Detergent systems for antioxidant use in lubricants

Abstract

This disclosure relates to a lubricating composition having a stable viscosity after oxidation by means of selected amounts and relationships of detergent metal and soap content.

Description

Technical Field

[0001] This disclosure relates to lubricating compositions, particularly lubricating compositions that exhibit oxidative viscosity stability in the presence of biodiesel contaminants. Background Technology

[0002] Automakers continue to push for improvements in efficiency and fuel economy, resulting in a continued increase in demand for engines, lubricants, and their components. Modern spark-ignition bus engines are typically smaller, lighter, and more efficient, with technology designed to improve fuel economy, performance, and power. These requirements also mean that engine oil performance must evolve to meet the higher demands of such modern engines and their corresponding performance standards related to their unique uses and applications. Due to these stringent requirements for engine oils, lubricant manufacturers often customize lubricants and their additives to meet certain performance requirements for industrial and / or manufacturing applications. Often, each application requires specific performance standards, meaning that lubricants designed for one application cannot meet all performance specifications for different applications.

[0003] For example, when contaminated with, for instance, biodiesel, many automakers have introduced lubricant performance standards related to oxidative stability. Tests, such as those using CEC L-109-14 with up to 7 wt% B100 biodiesel contaminants or GFC Lu-43-A-11 with up to 30 wt% B10 biodiesel contaminants, involve bubbling oxygen through an oil sample doped with an iron catalyst. Acceptance criteria for these tests include, among other requirements, minimizing lubricant viscosity increase to maintain a stable viscosity over time.

[0004] However, in many cases, altering the components within a lubricant composition to meet newer performance characteristics tends to adversely affect one or more other performance characteristics. Therefore, it becomes challenging for lubricant manufacturers to meet newer industrial performance requirements while maintaining traditional fluid properties. Attached Figure Description

[0005] Figure 1 and Figure 2 The graph shows the percentage increase in viscosity (KV100) after 144 hours of oxidation with GFC Lu-43-A-11; and

[0006] Figure 3 It is a graph showing the change in viscosity (KV100) of GFC Lu-43-A-11 over time. Summary of the Invention

[0007] This disclosure relates to lubricating compositions for maintaining stable viscosity and minimizing oxidative degradation of lubricants containing oils of lubricating viscosity contaminated with biodiesel fuel. In one aspect, the lubricating composition comprises one or more base oils of lubricating viscosity; a sulfurized additive providing at least about 1500 ppm sulfur to the lubricating composition; one or more boronized dispersants providing about 40 ppm or more boron to the lubricating composition; and a detergent system providing the lubricating composition with about 0.2 to about 1.0 wt% soap content (in other methods, about 0.2 to about 0.8 wt%) and providing magnesium, sodium, and calcium. In some methods or embodiments, the detergent system provides the lubricating composition with more than about 90 ppm sodium and no more than about 2500 ppm magnesium, and wherein the detergent system has a sodium to magnesium weight ratio of at least about 0.1 and a sulfur to sodium weight ratio of about 15 or less; the lubricating composition is contaminated with up to about 30 wt% biodiesel fuel.

[0008] In other methods or embodiments, the lubricating composition of the preceding paragraph may be combined with one or more optional features or embodiments in any combination. Such optional features or embodiments may include one or more of the following: said lubricating composition contains about 90 ppm to about 1,000 ppm sodium, about 500 ppm to about 2,000 ppm calcium, about 100 to about 1,000 ppm magnesium and / or about 1,500 to about 4,000 ppm sulfur; and / or said lubricating composition has a calcium-to-magnesium weight ratio of at least about 0.5, and / or said lubricating composition contains about 15 to about 25% by weight sulfur provided by a sulfurized olefin antioxidant; and / or said lubricating composition contains, according to GFC When tested using the Lu-43-A-11 test, the lubricating composition exhibits an increase in viscosity after oxidation of no more than about 150% after 144 hours; wherein the viscosity increase of the lubricating composition after 144 hours is up to about 50% higher than the viscosity increase of a lubricating composition without biodiesel contaminants after 144 hours; and / or and / or wherein the soap component is a sulfonate soap, a phenolate soap, or a combination thereof, preferably a sulfonate soap; and / or wherein the lubricating composition contains at least about 0.1 wt% to about 5.0 wt% of linear or branched sodium sulfonate (about 0.25 to about 5.0 wt% in other methods); and / or wherein the lubricating composition has no more than about 500 ppm of boron; wherein the sodium to magnesium ratio is about 0.1 to about 2.0; and / or and / or wherein the base oil for the lubricating viscosity comprises API Group I base oil, API Group II base oil, API Group III base oil, API Group IV base oil, API Group V base oil, or a combination thereof; and / or wherein the base oil for the lubricating viscosity is API Group III base oils; and / or the lubricating composition thereof is substantially free of phenolic antioxidants; and / or further contains amine antioxidants; and / or the amine antioxidant is selected from aromatic amines, alkylated diphenylamine, nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, or combinations thereof; further contains molybdenum and not more than about 400 ppm of molybdenum; and / or further contains phosphorus and not more than about 1200 ppm of phosphorus; and / or and / or further contains imidazoline, amide, amine, succinimide, alkoxy Friction modifiers provided by amines, alkoxylated ether amines, amine oxides, amides, nitriles, betaine, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized aliphatic compounds and olefins, fatty acids, dicarboxylic acid esters, polyols and esters or metaesters of one or more aliphatic or aromatic carboxylic acids, or combinations thereof; and / or wherein the lubricating composition comprises neutral or highly basic magnesium sulfonate, sodium sulfonate and calcium sulfonate, each having a total base number (TBN) of up to about 500; and / or wherein the lubricating composition comprises neutral or highly basic metal phenolates with a total base number (TBN) of up to about 500.

[0009] In other methods, this document describes the use of any embodiment of the lubricating composition and / or its detergent system as described in the preceding paragraphs for maintaining a viscosity increase of no more than about 150% after 144 hours of oxidation when tested according to the GFC Lu-43-A-11 test.

[0010] In another approach, this document provides a method for maintaining a stable viscosity of a lubricating composition after oxidation. In several aspects, the method includes subjecting the lubricating composition to an oxidation test according to GFC Lu-43-A-11, wherein the lubricating composition comprises one or more base oils providing lubricating viscosity, a sulfurizing additive providing at least about 1500 ppm sulfur, one or more boronizing dispersants providing about 40 ppm or more boron, and a detergent system providing the lubricating composition about 0.2 to about 1.0 wt% soap (in other methods, about 0.2 to about 0.8 wt% soap content), and providing magnesium, sodium, and calcium, wherein the detergent system provides the lubricating composition with more than about 90 ppm sodium and no more than about 2500 ppm magnesium, and wherein the detergent system has a sodium to magnesium weight ratio of at least about 0.1 and a sulfur to sodium weight ratio of about 15 or less; wherein the lubricating composition exhibits a viscosity increase of no more than about 150% after oxidization for 144 hours.

[0011] In other methods or embodiments, the method embodiments described in the preceding paragraph may be combined with one or more optional features, steps, or limitations in any combination. Such optional features, method steps, or embodiments may include one or more of the following: wherein the lubricating composition comprises about 90 ppm to about 1,000 ppm of sodium, about 500 ppm to about 2,000 ppm of calcium, about 100 to about 1,000 ppm of magnesium, and / or about 1,500 to about 4,000 ppm of sulfur; and / or wherein the lubricating composition has a calcium-to-magnesium weight ratio of at least about 0.5; wherein about 15 to about 25% by weight of sulfur is provided by a sulfurized olefin antioxidant; and / or and / or wherein, according to GFC... When tested using the Lu-43-A-11 test, the lubricating composition exhibits an increase in viscosity after oxidation of no more than about 150% after 144 hours; wherein the viscosity increase of the lubricating composition after 144 hours is up to about 50% higher than the viscosity increase of a lubricating composition without biodiesel contaminants after 144 hours; and / or and / or wherein the soap component is a sulfonate soap, a phenolate soap, or a combination thereof, preferably a sulfonate soap; and / or wherein the lubricating composition contains at least about 0.1 wt% to about 5.0 wt% of linear or branched sodium sulfonate (about 0.25 to about 5.0 wt% in other methods); and / or wherein the lubricating composition has no more than about 500 ppm of boron; wherein the sodium to magnesium ratio is about 0.1 to about 2.0; and / or and / or wherein the base oil for the lubricating viscosity comprises API Group I base oil, API Group II base oil, API Group III base oil, API Group IV base oil, API Group V base oil, or a combination thereof; and / or wherein the base oil for the lubricating viscosity is API Group III base oils; and / or the lubricating composition thereof is substantially free of phenolic antioxidants; and / or further contains amine antioxidants; and / or the amine antioxidant is selected from aromatic amines, alkylated diphenylamine, nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, or combinations thereof; further contains molybdenum and not more than about 400 ppm of molybdenum; and / or further contains phosphorus and not more than about 1200 ppm of phosphorus; and / or and / or further contains imidazoline, amide, amine, succinimide, alkoxy Friction modifiers provided by amines, alkoxylated ether amines, amine oxides, amides, nitriles, betaine, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized aliphatic compounds and olefins, fatty acids, dicarboxylic acid esters, polyols and esters or metaesters of one or more aliphatic or aromatic carboxylic acids, or combinations thereof; and / or wherein the lubricating composition comprises neutral or highly basic magnesium sulfonate, sodium sulfonate and calcium sulfonate, each having a total base number (TBN) of up to about 500; and / or wherein the lubricating composition comprises neutral or highly basic metal phenolates with a total base number (TBN) of up to about 500. Detailed Implementation

[0012] This disclosure relates to lubricating compositions and methods for lubricating internal combustion engines, effectively maintaining stable viscosity and / or minimizing oxidative degradation in the event of increased lubricant viscosity when the lubricant (1) comprises an oil with a lubricating viscosity contaminated by biodiesel fuel and (2) comprises one or more additives known to adversely affect the increase of oxidative viscosity. In one method or embodiment, a lubricating composition is described herein comprising a base oil having one or more lubricating viscosities, a sulfurized additive providing at least about 1500 ppm sulfur to the lubricating composition, one or more boronized dispersants providing about 40 ppm or more boron to the lubricating composition, and wherein the lubricating composition is contaminated with up to about 30% by weight of biodiesel fuel. Such lubricating compositions tend not to meet industrial performance standards related to oxidative viscosity stability.

