Hydrolysis-stable hydraulic lubricant

Abstract

The lubricant composition may provide corrosion resistance, oxidation resistance, and reduced wear to the hydraulic system. A lubricant composition can include an ashless dithiophosphate ester in an amount sufficient to provide the lubricant composition with a phosphorus concentration in the range of from 10 ppm to 250 ppm, a metal dialkyldithiophosphate salt, such as zinc dialkyldithiophosphate (ZDDP), in an amount sufficient to provide the lubricant composition with a phosphorus concentration in the range of from 50 ppm to 1000 ppm, a corrosion inhibitor comprising an alkyl triazole derivative in an amount sufficient to provide the lubricant composition with a nitrogen concentration in the range of from 0.75 ppm to 100 ppm; and a major amount of a base oil.

Description

Technical Field

[0001] This disclosure relates to a lubricating fluid for a hydraulic system and a method for lubricating the hydraulic system. Specifically, the disclosed method and lubricating fluid relate to a hydraulic lubricating fluid that requires a balance of anti-wear, anti-oxidation, and hydrolytic stability properties. Background Technology

[0002] A major challenge in developing hydraulic lubricants is achieving acceptable anti-wear and anti-oxidation properties while also ensuring resistance to chemical degradation in the presence of water. In the past, lubricant chemists have used various combinations of phosphorus-containing anti-wear compounds with benzotriazole derivatives as corrosion inhibitors to provide good wear and oxidation protection. However, these lubricants may often face issues with hydrolytic stability. Summary of the Invention

[0003] This disclosure relates to lubricant compositions. The lubricant compositions can be hydraulic lubricating fluids exhibiting improved anti-wear and corrosion resistance, while also being resistant to chemical decomposition in the presence of water. The lubricant compositions can be hydrolyzed stable and comprise a metal dithiophosphate salt and an ashless dithiophosphate ester with an alkylated triazole, which is not classified as a benzotriazole corrosion inhibitor commonly used in hydraulic lubricants.

[0004] In one embodiment, this document describes a hydraulic lubricating fluid with improved hydrolytic stability.

[0005] In one embodiment, the lubricating oil composition disclosed herein comprises a major amount of an oil having lubricating viscosity and an ashless dithiophosphate ester, a dialkyl dithiophosphate metal salt, and a corrosion inhibitor comprising an alkyltriazole derivative. The corrosion inhibitor comprising the alkyltriazole derivative may be present in an amount sufficient to provide the lubricating oil composition with a nitrogen concentration ranging from 0.75 ppm to 100 ppm.

[0006] In one embodiment, the lubricating oil composition disclosed herein comprises a major amount of an oil having a lubricating viscosity, an amount sufficient to provide the lubricant composition with a phosphorus concentration ranging from 10 ppm to 250 ppm, an amount sufficient to provide the lubricant composition with a phosphorus concentration ranging from 50 ppm to 1000 ppm of a dialkyl dithiophosphate metal salt, and an amount sufficient to provide the lubricant composition with a nitrogen concentration ranging from 0.75 ppm to 100 ppm of a corrosion inhibitor comprising an alkyltriazole derivative. The dialkyl dithiophosphate metal salt may comprise (or) zinc dialkyl dithiophosphate (ZDDP).

[0007] In one embodiment, the lubricating oil composition disclosed herein comprises an ashless dithiophosphate ester comprising 3-[[bis(2-methylpropoxy)thiophosphino]thio]-2-methylpropionic acid, ethyl 3-[[bis(1-methylpropoxy)thiophosphino]thio]propionate, or a combination thereof.

[0008] In another embodiment, the lubricating oil composition disclosed herein comprises an ashless dithiophosphate present in an amount sufficient to provide the lubricant composition with a phosphorus concentration ranging from 10 ppm to 40 ppm.

[0009] In yet another embodiment, the lubricating oil composition disclosed herein comprises zinc dialkyl dithiophosphate (ZDDP) as a dialkyl dithiophosphate metal salt, wherein ZDDP includes primary ZDDP, secondary ZDDP, or a combination thereof.

[0010] In yet another embodiment, the lubricating oil composition disclosed herein comprises a dialkyl dithiophosphate metal salt present in an amount sufficient to provide the lubricant composition with a phosphorus concentration ranging from 50 ppm to 300 ppm.

[0011] In another embodiment, the corrosion inhibitor comprises N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methylamine.

[0012] In yet another embodiment, the corrosion inhibitor is present in an amount sufficient to provide the lubricant composition with a nitrogen concentration ranging from 0.75 ppm to 15 ppm.

[0013] In another embodiment, the lubricant composition is substantially free of (or otherwise free of) benzotriazole and benzotriazole derivative corrosion inhibitors. As used herein, it is substantially free of nitrogen at 0.5 ppm or less, or 0.25 ppm or less, or 0.1 ppm or less, or in other embodiments, functional amounts of benzotriazole or benzotriazole derivative corrosion inhibitors.

[0014] In another embodiment, the lubricant composition is substantially free of (or otherwise free of) tolyltriazole and tolyltriazole derivative corrosion inhibitors. As used herein, it is substantially free of nitrogen at 0.5 ppm or less, or 0.25 ppm or less, or 0.1 ppm or less, or in other embodiments, no functional amount of tolyltriazole or tolyltriazole derivative corrosion inhibitors.

[0015] In yet another embodiment, the lubricant composition exhibits a hydrolytic stability of 0.2 mg / cm³ over 96 hours, as measured according to ASTM D2619-21. 2 Or even less copper weight loss.

[0016] In another embodiment, the lubricant composition herein has a Rotating Pressure Vessel Oxidation Test (RPVOT) value of at least 350 minutes as measured according to ASTM D2272-22.

[0017] In another embodiment, the lubricant composition herein has a 4-ball wear value of less than 0.60 mm as measured according to ASTM D4172-21.

[0018] In yet another embodiment, the lubricant composition herein further comprises a dispersant, a detergent, a friction modifier, or a combination thereof.

[0019] Another embodiment of this disclosure includes a hydraulic system lubricated with a lubricating oil composition comprising a major amount of an oil having a lubricating viscosity, an amount sufficient to provide the lubricating oil composition with a phosphorus concentration ranging from 10 ppm to 250 ppm, an amount sufficient to provide the lubricating oil composition with a phosphorus concentration ranging from 50 ppm to 1000 ppm, and an amount of a corrosion inhibitor comprising an alkyltriazole derivative sufficient to provide the lubricating oil composition with a nitrogen concentration ranging from 0.75 ppm to 100 ppm.

[0020] Another embodiment includes a method for lubricating a hydraulic component used in transportation applications, mobile machinery applications (e.g., construction equipment, i.e., wheel loaders, excavators, backhoe excavators, bulldozers, graders, skid steer loaders, articulated trucks, compact track loaders, or compactors), or industrial applications, and wherein the hydraulic component is lubricated with a lubricating oil composition comprising a major amount of an oil having a lubricating viscosity, an amount sufficient to provide the lubricant composition with a phosphorus concentration ranging from 10 ppm to 250 ppm, an amount sufficient to provide the lubricant composition with a phosphorus concentration ranging from 50 ppm to 1000 ppm of a dialkyl dithiophosphate metal salt, and an amount sufficient to provide the lubricant composition with a nitrogen concentration ranging from 0.75 ppm to 100 ppm of a corrosion inhibitor comprising an alkyltriazole derivative. The dialkyl dithiophosphate metal salt may comprise (or) zinc dialkyl dithiophosphate (ZDDP).

[0021] Other embodiments of this disclosure will be apparent to those skilled in the art upon consideration of the specification and examples disclosed herein. Detailed Implementation

[0022] This document provides lubricant compositions that can provide improved performance. This disclosure relates to lubricant compositions that can combine hydraulic properties with corrosion resistance, oxidation resistance, and reduced wear to improve productivity.

[0023] In some cases, the lubricant compositions described herein can achieve extended service life in industrial and mobile machinery applications, resulting in lower maintenance and operating costs. In some examples, the lubricant composition may be a hydraulic fluid composition. Some conventional hydraulic lubricants may exhibit poor hydrolytic stability, experience high levels of wear, and / or fail to prevent or minimize corrosion and oxidation. The lubricant compositions described herein demonstrate extended durability and desired properties, such as hydrolytic stability, while providing excellent wear and oxidation protection.

[0024] Dialkyl dithiophosphate metal salts

[0025] This article describes lubricant compositions that may contain metal-containing dithiophosphates, such as zinc dialkyl dithiophosphate, in an amount sufficient to provide a phosphorus concentration of 50 ppm to 1000 ppm to the lubricant composition.

