar to those used to obtain refined oils, and are often further processed by techniques involving the removal of waste additives and oil decomposition products.

[0083] Natural oils include animal fats, vegetable oils (such as castor oil), mineral lubricants (such as kerosene and solvent-treated or acid-treated alkanes, cycloalkanes, or mixed alkane-cycloalkanes), and oils derived from coal or shale, or mixtures thereof. Examples of animal and vegetable oils include long-chain fatty acid esters such as linseed oil, sunflower oil, sesame oil, tallow, lard, palm oil, castor oil, cottonseed oil, corn oil, peanut oil, soybean oil, olive oil, whale oil, herring oil, sardine oil, coconut oil, palm kernel oil, babassu oil, rapeseed oil, and soybean oil.

[0084] Synthetic oils can be produced via the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil can be prepared via a Fischer-Tropsch gas-to-liquid synthesis process and other gas-to-liquid oils. Exemplary synthetic oils include hydrocarbon oils such as polyalphaolefins, synthetic esters and polyesters, polyacrylates and polymethacrylates, liquid esters of phosphorus-containing acids, and polymeric tetrahydrofurans.

[0085] Example synthetic esters include esters of dicarboxylic acids (e.g., selected from phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, octanoic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, and alkenyl malonic acid) and alcohols (e.g., selected from butanol, hexanol, dodecyl alcohol, 2-ethylhexanol, ethylene glycol, diethylene glycol monoether, and propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacic acid ester, di-n-hexyl fumarate, dioctyl sebacic acid, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacic acid, 2-ethylhexyl diester of linoleic acid dimer, and a complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid. Esters that are particularly suitable for use in synthetic oils include those from C5 to C6. 12 Monocarboxylic acids and polyols, as well as esters prepared from polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Esters can also be monoesters, such as those traded under the name Priolube 1976. ™ (C) 18 -alkyl-COO-C 20 Monoesters obtained from alkyl groups. The synthetic esters used in this paper can have a 2.5 mm... 2 / s to 30mm 2 / s of KV_100 (according to D445).

[0086] Exemplary synthetic hydrocarbon oils include polymerized and interpolymerized olefins (e.g., polybutene, polypropylene, propylene-isobutene copolymers); poly(1-hexene), poly(1-octene), poly(1-decene), and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)benzene); polybenzenes (e.g., biphenyl, terphenyl, alkylated polybenzene); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, and their derivatives, analogs, and homologues, or mixtures thereof.

[0087] Consider blends of such oils, such as blends of Group II and Group III base oils, or blends of Group III and Group IV base oils.

[0088] Oils with lubricating viscosity can have a kinematic viscosity (KV_100) of at least 1.8 cSt or at least 4 cSt at 100°C as determined according to D445, depending on the desired SAE grade of the lubricating composition. This viscosity can be obtained from a mixture of base oils, such as those containing Group I mineral bases, neutral solvents (e.g., 500 NS or 600 NS), and bright oil bases. In mixtures with additives, any other combination of mineral or synthetic bases or plant-derived bases with viscosities compatible with the desired SAE grade can be used.

[0089] The amount of oil present with lubricating viscosity is typically the balance remaining after subtracting the sum of the amounts of additives as described above and any other performance additives from 100% by weight.

[0090] The lubricating composition may be in the form of a concentrate and / or a fully formulated lubricant. If the lubricating composition is in the form of a concentrate (which may be combined with other oils to form a finished lubricating composition, either wholly or partially), the ratio of the components of the lubricating composition (excluding the oil having a lubricating viscosity) to the oil having a lubricating viscosity may be 20:80 to 90:10 by weight, or 40:60 to 80:20 by weight. If the lubricating composition is in the form of a finished lubricating composition, the ratio of the components of the lubricating composition (excluding the oil having a lubricating viscosity) to the oil having a lubricating viscosity may be 1:99 to 30:70 by weight, or 5:95 to 20:80 by weight.

[0091] In one embodiment, the oil having a lubricating viscosity (including diluent oil and oil present due to additives in the composition) accounts for at least 20% by weight, or at least 40% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 82% by weight, or at most 96% by weight, or at most 94% by weight, or at most 92% by weight, or at most 90% by weight of the lubricating composition.

[0092] b) Phenolic antioxidants

[0093] Phenolic antioxidants may be present in the lubricating composition at a total concentration of at least 0.1% by weight, or at least 0.5% by weight, or at least 1% by weight, or at least 1.5% by weight, or at least 2% by weight, or at most 8% by weight, or at most 6% by weight, or at most 5% by weight, or at most 4% by weight, or at most 3% by weight.

[0094] Exemplary phenolic antioxidants include hindered phenols, including hindered phenolic esters such as alkyl phenolate esters, hindered phenolic acetate esters, hindered phenolic alkoxides, bisphenols and polyphenols, condensates of phenol and formic acid, and mixtures thereof. Hindered phenolic antioxidants typically contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group may be further replaced by a hydrocarbon group (typically a straight-chain or branched alkyl group) and / or a bridging group connected to a second aromatic group.

[0095] Examples of phenolic antioxidants that can be used include: - Hindered phenols, such as 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-ethylphenol; 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol and 4-dodecyl-2,6-di-tert-butylphenol; - Hindered alkylphenol esters, such as C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid, alkyl esters of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, such as n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, n-butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 2'-ethylhexyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; - Hindered alkoxyphenols, such as 2,6-di-tert-butyl-4-alkoxyphenols, for example 2,6-di-tert-butyl-4-methoxyphenol and 2,6-di-tert-butyl-4-ethoxyphenol; - Hindered phenolic acetates, such as 3,5-di-tert-butyl-4-hydroxybenzyl mercaptooctyl acetate; - Hindered bisphenols, such as 2,2'-methylene-bis(4-alkyl-di-tert-butylphenol), e.g., 2,2'-methylene-bis(4-methyl-di-tert-butylphenol) and 2,2-methylene-bis(4-ethyl-di-tert-butylphenol), bisphenols such as 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), 4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 2,2-(di-p-hydroxyphenyl)propane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 4,4'-cyclohexylene-bis(2,6-tert-butylphenol), hexamethylene-bis(2,6-tert-butylphenol), etc. The following are listed: 3,9-diethylene glycol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 2,2'-thio-[diethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{1,1-dimethyl-2-[3-(3-tert-butyl-4-hydroxy-5-methyl-phenyl)propionyloxy]ethyl}2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(3-methyl-6-tert-butylphenol) and 2,2'-thiobis(4,6-di-tert-butylresorcinol); Polyphenols, such as tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, bis-[3,3'-bis(4'-hydroxy-3'-tert-butylphenyl)butyrate]ethylene glycol ester, 2-(3',5'-di-tert-butyl-4-hydroxyphenyl)methyl-4-(2'',4''-di-tert-butyl-3''-hydroxyphenyl)methyl-6-tert-butylphenol and 2,6-bis(2'-hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-methylphenol; -4-tert-butylphenol-formaldehyde condensate and 4-tert-butylphenol-acetaldehyde condensate; - and their mixtures.

[0096] Hindered phenolic antioxidants often contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group may be further replaced by a hydrocarbon group (typically a straight-chain or branched alkyl group) and / or a bridging group connected to a second aromatic group. Examples of suitable hindered phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, and 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenolic antioxidant is an ester and may include, for example, Irganox from BASF. ™L 135 or L 115. Irganox ™ L 135 is a high molecular weight phenolic antioxidant, specifically a mixture of C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid. (Irganox) ™ L 115 is 2,6-di-tert-butylphenol. A more detailed description of suitable ester-containing hindered phenolic antioxidant chemistry can be found in U.S. Patent No. 6,559,105. In another embodiment, the hindered alkylphenol is a C4 alkyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid. In another embodiment, the hindered alkylphenol is 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0097] The coupling phenols used in this article may contain two alkylphenols coupled to an alkylene group to form a bisphenol compound. Examples of suitable coupling phenol compounds include 4,4'-methylenebis(2,6-di-tert-butylphenol); 4-methyl-2,6-di-tert-butylphenol; 2,2'-bis(6-tert-butyl-4-heptylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol).

[0098] Other phenolic antioxidants may include polyhydroxy aromatic compounds and their derivatives. Examples of suitable polyhydroxy aromatic compounds include esters and amides of gallic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxynaphthoic acid, 3,7-dihydroxynaphthoic acid, and mixtures thereof. In one embodiment, the phenolic antioxidant includes a hindered phenol. In another embodiment, the hindered phenol is derived from 2,6-di-tert-butylphenol.

[0099] In one embodiment, the lubricating composition is free of or substantially free of substituted diphenylamine (SDPA) antioxidants. “Substantially free of” means that SDPA antioxidants may be present in amounts not exceeding 0.1% by weight, or not exceeding 0.01% by weight, or 0% by weight of the lubricating composition.

[0100] Substituted diphenylamines are defined as anilines having substituents on one or more carbon atoms of a benzene ring. The substituents can be alkyl substituents selected from aliphatic substituents (including alicyclic), aromatic substituents, substituents having alkyl and aryl moieties, and mixtures thereof. This type of substituted diphenylamine includes monoalkyl, dialkyl, trialkyl and polyalkyl, alkenyl, alkynyl, alkoxyalkyl, alkylamino, aryl, alkylaryl and / or alkoxyaryl substituted diphenylamines, such as C1-C24, especially C6 and higher alkyl substituted diphenylamines, such as monooctyl diphenylamine, dioctyl diphenylamine, monobutyl-monoctyl diphenylamine, nonyl diphenylamine, dinonyl diphenylamine, trinonyl diphenylamine, decyl diphenylamine and didecyl diphenylamine. Aniline, as described, for example, in U.S. Patents 2,943,112, 4,824,601, 5,672,752, 6,204,412, 6,315,925, 6,355,839 and U.S. Publications 2015 / 0307803 and 2016 / 0017252, and polymers of such monomers, as described, for example, in U.S. Publication 20190127526A1. Aryl-substituted diphenylamines include phenyl-α-naphthylamine (PANA) and alkylated phenylnaphthylamine.