[0013] In the methods and embodiments described herein, the lubricating composition further includes a specific detergent system that, in other characteristics, provides a soap content of about 0.2 wt% to about 1.0 wt%, or about 0.2 wt% to about 0.8 wt%, about 0.25 wt% to about 0.7 wt%, about 0.28 wt% to about 0.6 wt%, or about 0.4 wt% to about 0.6 wt%, preferably a sulfonate soap content, and provides the lubricating composition with a certain amount and relationship of magnesium, sodium, and calcium that are found to help minimize the increase in oxidative viscosity. In some embodiments, the detergent system provides the lubricating composition with more than about 90 ppm of sodium (or more than about 180 ppm of sodium or more than about 200 ppm of sodium) and no more than about 2500 ppm of magnesium (in other methods, up to 2000 ppm of magnesium, or up to 1000 ppm of magnesium), and has a sodium to magnesium weight ratio of at least about 0.1 (in other methods, at least about 0.3, at least about 0.4, or at least about 0.5), and a sulfur to sodium weight ratio of about 15 or less (in other methods, about 12 or less, or about 6 or less). In other embodiments, the detergent system may also provide at least about 500 ppm of calcium and includes about 15 to about 25% by weight of a sulfurized olefin antioxidant providing total sulfur. In some methods, the lubricant described herein may also have a calcium to magnesium weight ratio of at least about 0.5.

[0014] Surprisingly, detergent systems exhibiting these characteristics and relationships maintained stable viscosity (as defined below) after oxidation and after 144 hours, when the lubricant was contaminated with up to 30% by weight of biodiesel. Since sodium, magnesium, and calcium from detergents, as well as soap, are primarily provided for acid neutralization, detergency, dispersibility, corrosion inhibition, and / or anti-wear, the choice of the specific amount and relationship of detergent contribution in the fluid so significantly affects oxidative viscosity stability when the lubricant is contaminated with biofuels and when additives detrimental to oxidative stability are included (e.g., ...). Figures 1 to 3 (as shown in the image).

[0015] As defined herein, the lubricating composition exhibits viscosity stability, wherein the limited KV100 viscosity increase upon oxidation after 144 hours according to the GFC Lu-43-A-11 test is no greater than about 150%, no greater than about 100%, no greater than about 80%, no greater than about 50%, or no greater than about 35%. In other words, the KV100 viscosity increase after 144 hours according to this test scheme, compared to the initial viscosity, does not exceed such recorded percentages. In other methods, when contaminated with up to 30% by weight of biodiesel fuel, the viscosity increase of the lubricant described herein is surprisingly comparable to the viscosity increase upon oxidation in the GFC test when operating without biodiesel contaminants, and in some cases, when contaminated with biodiesel, the viscosity increase of the lubricating composition after 144 hours is only up to about 50% greater than the viscosity increase of the lubricating composition without biodiesel contaminants. In some methods, the initial KV100 of the lubricant described herein may be from about 5 cSt to about 25 cSt, from about 7 cSt to about 15 cSt, or from about 10.5 cSt to about 11.5 cSt. After oxidation testing, the KV100 of the lubricant described herein may be in the range of from about 6 to about 65 cSt, from about 9 to about 50 cSt, from about 10 to about 40 cSt, from about 12 to about 20 cSt, or from about 15 cSt to about 17 cSt. In any embodiment described herein, KV100 is measured according to ASTM D445.

[0016] Detergent system

[0017] The lubricating compositions described herein include a unique detergent system that provides selected amounts and relationships of calcium, magnesium, and sodium metals from soap (preferably sulfonate soap), which contribute to achieving oxidative viscosity stability of the lubricant when contaminated with biodiesel fuel and when including sulfur and borate additives and / or high levels of magnesium.

[0018] In the implementation scheme, the detergent system typically includes detergent additives, such as one or more alkali metals or alkali metal phenolates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, their sulfur derivatives, or combinations thereof, provided that they satisfy the metal content and relationship described herein as well as the soap content. Preferably, the detergent is a phenolate or sulfonate, and most preferably a sulfonate having the soap and metal relationship discovered herein.

[0019] Suitable cleaning agents and methods of their preparation are described in more detail in several patent publications, including US7,732,390 and references thereto, which are incorporated herein by reference. The lubricant compositions described herein may contain about 0.1 to about 5% by weight of individual and / or total detergent additives, and in other methods, about 0.15 to about 3% by weight, and in other methods, about 0.15 to 2.6% by weight of individual and / or total detergent additives, provided that the detergent additives satisfy the metal content and relationships described herein.

[0020] As described above and in some methods, the detergent system provides a selected amount of soap and a selected amount and / or relationship of metal from the soap, and in other methods, a selected amount and relationship of calcium, sodium and / or magnesium and / or the amount of metal relative to sulfur in the lubricant provided by sulfonate soap. For example, the detergent system provides a metal in amounts greater than about 50 ppm of the total lubricating composition, and in other methods, amounts of about 50 ppm to about 800 ppm of the metal, about 100 ppm to about 800 ppm of the metal, about 1400 to about 800 ppm of the metal, or about 200 ppm to about 5000 ppm of the metal. In other methods, the detergent metal is calcium, sodium and / or magnesium, preferably calcium, sodium and magnesium provided by sulfonates, more preferably highly alkaline calcium sulfonates, sodium sulfonates and magnesium sulfonates. The detergent may also optionally include calcium phenolate and / or other detergents required for a particular application, provided that the amounts of soap and metal are satisfied.

[0021] In one method, suitable cleaning agents in the system may include alkali metal or alkaline earth metal salts of petroleum sulfonic acid and long-chain mono- or dialkyl aryl sulfonic acid, such as calcium or magnesium salts, wherein the aryl group is benzyl, tolyl, and xylyl, and / or various phenolic salts or phenolic salt derivatives. Examples of suitable cleaning agents include, but are not limited to, low-alkaline / neutral and high-alkaline forms of the following cleaning agents: calcium phenolate, calcium sulfur-containing phenolate, calcium sulfonate, calcium calixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium monothiophosphate and / or calcium dithiophosphate, calcium alkylphenolate, calcium thiocoupled alkylphenolate compound, methylene-bridged calcium phenolate, magnesium phenolate, magnesium sulfur-containing phenolate, magnesium sulfonate, magnesium calixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium monothiophosphate and / or magnesium dithiophosphate, magnesium alkylphenolate, magnesium thiocoupled alkylphenolate compound, methylene-bridged magnesium phenolate, sodium phenolate, sodium sulfur-containing phenolate, sodium sulfonate, sodium calixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium monothiophosphate and / or sodium dithiophosphate, sodium alkylphenolate, sodium thiocoupled alkylphenolate compound, or sodium methylene-bridged sodium phenolate.

[0022] The cleaning additive can be neutral, low-alkaline, or high-alkaline, and is preferably high-alkaline as described above. It should be understood that high-alkaline cleaning additives are well known in the art and can be alkali metal or alkaline earth metal high-alkaline cleaning additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a matrix and carbon dioxide gas. The matrix is ​​typically an acid, such as aliphatic-substituted sulfonic acids, aliphatic-substituted carboxylic acids, or aliphatic-substituted phenols.

[0023] The term "highly basic" refers to metal salts, such as those of sulfonic acids, carboxylic acids, salicylic acids, and / or phenols, in which the amount of metal present exceeds the stoichiometric amount. These salts can have conversion levels exceeding 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its "normal," "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to represent the ratio of the total stoichiometric amount of metal in a highly basic salt to the stoichiometric amount of metal in a neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, MR is one, and in highly basic salts, MR is greater than one. These are often referred to as highly basic, super-basic, or extremely basic salts and can be salts of organic sulfuric acids, carboxylic acids, or phenols.

[0024] As used herein, the term "TBN" is used to indicate the total base number in mg KOH / g as measured by the ASTM D2896 method. The total base number (TBN) of a highly alkaline detergent composition for lubricating oils can be greater than about 200 mg KOH / g or more, or about 250 mg KOH / g or more, or about 350 mg KOH / g or more, or about 375 mg KOH / g or more, or about 400 mg KOH / g or more. Highly alkaline detergents can have a metal-to-substrate ratio of 1.1:1 or less, or 2:1 or less, or 4:1 or less, or 5:1 or less, or 7:1 or less, or 10:1 or less, or 12:1 or less, or 15:1 or less, or 20:1 or less.

[0025] Examples of suitable high-alkaline detergents include, but are not limited to: high-alkaline calcium phenolate, high-alkaline calcium sulfur-containing phenolate, high-alkaline calcium sulfonate, high-alkaline calcium calixarate, high-alkaline calcium salicylate, high-alkaline calcium carboxylate, high-alkaline calcium phosphate, high-alkaline calcium monothiophosphate and / or calcium dithiophosphate, high-alkaline calcium alkylphenolate, high-alkaline calcium sulfur-coupled alkylphenolate compound, high-alkaline calcium methylene-bridged phenolate, high-alkaline magnesium phenolate, high-alkaline magnesium sulfur-containing phenolate, high-alkaline magnesium sulfonate, high-alkaline magnesium calixarate, high-alkaline magnesium salicylate, high-alkaline magnesium carboxylate, high-alkaline magnesium phosphate, high-alkaline magnesium monothiophosphate and / or magnesium dithiophosphate, high-alkaline magnesium alkylphenolate, high-alkaline magnesium sulfur-coupled alkylphenolate compound, or high-alkaline magnesium methylene-bridged phenolate.

[0026] When low-alkaline or neutral detergents are incorporated into detergent systems, they typically have a total nitrogen (TBN) of up to 175 mg KOH / g, up to 150 mg KOH / g, up to 100 mg KOH / g, or up to 50 mg KOH / g. Low-alkaline / neutral detergents may include detergents containing calcium or magnesium. Examples of suitable low-alkaline / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenolate, calcium salicylate, magnesium sulfonate, magnesium phenolate, and / or magnesium salicylate.

[0027] In some embodiments, the detergents used in the lubricants described herein are highly basic calcium sulfonate, highly basic sodium sulfonate, and highly basic magnesium sulfonate (optionally also including highly basic metal phenolates), each having a total base number (TBN) of 150-400 and, in other methods, about 200-350. The above TBN values ​​reflect the values ​​of the finished detergent components diluted in the base oil.

[0028] In other embodiments, the TBN of the cleaning agents described herein may reflect the pure or undiluted form of the cleaning agent components. For example, the fluids described herein may include highly basic calcium sulfonate or sodium sulfonate as net additives, having a TBN of about 300 to about 450, and in other cases about 380 to about 420, and / or highly basic magnesium sulfonate as net additives, having a TBN of about 500 to about 700, and in other cases about 600 to about 700.