[0026] In some examples, the dialkyl dithiophosphate metal salt may comprise (or) zinc dialkyl dithiophosphate (ZDDP). In some examples, zinc dialkyl dithiophosphate (ZDDP) may comprise (or) primary ZDDP, secondary ZDDP, or a combination thereof. ZDDP may have the chemical structure of formula (I):

[0027] (I).

[0028] In some examples, R 1 R 2 R 3 and R 4 Each can be an alkyl or cycloalkyl group containing 1 to 18 carbon atoms. In some examples, R 1 R 2 R 3 and R 4 Each can be an alkyl group containing 6 to 8 carbon atoms. Therefore, the alkyl and / or cycloalkyl groups can be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, cyclohexyl, methylcyclopentyl, propenyl, 4-methyl-2-pentyl (MIBC) or butenyl.

[0029] In some examples, ZDDP may be present in amounts sufficient to provide the lubricant composition with a phosphorus concentration of 50 ppm to 1000 ppm (e.g., 65 ppm to 285 ppm, 110 ppm to 460 ppm, or 80 ppm to 930 ppm). ZDDP may be present in the lubricant composition to provide approximately 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 225 ppm, 250 ppm, 275 ppm, 300 ppm, 325 ppm, 350 ppm, etc. Phosphorus concentrations of 375 ppm, 400 ppm, 425 ppm, 450 ppm, 475 ppm, 500 ppm, 525 ppm, 550 ppm, 575 ppm, 600 ppm, 625 ppm, 650 ppm, 675 ppm, 700 ppm, 725 ppm, 750 ppm, 775 ppm, 800 ppm, 825 ppm, 850 ppm, 875 ppm, 900 ppm, 925 ppm, 950 ppm, 975 ppm, or 1000 ppm are present.

[0030] Ash-free dialkyl dithiophosphate

[0031] This article describes lubricant compositions that may contain ashless dithiophosphate in an amount sufficient to provide a phosphorus concentration of 10 ppm to 250 ppm to the lubricant composition.

[0032] In some examples, ashless dithiophosphates may comprise dithiophosphorylated carboxylic acids. Ashless dithiophosphates may have the chemical structure of formula (IIA) and / or a tribologically acceptable salt thereof:

[0033] (IIA).

[0034] Each R 1 and R 2 It can be an independent hydrocarbon group containing 1 to 20 carbon atoms. R 3 It can be a divalent hydrocarbon group containing 1 to 20 carbon atoms. X 1 It can be —C(O)O— or —O—. R 4 It can be hydrogen or a hydrocarbon group containing 1 to 20 carbon atoms. Preferably, each R 1 and R 2 It can independently contain 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. More preferably, each R1 and R 2 It can independently contain 2 to 6 carbon atoms. R 1 and R 2 Preferred examples are alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. Particularly preferred are isopropyl and isobutyl groups. Preferably, R 3 It can be a straight-chain or branched alkylene group or an arylene (i.e., a divalent aryl) group, such as phenylene. Preferably, R 3 It can be a straight-chain or branched alkylene group. Preferably, R 3 It can contain 1 to 12 carbon atoms. More preferably, R 3 It can contain 1 to 8 carbon atoms, or 2 to 6 carbon atoms. R 3 Preferred examples include alkylene groups, such as —CH2—, —CH2—CH2—, —CH2—CH2—CH2—, —CH(CH3)—CH2—, —CH2—CH(CH3)—, —CH2—CH2—CH2—CH2—, —CH(CH3)—CH2—, —CH2—CH(CH3)—CH2—, —CH2—CH2—CH(CH3)—, —CH(CH3)—CH(CH3)—, —C(CH3)2—CH2— and —CH2—C(CH3)2—. Among these, groups containing two or three carbon atoms are preferred, particularly —CH2—CH2— and —CH2—CH(CH3)—. 1 Preferably, it is —C(O)O—. When R 4 When the hydrocarbon group contains 1 to 20 carbon atoms, it preferably contains 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. Preferably, R... 4 It can be hydrogen, a straight-chain or branched alkyl group, or an aryl group such as phenyl. More preferably, R 4 It can be hydrogen or a straight-chain or branched alkyl group. When R... 4 When it is a straight-chain or branched alkyl group, R 4 Preferred examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. Particularly preferred are ethyl, n-propyl, and isopropyl, with isopropyl being the most preferred. In some examples, each R... 1 and R 2 It can be an alkyl group containing 2 to 6 carbon atoms independently, R 3 It can be a divalent alkyl group containing 2 to 6 carbon atoms, X 1 It can be —C(O)O—, and R 4 It can be hydrogen or an alkyl group containing 2 to 6 carbon atoms.

[0035] In some examples, ashless dithiophosphate may contain (or) 3-[[bis(2-methylpropoxy)thiophosphino]thio]-2-methylpropionic acid (CAS No.: 268567-32-4), ethyl 3-[[bis(1-methylpropoxy)thiophosphino]thio]propionate (CAS No.: 71735-74-5), or combinations thereof. In some examples, ashless dithiophosphate may have the chemical structure of formula (IIB):

[0036] (IIB).

[0037] In some examples, ashless dithiophosphates can have the chemical structure of formula (IIC):

[0038] (IIC).

[0039] In some examples, the ashless dithiophosphate contained in the composition may contain components having both formula (IIB) and formula (IIC), that is, the composition may contain a certain amount of a component having the chemical structure of formula (IIB) and a certain amount of a component having the chemical structure of formula (IIC).

[0040] In some examples, ashless dithiophosphates can provide the lubricant composition with a phosphorus concentration of 10 ppm to 250 ppm (e.g., 10 ppm to 40 ppm, 12 ppm to 155 ppm, or 18 ppm to 210 ppm). For example, ashless dithiophosphate may be present in amounts providing the lubricant composition with phosphorus concentrations of about 10 ppm, 11 ppm, 12 ppm, 13 ppm, 14 ppm, 15 ppm, 16 ppm, 17 ppm, 18 ppm, 19 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 210 ppm, 220 ppm, 230 ppm, 240 ppm, or 250 ppm.

[0041] Corrosion inhibitors

[0042] In some examples, the corrosion inhibitor may comprise (or) N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methylamine. In some examples, the corrosion inhibitor comprising an alkyltriazole derivative may be present in an amount sufficient to provide the lubricant composition with a nitrogen concentration of 0.75 ppm to 100 ppm (e.g., 0.75 ppm to 15 ppm, 3 ppm to 48 ppm, or 8 ppm to 92 ppm). Corrosion inhibitors containing alkyltriazole derivatives may be present in amounts providing the lubricant composition with nitrogen concentrations of about 0.75 ppm, 0.8 ppm, 0.9 ppm, 1 ppm, 1.5 ppm, 2 ppm, 2.5 ppm, 3 ppm, 3.5 ppm, 4 ppm, 4.5 ppm, 5 ppm, 5.5 ppm, 6 ppm, 6.5 ppm, 7 ppm, 7.5 ppm, 8 ppm, 8.5 ppm, 9 ppm, 9.5 ppm, 10 ppm, 11 ppm, 12 ppm, 13 ppm, 14 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, or 100 ppm. In some examples, the corrosion inhibitor may be substantially free of (and in other embodiments, free of) benzotriazole and benzotriazole derivatives. The corrosion inhibitor may be substantially free of (and in other embodiments free of) tolyltriazole and / or tolyltriazole derivatives. In some examples, the corrosion inhibitor may have the chemical structure of formula (III):

[0043] (III).

[0044] In some examples, corrosion inhibitors may be substantially free of (and in other embodiments free of) components having the chemical structure of formula (IV):

[0045] (IV).

[0046] In some examples, corrosion inhibitors may be substantially free of (and in other embodiments free of) components having the chemical structure of formula (V):

[0047] (V).

[0048] In some examples, corrosion inhibitors may be substantially free of (and in other embodiments free of) components having chemical structures of formulas (IV) and (V):

[0049] As used herein, unless the context otherwise requires, the substance is substantially free of about 0.5 ppm or less of nitrogen, or 0.25 ppm or less of nitrogen, or 0.1 ppm or less of nitrogen, depending on the type of corrosion inhibitor. This means that the corrosion inhibitor is derived from benzotriazole or benzotriazole derivative corrosion inhibitors, or tolyltriazole or tolyltriazole derivative corrosion inhibitors, or components having the chemical structure of formula (IV), formula (V), or combinations thereof. In other embodiments, the substance is substantially free of corrosion inhibitors comprising no functional amount of benzotriazole or benzotriazole derivative corrosion inhibitors, or tolyltriazole or tolyltriazole derivative corrosion inhibitors, or components having the chemical structure of formula (IV), formula (V), or combinations thereof. This means that the corrosion inhibitor is substantially free of nitrogen, depending on the type of corrosion inhibitor.