[0101] Other amine antioxidants that can be excluded or are substantially absent include 2,6-di-tert-butyl-α-dimethylamino-p-cresol.

[0102] In one embodiment, the lubricating composition contains no or substantially no (less than 0.01% by weight, or less than 0.001% by weight, or 0% by weight) any amine antioxidants.

[0103] c) Succinimide dispersant

[0104] An exemplary lubricating composition comprises at least one succinimidyl dispersant. The succinimidyl dispersant is at least substantially free of boron. The succinimidyl dispersant may provide the lubricating composition with no more than 0.001% boron (B), or no more than 0.0001% boron, or no more than 0.00005% boron, or no more than 0.00001% boron, or 0% boron.

[0105] Succinimide dispersants can be N-substituted long-chain alkenyl succinimides. An example of an N-substituted long-chain alkenyl succinimide is polyisobutylene succinimide. Polyisobutylene succinic anhydride from which polyisobutylene is derived has a number-average molecular weight M of at least 300, or at least 350, or at least 500, or at least 550, or at least 750, or at least 1000. nAnd it can be up to 5000, or up to 3000, or up to 2500. Such succinimides can be formed, for example, from high-ethylene polyisobutylene and maleic anhydride. Succinimid dispersants and their preparation are disclosed, for example, in U.S. Patent Nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433, 6,165,235, and 7,238,650 and EP0355895A2.

[0106] In one embodiment, the succinimide dispersant is derived from 1800M n Up to 2200M n A polyisobutylene succinimide dispersant containing 0.80% to 1.0% nitrogen by weight.

[0107] In addition to succinimide detergents, other dispersants may be used such as Mannich dispersants, succinamide dispersants, and polyolefin succinates, amides, and ester-amides, as well as mixtures thereof.

[0108] In one embodiment, the lubricating composition is free of or at least substantially free of polyisobutylene succinic anhydride (PIBSA). This means that the lubricating composition contains no more than 0.001% by weight of PIBSA or no more than 0.0001% by weight of PIBSA.

[0109] Exemplary polyolefin succinate-amides can be polyisobutylene succinates that react with alcohols (such as pentaerythritol) and polyamines. Exemplary polyolefin succinates include polyisobutylene succinates of pentaerythritol and mixtures thereof.

[0110] Exemplary dispersants can also be post-treated by conventional methods through reaction with any of a variety of reagents. In one embodiment, such post-treatment does not involve treatment with boron compounds (such as boric acid), so the dispersant is not borated. Post-treatment with urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids (such as terephthalic acid), hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, and phosphorus compounds is contemplated. In one embodiment, the dispersant is post-treated by reacting with dimercaptothiadiazole. In another embodiment, the dispersant is post-treated by reacting with phosphoric acid or phosphorous acid.

[0111] To indicate the amount of components in a composition, dispersants and viscosity modifiers are classified as viscosity modifiers rather than dispersants.

[0112] In one embodiment, the lubricating composition comprises at least 0.1 wt%, or at least 0.2 wt%, or at least 0.5 wt%, or at most 1.0 wt%, or at most 7.0 wt%, or at most 6.0 wt% of a boron-free (unboronized) succinimidyl dispersant. Therefore, the lubricating composition may be boron-free or at least substantially boron-free, as described above.

[0113] The lubricating composition may contain a total of at least 0.01% by weight, or at least 0.1% by weight, or at least 0.2% by weight, or at least 0.5% by weight, or at least 1% by weight, or at least 1.5% by weight, or at least 2% by weight, or at least 3% by weight of a dispersant, and in some embodiments, at most 15% by weight, or at most 10% by weight, or at most 8% by weight, or at most 7% by weight, or at most 5% by weight of all the dispersant.

[0114] Sulfurized organic compounds

[0115] Exemplary sulfurized organic compounds help control wear in lubrication systems such as engines, especially under extreme pressure conditions in automobile, truck, and industrial engines. They also exhibit excellent thermal oxidative stability and rust prevention properties.

[0116] The term "active sulfur" in sulfur-containing compounds refers to the relative ability of a sulfur-containing compound to chemically react with a metal surface to form a metal sulfide. As used herein, active sulfur is the weight percentage of sulfur available for reaction at 150°C, as determined by ASTM D1662-19, "Standard Test Method for Active Sulfur in Cutting Oils," hereinafter ASTM D1662. It should be noted that the active sulfur of a sulfur-containing compound is not solely a function of its molar percentage of sulfur, and two sulfur-containing compounds can have very similar sulfur molar percentages (or weight percentages) but significantly different active sulfur weight percentages. The balance of sulfur is referred to as inactive sulfur.

[0117] Sulfated organic compounds are typically compounds with low active sulfur. Sulfated organic compounds with low active sulfur have a low weight percentage of active sulfur or a low weight % of active sulfur in the total sulfur of the sulfurized organic compound, or both.

[0118] Sulfurized organic compounds include those compounds that are essentially nitrogen-free (i.e., they do not contain nitrogen functional groups). Sulfurized organic compounds can be formed by sulfiding an organic compound containing at least one olefinic double bond (a non-aromatic double bond), i.e., a double bond connecting two aliphatic carbon atoms. In some cases, the organic compound to be sulfided may contain a metal cation (e.g., from Group I or II, such as sodium, potassium, barium, calcium); a halogen group (e.g., chlorinated, brominated, or iodinated); and / or an oxygen-containing group, such as an ester group.

[0119] Examples of sulfurized organic compounds include dibenzyl monosulfides and disulfides, sulfurized isobutylene, sulfurized methyl oleate, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpenes and sulfurized Diels-Alder adducts, as well as phosphorus sulfurized hydrocarbons, such as the reaction products of phosphorus sulfide with rosin or methyl oleate.

[0120] The sulfurized organic compounds or mixtures of compounds used in this article, particularly, contain little or no active sulfur. Active sulfur compounds consist of chains with at least two linked sulfur atoms. These chains of sulfur atoms make the molecule prone to breakage between the sulfur atoms, and the resulting reactive sulfur compounds can cause corrosion of some metals, such as copper. Inactive sulfur compounds contain fewer than two linked sulfur atoms, meaning each sulfur atom is linked to an atom other than sulfur. Some compounds may contain both active and inactive sulfur, with some sulfur elements in chains of two or more sulfur atoms, while the remainder exists as a single sulfur atom.

[0121] The sulfurized organic compound or mixture of sulfurized organic compounds (when using two or more such compounds) may have an active sulfur content of no more than 8% by weight, or no more than 6% by weight, or no more than 5% by weight, or no more than 4% by weight, or no more than 3.5% by weight, or no more than 3% by weight, or no more than 2.5% by weight, or as low as 0% by weight, as determined by ASTM D1662 at 150°C. In some embodiments, the active sulfur accounts for at least 0.1% by weight, or at least 0.5% by weight, or at least 1.0% by weight, or at least 1.5% by weight, or at least 1.8% by weight of the sulfurized organic compound or mixture of sulfurized organic compounds. When two or more sulfurized organic compounds are used, the active sulfur content is the average (weighted average) active sulfur content.

[0122] Organic sulfur compounds or mixtures of organic sulfur compounds (when two or more such compounds are used) may have a total sulfur content of at least 1 wt%, or at least 1.5 wt%, or at least 2 wt%, or not more than 18 wt%, or not more than 15 wt%, or not more than 14.0 wt%, or not more than 12.0 wt%, or not more than 5 wt%, as determined by ASTM D1552-16 (2021), “Standard Test Method for Sulfur in Petroleum Products by High Temperature Combustion and Infrared (IR) Detection or Thermal Conductivity Detection (TCD)”, hereinafter D1552. When two or more organic sulfur compounds are used, the total sulfur content is the average (weighted average) sulfur content.

[0123] In one embodiment, the weight percentage of total sulfur (as determined by ASTM D1552) in the sulfurized organic compound, which is active sulfur (as determined by ASTM D1662), may not exceed 25% by weight, or not exceed 22% by weight, or not exceed 20% by weight, or not exceed 19% by weight, and may be as low as 0% by weight, or in some embodiments, at least 1% by weight, or at least 1.5% by weight, or at least 6% by weight, or at least 10% by weight, or at least 15% by weight. In other words, the weight ratio of active sulfur to non-active sulfur in the sulfurized organic compound may not exceed 25:75, or not exceed 22:82, or not exceed 20:80.

[0124] The sulfurized organic compound may be present in an amount sufficient to provide at least 0.01% by weight, or at least 0.03% by weight, or at least 0.05% by weight, or at most 0.5% by weight, or at most 0.12% by weight, or at most 0.09% by weight of sulfur to the lubricating composition. Other sulfur sources in the lubricating composition may provide additional amounts of sulfur. In one embodiment, the lubricating composition contains no more than 0.4% by weight of total sulfur, or no more than 0.3% by weight of total sulfur.

[0125] The sulfurized organic compound may be present in an amount sufficient to provide no more than 0.04% by weight, or no more than 0.03% by weight, or no more than 0.025% by weight, or no more than 0.02% by weight, or no more than 0.015% by weight of active sulfur to the lubricating composition, and in some embodiments, in an amount providing at least 0.005% by weight, or at least 0.008% by weight, or at least 0.01% by weight of active sulfur to the lubricating composition. Generally, the sulfurized organic compound is the sole source of active sulfur in the lubricating composition.

[0126] The sulfurized organic compounds can be selected from oligopolysulfides, alkyl polysulfides, sulfurized esters, sulfurized α-olefins, sulfurized fats, and sulfurized soybean oil.