[0029] More specifically, the detergent system described herein includes a neutral to highly alkaline detergent (preferably, neutral to highly alkaline calcium sulfonate) providing at least about 90 ppm sodium, at least about 180 ppm sodium, at least about 200 ppm sodium, at least 300 ppm sodium, or at least about 400 ppm sodium (preferably about 90 ppm to about 1,000 ppm sodium, about 180 ppm to about 1,000 ppm sodium, about 200 ppm to about 1,000 ppm sodium, about 300 ppm to about 1,000 ppm sodium, or about 400 ppm to about 1,000 ppm sodium). Neutral to highly basic sodium sulfonate and neutral to highly basic magnesium sulfonate; not more than about 2,500 ppm of magnesium, not more than about 2,000 ppm of magnesium, not more than about 1,500 ppm of magnesium or preferably not more than about 1,000 ppm of magnesium (in other methods, about 100 to about 2,500 ppm, about 500 to about 2,000 ppm, about 600 to about 1,500 ppm, or about 800 or about 1,000 ppm of magnesium); in some embodiments, at least about 500 ppm of calcium (preferably about 500 ppm to about 2,000 ppm of calcium). In the methods or embodiments described herein, the detergent system may further include a sodium to magnesium ratio of at least about 0.1, at least about 0.3, at least about 0.4, or at least about 0.5 (in other methods, about 0.1 to about 2.0, about 0.3 to about 2.0, about 0.4 to about 2.0, or about 0.5 to about 2.0), and a sulfur to sodium weight ratio of about 15 or less, about 12 or less, about 10 or less, about 8 or less, or about 6 or less (in other methods, about 2 to about 12, about 2 to about 10, or about 2 to about 6). In some methods, the lubricant may also have a calcium to magnesium weight ratio of at least about 0.5 (in other methods, about 0.5 to about 2.5). As shown in the following examples, lubricants that meet the requirements of such detergent systems surprisingly achieve oxidative viscosity stability when contaminated with biodiesel and when including vulcanized and borated additives of conventional lubricants.

[0030] In other embodiments, the lubricating composition herein comprises amounts of sodium sulfonate, magnesium sulfonate, and calcium sulfonate to achieve the aforementioned metal amounts and relationships. The lubricating composition may also contain, alone or in combination, about 0 to about 5% by weight of any detergent. Other detergents may also be included as needed for the specific application, provided that the amounts and relationships of magnesium, sodium, and calcium are satisfied.

[0031] The detergent system described herein also provides the lubricant composition with a selected level of soap content, particularly sulfonate soap content, and the amount of soap provided is balanced with the metal level to achieve oxidative viscosity stability when contaminated with up to about 30 wt% biodiesel. In one method, the detergent provides the final lubricant composition with about 0.2 wt% to about 1.0 wt% soap content, and in other methods, the detergent system provides about 0.2 wt% to about 0.8 wt% soap content, about 0.25 wt% to about 0.7 wt% soap content, or about 0.28 wt% to about 0.6 wt% soap content, and in other methods, about 0.4 to about 0.6 wt% soap content of calcium, sodium, and magnesium metals (preferably, the soap content is sulfonate soap). In some methods, the detergent system may also contain an optional phenolic soap content, and if included, it may be provided in an amount of up to about 0.7 wt%, or up to about 0.1 wt% (or any range thereof).

[0032] Soap content typically refers to the amount of neutral organic acid salts, reflecting the cleaning power or detergency and dirt-suspending ability of a detergent. An example is a calcium sulfonate cleaner (made of RSO3). v Ca w (CO3) x (Oh) y The formula (where v, w, x, and y represent the number of sulfonate groups, calcium atoms, carbonate groups, and hydroxyl groups, respectively) indicates the soap content, which can be determined using the following formula:

[0033]

[0034] The effective formula is the composition formula (RSO3). v Ca w (CO3) x (OH) y The total weight of all atoms plus the weight of any other lubricant components. Further discussion on determining soap content can be found in "Fuels and Lubricants". HANDBOOK, TECHNOLOGY, PROPERTIES, PERFORMANCE, AND TESTING, edited by George Totten, ASTM International, 2003, the relevant section of which is incorporated herein by reference.

[0035] Vulcanizing additives

[0036] The lubricating compositions described herein also include a number of additives providing sulfur, including at least one or more extreme pressure additives, anti-wear additives, and / or antioxidants. In some methods, the lubricating compositions described herein contain more than 1500 ppm or more than 2000 ppm of sulfur, and in other methods contain about 1500 ppm to about 4000 ppm of sulfur, about 2000 ppm to about 4000 ppm (or any other range thereof). In the GFC test described herein, sulfurized additives may be detrimental to oxidative viscosity stability. In some embodiments, the lubricant described herein includes a sulfurized olefin additive in an amount of about 0.1 to about 0.6% by weight, in other embodiments about 0.1 to about 0.5% by weight, and in still other embodiments about 0.1 to about 0.4% by weight, wherein the sulfurized olefin additive constitutes about 15 to about 25% by weight of the total sulfur in the lubricating composition.

[0037] The lubricants described herein may contain a variety of sulfur-containing or sulfurized additives for extreme pressure, antioxidant, and / or anti-wear purposes, and may contain sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, or preferably sulfurized olefins. (See, for example, US 2,995,569; US 3,673,090; US 3,703,504; US 3,703,505; US 3,796,661; US ​​3,873,454; US 4,119,549; US 4,119,550; US 4,147,640; US 4,191,659; US 4,240,958; US 4,344,854; US 4,472,306; and / or US 4,711,736, each of which is incorporated herein by reference.)

[0038] Examples of suitable olefins that can be vulcanized to form vulcanized olefins suitable for use in the lubricants described herein include propylene, butene, isobutylene, polyisobutylene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly available olefins. Alternatively, the olefin may be a Diels-Alder adduct of a diene (such as 1,3-butadiene) and an unsaturated ester (such as butyl acrylate). Another class of vulcanized olefins may include vulcanized fatty acids and their esters. Fatty acids are typically derived from vegetable or animal oils and typically contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Fatty acids are typically obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins (such as α-olefins).

[0039] Another suitable sulfiding agent for the lubricant of the present invention can be sulfurized isobutylene prepared by reacting an olefin such as isobutylene with sulfur. Sulfurized isobutylene (SIB), particularly sulfurized polyisobutylene, typically has a sulfur content of about 10% to about 55% by weight, and preferably about 30% to about 50%. A variety of other olefins or unsaturated hydrocarbons, such as isobutylene dimers or trimers, can be used to form sulfurized olefin extreme pressure agents. (See, for example, US 3471404; US 4,204,969; US 4,954,274; US 4,966,720; and / or US 3703504, each of which is incorporated herein by reference.) Methods for preparing sulfurized olefins, including those disclosed in the aforementioned patents, typically involve forming a material commonly referred to as an "adduct," wherein the olefin reacts with a sulfur halide, such as sulfur monochloride. The adduct is then reacted with a sulfur source to provide a sulfurized olefin.

[0040] As shown in the following examples, when a lubricant contains such sulfurized olefin additives and fails to contain the detergent system selected herein, the lubricant exhibits an undesirable increase in viscosity in the presence of biodiesel contaminants.

[0041] Boronized dispersant

[0042] The lubricating composition of the present invention further includes one or more dispersants, wherein at least a portion of the dispersant is boronized. In some methods, the one or more dispersants provide at least about 40 ppm boron, at least about 80 ppm boron, at least about 100 ppm boron, at least about 200 ppm boron, or at least about 300 ppm boron to the lubricating composition, and in other methods, about 40 ppm to about 700 ppm, about 80 ppm to about 700 ppm, about 100 ppm to about 700 ppm, about 40 ppm to about 500 ppm, about 80 ppm to about 500 ppm, about 100 ppm to about 500 ppm, about 150 ppm to about 700 ppm, or about 150 ppm to about 500 ppm boron.

[0043] Dispersants are commonly referred to as ashless dispersants because they do not contain ash-forming metals before being incorporated into a lubricating composition, and typically do not provide any ash when added to a lubricant. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides, wherein, as measured by GPC, the number average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000, or about 5,000, or about 3,000. Succinimid dispersants and their preparation are disclosed, for example, in U.S. Patent Nos. 7,897,696 and 4,234,435, which are incorporated herein by reference. The alkenyl substituent can be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically composed of polyamines, usually poly(ethylene amine) imides.

[0044] In this method, the preferred amine used as a dispersant can be selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologues such as pentaethylaminehexamine (PEHA). Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily containing oligomers with 6 or more nitrogen atoms per molecule, 2 or more primary amines, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably comprise polyamine oligomers containing 7 or more nitrogen atoms per molecule and 2 or more primary amines per molecule.

[0045] In some embodiments, when included, the terminal double bond content of polyisobutylene (PIB) may be greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. This type of PIB is also referred to as highly reactive PIB (“HR-PIB”). HR-PIB with a number-average molecular weight in the range of about 800 to about 5000, as determined by GPC, is suitable for embodiments of this disclosure. Conventional PIB typically has terminal double bonds in contents of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0046] HR-PIBs with a number-average molecular weight in the range of about 900 to about 3000, as determined by GPC, are suitable. Such HR-PIBs are commercially available or can be synthesized by polymerization of isobutylene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patents 4,152,499 and 5,739,355. When used in the aforementioned thermopolymerization reaction, HR-PIBs can increase conversion rates and reduce sediment formation due to enhanced reactivity. Suitable methods are described in U.S. Patent No. 7,897,696. In one embodiment, this disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride (“PIBSA”). PIBSA may have an average succinic acid moiety of between about 1.0 and about 2.0 per polymer.

[0047] In some methods, at least a portion of the dispersant in the lubricant described herein may also be post-treated by conventional methods through reaction with any of a variety of reagents. These reagents include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitrile compounds, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. (See, for example, US 7645726; US 7,214,649; US 8,048,831; and US 5,241,003, all of which are incorporated herein by reference). As described above, at least a portion of the dispersant in the lubricant described herein is post-treated with one or more boron compounds to effectively provide the stated level of boron to the lubricating composition.

[0048] The boron compound used as a post-treatment agent may be selected from boron oxide, boron halide, boric acid, and borate esters, in an amount from about 0.1 atomic proportions of boron per mole of nitrogen composition to about 20 atomic proportions of boron per atomic proportion of the nitrogen used. The boron-post-treated additive may contain about 0.05 to about 2.0% by weight, or in other methods, about 0.05 to about 0.7% by weight of boron, based on the total weight of the borate dispersant.

[0049] The carboxylic acid used as a post-treatment reagent can be saturated or unsaturated mono-, di-, or poly-carboxylic acids. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, and naphthalic acid (e.g., 1,8-naphthalic acid). The acid anhydride used as a post-treatment reagent can be selected from the group consisting of monounsaturated acid anhydrides (e.g., maleic anhydride), cyclic acid anhydrides substituted with alkyl or alkylene groups (e.g., succinic anhydride or glutamic acid anhydride), and aromatic carboxylic acid anhydrides (including naphthalenedicarboxylic anhydride, e.g., 1,8-naphthalenedicarboxylic anhydride).

[0050] In one embodiment, the method of post-treating the dispersant includes first forming a succinimide product as described above, and then further reacting the succinimide product with a post-treatment agent such as a boron compound such as boric acid. In some cases, the olefin copolymer viscosity index improvers described herein can be post-treated with more than one post-treatment agent. For example, the copolymer can be post-treated with an amine first and then with a boron compound such as boric acid and anhydrides such as maleic anhydride and / or 1,8-naphthalenedicarboxylic anhydride.

[0051] The dispersant may be used in an amount sufficient to provide up to about 20% by weight of the lubricating composition, and one or more of the dispersants may be post-treated to provide at least about 40 ppm of boron and up to 500 ppm of boron to the lubricating composition. In other methods, the dispersant may be used in the lubricating composition in an amount of about 0.1% to about 15% by weight, or about 0.1% to about 10% by weight, or about 0.1% to about 8% by weight, or about 1% to about 10% by weight, or about 1% to about 8% by weight, or about 1% to about 6% by weight, based on the final weight of the lubricating composition.