[0050] base oil

[0051] The lubricating compositions described herein can be transmission system or industrial lubricating compositions and may include one or more base oils having a lubricating viscosity. Base oils suitable for formulating lubricating compositions according to this disclosure may be selected from any suitable synthetic oil or natural oil or mixtures thereof having a suitable lubricating viscosity. Natural oils may include animal and vegetable oils (e.g., castor oil, lard) and mineral oils, such as liquid petroleum and solvent-treated or acid-treated alkanes, naphthenes, or mixed alkanes-naphthenes. Oils derived from coal or shale may also be suitable. Furthermore, oils derived from gas-to-liquid processes are also suitable. The base oil may have a kinematic viscosity of about 2 cSt to about 15 cSt at 100°C, as measured by ASTM D2270-10.

[0052] The base oil used in the lubricating compositions described herein may be a single base oil or a mixture of two or more base oils selected from API Groups I-V. In one embodiment, the one or more base oils may be selected from any Group III and / or Group IV base oils as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guide. These base oil classes are shown in Table 1 below:

[0053] Table 1

[0054]

[0055] API Group III base oils may include oils derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are prepared from syngas containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing before use as base oils. These types of oils are commonly referred to as gas-to-liquid (GTL) oils. For example, the hydrocarbons can be hydroisomerized using the methods disclosed in U.S. Patent 6,103,099 or 6,180,575; hydrocracking and hydroisomerized using the methods disclosed in U.S. Patent 4,943,672 or 6,096,940; dewaxing using the methods disclosed in U.S. Patent 5,882,505; or hydroisomerized and dewaxing using the methods disclosed in U.S. Patent 6,013,171, 6,080,301; or 6,165,949.

[0056] API Group IV base oils, PAOs are typically derived from monomers having 4 to 30, 4 to 20, or 6 to 16 carbon atoms. Examples of PAOs that can be used in the lubricant compositions described herein include those derived from octene, decene, mixtures thereof, etc. PAOs can have a kinematic viscosity of 2 to 15, 3 to 12, or 4 to 8 cSt at 100°C, as measured by ASTM D2270-10. Examples of PAOs include PAOs with a viscosity of 4 cSt at 100°C, PAOs with a viscosity of 6 cSt at 100°C, and mixtures thereof.

[0057] The base oil can be combined with additive compositions as disclosed in the embodiments herein to provide a lubricating composition for hydraulic systems. Based on the total weight of the lubricating composition, the base oil may be present in an amount greater than about 80% by weight in the lubricating composition. In some embodiments, based on the total weight of the lubricating composition, the base oil may be present in an amount greater than about 85% by weight in the lubricating composition.

[0058] Other additives

[0059] In addition to the components described above, the lubricating compositions described herein may also contain other types of additives for hydraulic fluid compositions. Depending on the specific application, such additives include, but are not limited to, antioxidants, viscosity modifiers, phosphorus-containing components, detergents, rust inhibitors, defoamers, demulsifiers, pour point depressants, sealing and swelling agents, dispersants, and / or sulfur-containing components.

[0060] antioxidants

[0061] In some embodiments, the lubricating composition may contain one or more antioxidants. Suitable antioxidants include phenolic antioxidants, aromatic amine antioxidants, sulfur-containing antioxidants, and organophosphites, etc.

[0062] Examples of phenolic antioxidants include 2,6-di-tert-butylphenol, liquid mixtures of tert-butylphenol, 2,6-di-tert-butyl-4-cresol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and mixtures of methylene-bridged polyalkylphenols and 4,4'-thiobis(2-methyl-6-tert-butylphenol), N,N'-di-sec-butylphenylenediamine, 4-isopropylaminodiphenylamine, benzene-α-naphthylamine, benzene-α-naphthylamine, and cycloalkylated diphenylamines. Examples include sterically hindered tert-butylated phenols, bisphenols, and cinnamic acid derivatives, and combinations thereof.

[0063] Aromatic amine antioxidants include, but are not limited to, diarylamines having formula (VI):

[0064] (VI),

[0065] R' and R'' each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Examples of substituents for aryl groups include aliphatic hydrocarbon groups such as alkyl, hydroxyl, halogen, carboxylic, ester, or nitro groups having 1 to 30 carbon atoms.

[0066] The aryl group is preferably a substituted or unsubstituted phenyl or naphthyl group, particularly wherein one or both of these aryl groups are substituted with at least one alkyl group having 4 to 30 carbon atoms, preferably 4 to 18 carbon atoms, and most preferably 4 to 9 carbon atoms. It is preferred that one or both aryl groups are substituted, for example, monoalkylated diphenylamine, dialkylated diphenylamine, or a mixture of monoalkylated diphenylamine and dialkylated diphenylamine.

[0067] Examples of diarylamines that may be used include, but are not limited to: diphenylamine; various alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, monobutyldiphenylamine, dibutyldiphenylamine, monooctyldiphenylamine, dioctyldiphenylamine, monononyldiphenylamine, dinonyldiphenylamine, monotetradecyldiphenylamine, tetradecyldiphenylamine, benzene-α-naphthylamine, monooctylphenyl-α-naphthylamine, benzene-β-naphthylamine, monoheptyldiphenylamine, diheptyldiphenylamine, p-oriented styrylated diphenylamine, mixed butyloctyldiphenylamine and mixed octylstyryldiphenylamine.

[0068] Sulfur-containing antioxidants include, but are not limited to, sulfurized olefins, characterized by the type of olefin used in their production and the final sulfur content of the antioxidant. High molecular weight olefins (i.e., those with an average molecular weight of 168 g / mol to 351 g / mol) are preferred. Examples of olefins that can be used include α-olefins, isomerized α-olefins, branched olefins, cycloolefins, and combinations thereof.

[0069] α-olefins include, but are not limited to, any C4 to C5 olefins. 25 α-Alkenes. α-Alkenes can be isomerized before or during sulfidation. Structural and / or conformational isomers of α-alkenes containing internal double bonds and / or branches can also be used. For example, isobutene is a branched alkene counterpart of the α-alkene 1-butene.

[0070] Sulfur sources that can be used in olefin sulfidation reactions include elemental sulfur, sulfur monochloride, sulfur dichloride, sodium sulfide, sodium polysulfide, and mixtures thereof, either together or added at different stages of the sulfidation process.

[0071] Unsaturated oils, due to their unsaturation, can also be sulfurized and used as antioxidants. Examples of oils or fats that can be used include corn oil, canola oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, coconut oil, rapeseed oil, safflower oil, sesame oil, soybean oil, sunflower oil, tallow, and combinations thereof.

[0072] The total amount of antioxidant in the lubricating composition described herein can be from 500 ppm to 25,000 ppm. The lower limit can preferably be, for example, 600 ppm, 700 ppm, 800 ppm, 900 ppm, or 1000 ppm. The upper limit can preferably be, for example, 20,000 ppm, 15,000 ppm, 10,000 ppm, or 5,000 ppm. Typical preferred concentration ranges are, for example, 800 ppm to 15,000 ppm, 900 ppm to 10,000 ppm, or 1,000 ppm to 5,000 ppm. When the composition contains one or more nitrogen-containing antioxidants (e.g., aromatic amines), said antioxidants can be present in amounts delivering up to about 200 ppm nitrogen, up to about 150 ppm nitrogen, or about 100 ppm to about 150 ppm nitrogen.

[0073] Cleaning agents

[0074] The metal cleaners that may be included in the lubricating compositions described herein typically contain a polar head with a long, hydrophobic tail, wherein the polar head contains a metal salt of an acidic organic compound. The salts may contain substantially stoichiometric amounts of metal, in which case they are typically described as normal or neutral salts and will generally have a total base number (TBN) of 0 to less than 150 (as measured by ASTM D2896). A significant amount of metal base may be included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide. The resulting highly alkaline cleaner contains micelles of neutralizing cleaner surrounding an inorganic metal base (e.g., hydrated carbonate) core. Such highly alkaline cleaners may have a TBN of 150 or higher, such as 150 to 450 or higher.