[0127] Oligomeric polysulfides can have the general formula shown in Formula I: R 1 —S x ―[(C(R') v H 2-v ) n —S x ] p —R 2 Formula I, Where R 1 and R 2 Each is independently a C2-C20 alkyl group, such as C3 or C4 or higher alkyl groups, or C16 or lower alkyl groups; Each R' is independently a C1-C20 alkyl, or a C6 or lower alkyl; Each n is independently at least 1, or at least 2, or at most 8, such as 3-5, like 3 or 4; p independently is at least 1, or at least 2, or at most 8; Each v is between 0 and 2, for example, v is 0; and Each x is independently at least 1, or at least 2, or at most 3, or higher, provided that the above-mentioned restrictions on the active sulfur of the sulfurized organic compound are met.

[0128] Generally speaking (for example, for at least 80% of S) x Group, or at least 90% S x Groups, or in some cases for all S x (group), where x is no more than 1. Therefore, the lubricating composition may be substantially free of compounds of formula (I) where x is 4 or higher. In this context, "substantially free" means in no more than 5%, or no more than 2%, or no more than 1%, or no more than 0.5% of S xThe x in the group is 4 or higher. The total sulfur content (ASTM D1552) of such oligomeric polysulfides and mixtures thereof may be in the range of 5% to 45% by weight, or at least 10% by weight. The active sulfur content (ASTM D1662) of such oligomeric polysulfides and mixtures thereof may be in the range of 0.5% to 10% by weight, or at most 9% by weight.

[0129] Alkyl polysulfides can have the general formula shown in Formula II: R 1 —S x —R 2 Formula II, Where R 1 and R 2 Each is independently a C2-C20 alkyl group, such as a C3 or higher alkyl group, or a C16 or lower alkyl group; and Each x is independently at least 1, and in some cases can be at least 2, or at most 3, or higher, provided that the above-mentioned limits on the active sulfur of the sulfurized organic compound are met. This generally means that the value of x does not exceed 1.5 on average, or does not exceed 1.2, and the lubricating composition is substantially free of compounds of formula II (where x is 4 or higher).

[0130] The total sulfur content (ASTM D1552) of such alkyl polysulfides and mixtures thereof may be in the range of 5% to 20% by weight, or at least 10% by weight. The active sulfur content (ASTM D1662) of such alkyl polysulfides and mixtures thereof may be in the range of 0.5% to 45% by weight, or at most 10% by weight, or at most 9% by weight, or at most 5% by weight. The molecular weight may be in the range of 200 Daltons to 2000 Daltons.

[0131] Example sulfide esters include sulfide fatty acid esters of fatty alcohols (such as glycerol), such as monoglycerides, diglycerides, and triglycerides, such as sulfide triglycerides of the general formula shown in Formula III:

[0132] Formula III, Where R 3 R 4 and R 5 Each of the following is independently a C8 or higher alkyl or alkenyl group, or a C10 or higher alkyl or alkenyl group, or at most a C30 or at most a C24 alkyl or alkenyl group; and Where R 3 R 4 and R 5 At least one of them is attached to the sulfur atom of the sulfur-containing portion or the middle end of the alkyl group.

[0133] Example sulfur-containing fractions can have the following general formula: —S x —, its location in R 3 R 4 and R 5 A connection is formed between the two; or —S x —R 6 , where R 6 A straight-chain or branched alkyl or alkenyl group of C4 or higher, or C6 or higher, or C8 or higher, or C10 or higher, or up to C50, such as ―CH2CH=CHCH2(CH2CH2). q CH3, wherein q is at least 5, or at least 10, or at most 15; Or mixtures thereof; Each x is independently at least 1, and in some cases can be at least 2, or at most 3, or higher, but substantially contains no compounds of formula II in which x is 4 or higher, provided that the above-mentioned restrictions on the active sulfur of sulfurized organic compounds are met.

[0134] An example of a sulfurized fatty acid ester is a sulfurized triglyceride of the general formula shown in Formula IV:

[0135] Formula IV, Where R 6 As mentioned above, for example, CH2CH=CHCH2(CH2CH2) 13-15 CH3; R 7 R 8 R 9 R 10 R 11 and R 12 Each of them is independently a C2 to C8 alkyl or alkenyl group, for example, R 7 For (CH2)6, R 8 It is (CH2)6CH3, R 9 It is (CH2)7, R 10 It is (CH2)5CH3, R 11 It is (CH2)6, and R 12 It is (CH2)6CH3; And each x is independent as described above.

[0136] The total sulfur content of the sulfurized triglycerides according to Formula III or IV (ASTM D1552) may be at least 5% by weight, or at least 7% by weight, or at most 15% by weight, or at most 12% by weight.

[0137] The active sulfur (ASTM D1662) in sulfide esters or mixtures thereof may be less than 5% by weight, for example 3% to 4% by weight.

[0138] Other sulfurized esters include sulfurized alicyclic dialkyl esters and dienyl esters of the general formula shown in Formula V:

[0139] Formula V, Where R 13 and R 14 Each of them is independently a C2 or higher alkyl group, such as C3 or higher, or C4 or higher, or at most C10, or at most C6 alkyl or alkenyl groups, such as straight-chain C4 alkyl groups; and x is as described above, for example, x is 1 or 2.

[0140] The sulfur content of the sulfur-containing alicyclic diester can be at least 5% by weight, at least 10% by weight, or at most 15% by weight, such as 10% to 14% by weight, and the active sulfur content can be from 1% to 5% by weight. For example, the active sulfur content of a mixture of sulfur-containing alicyclic dibutyl esters in the form shown in Formula V can be at least 1% by weight, at least 1.5% by weight, or at most 5% by weight, such as at most 3% by weight.

[0141] Example sulfurized organic compounds include sulfurized olefins (sulfurized chain olefins), which can be obtained by reacting a sulfurizing agent with a chain olefin such as isobutylene in the presence of a catalyst. Sulfurizing agents include elemental sulfur, hydrogen sulfide, sulfur halides, sodium sulfide, and mixtures of hydrogen sulfide and sulfur or sulfur dioxide. The amount of sulfurizing agent used can be calculated based on the total number of olefinically unsaturated groups in the mixture. For example, 0.5 to 1.2 moles of sulfur are used per mole of olefinic bond. Olefin compounds may contain 2 to 50 carbon atoms.

[0142] Example sulfurized olefins can be obtained from isobutylene, sulfur, and hydrogen sulfide by reacting a thiol with sulfur in the presence of a basic catalyst using a catalytic method employing a solid catalyst (such as the solid catalysts described in U.S. Patents 6,472,354B2 and 4,876,389A). They can also be produced by a two-step process as described in U.S. Patent 4,937,385A, which involves synthesizing a thiol from an olefin and H₂S in the presence of a solid catalyst, followed by reacting the thiol with sulfur and another heterogeneous catalyst to form a sulfurized olefin.

[0143] The sulfurized olefins shown in Formula IV can be prepared as described in U.S. Patent No. 4,957,651. The method employs a mixture of two or more reactants selected from the group consisting of: (1) a fatty acid ester of at least one polyol, (2) at least one fatty acid, (3) at least one olefin, and (4) a fatty acid ester of at least one monohydric alcohol. Reactant (3) (the olefin component) comprises at least one olefin. The olefin can be an aliphatic olefin containing 4 to 40 carbon atoms, such as 8 to 36 or 12 to 18 carbon atoms. Terminal olefins or α-olefins are particularly suitable, especially those having 12 to 20 carbon atoms.

[0144] The sulfurized organic compound shown in Formula V can be a reaction product of a sulfurizing agent and at least one Diels-Alder adduct in a molar ratio of at least 0.75:1. The molar ratio of the sulfur source to the Diels-Alder adduct can be from 0.75:1 to 1:1.2. The Diels-Alder adduct can be formed by a reaction product having at least one component consisting of —C(O)O—R o Preparation of dienophiles of carboxylic acid ester groups, wherein R o For saturated fatty alcohol residues with up to 40 carbon atoms, —R o The fatty alcohols derived from them are monohydric or polyhydric alcohols, which can be selected from alkylene glycols, alkanols, alkoxy-substituted alkanols, ethanol, ethoxyethanol, propanol, butanol, β-diethylamino-ethanol, dodecyl alcohol, diethylene glycol, tripropylene glycol, tetrabutanediol, hexanol, octanol, isooctanol, and mixtures thereof. Generally, no more than two —C(O)O—R o Group, and in one embodiment, only one —C(O)O—R o Groups. Such substances can also be described as cyclohexene compounds with ester substituents. An example of this type of sulfurized organic compound is sulfide 4-butoxycarbonylcyclohexene. This and other sulfurized organic compounds can be further processed with other substances such as aryl phosphate esters (e.g., triphenyl phosphite).

[0145] The vulcanization reaction can be carried out at elevated temperatures (e.g., 50°C-350°C or 100°C-200°C), with effective stirring, and typically in an inert atmosphere such as nitrogen, optionally in the presence of an inert solvent.

[0146] d) Performance Additives

[0147] ii) Detergent

[0148] The lubricating composition also includes at least one detergent. The detergent is an additive that reduces the formation of deposits on lubricated surfaces, such as high-temperature varnish and paint deposits on piston surfaces in an engine. Exemplary detergents that may be used herein include metal-containing detergents, which may be neutral or highly alkaline. Metal-containing detergents may be borated with a borater, such as boric acid. In one embodiment, the detergent is not borated.

[0149] In one embodiment, the detergent comprises or is composed of an unboronized, hydrocarbon-substituted alkaline earth metal salicylate. Alkaline earth metal salicylates may have the general formula of Formula VI:

[0150] Style VI

[0151] Where M is an alkaline earth metal selected from calcium, barium, magnesium, and mixtures thereof; Each x is an independent hydrocarbon group; a is at least 1, such as at most 8, or at most 4; and n can be 2, or less than 2 if another counterion is present, or greater than 2 if the salicylate is highly basic.