[0052] Base oil or base oil blend :

[0053] The base oils used in the lubricating oil compositions described herein may be oils with lubricating viscosity and are selected from any of the Group I to Group V base oils specified in the American Petroleum Institute (API) Base Oil Interchange Guide. The five base oil groups are generally listed in Table 1 below:

[0054] Table 1

[0055]

[0056]

[0057] Groups I, II, and III are mineral oil processing feedstocks. Group IV base oils contain truly synthetic molecules prepared through the polymerization of olefinic unsaturated hydrocarbons. Many Group V base oils are also truly synthetic products and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatic compounds, polyphosphates, polyethylene ethers, and / or polyphenylene ethers, but can also be naturally occurring oils such as vegetable oils. It should be noted that although Group III base oils are derived from mineral oils, the rigorous processing these fluids undergo results in physical properties very similar to some truly synthetic oils, such as PAO. Therefore, oils derived from Group III base oils may be referred to as synthetic fluids in industry. Group II+ may include high viscosity index Group II oils.

[0058] The base oil blend used in the disclosed lubricating oil compositions may be mineral oil, animal oil, vegetable oil, synthetic oil, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracked, hydrogenated, hydrorefined, unrefined, refined, and refined oils, as well as mixtures thereof.

[0059] Unrefined oils are those derived from natural, mineral, or synthetic sources with little or no further purification. Refined oils are similar to unrefined oils, except that they undergo one or more purification steps, which may result in improvements in one or more properties. Examples of suitable purification techniques are solvent extraction, double distillation, acid or alkali extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not contain edible oils or white oils.

[0060] Refined oils, also known as recycled or reprocessed oils, are obtained using the same or similar processes as refined oils. These oils are typically further processed using techniques designed to remove waste additives and oil decomposition products.

[0061] Mineral oils may include oils obtained through drilling or oils derived from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricants, such as liquid petroleum and solvent-treated or acid-treated alkanes, naphthenes, or mixed alkanes-naphthenes. If desired, such oils may be partially or fully hydrogenated. Oils derived from coal or shale may also be applicable.

[0062] Useful synthetic lubricants may include hydrocarbon oils such as polymeric, oligomeric, or copolymeric olefins (e.g., polybutene, polypropylene, propylene-isobutylene copolymers); trimers or oligomers of poly(1-hexene), poly(1-octene), and 1-decene, such as poly(1-decene), which are commonly referred to as α-olefins, 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. Polyα-olefins are typically hydrogenated materials.

[0063] Other synthetic lubricants include phosphoric acid-containing polyol esters, diesters, liquid esters (e.g., diethyl esters of toluene phosphate, trioctyl phosphate, and decanephosphonic acid), or polytetrahydrofurans. 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-liquid synthesis process, as well as other gas-liquid oils.

[0064] The base oil included in the lubricating composition in a major amount may be selected from Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the base oil in a major amount is different from the base oil produced by providing additive components or viscosity index improvers in the composition. In another embodiment, the base oil included in the lubricating composition in a major amount may be selected from Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the base oil in a major amount is different from the base oil produced by providing additive components or viscosity index improvers in the composition.

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

[0066] In some methods or implementations, the base oil system of this article, which includes blends of Group I to Group V base oils as first base oils and the mentioned ester base oils, may have a KV100 of about 2 to about 20 cSt, in other methods about 2 to about 10 cSt, about 2.5 to about 6 cSt, in still other methods about 2.5 to about 3.5 cSt, and in other methods about 2.5 to about 4.5 cSt.

[0067] As used herein, the terms “oil composition,” “lubricating composition,” “lubricating oil composition,” “lubricating oil,” “lubricant composition,” “fully formulated lubricant composition,” “lubricant,” and “lubricating and cooling fluid” are considered synonymous and fully interchangeable terms, referring to finished lubricating products containing a major amount of base oil components plus small amounts of detergents and other optional components.

[0068] Optional additives :

[0069] The lubricating oil compositions described herein may also include, as needed, a number of optional additives in combination with detergent systems, sulfurized additives, and borated detergents to meet performance standards. These optional additives are described in the following paragraphs.

[0070] dispersant Lubricating oil compositions may optionally include one or more dispersants or mixtures thereof. Dispersants are generally referred to as ashless dispersants because they do not contain ash-forming metals before being incorporated into the lubricating oil composition, and typically do not provide any ash when added to the lubricant. Ashless dispersants are characterized by polar groups linked to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides, wherein, as measured by GPC, the number average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000 or to about 5,000 or to about 3,000. Succinimid dispersants and their preparation are disclosed, for example, in U.S. Patent Nos. 7,897,696 or 4,234,435. The alkenyl substituent can be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Succinimid dispersants are typically polyamines, usually poly(ethylidene) imides.

[0071] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologues such as pentaethylaminehexamine (PEHA).

[0072] Suitable heavy polyamines are mixtures of polyalkylene polyamines containing small amounts of lower polyamine oligomers (such as TEPA and PEHA (pentaethylenehexamine)) but primarily having 6 or more nitrogen atoms per molecule, 2 or more primary amines, and oligomers with more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably comprise polyamine oligomers containing 7 or more nitrogen atoms per molecule and 2 or more primary amines per molecule. Heavy polyamines contain greater than 28 wt.% (e.g., >32 wt.%) of total nitrogen and 120-160 g / equivalent of primary amine groups by equivalent weight.

[0073] In some methods, the appropriate polyamine is often referred to as PAM and contains a mixture of ethylenediamines, in which TEPA and pentaethylenehexamine (PEHA) are the main components of the polyamine, typically less than about 80%.

[0074] Typically, PAM contains 8.7–8.9 milliequivalents of primary amine per gram (equivalent to 115–112 grams of primary amine) and approximately 33–34 wt.% total nitrogen. Heavy fractions of PAM oligomers, which contain little to no TEPA and only trace amounts of PEHA but primarily oligomers with more than six nitrogen atoms and greater branching, can produce dispersants with improved dispersibility.

[0075] In one embodiment, this disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene with a number average molecular weight in the range of about 350 to about 50,000 or about 5,000 or about 3,000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0076] In some embodiments, polyisobutylene (when included) may have terminal double bonds in amounts greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. This type of PIB is also referred to as highly reactive PIB (“HR-PIB”). HR-PIBs with a number-average molecular weight in the range of about 800 to about 5000, as determined by GPC, are suitable for embodiments of this disclosure. Conventional PIBs typically have terminal double bonds in amounts less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0077] HR-PIBs with a number-average molecular weight in the range of about 900 to about 3000, as determined by GPC, are suitable. These HR-PIBs are commercially available or can be synthesized by polymerizing isobutylene in the presence of a non-chlorinated catalyst (such as boron trifluoride), as described in U.S. Patent No. 4,152,499 to Boerzel et al. and U.S. Patent No. 5,739,355 to Gateau et al. When used in the aforementioned thermo-olefin reaction, HR-PIBs can increase the conversion rate and reduce the amount of sediment formed due to enhanced reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0078] In one embodiment, this disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride (“PIBSA”). PIBSA may have an average succinic acid fraction between about 1.0 and about 2.0 per polymer.

[0079] Chromatographic techniques can be used to determine the activity percentage of alkenyl or alkyl succinic anhydrides. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0080] The conversion percentage of polyolefins is calculated from the activity percentage using the equations in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0081] Unless otherwise stated, all percentages are by weight, and all molecular weights are number average molecular weights determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (with a number average molecular weight of 180 to about 18,000 as a calibration reference).

[0082] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In another embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. For example, the dispersant may be described as polyPIBSA. In another embodiment, the dispersant may be derived from an anhydride grafted onto an ethylene-propylene copolymer.

[0083] Suitable classes of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically, ethylene-propylene dispersants, which may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can react with functionalized OCPs is described in U.S. Patents 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383; and / or are commercially available.

[0084] Another suitable class of dispersants is the Mannich base. Mannich bases are substances formed by the condensation of alkyl-substituted phenols, polyalkylene polyamines, and aldehydes (e.g., formaldehyde) with higher molecular weight alkyl groups. Mannich bases are described in more detail in U.S. Patent No. 3,634,515.

[0085] Suitable dispersants can also be high molecular weight esters or hemiesteramides. Suitable dispersants can also be post-treated by conventional methods through reaction with any of a variety of reagents. These include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. US 7,645,726; US 7,214,649; and US 8,048,831 are incorporated herein by reference in their entirety.

[0086] In addition to carbonate and boric acid posttreatments, both compounds can be posttreated or further posttreated using a variety of posttreatment methods designed to improve or impart different properties. Such posttreatments include those outlined in columns 27 through 29 of U.S. Patent No. 5,241,003, which are incorporated herein by reference. Such treatments include treatments with: inorganic phosphorous acid or anhydrous substances (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980); organophosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as mentioned above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, acid anhydrides, and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948). 386); epoxides, polyepoxides, or thioepoxides (e.g., U.S. Patents 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Patent No. 3,458,530); carbon disulfide (e.g., U.S. Patent No. 3,256,185); glycidyl (e.g., U.S. Patent No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Patent Nos. 3,312,619; 3,865,813; and British Patent GB 1,065,595); organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent GB 1,065,595). 2,140,811); alkenyl cyanides (e.g., U.S. Patent Nos. 3,278,550 and 3,366,569); dienoketones (e.g., U.S. Patent No. 3,546,243); diisocyanates (e.g., U.S. Patent No. 3,573,205); alkane sulcolepsy (e.g., U.S. Patent No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Patent No. 3,954,6... 39); cyclic lactones (e.g., U.S. Patent Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711); cyclic carbonates or thiocarbonates; linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132; 4,647,390; 4,648,886; 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent GB). 2,140,811); hydroxyl-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); cyclic carbonates or thiocarbonates; linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132; 4,647,390; 4,646,860; and 4,670,170);Nitrogen-containing carboxylic acids (e.g., US Patent No. 4,971,598 and British Patent GB 2,440,811); hydroxyl-protected chlorodicarbonyloxy compounds (e.g., US Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., US Patent Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., US Patent Nos. 4,663,062 and 4,666,459); hydroxy aliphatic carboxylic acids (e.g., US Patent Nos. 4,482,464; 4,521,318; 4,713,189); oxidizing agents (e.g.) Examples include: US Patent No. 4,379,064; combinations of phosphorus pentasulfide and polyalkylene polyamine (e.g., US Patent No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., US Patent Nos. 3,390,086; 3,470,098); combinations of hydrazine and carbon disulfide (e.g., US Patent No. 3,519,564); combinations of aldehydes and phenols (e.g., US Patent Nos. 3,649,229; 5,030,249; 5,039,307); and combinations of aldehydes and O-diesters of dithiophosphate (e.g., US Patent No. 3,865,7). 40); combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Patent No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids, then formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064); combinations of formaldehyde and phenol and then glycolic acid (e.g., U.S. Patent No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid, and then diisocyanates (e.g., U.S. Patent No. 4,713,191); inorganic acids or anhydrides of phosphorus or portions thereof. Combinations of all sulfur analogs with boron-containing compounds (e.g., U.S. Patent No. 4,857,214); combinations of organic diacids, then unsaturated fatty acids, then nitrosoaromatic amines, optionally followed by boron compounds, and then alcohol acidifying agents (e.g., U.S. Patent No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278); combinations of aldehydes and triazoles, then boron compounds (e.g., U.S. Patent No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Patent Nos. 4,963,275 and 4,971,711). The patents mentioned above are incorporated herein by reference in their entirety.