[0075] Cleaning agents suitable for embodiments of the present invention include oil-soluble highly alkaline, low alkaline, and neutral sulfonates, phenolates, sulfurized phenolates, and metal salicylates, particularly alkali metals or alkaline earth metals such as sodium, potassium, lithium, calcium, and magnesium. More than one metal may be present, such as calcium and magnesium. Mixtures of calcium and / or magnesium with sodium are also suitable. Suitable metal cleaning agents may be highly alkaline calcium or magnesium sulfonates with a TBN of 150 to 450 TBN, highly alkaline calcium or magnesium phenolates or sulfurized phenolates with a TBN of 150 to 300 TBN, and highly alkaline calcium or magnesium salicylate with a TBN of 130 to 350 TBN. Mixtures of these salts may also be used.

[0076] Based on the total weight of the lubricating composition, the metal-containing cleaning agent may be present in the fluid in an amount sufficient to provide up to 500 ppm of alkali metals and / or alkaline earth metals. In one example, the metal-containing cleaning agent may be present in an amount sufficient to provide about 50 ppm to about 500 ppm of alkali metals and / or alkaline earth metals. In another embodiment, the metal-containing cleaning agent may be present in an amount sufficient to provide about 100 ppm to about 400 ppm of alkali metals and / or alkaline earth metals. In one method, the preferred cleaning agent may be a neutral, low-alkaline, or high-alkaline sulfonate, and in some methods it is a high-alkaline calcium sulfonate. A suitable cleaning agent may be calcium sulfonate having a TBN of 250 or higher (such as about 250 to about 450 or 280 to 400) and providing more than about 50 ppm of calcium to the lubricant. In other methods, the cleaning agent may provide the lubricating composition herein with about 50 ppm to about 500 ppm of calcium, about 100 ppm to about 400 ppm of calcium, or about 100 ppm to about 300 ppm of calcium, or about 100 ppm to 200 ppm of calcium.

[0077] dispersant

[0078] Lubricating compositions may contain one or more dispersants of their choice, or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals before being incorporated into the lubricating composition and typically do not provide any ash when added to the lubricant. Ashless dispersants are characterized by having polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. N-substituted long-chain alkenyl succinimides include polyisobutylene (PIB) substituents, wherein the number-average molecular weight of the polyisobutylene substituent is in the range of about 800 to about 2500, as determined by gel permeation chromatography (GPC) using polystyrene (number-average molecular weight from 180 to about 18,000) as a calibration benchmark. The PIB substituents used in dispersants typically have a viscosity of about 2100 cSt to about 2700 cSt at 100°C, as determined using ASTM D445-18. Succinimidide 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. Succinimidide dispersants are typically composed of polyamines, typically poly(ethylenediamine) imides. The dispersant may comprise two succinimidide moieties linked by a polyamine. The polyamine may be tetraethylenepentamine (TEPA), triethylenetetramine (TETA), pentaethylenehexamine (PEHA), other higher ethylenediamines, and / or mixtures thereof. The polyamine may be a mixture of linear, branched, and cyclic amines. PIB substituents may be linked to each succinimidide moieties.

[0079] In some embodiments, the lubricant composition comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene with a number average molecular weight in the range of about 350 to about 5000, or about 500 to about 3000, as measured by the GPC method described herein. Polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0080] In some embodiments, when polyisobutylene (PIB) is included, it may have terminal double bonds in an amount greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIBs are also referred to as highly reactive PIBs (“HR-PIB”). HR-PIBs with a number average molecular weight in the range of about 800 to about 5000 are suitable for embodiments of this disclosure. Conventional non-highly reactive PIBs typically have terminal double bonds in an amount less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0081] HR-PIB with a number average molecular weight in the range of about 900 to about 3000 is suitable, as measured by the GPC method described herein. This HR-PIB is commercially available or can be synthesized by polymerizing isobutylene in the presence of a non-chlorinated catalyst (e.g., boron trifluoride), as described in U.S. Patents 4,152,499 and 5,739,355. When used in thermal olefin reactions, HR-PIB can improve conversion rates and reduce sediment formation due to enhanced reactivity.

[0082] In some embodiments, the lubricant composition comprises at least one dispersant derived from polyisobutylene succinic anhydride. In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. For example, the dispersant may be described as polyPIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted onto an ethylene-propylene copolymer.

[0083] One suitable class of dispersants is the Mannich base. Mannich bases are substances formed by the condensation of alkyl-substituted phenols, polyalkylene polyamines, and aldehydes (such as formaldehyde) with higher molecular weight alkyl groups. Mannich bases are described in more detail in U.S. Patent 3,634,515.

[0084] Suitable dispersants can be high molecular weight esters or hemiesteramides. Dispersants can 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, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. Suitable post-treatment methods and post-treatment products are described in U.S. Patents 7,645,726, 7,214,649, and 8,048,831.

[0085] Suitable boron compounds that can be used to form the dispersants of the present invention include any boron compound or mixture of boron compounds capable of introducing boron-containing substances into ashless dispersants. Any organic or inorganic boron compound capable of carrying out this reaction can be used. Therefore, boron oxide, boron oxide hydrate, boron trifluoride, boron tribromide, boron trichloride, HBF4, boric acids such as borous acid (e.g., alkyl-B(OH)2 or aryl-B(OH)2), boric acid (i.e., H3BO3), tetraboric acid (i.e., H2B5O7), metaboric acid (i.e., HBO2), ammonium salts of such boric acids, and esters of these boric acids can be used. Using complexes of boron trihalides with ethers, organic acids, inorganic acids, or hydrocarbons is a convenient method for introducing boron reactants into the reaction mixture. Such complexes are known, for example, boron trifluoride-diethyl ether, boron trifluoride-phenol, boron trifluoride-phosphoric acid, boron trichloride-chloroacetic acid, boron tribrom ... Alkane and boron trifluoride-methyl ethyl ether.

[0086] Suitable phosphorus compounds for forming the dispersants of the present invention include phosphorus compounds or mixtures of phosphorus compounds capable of introducing phosphorus-containing substances into ashless dispersants. Therefore, any organic or inorganic phosphorus compound capable of carrying out such a reaction can be used. Thus, such inorganic phosphorus compounds, including inorganic phosphoric acid compounds and inorganic phosphorus oxides, including their hydrates, can be used. Typical organic phosphorus compounds include phosphoric acid-containing peresters and partial esters, such as monophosphates, diesters, triphosphates, thiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid, and tetrathiophosphoric acid; monophosphite, diester, triphosphite, thiophosphorous acid, dithiophosphorous acid, and trithiophosphorous acid; trialkylphosphine oxides: trialkylphosphine sulfides; monoalkylphosphinates and dialkylphosphinates (RPO(OR')(OR"), where R and R' are hydrocarbon groups and R" is hydrogen or a hydrocarbon group), and their mono, di, and trithiophosphinate analogs; monoalkylphosphinates and dialkylphosphinates (RP(OR')(O)). R), where R and R' are hydrocarbon groups, and R" is a hydrogen or hydrocarbon group) and their monothio and dithio analogs; etc. Therefore, compounds such as phosphorous acid (H3PO3, sometimes described as H2(HPO3), sometimes called orthophosphorous acid or phosphonic acid), phosphoric acid (H3PO4, sometimes called orthophosphoric acid), hypophosphorous acid (H4P2O6), metaphosphoric acid (HPO3), pyrophosphoric acid (H4P2O7), hypophosphorous acid (H3PO2, sometimes called hypophosphonic acid), pyrophosphorous acid (H4P2O5, sometimes called pyrophosphonic acid), hypophosphonic acid (H3PO), tripolyphosphoric acid (H5P3O) 10 ), tetrapolyphosphoric acid (H5P4O) 13Phosphoric acid includes trimethomorphic acid (H3P3O9), phosphorus trioxide, phosphorus tetroxide, and phosphorus pentoxide. Some or all of these are sulfur analogues, such as tetrathioacetic acid (H3PS4), thiophosphoric acid (H3PO3S), dithiophosphoric acid (H3PO2S2), trithiophosphoric acid (H3POS3), sesquisulfide, phosphorus heptasulfide, and phosphorus pentasulfide (P2S5, sometimes called P4S). 10 ( ), and can also be used to form the dispersant of this disclosure. Inorganic phosphorus halide compounds, such as PCl3, PBr3, POCl3, PSCl3, etc., can also be used.