[0152] In one implementation, M is not magnesium (Mg). In another specific implementation, M is calcium (Ca).

[0153] Alkaline earth metal salicylates can be highly alkaline.

[0154] An exemplary neutral calcium salicylate may have a total base value of about 100 or 125. An exemplary highly basic salicylate may have a total base value of at least 125, or at least 200, or at most 500, or at most 350 (based on oil-free).

[0155] In one embodiment, X is a C10-C40 alkyl or alkenyl group, or a C14 or higher, or at most C20 alkyl or alkenyl group. Examples of C10-C40 alkyl groups (which may be straight-chain or branched) include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecanyl, eicosyl, etc. Examples of C10-C40 alkenyl groups (which may be straight-chain or branched, and the position of the double bond is arbitrary) include decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecanenyl, etc.

[0156] In another embodiment, X is a C8-C30 alkyl-aromatic group.

[0157] Alkaline earth metal salicylates can be prepared, for example, by alkylating salicylic acid with a straight-chain α-olefin containing at least 10 or at least 14 carbon atoms (or otherwise substituting the hydrocarbon group) in the presence of a strong acid catalyst (such as methanesulfonic acid) to form oil-soluble alkylated salicylic acid, neutralizing the oil-soluble alkylated salicylic acid, and optionally over-alkalizing the oil-soluble alkylated salicylic acid by carbonation (e.g., using CO2).

[0158] Calcium salicylate detergents may be present in an amount sufficient to provide at least 0.02% by weight of Ca to the lubricating composition, such as at least 0.04% by weight, or at least 0.1% by weight, or at most 0.3% by weight, or at most 0.2% by weight, or at most 0.15% by weight of Ca, as determined according to ASTM D4951.

[0159] Alkaline earth metal salicylates may be at least 15 mmol / kg, or at least 17 mmol / kg, or at least 20 mmol / kg, or at most 30 mmol / kg, or at most 25 mmol / kg, such as 15 mmol / kg to 32 mmol / kg, in the lubricating composition.

[0160] The amount of alkaline earth metal salicylates, expressed in mmol / kg, can be determined by potentiometric titration using a method similar to that described in U.S. Patent No. 5,558,802. In this method, a salicylate soap sample is dissolved in a solvent and then treated with a strong acid to neutralize any alkalinity. An alcohol is then added to the liquid, and the mixture is briefly boiled to neutralize any residual alkali. The alcohol is then added to the liquid, and the solution is titrated with an alcoholic alkali metal hydroxide using a pH electrode. The endpoints correspond to the amounts of the strong acid and organic acid components. The difference between the strong acid endpoint and the organic acid endpoint, multiplied by the equivalent concentration of the alcoholic alkali hydroxide solution, gives the salicylic acid concentration.

[0161] Metal-containing detergents may optionally include one or more additional detergents selected from sulfonates, sulfur-free phenolates, sulfur-containing phenolates, salicylates, and mixtures thereof. Metal-containing detergents may also include “mixed” detergents formed with a mixed surfactant system comprising phenolate and / or sulfonate components, such as phenolate / salicylate, sulfonate / phenolate, sulfonate / salicylate, sulfonate / phenolate / salicylate, as described, for example, in U.S. Patents 6,429,178, 6,429,179, 6,153,565, and 6,281,179. In the case of a mixed sulfonate / phenolate detergent, the mixed detergent can be considered equivalent to the amounts of different phenolate and sulfonate detergents, each introducing equal amounts of phenolate and sulfonate soaps.

[0162] Example sulfonate detergents include linear and branched alkylbenzene sulfonate detergents and mixtures thereof, which may have a metal ratio of at least 8, as described, for example, in U.S. Publication No. 2005065045. The linear alkylbenzene may have a benzene ring or mixture thereof attached anywhere on the linear chain (typically at the 2, 3, or 4 position). In one embodiment, the alkylbenzene sulfonate detergent may be a branched alkylbenzene sulfonate, a linear alkylbenzene sulfonate, or a mixture thereof. The sulfonate detergent may be a metal salt of one or more oil-soluble alkyltoluene sulfonate compounds, as described in U.S. Publication No. 20080119378 A1.

[0163] In one embodiment, the lubricating composition comprises a total of at least 0.1% by weight, or at least 0.2% by weight, or at least 0.25% by weight, or at least 0.4% by weight, or at most 3.0% by weight, or at most 2.0% by weight, or at most 1.5% by weight, or at most 1.25% by weight of all detergents. In one embodiment, all detergents used in the lubricating composition are free of or substantially free of magnesium, such that the lubricating composition contains no more than 0.01% by weight of magnesium or 0% magnesium.

[0164] The lubricating composition may also contain one or more of the following other performance additives: iii. anti-wear agent The lubricating composition may also optionally contain at least one anti-wear agent other than a sulfurized organic compound. Examples of suitable anti-wear agents applicable herein include metal dialkyl dithiophosphates (such as zinc dialkyl dithiophosphate (ZDDP)), titanium compounds, tartrates, tartrate imides, oil-soluble amine salts of phosphorus compounds, phosphites (such as dibutyl phosphite), phosphonates, and compounds containing thiocarbamates (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates, and bis(S-alkyl dithiocarbamate) disulfides).

[0165] In one embodiment, the anti-wear agent comprises zinc dialkyl dithiophosphate. The alkyl group of the dialkyl dithiophosphate may be straight-chain or branched, and may contain 2 to 20 carbon atoms, provided that the total number of carbons is sufficient to make the zinc dialkyl dithiophosphate soluble in oil. Suitable examples of zinc dialkyl dithiophosphate (ZDDP) include zinc di(2-methylpropyl)dithiophosphate, zinc di(pentyl)dithiophosphate, zinc di(1,3-dimethylbutyl)dithiophosphate, zinc di(heptyl)dithiophosphate, zinc di(octyl)dithiophosphate, zinc di(2-ethylhexyl)dithiophosphate, zinc di(nonyl)dithiophosphate, zinc di(decyl)dithiophosphate, zinc di(dodecyl)dithiophosphate, zinc di(dodecylphenyl)dithiophosphate, zinc di(heptylphenyl)dithiophosphate, and ZDDP prepared from mixed alcohols such as methylpropyl alcohol and pentanol, 2-ethylhexyl alcohol and isopropanol, 4-methyl-2-pentyl alcohol and isopropanol, and mixtures thereof.

[0166] In one embodiment, ZDDP comprises at least 0.1% by weight, or at least 0.25% by weight, or at least 0.5% by weight, or at most 5% by weight, or at most 4% by weight, or at most 3% by weight of the lubricating composition.

[0167] In one embodiment, ZDDP is present in an amount sufficient to provide at least 0.03% by weight, or at least 0.06% by weight, or at most 0.5% by weight, or at most 0.1% by weight of Zn in the lubricating composition.

[0168] In another embodiment, the anti-wear agent may include tartrates or tartrate imides, as described in U.S. Publications 2006 / 0079413, 2006 / 0183647, and 2010 / 0081592. The tartrates or tartrate imides may contain alkyl ester groups, wherein the total number of carbon atoms on the alkyl groups is at least 8. In one embodiment, the anti-wear agent may include citrates, as disclosed in U.S. Publication 20050198894.

[0169] In one embodiment, the lubricating composition contains no or substantially no metal-containing anti-wear agents. In other embodiments, the lubricating composition contains no or substantially no phosphorus-containing anti-wear agents. For example, phosphorus-containing anti-wear agents are absent, or when present, their amount provides the lubricating composition with no more than 0.8% by weight of phosphorus, or no more than 0.15% by weight of phosphorus. For example, C3 / 6 blended secondary ZDDP may be present in a maximum of 1.2% by weight, or a maximum of 1% by weight, or a maximum of 0.5% by weight.

[0170] When present, the lubricating composition may contain at least 0.01% by weight, or at least 0.1% by weight, or at least 0.25% by weight, or at least 0.5% by weight of an anti-wear agent, and in some embodiments, at most 5% by weight, or at most 4% by weight, or at most 3% by weight of an anti-wear agent.

[0171] iv) Extreme pressure (EP) agent

[0172] In addition to sulfurized organic compounds with low sulfur activity, lubricating compositions may also contain extreme pressure agents. Examples of such non-sulfur EP agents include chlorinated waxes; phospholipids, such as dialkyl phosphites and trialkyl phosphites, for example, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearate phosphite, and polypropylene-substituted phenolic phosphites; and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates and their derivatives, including, for example, amine salts of products of the reaction of dialkyl dithiophosphate with propylene oxide and subsequently with P2O5; and mixtures thereof. Other useful extreme pressure agents are described in U.S. Patent No. 3,197,405.

[0173] When present, the lubricating composition may contain at least 0.01% by weight, or at least 0.1% by weight, or at least 0.5% by weight of an extreme pressure agent, and in some embodiments, at most 3% by weight, or at most 1.5% by weight, or at most 0.9% by weight of an extreme pressure agent.

[0174] v. Foam inhibitors

[0175] The lubricating composition may contain a foam inhibitor. Foam inhibitors that can be used in lubricant compositions include polysiloxanes; copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers include fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers.

[0176] When present, the lubricating composition may contain at least 0.005% by weight or at least 0.08% by weight of foam inhibitor, and in some embodiments, at most 3% by weight, at most 1.5% by weight, or at most 0.4% by weight of foam inhibitor.