[0087] The TBN of a suitable dispersant on an oil-free basis can be approximately 10 to approximately 65 mg KOH / g, and if measured on a dispersant sample containing approximately 50% diluted oil, it is equivalent to approximately 5 TBN to approximately 30 TBN. TBN is measured according to the method of ASTM D2896.

[0088] In other embodiments, the optional dispersant additive may be a hydrocarbon-substituted succinamide or succinimide dispersant. In the method, the hydrocarbon-substituted succinamide or succinimide dispersant is derived from a hydrocarbon-substituted acylated agent reacting with a polyalkylene polyamine, and wherein, as measured by GPC using polystyrene as a calibration reference, the hydrocarbon substituent of the succinamide or succinimide dispersant is a straight-chain or branched hydrocarbon group with a number average molecular weight of about 250 to about 5,000.

[0089] In some methods, the polyalkylene polyamine used to form the dispersant has the formula...

[0090]

[0091] Each R and R' is independently a divalent C1 to C6 alkylene linking group, and each R1 and R2 is independently hydrogen, a C1 to C6 alkyl group, or, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring optionally fused with one or more aromatic or non-aromatic rings, and n is an integer between 0 and 8. In other methods, the polyalkylene polyamine is selected from the group consisting of: mixtures of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0092] If a dispersant is present, it may be sufficient to provide an amount of up to about 20% by weight for use, based on the final weight of the lubricating oil composition. Another amount of dispersant that may be used, based on the final weight of the lubricating oil composition, may be from about 0.1 wt% to about 15 wt%, or from about 0.1 wt% to about 10 wt%, or from about 0.1 wt% to about 8 wt%, or from about 1 wt% to about 10 wt%, or from about 1 wt% to about 8 wt%, or from about 1 wt% to about 6 wt%. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type of dispersant or a mixture of two or more types of dispersants may be used in any desired ratio.

[0093] antioxidants The lubricating oil compositions described herein may optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenol salts, phenol sulfides, sulfide olefins, phosphosulfur terpenes, sulfide esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered nonaromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

[0094] Hindered phenolic antioxidants may contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group may be further substituted with a hydrocarbon group and / or a bridging group attached 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, or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenolic antioxidant may be an ester and may include, for example, Irganox, available from BASF. TM L-135 may be derived from an addition product of 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenolic antioxidant may be an ester and may include Ethanox, available from Albemarle Corporation. TM 4716.

[0095] Available antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be sufficient to provide up to about 5% by weight based on the final weight of the lubricating oil composition. In another embodiment, based on the final weight of the lubricating oil composition, the antioxidant may be a mixture of about 0.3 to about 1.5% by weight of diarylamine and about 0.4 to about 2.5% by weight of high molecular weight phenols.

[0096] Examples of suitable olefins that can be vulcanized to form vulcanized olefins include propylene, butene, isobutene, polyisobutene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecadecene, nonadecadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecadecene, nonadecadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly suitable olefins. Alternatively, the olefin may be a Diels-Alder adduct of a diene (such as 1,3-butadiene) and an unsaturated ester (such as butyl acrylate).

[0097] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are typically derived from vegetable or animal oils and typically contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitic acid, or mixtures thereof. Fatty acids are often derived from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins (such as α-olefins).

[0098] In another alternative embodiment, in addition to the phenolic and / or amine antioxidants discussed above, the antioxidant composition also contains a molybdenum-containing antioxidant. When using a combination of these three antioxidants, preferably, the ratio of the phenolic antioxidant to the amine antioxidant to the molybdenum-containing antioxidant is (0 to 3):(0 to 3):(0 to 3).

[0099] The one or more antioxidants may be present in the lubricating oil composition in the range of about 0% by weight to about 20% by weight, or about 0.1% by weight to about 10% by weight, or about 1% by weight to about 5% by weight.

[0100] Anti-wear agent The lubricating oil compositions described herein may optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyl dithiophosphates; phosphate esters or salts thereof; phosphate esters; phosphites; phosphorus-containing carboxylic esters, ethers or amides; sulfurized olefins; compounds containing thiocarbamates, including thiocarbamates, alkylene-coupled thiocarbamates and bis(S-alkyldithiocarbamoyl) disulfides; and mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are described more fully in European Patent 612 839. The metal in the dialkyl dithiophosphate may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. A suitable anti-wear agent may be zinc dialkyl dithiophosphate.

[0101] Another example of a suitable anti-wear agent includes titanium compounds, tartrate esters, tartrate imides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, and compounds containing thiocarbamates (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamoyl) disulfides). The tartrate ester or tartrate imide may contain an alkyl ester group, wherein the total number of carbon atoms in the alkyl group may be at least 8. In one embodiment, the anti-wear agent may include a citrate ester.

[0102] The anti-wear agent may be present in the range of about 0% to about 15% by weight, or about 0.01% to about 10% by weight, or about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0103] Boron-containing compoundsThe lubricating oil compositions described herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, boronized fatty amines, boronized epoxides, boronized detergents, and boronized dispersants, such as boronized succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057. The boron-containing compound (if present) may be used in an amount sufficient to provide the lubricating oil composition of up to about 8 wt%, about 0.01 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt%.

[0104] Cleaning agents The lubricating oil composition may optionally further comprise one or more neutral, low-alkaline, or high-alkaline detergents, or mixtures thereof. Suitable detergent matrices include benzoates, sulfur-containing benzoates, sulfonates, calixates, salicylates, salicylates, carboxylic acids, phosphoric acid, monothiophosphoric acid and / or dithiophosphoric acid, alkylphenols, thiocoupled alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods of their preparation are described in more detail in several patent publications, including US 7,732,390 and the references cited therein.

[0105] The detergent matrix can be salted with, for example, but not limited to, the following alkali metals or alkaline earth metals: calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or dialkyl aryl sulfonic acids, wherein the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to: calcium phenolate, calcium sulfonate, calcium calixarates, calcium salixarates, calcium salicylate, calcium carboxylate, calcium phosphate, calcium monothiophosphate and / or calcium dithiophosphate, calcium alkylphenolate, calcium thiocoupled alkylphenolate compounds, methylene-bridged calcium phenolate, magnesium phenolate, magnesium sulfonate, magnesium calixarates, magnesium salixarates, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium monothiophosphate and / or magnesium dithiophosphate, magnesium alkylphenolate, magnesium thiocoupled alkylphenolate compounds, methylene-bridged magnesium phenolate, sodium phenolate, sodium sulfonate, sodium calixarates, sodium salixarates, sodium salixarates. Sodium salicylates, sodium carboxylate, sodium phosphate, sodium monothiophosphate and / or sodium dithiophosphate, sodium alkylphenolate, sodium thiocoupled alkylphenolate compounds, or sodium methylene-bridged phenolate.

[0106] High-alkalinity detergent additives are well known in the art and can be alkali metal or alkaline earth metal high-alkalinity detergent additives. These detergent additives are prepared by reacting a metal oxide or metal hydroxide with a matrix and carbon dioxide gas. The matrix is ​​typically an acid, such as aliphatic-substituted sulfonic acids, aliphatic-substituted carboxylic acids, or aliphatic-substituted phenols.

[0107] The term "highly basic" refers to metal salts, such as those containing sulfonic acids, carboxylic acids, and phenols, in which the amount of metal present exceeds the stoichiometric amount. These salts can have conversion levels exceeding 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its "normal," "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to represent the ratio of the total stoichiometric amount of metal in a highly basic salt to the stoichiometric amount of metal in a neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in highly basic salts, MR is greater than one. These are often referred to as highly basic, super-basic, or extremely basic salts and can be salts of organic sulfuric acids, carboxylic acids, or phenols.

[0108] The total base number (TBN) of the highly alkaline detergent in the lubricating oil composition may be about 200 mg KOH / g or greater, or, as in other examples, about 250 mg KOH / g or greater, or about 350 mg KOH / g or greater, or about 375 mg KOH / g or greater, or about 400 mg KOH / g or greater. TBN is measured according to the method of ASTM D2896.

[0109] Examples of suitable high-alkaline detergents include, but are not limited to: high-alkaline calcium phenolate, high-alkaline calcium sulfur-containing phenolate, high-alkaline calcium sulfonate, high-alkaline calcium calixarate, high-alkaline calcium salicylate, high-alkaline calcium carboxylate, high-alkaline calcium phosphate, high-alkaline calcium monothiophosphate and / or calcium dithiophosphate, high-alkaline calcium alkylphenolate, high-alkaline calcium sulfur-coupled alkylphenolate compound, high-alkaline calcium methylene-bridged phenolate, high-alkaline magnesium phenolate, high-alkaline magnesium sulfur-containing phenolate, high-alkaline magnesium sulfonate, high-alkaline magnesium calixarate, high-alkaline magnesium salicylate, high-alkaline magnesium carboxylate, high-alkaline magnesium phosphate, high-alkaline magnesium monothiophosphate and / or magnesium dithiophosphate, high-alkaline magnesium alkylphenolate, high-alkaline magnesium sulfur-coupled alkylphenolate compound, or high-alkaline magnesium methylene-bridged phenolate.

[0110] The total base value of highly alkaline calcium phenolate cleaners is at least about 150 mg KOH / g, at least about 225 mg KOH / g, from at least about 225 mg KOH / g to about 400 mg KOH / g, from at least about 225 mg KOH / g to about 350 mg KOH / g, or from about 230 mg KOH / g to about 350 mg KOH / g, all as measured by the method of ASTM D2896. When such detergent compositions are formed in an inert diluent (such as process oil, typically mineral oil), the total base value reflects the alkalinity of the overall composition, which includes the diluent and any other materials that may be contained in the detergent composition (such as accelerators, etc.).

[0111] The metal-to-matrix ratio of highly alkaline detergents can be 1.1:1, 2:1, 4:1, 5:1, 7:1, or 10:1. In some embodiments, the detergent is effective in reducing or preventing rust in engine or other automotive parts such as transmissions or gears. The detergent may be present in about 0 wt% to about 10 wt%, or about 0.1 wt% to about 8 wt%, or about 1 wt% to about 4 wt%, or greater than about 4 wt% to about 8 wt%.