[0087] Such organophosphorus compounds can also be used, such as mono, di, and triesters of phosphoric acid (e.g., trialkyl phosphate, dialkyl monoacid phosphate, monoalkyl diacid phosphate, and mixtures thereof), mono, di, and triesters of phosphorous acid (e.g., trialkyl phosphite, dialkyl hydrogen phosphite, alkyl diacid phosphite, and mixtures thereof), esters of phosphonic acids (“primary” RP(O)(OR)2 and “secondary” R2P(O)(OR)), esters of hypophosphonic acids, and phosphonyl halides (e.g., RP(O)Cl2 and R2...). P(O)Cl), halophosphites (e.g., (RO)PCl2 and (RO)2PCl), halophosphates (e.g., ROP(O)Cl2 and (RO)2P(O)Cl), pyrophosphate triesters (e.g., (RO)2P(O)-OP(O)(OR)2), and partial sulfur analogs of any of the aforementioned organophosphorus compounds, wherein each hydrocarbon group contains up to about 100 carbon atoms, or up to about 50 carbon atoms, or up to about 24 carbon atoms, or up to about 12 carbon atoms. Halogenated phosphine halides (e.g., alkyl tetrahalides, dialkyl trihalides, and trialkyl dihalides) and phosphine halides (monohalides and dihalides) may also be used.

[0088] The lubricant described herein may include a mixture of one or more of the above-described boronized and phosphoricated dispersants with non-boronized and non-phosphoricated dispersants.

[0089] In one embodiment, the lubricating composition may comprise at least one borate dispersant, wherein the dispersant is a reaction product of an olefin copolymer or an olefin copolymer with succinic anhydride, and at least one polyamine. The PIBSA:polyamine ratio may be from 1:1 to 10:1, or from 1:1 to 5:1, or from 4:3 to 3:1, or from 4:3 to 2:1. Particularly suitable dispersants contain polyisobutylene groups of PIBSA with a number average molecular weight (Mn) in the range of about 500 to 5000, as determined by the GPC method described herein, and (B) a polyamine having the general formula H2N(CH2). m -[NH(CH2) m ] n —NH2, where m is in the range of 2 to 4 and n is in the range of 1 to 2.

[0090] In addition to the above, the dispersant can be post-treated with aromatic carboxylic acids, aromatic polycarboxylic acids, or aromatic anhydrides, wherein all carboxylic acid or anhydride groups are directly attached to the aromatic ring. The carboxyl-containing aromatic compounds may be selected from 1,8-naphthalenedicarboxylic acid or anhydride and 1,2-naphthalenedicarboxylic acid or anhydride, 2,3-naphthalenedicarboxylic acid or anhydride, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, phthalic anhydride, phenylmethyltetracarboxylic anhydride, 1,2,4-phenyltricarboxylic acid anhydride, biphenyl acid or anhydride, 2,3-pyridinedicarboxylic acid or anhydride, 3,4-pyridinedicarboxylic acid or anhydride, 1,4,5,8-naphthalenetetracarboxylic acid or anhydride, perylene-3,4,9,10-tetracarboxylic acid anhydride, pyrene dicarboxylic acid or anhydride, etc. The molar ratio of this post-treatment component per mole of polyamine reaction can range from about 0.1:1 to about 2:1. In the reaction mixture, the typical molar ratio of this post-treatment component to the polyamine can range from about 0.2:1 to about 2:1. Another usable molar ratio of this post-treatment component to the polyamine can range from 0.25:1 to about 1.5:1. This post-treatment component can react with other components at temperatures ranging from about 140°C to about 180°C.

[0091] Alternatively, or in addition to the post-treatments described above, the dispersant may be post-treated with a non-aromatic dicarboxylic acid or anhydride. The number-average molecular weight of the non-aromatic dicarboxylic acid or anhydride may be less than 500, as measured by the GPC method described herein. Suitable carboxylic acids or their anhydrides may include (but are not limited to) acetic acid or anhydride, oxalic acid and anhydride, malonic acid and anhydride, succinic acid and anhydride, alkenyl succinic acid and anhydride, glutaric acid and anhydride, adipic acid and anhydride, pimelic acid and anhydride, octanoic acid and anhydride, azelaic acid and anhydride, sebacic acid and anhydride, maleic acid and anhydride, fumaric acid and anhydride, tartaric acid and anhydride, glycolic acid and anhydride, 1,2,3,6-tetrahydronaphthalenedicarboxylic acid and anhydride, etc.

[0092] Non-aromatic carboxylic acids or anhydrides react with polyamines in a molar ratio ranging from about 0.1 mol to about 2.5 mol per mole of polyamine. Typically, the amount of non-aromatic carboxylic acid or anhydride used will be relative to the number of secondary amino groups in the polyamine. Thus, about 0.2 to about 2.0 mol of non-aromatic carboxylic acid or anhydride per secondary amino group in component B can react with other components to provide a dispersant according to embodiments of this disclosure. Another molar ratio of non-aromatic carboxylic acids or anhydrides to polyamines that can be used can be from about 0.25:1 to about 1.5:1 per mole of polyamine. Non-aromatic carboxylic acids or anhydrides can react with other components at a temperature of about 140°C to about 180°C.

[0093] The percentage by weight of active ingredient (%) of alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent 5,334,321. The conversion percentage of the polyolefin is calculated from the percentage of active ingredient (%) using the equations in columns 5 and 6 of U.S. Patent 5,334,321.

[0094] The TBN of a suitable borate dispersant can be from about 10 mg to about 65 mg KOH per gram of composition on an oil-free basis, or, if measured based on a dispersant sample containing about 50% dilution oil, it is equivalent to about 5 mg to about 30 mg KOH per gram of composition.

[0095] Typically, the above-mentioned dispersant is provided in the lubricant in an amount of about 1% to about 15% by weight, and in other methods in an amount of about 1.5% to about 8% by weight, and in other methods in an amount of about 2% to about 6% by weight.

[0096] Viscosity modifier

[0097] The lubricating composition may optionally contain one or more viscosity modifiers. Suitable viscosity modifiers may include 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, polymethacrylates, polyacrylates, polyalkylstyrene, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity modifiers may include star polymers, and suitable examples are described in U.S. Publication 2012 / 0101017 A1.

[0098] In addition to or in place of viscosity modifiers, the lubricating compositions described herein may optionally contain one or more dispersant viscosity modifiers. Suitable dispersant viscosity modifiers 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.

[0099] When present, the total amount of viscosity modifier and / or dispersant may be up to about 2.0% by weight, or up to about 1.0% by weight, or up to about 0.5% by weight, or up to about 0.3% by weight, based on the total weight of the lubricating composition.

[0100] Demulsifier

[0101] Demulsifiers include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof, including polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers. When present, the amount of demulsifier in the lubricating composition may be up to about 0.05% by weight, up to about 0.02% by weight, or less than about 0.015% by weight, based on the total weight of the lubricating composition.

[0102] Defoamer

[0103] Defoamers used to reduce or prevent the formation of stable foams include siloxanes, polyacrylates, or organic polymers. Foam inhibitors that can be used in the disclosed compositions include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate. When present, the amount of defoamer in the lubricating composition may be at most about 0.1% by weight, or at most about 0.05% by weight, or less than about 0.04% by weight, based on the total weight of the lubricating composition.

[0104] Generally, the lubricating compositions described herein may include additive components within the range listed in Table 2.

[0105] Table 2

[0106]

[0107] In some cases, the lubricating composition may contain 0.04% to 0.5% by weight of corrosion inhibitor; 0.08% to 0.3% by weight of detergent; 0.15% to 1% by weight of dispersant; 0.2% to 1% by weight of vulcanizing component; 0.05% to 0.5% by weight of anti-wear additive; 0.1% to 0.5% by weight of antioxidant; 0.01% to 0.04% by weight of defoamer; 0% to 5% by weight of viscosity index improver; and the balance being base oil. All weight percentages are based on the total weight of the lubricating composition.

[0108] The percentages for each component above represent the weight percentage of each component based on the total weight of the lubricating composition containing said component. Additives used to formulate the compositions described herein can be blended into the base oil individually or in various sub-combinations. However, it may be suitable to simultaneously blend all components using an additive concentrate (i.e., an additive plus a diluent, such as a hydrocarbon solvent). The use of an additive concentrate utilizes the compatibility offered by the combination of components in additive concentrate form. Furthermore, the use of a concentrate reduces blending time and the possibility of blending errors.

[0109] The lubricant composition described herein exhibits a hydrolytic stability of 0.2 mg / cm³ measured over 96 hours according to ASTM D2619-21. 2 Or even smaller copper weight loss (e.g., 0.03 mg / cm³). 2 0.09 mg / cm 2 Or 0.15 mg / cm 2 According to ASTM D2619-21, the loss of hydrolytic stability over 96 hours can be less than 0.2, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.01 mg / cm³. 2 This test method can distinguish the relative stability of lubricants in the presence of water. Hydrolytically unstable lubricants can form acidic and insoluble contaminants, which can cause hydraulic system failures due to corrosion, valve adhesion, or changes in fluid viscosity.