[0177] vi. Viscosity modifier

[0178] Lubricating compositions may contain viscosity modifiers. Viscosity modifiers (sometimes also called viscosity index improvers or viscosity enhancers) that can be used in lubricant compositions are typically polymers, including polyisobutylene, polymethacrylate (PMA) and polymethacrylate, diene polymers, polyalkylstyrene, esterified styrene-maleic anhydride copolymers, hydrogenated alkenyl aromatic-conjugated diene copolymers (such as styrene-butadiene copolymer resins (SBR)); and polyolefins, also known as olefin copolymers or OCPs. PMA is prepared from a mixture of methacrylate monomers with different alkyl groups. The alkyl groups may be straight-chain or branched groups containing 1 to 18 carbon atoms. Most PMAs are viscosity modifiers and pour point depressants. In one embodiment, the viscosity modifier includes a styrene-butadiene resin. In another embodiment, the viscosity modifier includes a polyolefin containing ethylene and one or more higher olefins, such as propylene.

[0179] In one embodiment, the viscosity modifier comprises one or more dispersant viscosity modifiers (DVMs). DVMs provide dispersibility and viscosity modulation. Example DVMs are made from polymers (such as olefin polymers (e.g., ethylene-propylene copolymers) and / or vinyl aromatic polymers (e.g., polystyrene)) that have been radically grafted with an olefinically unsaturated carboxylic acid material (such as maleic anhydride), the olefinically unsaturated carboxylic acid material being functionalized with one or more amines and / or side-chain functional groups having sulfonate functional groups. This type of DVM is disclosed, for example, in U.S. Patent Nos. 4,863,623, 5,264,140, ​​5,409,623, 6,107,257, 6,107,258, 6,117,825; U.S. Publications Nos. 20120178656A1, 20120178659A1, 20090305923A1, and 20170283733A1.

[0180] When present, the lubricating composition may contain at least 0.01 wt%, or at least 0.1 wt%, or at least 0.2 wt%, or at least 0.4 wt% of a viscosity modifier (including a dispersant viscosity modifier), and in some embodiments, at most 10 wt%, or at most 5 wt%, or at most 4 wt%, or at most 2 wt% of such a viscosity modifier. In one embodiment, the lubricating composition contains at least 0.2 wt%, or at least 0.3 wt%, or at least 0.5 wt%, or at most 3.0 wt%, or at most 2.0 wt% of a dispersant viscosity modifier, which may be borated or otherwise post-treated.

[0181] In some implementations, viscosity modifiers are not used.

[0182] vii. Corrosion inhibitors and metal passivators

[0183] The lubricating composition may contain a corrosion inhibitor. Corrosion inhibitors / metal passivators that can be used in exemplary lubricating compositions include condensation products of fatty amines, octylamine octanoate, dodecenylsuccinic acid or anhydrides and fatty acids (such as oleic acid with polyamines), derivatives of benzotriazole (e.g., tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole and 2-alkyldithiobenzothiazole.

[0184] When present, the lubricating composition may contain at least 0.005% by weight, or at least 0.01% by weight, or at least 0.015% by weight, or at least 0.02% by weight of a corrosion inhibitor, and in some embodiments, at most 5% by weight, or at most 2.5% by weight, or at most 0.1% by weight of a corrosion inhibitor. In some embodiments, no corrosion inhibitor is used.

[0185] viii. Pour point depressant

[0186] The lubricating composition may include a pour point depressant. Pour point depressants that can be used in exemplary lubricating compositions include polyalphaolefins, esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, and polyacrylamide. In one embodiment, the pour point depressant is a maleic anhydride-styrene copolymer.

[0187] When present, the lubricating composition may contain at least 0.005% by weight, or at least 0.01% by weight, or at least 0.1% by weight, or at least 0.15% by weight of a pour point depressant, and in some embodiments, at most 5% by weight, or at most 2% by weight, or at most 1% by weight of a pour point depressant. In some embodiments, no pour point depressant is used.

[0188] ix. Friction modifier

[0189] Lubricating compositions may contain friction modifiers. Friction modifiers that may be used in exemplary lubricating compositions include fatty acid derivatives, such as condensations of amines, esters, epoxides, fatty imidazolines, carboxylic acids, and polyalkylene polyamines, and amine salts of alkyl phosphates. Friction modifiers may be ashless friction modifiers. Such friction modifiers are those that typically do not produce any sulfated ash when subjected to the conditions of ASTM D874-13a (2018). An additive is referred to as “metal-free” if it does not contribute to the metal content of the lubricating composition. As used herein, the terms “fatty alkyl” or “fatty” with respect to friction modifiers refer to a carbon chain having 8 to 30 carbon atoms, typically a straight carbon chain.

[0190] In one implementation, the ashless friction modifier can be represented by the following formula:

[0191] Where D and D' are independently selected from -O-, >NH, and >NR. 23 By combining the D and D' groups together and forming R between the two >C=O groups 21 An imide group formed by -N< groups; 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 between 0 and 10, provided that when q=1, E is not greater than CH2, and when n=2, neither E is greater than CH2; p is 0 or 1; R 21 Independently hydrogen or a hydrocarbon group typically containing 1 to 150 carbon atoms, provided that R 21 When it is hydrogen, p is 0 and q is greater than or equal to 1; R 22 It is a hydrocarbon group that typically contains 1 to 150 carbon atoms; R 23 R 24 R 25 R 26 and R 27 Independently a hydrocarbon group; and R 28 It is a hydrogen group or a hydrocarbon group that typically contains 1 to 150 carbon atoms, or 4 to 32 carbon atoms, or 8 to 24 carbon atoms. In some embodiments, the hydrocarbon group R 23 R 24 and R 25 It can be a straight-chain or mainly straight-chain alkyl group.

[0192] In some 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 (i.e., di(2-ethylhexyl) tartrate), di(C8-C... 10 ) ester, di(C) tartaric acid 12 - 15 ) ester, dioleoyl tartrate, oleoyltriamide and oleoylmaleimide.

[0193] In some 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 phosphates; fatty alkyl tartrate esters; fatty alkyl tartrate imides; fatty alkyl tartrate amides; fatty phosphonates; fatty phosphites; boronized phospholipids, boronized fatty epoxides; glycerides; boronized glycerides; fatty amines; alkoxylated fatty amines; boronized alkoxylated fatty amines; hydroxy and polyhydroxy fatty amines, including tertiary hydroxy fatty amines; hydroxyalkylamides; metal salts of fatty acids; metal salts of alkyl salicylate; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or products derived from the reaction of fatty carboxylic acids with guanidine, aminoguanidine, urea or thiourea and their salts.

[0194] Friction modifiers can also include substances such as sulfurized fatty compounds and olefins, sunflower oil or polyols and soybean oil monoesters of aliphatic carboxylic acids.

[0195] In another embodiment, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester, and in yet another embodiment, the long-chain fatty acid ester may be a triglyceride.

[0196] The amount of ashless friction modifier in the lubricant can be from 0.1% to 3% by weight (or 0.12% to 1.2% by weight or 0.15% to 0.8% by weight). The material can also be present alone or in a concentrate form with other additives and a smaller amount of oil. In the concentrate, the amount of material can be two to ten times the above concentrations.

[0197] In some embodiments, the lubricating composition contains no or substantially no friction modifier, for example, containing no more than 0.001% by weight of friction modifier. In other embodiments, the friction modifier may comprise at least 0.01%, or at least 0.05% by weight, or at least 0.1% by weight, or at most 6% by weight, or at most 4% by weight, or at most 2% by weight of the lubricating composition.

[0198] molybdenum compounds

[0199] In one embodiment, the lubricating composition contains a molybdenum compound. The molybdenum compound can function in the lubricating composition in various ways, such as as an anti-wear agent, friction modifier, and antioxidant.

[0200] For ease of description, the amount of molybdenum compounds is not included in the amounts of anti-wear agents, friction modifiers, and antioxidants described elsewhere.

[0201] Molybdenum-containing anti-wear agents and antioxidants include molybdenum dithiocarbamate, molybdenum dithiocarbamate dimer complexes, and other molybdenum and sulfur-containing compounds, such as those described, for example, in U.S. Patent No. 4,285,822. Other molybdenum-containing materials include molybdenum dialkyl dithiophosphate; molybdenum-amine compounds as described in U.S. Patent No. 6,329,327; organomolybdenum compounds prepared by reacting a molybdenum source, fatty oil, and diamine as described in U.S. Patent No. 6,914,037; and trinuclear molybdenum-sulfur complexes as described in U.S. Patent No. 6,232,276. Other molybdenum compounds are disclosed in U.S. Publication No. 20080280795.

[0202] Molybdenum amine compounds can be synthesized by reacting compounds containing hexavalent molybdenum atoms with compounds of formula NR. 29 R 30 R 31 The primary, secondary, or tertiary amines are reacted to obtain the amine, where R represents the primary, secondary, or tertiary amine. 29 R 30 and R 31 Each of them is independently hydrogen or a hydrocarbon group having 1 to 32 carbon atoms, and R 29 R 30 and R 31 At least one of them is a hydrocarbon group having four or more carbon atoms or represented by the following formula:

[0203] Where R 32 Represents a chain hydrocarbon group having 10 or more carbon atoms, where s is 0 or 1, and R 33 and / or R 34 Represents a hydrogen atom, a hydrocarbon group, an alkanolic group, or an alkylamino group having 2 to 4 carbon atoms, and when s=0, R 33 and R 34 Neither of them are hydrogen atoms or hydrocarbon groups.