[0112] Extreme pressure agent The lubricating oil compositions described herein may optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur-containing and chlorine-containing sulfur EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organosulfurs and polysulfides, such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyltetrasulfide, methyl oleate sulfur, alkyl phenol sulfur, dipentene sulfur, terpenes sulfur, Diels-Alder sulfur; phosphorus sulfides, such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; phosphites, 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 phenyl phosphites; metal thiocarbamates, such as zinc dioctyl dithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, amine salts of the reaction products of dialkyl dithiophosphite with propylene oxide; and mixtures thereof.

[0113] Friction modifierThe lubricating oil compositions described herein may optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amides, nitriles, betaine, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized aliphatic compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or metaesters of polyols, and one or more aliphatic or aromatic carboxylic acids.

[0114] Suitable friction modifiers may contain a hydrocarbon group selected from straight-chain, branched, or aromatic hydrocarbon groups or mixtures thereof, and may be saturated or unsaturated. The hydrocarbon group may consist of carbon and hydrogen or heteroatoms, such as sulfur or oxygen. The hydrocarbon group may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester, diester, or (tri)glycerol ester. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

[0115] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may comprise esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally contain polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to a lipophilic hydrocarbon chain. Examples of organic ashless and nitrogen-free friction modifiers are generally known as glyceryl monooleate (GMO), which may contain monoesters, diesters, and trimers of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0116] Amine-based friction modifiers may include amines or polyamines. These compounds may have straight-chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and may contain about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. These compounds may have straight-chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof. They may contain about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0117] Amines and amides may be used as is or as additions or reaction products with boron compounds such as boron oxide, boron halide, metaborates, boric acid or monoalkyl, dialkyl or trialkyl esters of borate. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291.

[0118] The friction modifier may optionally be present in the range of, for example, from about 0 wt% to about 10 wt%, or from about 0.01 wt% to about 8 wt%, or from about 0.1 wt% to about 4 wt%.

[0119] molybdenum-containing components The lubricating oil compositions described herein may optionally contain one or more molybdenum-containing compounds. Oil-soluble molybdenum compounds may have functional properties as anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum dithiophosphonite, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkanolate, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfide includes molybdenum dithiophosphate. Molybdenum dithiophosphate may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamate.

[0120] Suitable examples of usable molybdenum compounds include commercially available materials sold under trade names such as those from RTVanderbilt Co., Ltd. 822、 A, 2000 and 855, and Sakura-Lube available from Adeka Corporation. TM S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710, and mixtures thereof. Suitable molybdenum compositions are described in US 5,650,381; US ​​RE 37,363 E1; US ​​RE 38,929 E1; and US RE 40,595 E1, the entire contents of which are incorporated herein by reference.

[0121] Alternatively, the molybdenum compound can be an acidic molybdenum compound. This includes molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, these compositions may provide molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Patent Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94 / 06897, the entire contents of which are incorporated herein by reference.

[0122] Another suitable class of organomolybdenum compounds are trinuclear molybdenum compounds, such as Mo3S k L n Q z Those and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having organic groups having a sufficient number of carbon atoms such that the compound is soluble or dispersible in oil, n is 1 to 4, k is 4 to 7, Q is selected from neutral electron-donating compounds such as water, amines, alcohols, phosphine, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. A total of at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, may be present in the organic groups of all ligands. Other suitable molybdenum compounds are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0123] Oil-soluble molybdenum compounds may be present in amounts sufficient to provide molybdenum of about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 450 ppm, or about 90 ppm to about 350 ppm.

[0124] compounds containing transition metals In another embodiment, the oil-soluble compound may be a compound or metalloid containing a transition metal. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, and tungsten. Suitable metalloids include, but are not limited to, boron, silicon, antimony, and tellurium.

[0125] In one embodiment, the oil-soluble transition metal-containing compound may function as an anti-wear agent, friction modifier, antioxidant, deposit control additive, or more than one of these functions. In one embodiment, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium(IV) alkoxide. Various Ti(IV) compounds, such as titanium oxide (IV); titanium sulfide (IV); titanium nitrate (IV); titanium(IV) alkoxides, such as titanium methoxide, titanium ethanol, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexanoate; and other titanium compounds or complexes, including but not limited to titanium phenolate; titanium carboxylate, such as titanium 2-ethyl-1-3-adipic acid (IV) or titanium citrate or titanium oleate; and titanium (triethanolamine) isopropoxide (IV). Other forms of titanium covered within the disclosed technology include titanium phosphate, such as titanium dithiophosphate (e.g., dialkyl titanium dithiophosphate), and titanium sulfonate (e.g., titanium alkylbenzene sulfonate), or generally, reaction products of titanium compounds reacting with various acidic materials to form salts (e.g., oil-soluble salts). Titanium compounds can therefore be derived, in particular, from organic acids, alcohols, and glycols. Ti compounds can also exist in dimer or oligomeric forms, containing a Ti-O-Ti structure. These titanium materials are commercially available or can be readily prepared using suitable synthetic techniques readily apparent to those skilled in the art. They exist in solid or liquid form at room temperature, depending on the specific compound. They can also be provided in the form of solutions in suitable inert solvents.

[0126] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbon-substituted succinic anhydride (such as an alkenyl (or alkyl) succinic anhydride). The resulting titanate-succinate intermediate can be used directly, or it can react with any of a number of materials, such as (a) polyamine-based succinimide / amide dispersants having free, condensable --NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, namely alkenyl-(or alkyl-)succinic anhydrides and polyamines; and (c) hydroxyl-containing polyester dispersants prepared by reacting substituted succinic anhydrides with polyols, amino alcohols, polyamines, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other reagents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols, or polyols or fatty acids, and the product can be used directly to impart Ti to the lubricant, or additionally, as described herein, with a succinic acid dispersant. As an example, 1 part (molar) of tetraisopropyl titanate can be reacted with about 2 parts (molar) of polyisobutylene-substituted succinic anhydride at 140-150°C for 5 to 6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a mixture of a succinimide dispersant derived from polyisobutylene-substituted succinic anhydride and a polyethylidene polyamine mixture (127 g + diluent oil) at 150°C for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0127] Another titanium-containing compound can be a titanium alkoxide with C6 to C6 atoms. 25 The reaction products of carboxylic acids. The reaction products can be represented by the following formula:

[0128]

[0129] Where n is an integer selected from 2, 3, and 4, and R is a hydrocarbon group containing approximately 5 to approximately 24 carbon atoms, or is represented by the following formula:

[0130]

[0131] Where m+n=4 and n is in the range of 1 to 3, R4 is an alkyl moiety with 1 to 8 carbon atoms, R1 is selected from hydrocarbon groups containing about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbon groups containing about 1 to 6 carbon atoms, or titanium compounds can be represented by the following formula:

[0132]

[0133] Where x is in the range of 0 to 3, R1 is selected from hydrocarbon groups containing about 6 to 25 carbon atoms, R2 and R3 are the same or different and are selected from hydrocarbon groups containing about 1 to 6 carbon atoms, and R4 is selected from H, or C6 to C4. 25 A group consisting of carboxylic acid moieties.

[0134] Suitable carboxylic acids may include, but are not limited to, hexanoic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, etc.

[0135] In embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in amounts of 0 to 3000 ppm titanium by weight, or 25 to 1500 ppm titanium by weight, or about 35 to 500 ppm titanium by weight, or about 50 ppm to 300 ppm titanium by weight.

[0136] Viscosity index improver The lubricating oil compositions described herein may optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may comprise polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene / maleate copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, α-olefin maleic anhydride copolymers, polymethyl methacrylates, polyacrylates, polyalkylstyrene, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, and suitable examples are described in U.S. Publication No. 20120101017A1.

[0137] In addition to or in place of viscosity index improvers, the lubricating oil compositions described herein may optionally contain one or more dispersant viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylation agent (such as maleic anhydride) and an amine; amine-functionalized polymethacrylates; or esterified maleic anhydride-styrene copolymers reacted with an amine.

[0138] The total amount of viscosity index improver and / or dispersant may be from about 0% to about 20% by weight, from about 0.1% to about 15% by weight, from about 0.1% to about 12% by weight, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0139] Other optional additives Other additives may be selected to perform one or more functions required for lubrication fluids. Furthermore, one or more of the mentioned additives may be multifunctional and provide functions other than those specified herein.

[0140] The lubricating oil compositions according to this disclosure may optionally contain other performance additives. These other performance additives may be additives other than those specified in this disclosure and / or may include one or more of the following: metal passivators, viscosity index improvers, detergents, ashless TBN accelerators, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, sealing swelling agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0141] Suitable metal passivating agents may include derivatives of benzotriazole (typically toluenetriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam inhibitors, including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers, including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants, including maleic anhydride-styrene esters, polymethacrylates, polyacrylates, or polyacrylamide.

[0142] Suitable foam inhibitors include silicon-based compounds, such as siloxanes.

[0143] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0 wt.% to about 1 wt.%, about 0.01 wt.% to about 0.5 wt.%, or about 0.02 wt.% to about 0.04 wt.% based on the final weight of the lubricating oil composition.

[0144] Suitable rust inhibitors can be single compounds or mixtures of compounds that possess properties that inhibit corrosion of ferrous metal surfaces. Non-limiting examples of useful rust inhibitors include: oil-soluble high-molecular-weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and wax acids; and oil-soluble polycarboxylic acids, including dimer and trimer acids, such as those derived from pine fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain α,ω-dicarboxylic acids with molecular weights ranging from about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropylene succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another type of acidic corrosion inhibitor that can be used is a half-ester of alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol (such as polyethylene glycol). Corresponding semiamides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0145] If a rust inhibitor is present, it may be used in amounts sufficient to provide about 0% to about 5% by weight, about 0.01% to about 3% by weight, or about 0.1% to about 2% by weight, based on the final weight of the lubricating oil composition.

[0146] Generally, suitable lubricants may include additive components in the range listed in the table below.

[0147] Table 2: Suitable Lubricating Compositions

[0148] Based on the weight of the final lubricating oil composition, the percentages for each component above represent the weight percentage of each component. The remainder of the lubricating oil composition consists of one or more base oils. Additives used to formulate the compositions described herein may be blended into the base oils individually or in various sub-combinations. However, it may be suitable to simultaneously blend all components using an additive concentrate (i.e., additive plus a diluent, such as a hydrocarbon solvent). Fully formulated lubricants typically contain an additive package, referred herein as a dispersant / inhibitor package or DI package, which will supply the desired characteristics in the formulation.

[0149] definition

[0150] For the purposes of this disclosure, chemical elements are identified according to the Periodic Table of the Elements, CAS edition, Handbook of Chemistry and Physics, 75th edition. Additionally, the general principles of organic chemistry are described in “Organic Chemistry,” Thomas Sorrell, University Science Books, Sausolito: 1999, and “March's Advanced Organic Chemistry,” 5th edition, edited by Smith, MB, and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0151] As described herein, compounds may optionally be substituted with one or more substituents, as generally described above, or as exemplified by specific classes, subclasses and species of this disclosure.