[0110] The lubricant compositions described herein may have a Rotating Pressure Vessel Oxidation Test (RPVOT) value of at least 350 minutes (e.g., 352 minutes, 438 minutes, or 506 minutes) as measured according to ASTM D2272-22. According to ASTM D2619-21, the RPVOT value can be at least 350 minutes, 355 minutes, 360 minutes, 365 minutes, 370 minutes, 375 minutes, 380 minutes, 385 minutes, 390 minutes, 395 minutes, 400 minutes, 405 minutes, 410 minutes, 415 minutes, 420 minutes, 425 minutes, 430 minutes, 435 minutes, 440 minutes, 445 minutes, 450 minutes, 455 minutes, 460 minutes, 465 minutes, 470 minutes, 475 minutes, 480 minutes, 485 minutes, 490 minutes, 495 minutes, 500 minutes, 505 minutes, 510 minutes, 515 minutes, 520 minutes, or 525 minutes within 96 hours. RPVOT can provide an estimate of the oxidative stability of the lubricant.

[0111] The lubricant compositions described herein can have a four-ball wear value of less than 0.6 mm (e.g., 0.58 mm, 0.52 mm, or 0.48 mm) as measured according to ASTM D4172-21. According to ASTM D4172-21, the four-ball wear value can be less than about 0.6 mm, 0.59 mm, 0.58 mm, 0.57 mm, 0.56 mm, 0.55 mm, 0.54 mm, 0.53 mm, 0.52 mm, 0.51 mm, 0.5 mm, 0.49 mm, 0.48 mm, 0.47 mm, 0.46 mm, or 0.45 mm. This test method can determine the relative anti-wear properties of the lubricating fluid in sliding contact using a four-ball wear tester.

[0112] Usage and System

[0113] This document also discloses methods of using lubricant compositions. In some examples, the lubricant composition may be located within a chamber of a hydraulic system. Non-limiting examples of hydraulic systems include applications for mobile machinery, such as construction equipment including wheel loaders, excavators, backhoe excavators, bulldozers, graders, skid-steer loaders, articulated trucks, compact track loaders, or compactors. Other non-limiting examples of hydraulic systems include parts and components for transportation and industrial applications, such as offshore oil and gas, cement manufacturing, off-highway equipment, assembly plants, subsea hydraulic systems, pulp and paper, glass, shipyards, food processing, marine, power generation, rubber and plastics, or metal manufacturing.

[0114] This document also discloses a method for lubricating hydraulic components. Examples of suitable components may include hydraulic systems for construction equipment, offshore oil and gas equipment, cement manufacturing equipment, off-highway equipment, assembly plant equipment, subsea hydraulic systems, pulp and paper equipment, glass equipment, shipyards, food processing equipment, marine equipment, power generation equipment, rubber and plastic equipment, or metal manufacturing equipment. One method for lubricating a hydraulic component may include lubricating the component with a lubricant comprising an ashless dithiophosphate, a dialkyl dithiophosphate metal salt, a corrosion inhibitor comprising an alkyltriazole derivative, and a major amount of a base oil. The lubricant may contain an ashless dithiophosphate in an amount sufficient to provide a phosphorus concentration of 9 ppm to 40 ppm to the lubricant composition. The dialkyl dithiophosphate metal salt may comprise (or) zinc dialkyl dithiophosphate (ZDDP). The lubricant may contain ZDDP or other suitable dialkyl dithiophosphate metal salts in an amount sufficient to provide a phosphorus concentration in the range of 65 ppm to 285 ppm to the lubricant composition. The lubricant may contain a corrosion inhibitor in an amount sufficient to provide a nitrogen concentration in the range of 0.75 ppm to 15 ppm to the lubricant composition. In some examples, the method may include lubricating equipment used in transportation applications, mobile machinery applications, or industrial applications.

[0115] definition

[0116] The following terminology definitions are provided to clarify the meaning of certain terms as used herein.

[0117] The terms “lubricating oil,” “lubricant composition,” “lubricating composition,” “lubricant,” and “transmission system lubricating composition” refer to finished lubricating products that contain a major amount of base oil plus a small amount of additives.

[0118] As used herein, the terms “additive package,” “additive concentrate,” and “additive composition” refer to a portion of a lubricating oil composition that does not include a major amount of base oil.

[0119] As used herein, the terms "hydrocarbon substituent" or "hydrocarbon group" are used in their common sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly connected to the rest of the molecule and having predominantly hydrocarbon characteristics. Each hydrocarbon group is independently selected from hydrocarbon substituents and hydrocarbon substituents containing one or more of a halogen group, hydroxyl group, alkoxy group, mercapto group, nitro group, nitroso group, amino group, pyridyl group, furanyl group, imidazolyl group, oxygen, and nitrogen, and wherein there are no more than two non-hydrocarbon substituents present for every ten carbon atoms in the hydrocarbon group.

[0120] As used herein, unless otherwise expressly stated, the terms “weight percentage” or “weight %” mean the percentage of the said component by weight of the whole composition.

[0121] As used herein, the terms “soluble,” “oil-soluble,” or “dispersible” may, but do not necessarily, indicate that a compound or additive is soluble, miscible, or capable of being suspended in oil in all proportions. However, the foregoing terms do mean that they are, for example, soluble, suspended, dispersible, or stably dispersed in oil to a degree sufficient to exert their intended effect in an environment where oil is used. Furthermore, if desired, additional admixtures may be permitted at higher levels of specific additives.

[0122] As used herein, the term "alkyl" refers to a straight-chain, branched, cyclic, and / or substituted saturated chain moiety of about 1 to about 200 carbon atoms. In one embodiment, it refers to an unsubstituted straight-chain, branched, or cyclic chain moiety.

[0123] As used herein, the term "alkenyl" refers to a straight-chain, branched, cyclic, and / or substituted unsaturated chain moiety of about 3 to about 30 carbon atoms. In one embodiment, it refers to an unsubstituted straight-chain, branched, or cyclic chain moiety.

[0124] As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds, which may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halogen substituents and / or heteroatoms including but not limited to nitrogen and oxygen.

[0125] As used herein, “number-average molecular weight” or “Mn” was determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (where Mn was approximately 180 to approximately 18,000 as a calibration reference).

[0126] It should be understood that throughout this disclosure, the terms “comprising,” “including,” “containing,” etc., are considered open-ended and include any element, step, or ingredient not expressly listed. The phrase “consisting substantially of…” means including any expressly listed element, step, or ingredient, as well as any additional element, step, or ingredient that does not substantially affect the basic and novel aspects of the invention. This disclosure also considers that any composition described using the terms “comprising,” “including,” or “containing” is also to be interpreted as including the disclosure of the same composition “consisting substantially of its specifically listed components” or “consisting of its specifically listed components.”

[0127] Example

[0128] The following examples will further clarify a better understanding of this disclosure and its many advantages. These examples are illustrative and do not limit the 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 discussed in the following examples and throughout the disclosure, claims, and examples, all percentages, ratios, and parts mentioned in this disclosure are by weight. Any standardized test methods pointed to in the examples, disclosure, or claims, unless obvious from the context of their use, refer to a version of a test method publicly available at the time of filing this disclosure.

[0129] Examples of preparations of the lubricant compositions described herein and performance evaluations were conducted. Working examples and comparative examples were prepared according to the compositions in Table 3 and tested according to the standard tests in Table 4. The formulations of the present invention in Examples 1 and 2 shown in Table 3 contain the same amount of alkyltriazole derivatives as corrosion inhibitors and the same amount of ashless dithiophosphate. The difference between Examples 1 and 2 is that Example 1 uses primary ZDDP, while Example 2 contains secondary (branched) ZDDP. One or more of the three main components in Comparative Examples 1-5 lack or use toluenetriazole or its derivatives as corrosion inhibitors. Each evaluated lubricant contains the same base additive package (except for the metal dithiophosphate, ashless dithiophosphate, and corrosion inhibitor components (as shown in Table 3)) and contains the same dispersants, antioxidants, defoamers, and viscosity modifiers. The formulations of the present invention and comparative formulations were tested at their respective processing rates in the same base oil blends of API Group II base oils to obtain a finished fluid (ASTM D445) with a kV of approximately 9 cSt at 100°C.