[0204] Specific examples of suitable amines include monoalkyl (or alkenyl)amines, such as tetradecylamine, stearylamine, oleylamine, tallow alkylamine, hardened tallow alkylamine, and soybean oil alkylamine; dialkyl (or alkenyl)amines, such as N-tetradecylmethylamine, N-pentadedecylmethylamine, N-hexadecylmethylamine, N-stearylmethylamine, N-oleylmethylamine, N-dodecyl(di)methylamine, N-tallow alkylmethylamine, N-hardened tallow alkylmethylamine, N-soybean oil alkylmethylamine, ditetradecylamine, dipentadedecylamine, and dihexadecylamine. Distearate, dioleylamine, N-cocoylmethylamine, discocoylamine, bis(2-hexyldecyl)amine, bis(2-octyldodecyl)amine, bis(2-decyltetradecyl)amine, tallow dialkylamine, hardened tallow dialkylamine, and soybean oil dialkylamine; and trialkyl(alkenyl)amines, such as tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, tallow alkyldimethylamine, hardened tallow alkyldimethylamine, soybean oil alkyldimethylamine, dioleylmethylamine, tri(tetradecyl)amine, tristearate, and trioleylamine. Suitable secondary amines have two alkyl (or alkenyl) groups having 14 to 18 carbon atoms.

[0205] Examples of compounds containing hexavalent molybdenum atoms include molybdenum trioxide or its hydrate (MoO3). nH2O), molybdic acid (H2MoO4), alkali metal molybdates (Q2MoO4) (where Q represents an alkali metal such as sodium and potassium), ammonium molybdate (e.g., (NH4)2MoO4 or heptamolybdate (NH4)6[Mo7O) 24 ] Molybdenum trioxide (Mo2O), MoOCl4, MoO2Cl2, MoO2Br2, Mo2O3Cl6, etc., are generally suitable due to their availability. In one embodiment, the lubricating composition comprises a molybdenum amine compound.

[0206] Other organomolybdenum compounds can be reaction products of fatty oils, monoalkylated alkylene diamines, and molybdenum sources. These materials are generally prepared in two steps: a first step involving the preparation of an aminoamide / glycerol ester mixture at high temperature, and a second step involving the incorporation of molybdenum.

[0207] Examples of fatty oils that can be used include cottonseed oil, peanut oil, coconut oil, flaxseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, rapeseed oil (low or high erucic acid), soybean oil, sunflower oil, herring oil, sardine oil, and animal fats. These fatty oils are often referred to as fatty acid glycerides, triglycerides, or triglycerides.

[0208] Examples of monoalkylated alkylene diamines that can be used include methylaminopropylamine, methylaminoethylamine, butylaminopropylamine, butylaminoethylamine, octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine, dodecylaminoethylamine, hexadecylaminopropylamine, hexadecylaminoethylamine, octadecylaminopropylamine, octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane, and octyloxypropyl-1,3-diaminopropane. Monoalkylated alkylene diamines derived from fatty acids can also be used. Examples include N-cocoylalkyl-1,3-propanediamine (Duomeen). ® C), N-Tallyl-1,3-propanediamine (Duomeen) ® T) and N-oleoyl-1,3-propanediamine (Duomeen) ® All items (O) are commercially available from Akzo Nobel.

[0209] The source of molybdenum used for incorporation into fatty oil / diamine complexes is generally an oxygen-containing molybdenum compound, similar to those mentioned above, including ammonium molybdate, sodium molybdate, molybdenum oxide, and mixtures thereof. A suitable molybdenum source includes molybdenum trioxide (MoO3).

[0210] Commercially available nitrogen-containing molybdenum compounds include, for example, Sakura-lube from Adeka. ® 710 (which is a molybdenum amine compound) and Molyvan purchased from RTVanderbilt ® 855.

[0211] When used, the nitrogen-containing molybdenum compound may comprise at least 0.001% by weight, or at least 0.002% by weight, or at most 2% by weight, or at most 1.0% by weight of the lubricating composition. When present, the molybdenum compound may provide the lubricating composition with at least 5 ppm, or at least 10 ppm, 5 ppm, or at most 300 ppm, or at most 800 ppm of molybdenum. In some embodiments, the lubricating composition contains less than 800 ppm of molybdenum, or less than 400 ppm, or less than 150 ppm, or less than 100 ppm, or less than 80 ppm, or less than 50 ppm, or less than 20 ppm, or less than 2 ppm, or less than 1 ppm of molybdenum, or 0 ppm.

[0212] In one embodiment, the molybdenum compound does not contain a dithiocarbamate moiety or ligand.

[0213] The lubricating composition may contain a molybdenum compound in an amount providing the composition with 40 wt ppm to 1200 wt ppm, or at least 50 wt ppm, or at least 60 wt ppm, or at least 100 wt ppm, or at least 300 wt ppm, or at most 1000 wt ppm, or at most 800 wt ppm, or at most 500 wt ppm, or at most 400 wt ppm, or at most 250 wt ppm, or at most 200 wt ppm of molybdenum. The actual amount of the compound will depend in part on the nature and molecular weight of the anion or complexing agent associated with molybdenum, in a manner that can be readily calculated. In some embodiments, the molybdenum compound is present in the lubricating composition in an amount of 0 wt% to 1.1 wt%, or at least 0.01 wt%, or at least 0.02 wt%, or at least 0.03 wt%, or at least 0.04 wt%, or at least 0.07 wt%, or at most 0.5 wt%, or at most 0.35 wt%, or at most 0.2 wt%, or at most 0.18 wt%.

[0214] Additional sediment control additives

[0215] The lubricating composition may contain one or more deposit control additives selected from alkyl aryl sulfonates, amine oxides, carboxylated alcohol ethoxylates, ethoxylated amines, ethoxylated amides, glycerides, ethylene glycol esters, imidazolines, lecithin, lecithin derivatives, lignin, monoglycerides, monoglyceride derivatives, olefin sulfonates, phosphate esters, phosphate ester derivatives, propoxylated fatty acids, ethoxylated fatty acids, propoxylated alcohols or alkylphenols, sucrose esters, sulfonates of dodecylbenzene or tridecylbenzene, naphthalene sulfonates, petroleum sulfonates, tridecylbenzene sulfonic acid or dodecylbenzene sulfonic acid, sulfosuccinates, sulfosuccinate derivatives, or mixtures of two or more thereof, each of these compounds having a hydrocarbon group with at least about eight carbon atoms.

[0216] For example, alkoxylated hydrocarbon-substituted phenolic compounds, such as propoxylated polyisobutylene phenol, as described in WO2014 / 193543A1, can be used.

[0217] When present, the additional sediment control additive may be at least 0.01% by weight, or at least 0.10% by weight, or at least 0.5% by weight, or at most 6% by weight, or at most 3.0% by weight.

[0218] In some implementations, sediment control additives are not used.

[0219] Demulsifier

[0220] Demulsifiers that may be used herein include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, and mixtures thereof. When present, the demulsifier may comprise at least 0.001% by weight, or at least 0.01% by weight, or at most 0.10% by weight of the lubricating composition.

[0221] Sealing expander

[0222] Sealing expanders that can be used in this article include cyclobutene sulfone derivatives, such as Exxon Necton-37. ™ (FN1380) and Exxon Mineral Seal Oil ™ (FN 3200).

[0223] Example lubricating composition

[0224] Engine lubricants can have compositions as shown in any of the embodiments listed in Table 1. Unless otherwise stated, all additives are expressed as a weight percentage excluding oil.

[0225] Table 1: Example lubricating composition

[0226] As will be understood, the lubricating composition may include amounts of two or more of Examples A, B and C.

[0227] Uses of lubricating compositions

[0228] The end uses of the lubricating compositions described herein include as cylinder lubricants for internal combustion engines (e.g., for passenger cars, heavy-duty, medium- or light-duty diesel vehicles, small engines such as motorcycles and three-stroke oil engines, and two-stroke marine diesel engines), but can also be used as engine oils (including gear and automatic transmission fluids) as transmission system lubricants, and for other industrial oils (such as hydraulic lubricants).

[0229] An exemplary method of lubricating a mechanical device, such as the engine of a car or truck, includes supplying the device with an exemplary lubricating composition.

[0230] Generally, a lubricating composition is added to the lubrication system of an internal combustion engine, which then delivers the lubricating composition to the engine cylinders during its operation, a small amount of which can be ignited by fuel.

[0231] An internal combustion engine can be an engine that uses diesel fuel, an engine that uses gasoline fuel, an engine that uses natural gas fuel, an engine that uses a mixture of gasoline / alcohol fuel, or an engine that uses biodiesel fuel. An internal combustion engine can be a 2-stroke engine or a 4-stroke engine.

[0232] In one implementation, the engine is a heavy-duty diesel engine.

[0233] The lubricating composition can be used as a cylinder lubricant regardless of the phosphorus or sulfated ash content of the fuel (ASTM D874-13a (2018)).

[0234] Without being intended to limit the scope of the exemplary embodiments, the following examples illustrate the preparation and evaluation of example lubricating compositions.

[0235] Example

[0236] As shown in Table 2, the sulfurized organic compounds designated AF were obtained from Lubrizol Corporation. Active sulfur was determined by ASTM D1662. Total sulfur was determined by ASTM D1552.

[0237] Table 2: Sulfurized organic compounds

[0238] Preparation of lubricating compositions

[0239] Engine lubricant formulations for heavy-duty diesel engines with a viscosity grade of SAE 5W-30, prepared in Group III base oils containing the sulfurized organic compounds described herein, are prepared according to the formulations shown in Table 3.

[0240] Except for oil and calcium salicylate (expressed as mmol / kg lubricating composition), all components are expressed as active material (oil-free) in weight percentage.

[0241] Table 3: Example lubricating composition

[0242] 1 4-cSt Group III base oil, hydrotreated heavy alkane petroleum distillate, sold as Yubase 4, obtained from SK Lubricants Co., Ltd.

[0243] 2 6-cSt Group III base oil, hydrotreated heavy alkane petroleum distillate, sold as Yubase 6, obtained from SK Lubricants Co., Ltd.

[0244] 3 The substituted diphenylamine (SDPA) antioxidant (nonylated diphenylamine) is sourced from Lubrizol.

[0245] 4 Irganox from BASF ™ L 135, ((3,5-dibutyl-4-hydroxyphenyl)propionate).