[0152] Unless obvious from the context, the term “major amount” should be understood to mean an amount greater than or equal to 50% by weight relative to the total weight of the composition, for example, about 80 to about 98% by weight. Furthermore, as used herein, the term “minor amount” should be understood to mean an amount less than 50% by weight relative to the total weight of the composition.

[0153] As used herein, the term "hydrocarbyl group" is used in its general sense as is well known to those skilled in the art. Specifically, it refers to a group having carbon atoms directly attached to the remainder of the molecule and possessing predominantly hydrocarbon characteristics. Examples of hydrocarbon groups include: (1) hydrocarbon substituents, namely aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic substituents substituted with aromatic, aliphatic, and alicyclic groups, as well as cyclic substituents in which the ring is completed through another part of the molecule (e.g., two substituents together form an alicyclic group); (2) substituted hydrocarbon substituents, namely substituents containing non-hydrocarbon groups that, in the context described herein, do not alter the predominant hydrocarbon substituent (e.g., halogens (especially chlorine and fluorine), hydroxyl, alkoxy, mercapto, alkyl mercapto, nitro, nitroso, amino, alkylamino, and thiooxy); and (3) heterosubstituents, namely substituents that, in the context of this specification, are predominantly hydrocarbon-characteristic but contain atoms other than carbon in a ring or chain originally composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and encompass substituents such as pyridyl, furanyl, thiophene, and imidazolyl. Generally speaking, for every ten carbon atoms in a hydrocarbon group, there are no more than two non-hydrocarbon substituents, or, in another embodiment, no more than one; in some embodiments, there are no non-hydrocarbon substituents in the hydrocarbon group.

[0154] As used herein, the term "aliphatic" includes the terms alkyl, alkenyl, and ynyl, each of which may optionally be substituted as described below.

[0155] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1-12 (e.g., 1-8, 1-6, or 1-4) carbon atoms. Alkyl groups can be straight-chain or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, n-pentyl, n-heptyl, or 2-ethylhexyl. Alkyl groups can be substituted (i.e., optionally substituted) with one or more of the following substituents: halogen, phosphate, cycloaliphatic group [e.g., cycloalkyl or cycloalkenyl], heterocycloaliphatic group [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, arylyl, heteroarylyl, acyl [e.g., (aliphatic)carbonyl, (cycloaliphatic)carbonyl, or (heterocycloaliphatic)carbonyl], nitro, cyano, amide [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, arylalkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino] [Heteroarylcarbonylamino, heteroarylalkylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocyclic alkylaminocarbonyl, arylaminocarbonyl or heteroarylaminocarbonyl], amino [e.g. aliphatic amino, cycloaliphatic amino or heterocyclic aliphatic amino], sulfonyl [e.g. aliphatic group -SO2-], sulfinyl, thio, thiooxy, urea, thiourea, aminosulfonyl, sulfonamide, side oxygen, carboxyl, carbamoyl, cycloaliphatic oxygen, heterocyclic aliphatic oxygen, aryloxy, heteroaryloxy, arylalkoxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyl or hydroxyl. In a non-limiting manner, some examples of substituted alkyl groups include carboxylalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO2-amino)alkyl), aminoalkyl, acylaminoalkyl, (cycloaliphatic)alkyl, or haloalkyl.

[0156] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like alkyl groups, alkenyl groups can be straight-chain or branched. Examples of alkenyl groups include, but are not limited to, allyl, isopropenyl, 2-butenyl, and 2-hexenyl. The alkenyl group may optionally be substituted by one or more substituents such as: halogen, phosphate, cycloaliphatic group [e.g., cycloalkyl or cycloalkenyl], heterocyclic aliphatic group [e.g., heterocyclic alkyl or heterocyclic alkenyl], aryl, heteroaryl, alkoxy, arylyl, heteroarylyl, acyl [e.g., (aliphatic)carbonyl, (cycloaliphatic)carbonyl, or (heterocyclic aliphatic)carbonyl], nitro, cyano, amide [e.g., (cycloalkyl)carbonylamino, arylcarbonylamino, arylalkylcarbonylamino, (heterocyclic)carbonylamino, (heterocyclic alkyl)carbonylamino, heteroarylcarbonylamino, heteroarylalkylcarbonyl] [Amino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocyclic alkylaminocarbonyl, arylaminocarbonyl or heteroarylaminocarbonyl], amino [e.g. aliphatic amino, cycloaliphatic amino, heterocyclic aliphatic amino or aliphatic sulfonylamino], sulfonyl [e.g. alkyl-SO2-, cycloaliphatic-SO2- or aryl-SO2-], sulfinyl, thio, thiooxy, urea, thiourea, aminosulfonyl, sulfonamide, side oxygen, carboxyl, carbamoyl, cycloaliphatic oxygen, heterocyclic aliphatic oxygen, aryl oxygen, heteroaryl oxygen, arylalkoxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyl or hydroxyl. In a non-limiting manner, some examples of substituted alkenyl groups include cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aryl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO2-amino)alkenyl), aminoalkenyl, acylaminoalkenyl, (cycloaliphatic)alkenyl, or haloalkenyl.

[0157] As used herein, "alkynyl" refers to an aliphatic carbon group containing 2-8 (e.g., 2-12, 2-6, or 2-4) carbon atoms and having at least one triple bond. The alkynyl group can be straight-chain or branched. Examples of alkynyl groups include, but are not limited to, propynyl and butynyl. The alkynyl group may optionally be substituted by one or more substituents such as: aryl, heteroaryl, alkoxy, cycloalkyloxy, heterocycloalkoxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxyl, cyano, halogen, hydroxyl, sulfonic acid, mercapto, thio (e.g., aliphatic thio or cycloaliphatic thio), sulfinyl (e.g., aliphatic sulfinyl or cycloaliphatic sulfinyl), sulfonyl (e.g., aliphatic -SO2-, aliphatic amino -SO2-, or cycloaliphatic -SO2-), amide (e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, ... Cycloalkylcarbonylamino, arylaminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocyclic alkyl)carbonylamino, (cycloalkyl alkyl)carbonylamino, heteroarylalkylcarbonylamino, heteroarylcarbonylamino or heteroarylaminocarbonyl], urea, thiourea, aminosulfonyl, sulfonamide, alkoxycarbonyl, alkylcarbonyloxy, cycloaliphatic, heterocyclic aliphatic, aryl, heteroaryl, acyl [e.g. (cycloaliphatic)carbonyl or (heterocyclic aliphatic)carbonyl], amino [e.g. aliphatic amino], thiooxy, lateral oxy, carboxyl, carbamoyl, (cycloaliphatic)oxy, (heterocyclic aliphatic)oxy or (heteroaryl)alkoxy.

[0158] As used in this article, "amino" refers to -NR X R Y , where R X and R Y Each of these groups is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxyl, thio, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaryl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is prefixed with -NR. X - indicates. R X It has the same meaning as the definition above.

[0159] As used herein, a “cycloalkyl” group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3-10 (e.g., 5-10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cycloheptyl, octahydro-indenyl, decahydronaphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2.]decyl, bicyclo[2.2.2]octyl, adamantyl, or ((aminocarbonyl)cycloalkyl)cycloalkyl.

[0160] As used herein, a “heterocyclic alkyl” group refers to a 3- to 10-membered mono- or bicyclic (fused or bridged) (e.g., 5- to 10-membered mono- or bicyclic) saturated ring structure in which one or more ring atoms are heteroatoms (e.g., N, O, S or combinations thereof). Examples of heterocyclic alkyl groups include piperidinyl, piperazinyl, tetrahydropyranyl, tetrahydrofuranyl, 1,4-dioxolane, 1,4-dithiaalkyl, 1,3-dioxolane, oxazolidinyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, octahydrobenzofuranyl, octahydrochromenyl, octahydrothiochromenyl, octahydroindolyl, octahydropyridinyl, decahydroquinolinyl, octahydrobenzo[b]thiopheneyl, 2-oxa-bicyclo[2.2.2]octyl, 1-aza-bicyclo[2.2.2]octyl, 3-aza-bicyclo[3.2.1]octyl, and 2,6-dioxa-tricyclo[3.3.1.0]nonyl. Monocyclic heterocyclic alkyl groups can be fused with a phenyl moiety to form a structure, such as tetrahydroisoquinoline, which will be classified as a heteroaryl group.

[0161] As used herein, “heteroaryl” refers to a monocyclic, bicyclic, or tricyclic system having 4 to 15 ring atoms, wherein one or more of the ring atoms are heteroatoms (e.g., N, O, S, or combinations thereof), and wherein the monocyclic system is aromatic, or at least one ring in the bicyclic or tricyclic system is aromatic. Heteroaryl includes benzo[b]fused ring systems having 2 to 3 rings. For example, benzo[b]fused groups include benzo[b]fused with one or two 4 to 8-membered heterocyclic aliphatic moieties (e.g., indolizyl, indolyl, isoindolyl, 3H-indolyl, dihydroindolyl, benzo[b]furanyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl groups are pyridyl, 1H-indazolyl, furanyl, pyrroleyl, thiophenyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuranyl, isoquinolinyl, benzothiazolyl, xanthon, thiophene, phenothiazine, dihydroindole, benzo[1,3]m-dioxacyclopentene, benzo[b]furanyl, benzo[b]thiaphenyl, indazolyl, benzoimidazolyl, benzothiazolyl, furanyl, cinnolyl, quinolinyl, quinazolinyl, cinnolyl, phthalazyl, quinazolinyl, quinoxalinyl, isoquinolinyl, 4H-quinolizyl, benzo-1,2,5-thiadiazolyl, or 1,8-naphthyridyl.

[0162] In a non-limiting sense, monocyclic heteroaryl groups include furanyl, thiopheneyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridinyl, pyridinyl, pyrazolyl, pyrazinyl, or 1,3,5-triazinyl. Monocyclic heteroaryl groups are numbered according to standard chemical nomenclature.

[0163] In a non-limiting sense, bicyclic heteroaryl groups include indazinyl, indolyl, isoindolyl, 3H-indolyl, dihydroindolyl, benzo[b]furanyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolazinyl, isoindolyl, indolyl, benzo[b]furanyl, benzo[b]thiophenyl, indazoleyl, benzimidazolyl, benzothiazolyl, purinyl, 4H-quinazinyl, quinolinyl, isoquinolinyl, cenolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 1,8-naphthidyl, or pteridyl. Bicyclic heteroaryl groups are numbered according to standard chemical nomenclature.

[0164] As used herein, the term “processing rate” refers to the weight percentage of a component in the lubricating and cooling fluids.

[0165] Weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined using a gel permeation chromatography (GPC) instrument or similar instrument from Waters, and the data were processed using Waters Empower software or similar software. The GPC instrument can be equipped with a Waters separation module and a Waters refractive index detector (or similar optional equipment). GPC operating conditions may include a guard column, four Agilent PLgel columns (300 × 7.5 mm in length; 5 μm particle size, and pore size range of...). The column temperature is approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) can be used as a solvent at a flow rate of 1.0 mL / min. GPC instruments can be calibrated using commercially available poly(methyl methacrylate) (PMMA) standards with a narrow molecular weight distribution range of 960–1,568,000 g / mol. For samples with a mass less than 500 g / mol, calibration curves can be extrapolated. Samples and PMMA standards can be dissolved in THF and prepared at concentrations of 0.1–0.5 wt%, and used without filtration. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. GPC methods also provide molecular weight distribution information; see, for example, WWYau, JJ Kirkland, and DDBly, “Modern Size Exclusion Liquid Chromatography,” John Wiley and Sons, New York, 1979, which is also incorporated herein by reference.