[0130] Table 3

[0131]

[0132] Ashless dithiophosphate is 3-[[bis(2-methylpropoxy)thiophosphino]thio]-2-methylpropionic acid, which can be used as Irgalube ® 353 was obtained from BASF (Ludwigshafen, Germany).

[0133] Burr ZDDP is a standard ZDDP, for example, it can be used as HiTEC. ® 680 was obtained from Afton Chemical Corp., Richmond, VA.

[0134] Zhong ZDDP is a standard ZDDP, for example, it can be used as HiTEC. ®704 was obtained from Afton Chemical Corp., Richmond, VA.

[0135] Corrosion inhibitor 1 (C1) is available from Vanderbilt Worldwide Ltd. (Nantwich, UK) as Cuvan. ™ 313. Cuvan ™ 313 is N,N-bis(2-ethylhexyl)-1H-1,2,4-triazol-1-methylamine.

[0136] Corrosion inhibitor 2 (C2) is available from BASF (Ludwigshafen, Germany) and is produced by Irgamet. ® 39. Irgamet ® 39 is a toluenetriazole derivative.

[0137] Corrosion inhibitor 3 (C3) is Cobratec, available from Sherwin-Williams. ® TT-100. TT-100 is toluenetriazole.

[0138] Each lubricant composition was formulated to provide the target concentrations of phosphorus (P) and nitrogen (N) as shown in Table 3.

[0139] Table 4

[0140]

[0141] In Examples 1 and 2, the combination of ashless dithiophosphate, metal dithiophosphate, and alkylated triazole derivatives provides both wear protection and oxidation protection, while also providing hydrolytic stability. Without the use of phosphorus compounds, the hydrolytic stability of the fluid is maintained; however, the fluid exhibits poor performance in oxidation and wear resistance tests, as in Comparative Example 1. If the total phosphorus content is maintained as in Examples 1 and 2, but ashless dithiophosphate is not used, the lubricant becomes hydrolytically unstable, as in Comparative Example 2. In Comparative Example 3, the total phosphorus content is maintained and the desired anti-wear performance is preserved; however, in the absence of metal dithiophosphate, oxidation performance is poor and the lubricant is hydrolytically unstable. If the same anti-wear system used in the examples is employed, but the corrosion inhibitor is toluenetriazole or a derivative thereof, the oxidation protection of the lubricant decreases and the lubricant becomes hydrolytically unstable, as in Comparative Examples 4 and 5.

[0142] The combination of anti-wear and alkylated triazole provides protection across all three desired hydraulic fluid properties.

[0143] While various embodiments of this disclosure have been described to achieve the various objectives of this disclosure, it should be understood that these embodiments are merely illustrative of the principles of this disclosure. Many modifications and adaptations thereto will be apparent to those skilled in the art without departing from the spirit and scope of this disclosure as defined in the appended claims.

[0144] Other embodiments of this disclosure will be apparent to those skilled in the art upon consideration of this specification and the practices of the embodiments disclosed herein. As used throughout the specification and claims, “a” and / or “an” may refer to one or more. Unless otherwise specified, all figures expressing quantities of components and properties, such as molecular weight, percentage, ratio, reaction conditions, etc., used in the specification should be understood to be modified by the term “about” in all instances, regardless of whether the term “about” is present. Therefore, unless indicated to the contrary, the numerical parameters set forth in this specification are approximations that may vary depending on the desired properties 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. Although the numerical ranges and parameters set forth in the broad scope of this disclosure are approximations, the values ​​set forth in particular embodiments are reported as precisely as possible. However, any numerical value inherently contains some error necessarily caused by the standard deviation found in its corresponding test measurement.

[0145] 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.

[0146] 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, the range 1-4 will be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, as well as any range of these values, such as 1-4, 1-3, 1-2, 2-4, 2-3, etc.

[0147] 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 a 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.

[0148] 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.

[0149] It should be understood that although the lubricating compositions and formulations of this disclosure have been described in conjunction with their detailed description and summary herein, the foregoing description is intended to be illustrative and not limiting of the scope of this disclosure, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are also within the scope of the claims. This specification and the examples are intended to be illustrative only, wherein the true scope of this disclosure is indicated by the appended claims.

[0150] Exemplary implementation plan

[0151] Clauses (1) through (27) numbered below represent embodiments of the invention. These clauses are not claims of this application. Claims appear in the following sections below the exemplary embodiments (1) through (27).

[0152] As used below, any reference to a composition, method, system or use shall be construed as a separate reference to each of those compositions, methods, systems or uses (e.g., “illustrative embodiments (1) through (4) shall be construed as illustrative embodiments (1), (2), (3) or (4)”).

[0153] Exemplary embodiment (1): A lubricant composition comprising:

[0154] Ashless dithiophosphate;

[0155] Dialkyl dithiophosphate metal salts;

[0156] A corrosion inhibitor comprising an alkyltriazole derivative, said corrosion inhibitor being present in an amount sufficient to provide the lubricant composition with a nitrogen concentration ranging from 0.75 ppm to 100 ppm; and

[0157] The main component is base oil.

[0158] Exemplary embodiment (2): the lubricant composition according to (1), wherein the ashless dithiophosphate comprises 3-[[bis(2-methylpropoxy)thiophosphino]thio]-2-methylpropionic acid, ethyl 3-[[bis(1-methylpropoxy)thiophosphino]thio]propionate or a combination thereof.

[0159] Exemplary embodiment (3): The lubricant composition according to (1) or (2), wherein the ashless dithiophosphate is present in an amount sufficient to provide the lubricant composition with a phosphorus concentration ranging from 10 ppm to 250 ppm or from 8 ppm to 40 ppm.

[0160] Exemplary embodiment (4): a lubricant composition according to any one of (1) to (3), wherein the dialkyl dithiophosphate metal salt comprises (or) zinc dialkyl dithiophosphate (ZDDP), wherein the ZDDP comprises primary ZDDP, secondary ZDDP or a combination thereof.

[0161] Exemplary embodiment (5): a lubricant composition according to any one of (1) to (4), wherein the dialkyl dithiophosphate metal salt is present in an amount sufficient to provide the lubricant composition with a phosphorus concentration in the range of 50 ppm to 1000 ppm or 50 ppm to 300 ppm.

[0162] Exemplary embodiment (6): a lubricant composition according to any one of (1) to (5), wherein the corrosion inhibitor comprises N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methylamine.

[0163] Exemplary embodiment (7): a lubricant composition according to any one of (1) to (6), wherein the corrosion inhibitor is present in an amount sufficient to provide the lubricant composition with a nitrogen concentration in the range of 0.75 ppm to 15 ppm.

[0164] Exemplary embodiment (8): a lubricant composition according to any one of (1) to (7), wherein the corrosion inhibitor is substantially free of (in other embodiments) benzotriazole and benzotriazole derivatives.

[0165] Exemplary embodiment (9): a lubricant composition according to any one of (1) to (8), wherein the corrosion inhibitor is substantially free of (in other embodiments) toluenetriazole and toluenetriazole derivatives.

[0166] Exemplary embodiment (10): a lubricant composition according to any one of (1) to (9), wherein the composition has a copper weight loss of 0.2 mg / cm2 or less measured in a hydrolytic stability test according to ASTM D2619-21 within 96 hours.

[0167] Exemplary embodiment (11): a lubricant composition according to any one of (1) to (10), wherein the composition has a rotating pressure vessel oxidation test (RPVOT) value of at least 350 minutes as measured according to ASTM D2272-22.

[0168] Exemplary embodiment (12): a lubricant composition according to any one of (1) to (11), wherein the composition has a 4-ball wear value of less than 0.60 mm as measured according to ASTM D4172-21.

[0169] Exemplary embodiment (13): The lubricant composition according to any one of (1) to (12) further comprises a dispersant, a detergent, a friction modifier or a combination thereof.

[0170] Exemplary embodiment (14): The lubricant composition according to any one of (1) to (12) comprises, in addition to the ashless dithiophosphate, dialkyl dithiophosphate metal salt and corrosion inhibitor, the following components (or is substantially composed of the following components):

[0171] A corrosion inhibitor in amounts ranging from 0% to 1% by weight (or 0.04% to 0.5% by weight);

[0172] -0.05% to 0.5% by weight (or 0.08% to 0.3% by weight) of cleaning agent;

[0173] -0.1% to 2% by weight (or 0.15% to 1% by weight) of dispersant;

[0174] -0.05% by weight to 1.5% by weight (or 0.2% by weight to 1% by weight) of the vulcanizing component;

[0175] -0.01% to 1.5% by weight (or 0.05% to 0.5% by weight) of anti-wear additive;

[0176] -0.05% to 0.6% by weight (or 0.1% to 0.5% by weight) of antioxidant;

[0177] -0% to 0.05% by weight (or 0.01% to 0.04% by weight) of defoamer;

[0178] -0% to 10% by weight (or 0% to 5% by weight) of viscosity index improver; and

[0179] - Balance of base oil.