[0246] 5 Polyisobutylene direct alkylated succinimide dispersant derived from approximately 2000 Mn polyisobutylene, nitrogen (wt%) = 0.90, TBN = 17.

[0247] 6 A borate-derived polyisobutylene direct alkylated succinimide dispersant derived from approximately 2000 Mn polyisobutylene, with nitrogen (wt%) = 0.84 and TBN = 15.

[0248] 7 Neutral alkyl salicylate calcium: %Ca=3.6 wt%, 100% active material, TBN approx. 100, obtained from Lubrizol.

[0249] 8 Highly alkaline alkyl salicylate calcium: %Ca=6.2 wt%, 100% active material, TBN=300, obtained from Lubrizol.

[0250] 9 Magnesium sulfonate detergent, TBN approximately 690, obtained from Lubrizol.

[0251] 10 Hydrogenated styrene - b -Butadiene resin LZ 7418A, obtained from Lubrizol.

[0252] 11 Maleic anhydride / styrene copolymer ester, obtained from Lubrizol.

[0253] 12 Secondary ZDDP derived from C3 and C6 alcohols.

[0254] 13 Polydimethylsiloxane.

[0255] 14 Propanolated polyisobutylene phenol is obtained by the reaction of propylene oxide with polyisobutylene phenol and KOH as described in WO2014193543A1.

[0256] Table 4 provides the elemental analysis of the lubricating compositions.

[0257] Table 4: Elemental analysis Based on the theoretical values ​​of the composition.

[0258] For the above, the %Ca of calcium salicylate was determined according to ASTM D4951. See also U.S. Patent No. 5,558,802 (as described above), which describes the determination of millimoles per kilogram of salicylate by titration of acid content.

[0259] Evaluation of lubricating compositions

[0260] Various tests were performed on the lubricating compositions of the above embodiments: Total base number (TBN) The base number is measured according to ASTM D2896-21, "Standard Test Method for Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration".

[0261] % Sulfated Ash (%SA) ): Determined according to ASTM D874-23 "Standard Test Method for Sulfated Ash from Lubricating Oils and Additives".

[0262] Kinematic viscosity: The kinematic viscosity (KV_40) at 40°C and the kinematic viscosity (KV_100) at 100°C were measured according to ASTM D445-21, "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)".

[0263] Viscosity index: The determination was made according to ASTM D2270-10 (2016), “Standard Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 °C and 100 °C”.

[0264] Apparent viscosity According to ASTM D5481-21, "Standard Test Method for Measuring Apparent Viscosity at High-Temperature and High-Shear Rate by Multicell Capillary Viscometer", the apparent viscosity is determined by the High Temperature High Shear (HTHS) method, and the result is expressed in cP.

[0265] Antioxidant properties

[0266] Oxidation induction time (OIT): The antioxidant properties of the film are measured in OIT (in minutes), as determined according to CECL-85-99: "Oxidative Stability of Lubricants by PDSC (Pressure Differential Scanning Calorimetry)". This represents the time after oxygen uptake ceases, as measured by pressure drop. The longer the OIT, the better the antioxidant properties.

[0267] Sediment control Deposition control was evaluated using the following Komatsu hot tubing and MHT TEOST test.

[0268] Komatsu Heat Pipe Test (280℃), KES_07.803: In this test, a glass tube is inserted into an aluminum heater block and heated by the aluminum heater block. The sample is injected via a syringe pump at a rate of 0.31 cm. 3 The flow rate of / hour along with 10cm 3 An airflow of 0.5 m / min was pumped through the glass tube for 16 hours. At the end of the test, the tube was rinsed and visually rated on a scale of 0 to 10, with 0 being a black tube and 10 being a clean tube.

[0269] MHT TEOSTMeasurements were taken according to ASTM D7097-19, "Standard Test Method for Determination of Moderately High Temperature Piston Deposits by Thermo-Oxidation Engine Oil Simulation Test—TEOST MHT". Total deposits are reported in mg.

[0270] Oxidative performance was determined using the Renault Catalyst Oxidation Test (TOC-4) procedure (RNES-B-00023) from Renault. This test method evaluates the oxidation resistance of engine oil compositions and simulates harsh conditions of increased load and state, as well as changes in engine oil under heat. In the TOC-4 procedure, four tubes (each containing 150 g of oil containing anhydrous iron(III) acetylacetone catalyst (360 ppm iron)) were heated in a test cell at 170°C for 168 hours. During this period, air was blown through the oil in the tubes at a rate of 10 liters / hour. Oxidative degradation of samples (30 ml) of each oil was evaluated after 24, 120, 136, and 168 hours; the sample after 120 hours provides the average value of the TOC-4 procedure. The oxidative degradation of oil samples was assessed by measuring the area of ​​the infrared band between 1800 cm⁻¹ and 1650 cm⁻¹ (C=O) using infrared spectroscopy and comparing the increase in the area of ​​this band with the increase in the area of ​​the original oil (sample at t=0). A lower increase in peak area indicates lower oxidative degradation. To pass the TOC-4 test, the increase in peak area after 120 hours must be less than 400.

[0271] The total acid number (TAN) (mg KOH / g) was determined at 120 hours according to ASTM D664-18e2, "Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration".

[0272] Antioxidant properties: According to CEC-L-109 measurements: According to DIN 51453, oxidation (A / cm) after 216 hours (≤55 to meet VW 50400 / 50700 specifications).

[0273] The relative change % of KV_100 at 216 hours compared to the fresh lubricating composition (≤50 to meet VW 50800 specifications).

[0274] The results are shown in Table 5.

[0275] Table 5: Test Results TVTM = Too sticky to measure.

[0276] As can be seen from Table 5, Example 5, which contains a hindered phenolic antioxidant and has no magnesium or boron and no amine antioxidant, provides a good combination of performance, particularly in terms of oxidation performance, compared to similar compositions containing amine antioxidants. Example 3, which contains boron, has a good oxidation induction time, but this composition is too viscous for some applications.

[0277] Using the sulfurized organic compounds shown in Table 2, a series of engine lubrication compositions suitable for heavy-duty diesel engines were prepared in Group III base oils with lubricating viscosities as shown in Table 6. The amount of sulfurized organic compounds was adjusted to provide approximately the same total sulfur content.

[0278] Table 6

[0279] 7 As stated above.

[0280] Example 6 uses the same composition as Example 5 described above.

[0281] Table 7 provides the elemental analysis of the lubricating composition. Table 7 also shows the copper corrosion properties, as determined by ASTM D6594-20e1 "Standard Test Method for Evaluation of Corrosiveness of Diesel Engine Oil at 135 °C" and ASTM D130-19 "Standard Test Method for Corrosiveness to Copper from Petroleum Products by Copper Strip Test". Grade 1A indicates very little discoloration, while 4A and 4C indicate corrosiveness and severe corrosion, respectively.

[0282] Table 7: Elemental analysis Based on the theoretical value of the composition Based on the copper corrosion results, it can be concluded that the sulfurized olefins (sulfurized olefin AD) used in Examples 6, 7, 8 and 9 are particularly well-suited for this application.

[0283] Each document mentioned above is incorporated herein by reference. Unless explicitly stated in the examples or otherwise, all numerical quantities of matter, reaction conditions, molecular weight, number of carbon atoms, etc., specified in this specification should be understood to be modified by the word “about.” Unless otherwise stated, each chemical or composition mentioned herein should be interpreted as a commercial-grade substance that may contain isomers, byproducts, derivatives, and other such substances generally understood to be present in commercial-grade substances. However, unless otherwise stated, the amount of each chemical component does not include any solvents or diluents that are generally present in commercial substances. It should be understood that the upper and lower limits of the amounts, ranges, and proportions described herein can be combined independently. Similarly, the ranges and amounts of each element of the invention can be used in conjunction with the ranges or amounts of any other element.

[0284] Unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural referents.

[0285] It should be understood that variations or alternatives to the features and functions disclosed above and others can be combined to form many other different systems or applications. Various alternatives, modifications, variations, or improvements that are not currently foreseen or anticipated may subsequently be made by those skilled in the art and are also intended to be covered by the appended claims.

Claims

1. A lubricating composition comprising: an oil of lubricating viscosity; a phenolic antioxidant; a succinimide dispersant that is at least substantially free of boron; a detergent comprising an alkaline earth metal salicylate; and a sulfurized organic compound.

2. The composition of claim 1, wherein the lubricating composition is at least substantially free of substituted diphenylamine (SDPA) antioxidant.

3. The lubricating composition of claim 1 or claim 2, wherein the lubricating composition is substantially free of amine-based antioxidant.

4. The lubricating composition of any preceding claim, wherein the phenolic antioxidant comprises at least 0.1 wt%, or at least 0.5 wt%, or at least 1 wt%, or at least 1.5 wt%, or at least 2 wt% of the lubricating composition.

5. The lubricating composition of any preceding claim, wherein the phenolic antioxidant comprises no more than 8 wt%, or no more than 6 wt%, or no more than 5 wt%, or no more than 4 wt%, or no more than 3 wt% of the lubricating composition.

6. The lubricating composition of any preceding claim, wherein the phenolic antioxidant is selected from the group consisting of hindered phenols, hindered alkyl phenol esters, hindered alkoxy phenols, hindered phenol acetates, hindered bisphenols, polyphenols, 4-tert-butylphenol-formaldehyde condensates, 4-tert-butylphenol-acetaldehyde condensates, and mixtures thereof.

7. The lubricating composition of any preceding claim, wherein the phenolic antioxidant is selected from the group consisting of a mixture of C7-C9 branched alkyl esters of 3,5-bis(l,l-dimethylethyl)-4-hydroxybenzenepropionic acid, C4 alkyl esters of 3,5-bis(l,l-dimethylethyl)-4-hydroxybenzenepropionic acid, 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and mixtures thereof.