[0166] Example

[0167] The present disclosure and its many advantages can be better understood through the following examples. These examples are illustrative and do not limit its scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and apparatus described in these examples can be used. Unless otherwise stated or apparent from the context of the examples below and throughout this disclosure, all percentages, ratios, and parts mentioned herein are by weight.

[0168] Example 1

[0169] The viscosity stability of the lubricating composition was evaluated after 144 hours of oxidation according to GFC Lu-43-A-11. The lubricating composition evaluated in this example comprises sulfonate and phenolate detergents and borate dispersants in amounts providing the fluid relationships shown in Table 3 below, as well as a similar additive package including dispersants, anti-wear additives, amine antioxidants, phenolic antioxidants, molybdenum antioxidants, friction modifiers, defoamers, pour point depressants, viscosity modifiers, and a balanced Group III base oil to achieve an initial KV100 of approximately 10.8 cSt. (KV100 was measured according to ASTM D445.) Table 4 provides the oxidation results.

[0170] Table 3: Fluid Relationships

[0171] Element Comparative Example 1 Comparative Example 2 Invention 1 Invention 2 boron 214ppm 214ppm 214ppm 214ppm calcium 214ppm 214ppm 214ppm 214ppm magnesium 214ppm 214ppm 214ppm 214ppm sodium - - 214ppm 214ppm sulfur 214ppm 214ppm 214ppm 214ppm Sulfonate soap 0.39％ 0.41％ 0.42％ 0.43％ Phenolite soap 0.10％ 0.17％ 0.17％ 0.20％ Sodium to magnesium - - 1.0:1 0.5:1 Calcium-Magnesium 2.7:1 1.0:1 0.6:1 1.0:1 Sulfur-Sodium - - 1.9:1 4.0:1

[0172] Table 4: Viscosity increase of GFC Lu-43-A-11 KV100 after oxidation

[0173]

[0174] *The biofuel is GOPSA10LUB (B10).

[0175] Example 2

[0176] After 144 hours, the oxidative viscosity stability of the lubricating composition comprising the detergent and boronized dispersant of Example 1, and approximately 0.4% by weight of sulfurized olefins, was evaluated according to GFC Lu-43-A-11. The lubricant of this example includes the fluid relationships shown in Table 5, except for the same additive package containing antioxidants, anti-wear additives, phenolic antioxidants, and molybdenum antioxidants. Friction modifiers, defoaming additives, pour point depressants, viscosity modifiers, and the balance being Group III base oil to achieve a KV100 of approximately 10.5 cSt. (KV100 measured according to ASTM D445). Oxidation results are provided in Table 6.

[0177] Table 5: Fluid Relationships

[0178] Element Comparative Example 3 Comparative Example 4 This invention 3 Invention 4 boron 214ppm 214ppm 214ppm 214ppm calcium 214ppm 214ppm 214ppm 214ppm magnesium 214ppm 214ppm 214ppm 214ppm sodium 214ppm 214ppm 214ppm 214ppm sulfur 214ppm 214ppm 214ppm 214ppm Sulfonate soap 0.29％ 0.32％ 0.36％ 0.43％ Phenolite soap 0.36％ 0.36％ 0.36％ 0.36％ Sodium to Magnesium - 0.3:1 0.8:1 1.6:1 Calcium-Magnesium 2.3:1 2.3:1 2.3:1 2.3:1 Sulfur-Sodium - 13.3:1 5.3:1 2.7:1

[0179] Table 6: Viscosity increase of GFC Lu-43-A-11 KV100 after oxidation

[0180]

[0181] *The biofuel is GOPSA10LUB (B10).

[0182] A 1000% increase in viscosity reflects a sample that is too viscous to be measured.

[0183] Figures 1-3The paper demonstrates significant viscosity stability of the fluid after 144 hours of oxidation when the stated amount of clean metal and various relationships are met.

[0184] It should be noted that, unless explicitly and definitively limited to one indicator, the singular forms “a / an” and “the” as used in this specification and the appended claims include multiple indicators. Thus, for example, a reference to “antioxidant” includes two or more different antioxidants. The term “comprising” and its grammatical variations as used herein are intended to be non-limiting, such that the description of an item in the list does not exclude other similar items that may be substituted for or added to the listed items.

[0185] For the purposes of this specification and the appended claims, unless otherwise stated, all figures and other numerical values ​​used in the specification and claims to express quantities, percentages or proportions should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations that may vary depending on the desired characteristics sought to be obtained through this disclosure. To a minimum, and without attempting to limit the application of the equivalence principle to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying general rounding techniques.

[0186] It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as disclosed for use alone or in combination with one or more of each other component, compound, substituent or parameter disclosed herein.

[0187] It should also be understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range having the same significant digits. Thus, for example, the range 1 to 4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, and any range of such values.

[0188] It should also be understood that each lower limit of each range disclosed herein should be interpreted as a combination of each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Therefore, this disclosure should be interpreted as the disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it should also be understood that this document also discusses any range between endpoint values ​​within a wide range. Therefore, the range 1 to 4 also means the range 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0189] Furthermore, the specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in this specification or examples should be interpreted as disclosures of a lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or specific amount / value of the range of the same components, compounds, substituents, or parameters disclosed elsewhere in this disclosure to form such a range of components, compounds, substituents, or parameters.

[0190] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that may not currently be foreseen or likely to be foreseen by the applicant or others skilled in the art are likely to occur. Therefore, the appended claims, as filed and as may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A lubricating composition comprising: One or more base oils with lubricating viscosity; A sulfurizing additive, wherein the sulfurizing additive provides at least 1,500 ppm of sulfur to the lubricating composition; One or more boronizing dispersants, wherein the one or more boronizing dispersants provide 40 ppm or more of boron to the lubricating composition; A detergent system that provides the lubricating composition with a soap content of 0.2% to 1.0% by weight and provides magnesium, sodium, and calcium, wherein the detergent system provides the lubricating composition with greater than 90 ppm of sodium and not more than 2,500 ppm of magnesium, and wherein the detergent system has a sodium to magnesium weight ratio of at least 0.1 and a sulfur to sodium weight ratio of 15 or less; and The lubricating composition is contaminated with up to 30% by weight of biodiesel fuel.

2. The lubricating composition according to claim 1, wherein the lubricating composition comprises 90 ppm to 1,000 ppm sodium, 500 ppm to 2,000 ppm calcium, 100 ppm to 1,000 ppm magnesium and / or 1,500 ppm to 4,000 ppm sulfur, and the weight ratio of calcium to magnesium is at least 0.

5.

3. The lubricating composition according to claim 2, wherein 15% to 25% by weight of sulfur is provided by a sulfurized olefin antioxidant.

4. The lubricating composition according to claim 1, wherein when tested according to the GFC Lu-43-A-11 test, the lubricating composition exhibits an increase in viscosity after oxidation of no more than 150% after 144 hours.

5. The lubricating composition of claim 4, wherein the viscosity increase of the lubricating composition after 144 hours is up to 50% higher than that of the lubricating composition without biodiesel contaminants after 144 hours.

6. The lubricating composition according to claim 1, wherein the soap content is a sulfonate soap content; and / or wherein the lubricating composition comprises at least 0.1% to 5.0% by weight of linear or branched sodium sulfonate.

7. The lubricating composition according to claim 1, wherein the lubricating composition comprises neutral or high-alkalinity magnesium sulfonate, sodium sulfonate, and calcium sulfonate, each having a total base number (TBN) of up to 500; and / or wherein the lubricating composition comprises a neutral or high-alkalinity metal phenolate with a total base number (TBN) of up to 500.

8. The lubricating composition according to claim 1, wherein the lubricating composition has a boron content of not more than 500 ppm.

9. The lubricating composition according to claim 1, wherein the ratio of sodium to magnesium is from 0.1 to 2.

0.

10. The lubricating composition of claim 1, wherein the base oil having a lubricating viscosity comprises API Group I base oil, API Group II base oil, API Group III base oil, API Group IV base oil, API Group V base oil, or a combination thereof.

11. The lubricating composition of claim 1, wherein the lubricating composition is free of phenolic antioxidants; and / or wherein the lubricating composition further comprises amine antioxidants.

12. The lubricating composition of claim 1, wherein the lubricating composition further comprises an amine antioxidant selected from aromatic amines, hindered non-aromatic amines, or combinations thereof.

13. The lubricating composition according to claim 12, wherein the aromatic amine is an alkylated diphenylamine.

14. The lubricating composition according to claim 11, wherein the amine antioxidant is selected from nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered nonaromatic amines, or combinations thereof.

15. The lubricating composition according to claim 1, wherein the lubricating composition further comprises not more than 400 ppm of molybdenum.

16. The lubricating composition according to claim 1, wherein the lubricating composition further comprises not more than 1,200 ppm of phosphorus.

17. The lubricating composition of claim 1, further comprising a friction modifier provided by imidazoline, amide, amine, succinimide, alkoxylated amine, alkoxylated ether amine, amine oxide, amide, nitrile, betaine, quaternary amine, imine, amine salt, aminoguanidine, alkanolamide, phosphonate, metal-containing compound, glycerol ester, sulfurized aliphatic compound and olefin, dicarboxylic acid ester, and one or more aliphatic or aromatic carboxylic acids or combinations thereof.

18. The lubricating composition according to claim 1, wherein the lubricating composition further comprises a friction modifier provided by an ester or metaester of a polyol.

19. A method for maintaining a stable viscosity of a lubricating composition after oxidation, the method comprising: Oxidation tests were performed on the lubricating composition according to GFC Lu-43-A-11; The lubricating composition comprises: one or more base oils having a lubricating viscosity; a sulfurizing additive providing at least 1,500 ppm of sulfur; one or more boronizing dispersants providing 40 ppm or more of boron; and a detergent system providing the lubricating composition with 0.2 wt% to 1.0 wt% soap and providing magnesium, sodium, and calcium, wherein the detergent system provides the lubricating composition with greater than 90 ppm of sodium and no more than 2,500 ppm of magnesium, and wherein the detergent system has a sodium to magnesium weight ratio of at least 0.1 and a sulfur to sodium weight ratio of 15 or less; and The lubricating composition exhibits an increase in viscosity of no more than 150% after oxidation after 144 hours.

20. The method of claim 19, wherein the lubricating composition comprises 90 ppm to 1,000 ppm sodium, 500 ppm to 2,000 ppm calcium, 100 ppm to 1,000 ppm magnesium and / or 1,500 ppm to 4,000 ppm sulfur, and the weight ratio of calcium to magnesium is at least 0.5.

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