[0180] Exemplary embodiment (15): The lubricant composition according to any one of (1) to (12) further comprises, in addition to the ashless dithiophosphate, dialkyl dithiophosphate metal salt, corrosion inhibitor and base oil, the following components:

[0181] - For example, a dispersant in amounts of 0.1% to 2% by weight (or 0.15% to 1% by weight);

[0182] - For example, an amount of antioxidant of 0.05% to 0.6% by weight (or 0.1% to 0.5% by weight);

[0183] - For example, a defoamer in amounts of 0% to 0.05% by weight (or 0.01% to 0.04% by weight); and

[0184] - For example, a viscosity index improver in amounts of 0% to 10% by weight (or 0% to 5% by weight).

[0185] Exemplary embodiment (16): A hydraulic system comprising a lubricant composition as defined in any one of (1) to (15).

[0186] Exemplary embodiment (17): A method for lubricating a hydraulic component, the method comprising lubricating the component with a lubricant composition as defined in any one of (1) to (15).

[0187] Example implementation (18): The method according to (17) wherein the hydraulic component is used in a vehicle application, a mobile machinery application or an industrial application.

[0188] Example implementation (19): According to the method of (18), the mobile machinery application includes construction equipment.

[0189] Example implementation (20): According to the method of (19), the construction equipment includes wheel loaders, excavators, backhoe excavators, bulldozers, graders, skid steer loaders, articulated trucks, compact track loaders or compactors.

[0190] Exemplary implementation (21): According to the method of (18), the industrial applications include offshore oil and gas, cement manufacturing, off-highway equipment, assembly plants, subsea hydraulic systems, pulp and paper, glass, shipyards, food processing, ships, power generation, rubber and plastics or metal manufacturing.

[0191] Exemplary embodiment (22): A method for preparing a lubricant composition, the method comprising combining an ashless dithiophosphate, a dialkyl dithiophosphate metal salt, a corrosion inhibitor comprising an alkyltriazole derivative and a major amount of a base oil to produce a lubricant composition as defined in any one of (1) to (15).

[0192] Example embodiment (23): Use of ashless dithiophosphate, dialkyl dithiophosphate metal salt and corrosion inhibitors containing alkyltriazole derivatives in hydraulic fluids to inhibit wear and oxidation while maintaining hydrolytic stability, wherein the hydraulic fluid is preferably defined as in any one of (1) to (15).

[0193] Exemplary embodiment (24): Use of ashless dithiophosphate in hydraulic fluids to inhibit wear and oxidation while maintaining the hydrolytic stability of the fluid, wherein the hydraulic fluid contains an amount of dialkyl dithiophosphate metal salt sufficient to provide the lubricant composition with a phosphorus concentration in the range of 50 ppm to 1000 ppm, plus an amount of corrosion inhibitor comprising an alkyltriazole derivative sufficient to provide the lubricant composition with a nitrogen concentration in the range of 0.75 ppm to 100 ppm; and wherein preferably the hydraulic fluid is as defined in any one of (1) to (15).

[0194] Exemplary embodiment (25): Use of a dialkyl dithiophosphate metal salt in a hydraulic fluid to inhibit wear and oxidation while maintaining the hydrolytic stability of the fluid, wherein the hydraulic fluid comprises an amount of ashless dithiophosphate sufficient to provide the lubricant composition with a phosphorus concentration in the range of 10 ppm to 250 ppm, plus an amount of corrosion inhibitor comprising an alkyltriazole derivative sufficient to provide the lubricant composition with a nitrogen concentration in the range of 0.75 ppm to 100 ppm; and wherein preferably the hydraulic fluid is as defined in any one of (1) to (15).

[0195] Exemplary embodiment (26): Use of a combination of ashless dithiophosphate and dialkyl dithiophosphate metal salt in a hydraulic fluid to inhibit wear and oxidation while maintaining the hydrolytic stability of the fluid, wherein the hydraulic fluid contains an amount of alkyltriazole derivative sufficient to provide the lubricant composition with a nitrogen concentration in the range of 0.75 ppm to 100 ppm; and wherein preferably the hydraulic fluid is as defined in any one of (1) to (15).

[0196] Exemplary embodiment (27): Use of a corrosion inhibitor comprising an alkyltriazole derivative in a hydraulic fluid to improve hydrolytic stability and inhibit oxidation while maintaining the anti-wear properties of the fluid, wherein the hydraulic fluid comprises an amount of ashless dithiophosphate sufficient to provide the lubricant composition with a phosphorus concentration in the range of 10 ppm to 250 ppm, plus an amount of dialkyl dithiophosphate metal salt sufficient to provide the lubricant composition with a phosphorus concentration in the range of 50 ppm to 1000 ppm; and wherein preferably the hydraulic fluid is as defined in any one of (1) to (15).

Claims

1. A lubricant composition comprising: Ashless dithiophosphate; Dialkyl dithiophosphate metal salts; A corrosion inhibitor comprising an alkyltriazole derivative, said corrosion inhibitor being present in an amount sufficient to provide the lubricant composition with a nitrogen concentration ranging from 0.75 ppm to 100 ppm; and The main component is base oil.

2. The lubricant composition according to claim 1, wherein the ashless dithiophosphate comprises 3-[[bis(2-methylpropoxy)thiophosphino]thio]-2-methylpropionic acid, ethyl 3-[[bis(1-methylpropoxy)thiophosphino]thio]propionate, or a combination thereof; and / or wherein the ashless dithiophosphate is present in an amount sufficient to provide a phosphorus concentration in the range of 10 ppm to 40 ppm to the lubricant composition.

3. The lubricant composition of claim 1, wherein the dialkyl dithiophosphate metal salt comprises primary zinc dialkyl dithiophosphate (ZDDP), secondary ZDDP, or a combination thereof; and / or wherein the dialkyl dithiophosphate metal salt is present in an amount sufficient to provide the lubricant composition with a phosphorus concentration in the range of 50 ppm to 300 ppm.

4. The lubricant composition of claim 1, wherein the corrosion inhibitor comprises N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methylamine; and / or wherein the corrosion inhibitor is present in an amount sufficient to provide the lubricant composition with a nitrogen concentration in the range of 0.75 ppm to 15 ppm; and / or wherein the corrosion inhibitor is substantially free of benzotriazole and benzotriazole derivatives.

5. The lubricant composition of claim 1, wherein the corrosion inhibitor is substantially free of toluenetriazole and toluenetriazole derivatives.

6. The lubricant composition according to claim 1, wherein the composition has a hydrolytic stability of 0.2 mg / cm³ measured within 96 hours according to ASTM D2619-21 in a hydrolytic stability test. 2 Or less copper weight loss; and / or said composition has a Rotating Pressure Vessel Oxidation Test (RPVOT) value of at least 350 minutes as measured according to ASTM D2272-22; and / or said composition has a 4-ball wear value of less than 0.60 mm as measured according to ASTM D4172-21.

7. The lubricant composition according to claim 1, wherein the lubricant composition further comprises a dispersant, a detergent, a friction modifier, or a combination thereof.

8. A hydraulic system comprising the lubricant composition according to claim 1.

9. A method for lubricating a hydraulic component, the method comprising lubricating the component with a lubricant composition according to claim 1.

10. The method of claim 9, wherein the hydraulic component is used in transportation applications, mobile machinery applications, or industrial applications.

11. The method of claim 10, wherein the mobile mechanical equipment application includes construction equipment.

12. The method of claim 11, wherein the construction equipment includes a wheel loader, excavator, backhoe excavator, bulldozer, grader, skid steer loader, articulated truck, compact track loader, or compactor.

13. The method of claim 10, wherein the industrial applications include offshore oil and gas, cement manufacturing, off-highway equipment, assembly plants, subsea hydraulic systems, pulp and paper, glass, shipyards, food processing, marine, power generation, rubber and plastics or metal manufacturing.

14. A method for preparing a lubricant composition, the method comprising: Ashless dithiophosphate, dialkyl dithiophosphate metal salt, corrosion inhibitor containing alkyl triazole derivative, and base oil in a major amount are combined to produce the lubricant composition according to claim 1.

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