8. The lubricating composition of any preceding claim, wherein the alkaline earth metal salicylate or salt thereof comprises calcium salicylate or a salt thereof.

9. The lubricating composition of claim 8, wherein the detergent provides at least 0.04 wt%, or at least 0.08 wt%, or at most 0.4 wt%, or at most 0.3 wt% of calcium to the lubricating composition.

10. The lubricating composition of any preceding claim, wherein the lubricating composition is at least substantially free of magnesium.

11. The lubricating composition of any preceding claim, wherein the lubricating composition comprises at least 15, or at least 17, or at least 20, or at least 22 millimoles of the alkaline earth metal detergent per kilogram of the lubricating composition.

12. The lubricating composition of any preceding claim, wherein the lubricating composition comprises no more than 35, or no more than 32, or no more than 30, or no more than 25 millimoles of the alkaline earth metal detergent per kilogram of the lubricating composition.

13. The lubricating composition of any preceding claim, wherein the sulfurized organic compound has an active sulfur content of no more than 8 wt%, or no more than 6 wt%, or no more than 5 wt%, or no more than 4.0 wt%, or no more than 3 wt%, or no more than 2 wt% active sulfur.

14. The lubricating composition of any preceding claim, wherein the sulfurized organic compound has a total sulfur content of at least 1 wt%, or at least 1.5 wt%, or at least 2 wt%, or no more than 18 wt%, or no more than 15 wt%, or no more than 14.0 wt%, or no more than 12.0 wt%, or no more than 5 wt%.

15. The lubricating composition of any preceding claim, wherein the sulfurized organic compound provides at least 0.01 wt%, or at least 0.03 wt%, or at least 0.05 wt%, or at most 0.12 wt%, or at most 0.09 wt% of sulfur to the lubricating composition.

16. The lubricating composition of any preceding claim, wherein the sulfurized organic compound provides no more than 0.04 wt% active sulfur, or no more than 0.03 wt%, or no more than 0.025 wt%, or no more than 0.02 wt% active sulfur to the lubricating composition.

17. The lubricating composition of any preceding claim, wherein the sulfurized organic compound comprises at least 0.1 wt%, or at least 0.15 wt%, or at least 0.2 wt% of the lubricating composition.

18. The lubricating composition of any preceding claim, wherein the sulfurized organic compound comprises at most 1 wt%, or at most 0.8 wt%, or at most 0.6 wt%, or at most 0.5 wt% of the lubricating composition.

19. The lubricating composition of any preceding claim, wherein active sulfur comprises no more than 25 wt%, or no more than 22 wt%, or no more than 20 wt%, or no more than 19 wt% of the total sulfur in the sulfurized organic compound, or at least 1 wt%, or at least 1.5 wt%, or at least 6 wt% of the total sulfur in the sulfurized organic compound.

20. The lubricating composition of any preceding claim, wherein the sulfurized organic compound is selected from the group consisting of oligomeric polysulfides, alkyl polysulfides, sulfurized esters, sulfurized cycloaliphatic dialkyl esters, sulfurized cycloaliphatic dialkenyl esters, and mixtures thereof.

21. The lubricating composition of any preceding claim, wherein the sulfurized organic compound comprises oligomeric polysulfides or mixtures thereof.

22. The lubricating composition of any preceding claim, wherein the sulfurized organic compound comprises a sulfurized fatty acid ester of a fatty alcohol.

23. The lubricating composition of claim 22, wherein the sulfurized organic compound comprises a sulfurized triglyceride or mixtures thereof.

24. The lubricating composition of claim 23, wherein the sulfurized triglyceride or mixtures thereof is of Formula III: Formula III, wherein R 3 , R 4 , and R 5 are each independently a C8or higher alkyl or alkenyl group, or a C10or higher alkyl or alkenyl group, or a C30or a C24or lower alkyl or alkenyl group; and wherein at least one of R 3 , R 4 , and R 5 is attached to the sulfur atom of the sulfur-containing moiety, the middle end of the alkyl group.

25. The lubricating composition of claim 23 or claim 24, wherein the sulfurized triglyceride or mixture thereof has a total sulfur content of at least 5 wt.% and / or at most 15 wt.% and an active sulfur content of less than 5 wt.%.

26. The lubricating composition of any of claims 23-35, wherein the sulfurized triglyceride or mixture thereof is a sulfurized triglyceride of the general form shown in Formula IV: Formula IV, wherein R 6 is a linear or branched alkyl or alkenyl group of C4 or higher, or C6 or higher, or C8 or higher, or C10 or higher, or up to C50; R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 each independently is a C2to C8alkyl or alkenyl group; and each x is independently at least 1.

27. The lubricating composition of claim 26, wherein the sulfurized triglyceride has a total sulfur content according to ASTM D1552 of at least 5 wt.%, or at least 7 wt.%, or at most 15 wt.%, or at most 12 wt.%.

28. The lubricating composition of claim 26 or claim 27, wherein the sulfurized triglyceride has an active sulfur content according to ASTM D1662 of less than 5 wt.%, or less than 4 wt.%, or at least 3 wt.%.

29. The lubricating composition of any preceding claim, wherein the sulfurized organic compound comprises at least one of a cycloaliphatic dialkyl ester, a cycloaliphatic dialkenyl ester, and mixtures thereof.

30. The lubricating composition of claim 29, wherein the at least one of a cycloaliphatic dialkyl ester, a cycloaliphatic dialkenyl ester, and mixtures thereof is of the formula V: Formula V, wherein R 13 and each of R 14 is independently a C2or higher alkyl or alkenyl group; and x is at least 1.

31. The lubricating composition of claim 29 or 30, wherein the at least one of a cycloaliphatic dialkyl ester, a cycloaliphatic dialkenyl ester, and mixtures thereof has a total sulfur content of at least 5 wt.% and / or at most 15 wt.% and an active sulfur content of at least 1 wt.% and / or at most 5 wt.%.

32. The lubricating composition of any preceding claim, wherein the succinimide dispersant comprises at least 0.2 wt.%, or at least 0.5 wt.%, or at least 1.0 wt.% and / or at most 7.0 wt.%, or at most 6.0 wt.% of the lubricating composition.

33. The lubricating composition of any preceding claim, wherein the succinimide dispersant provides no more than 0.1 wt.% of the nitrogen of the lubricating composition.

34. The lubricating composition of any preceding claim, wherein the oil of lubricating viscosity comprises at least 70 wt.% of the lubricating composition and / or at most 94 wt.% of the lubricating composition.

35. The lubricating composition of any preceding claim, further comprising at least one of the group consisting of an anti-wear agent, a corrosion inhibitor, a viscosity modifier, a pour point depressant, an anti-foam agent, an extreme pressure agent, a friction modifier, a viscosity modifier, and combinations thereof.

36. The lubricating composition of claim 35, wherein the anti-wear agent provides 300 ppm to 850 ppm by weight of phosphorus of the lubricating composition based on the total weight of the lubricating composition.

37. The lubricating composition of claim 35 or claim 36, wherein the viscosity modifier comprises a dispersant viscosity modifier comprising at least one of: a reaction product of an olefin polymer comprising carboxylic acid functionality with 3-nitroaniline; and an amine-functionalized aromatic maleic anhydride-styrene copolymer.

38. The lubricating composition of any one of claims 35-37, wherein the dispersant viscosity modifier comprises at least 0.01 wt%, or at least 0.1 wt%, or at least 2 wt%, or not more than 8 wt%, or not more than 7 wt% of the lubricating composition.

39. The lubricating composition of claim 37, wherein the viscosity modifier comprises at least one of a hydrogenated styrene-butadiene copolymer resin viscosity modifier and an olefin copolymer resin viscosity modifier. b - a butadiene copolymer resin viscosity modifier and an olefin copolymer resin viscosity modifier.

40. The lubricating composition of any preceding claim, wherein molybdenum is not more than 800 ppm, or not more than 400 ppm, or not more than 150 ppm, or not more than 100 ppm, or not more than 80 ppm, or not more than 50 ppm, or not more than 20 ppm, based on the total weight of the lubricating composition.

41. The lubricating composition of any preceding claim, wherein the lubricating composition has a TBN of not more than 10, or not more than 9, or not more than 8, as determined according to ASTM D2896-21.

42. The lubricating composition of any preceding claim, wherein the lubricating composition is free of polyisobutylene succinic anhydride.

43. The lubricating composition of any preceding claim, wherein the lubricating composition has an oxidation induction time of at least 120 minutes, or at least 130 minutes, or at least 135 minutes, as determined according to CEC L-85-99.

44. A method for improving the oxidative stability of a lubricating oil composition in an engine, the method comprising supplying to the engine a lubricating composition according to any preceding claim.

45. The method of claim 44, wherein the oxidation induction time of the lubricating composition is at least 65 minutes or at least 120 minutes as determined according to CEC L-85-99.

46. Use of a lubricating composition according to any one of claims 1 to 43 for lubricating an engine.

47. A lubricating composition comprising: an oil of lubricating viscosity; a sulfurized organic compound sufficient to provide at least 0.1 wt% sulfur in the lubricating composition; at least 0.1 wt% of a phenolic antioxidant; at least 0.1 wt% of a succinimide dispersant that is at least substantially free of boron; and a calcium salicylate detergent present in an amount sufficient to provide at least 0.02 wt% Ca, or at least 0.04 wt%, or at least 0.1 wt%, or at most 0.3 wt%, or at most 0.2 wt%, or at most 0.15 wt% Ca to the lubricating composition; wherein the lubricating composition contains not more than 0.04 wt% active sulfur and not more than 0.01 wt% magnesium.

48. A method for improving the oxidative stability of a lubricating oil in an engine, the method comprising supplying to the engine a lubricating composition according to claim 47.

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