Ultra-low ash lubricant composition

Abstract

This invention provides a lubricating oil composition that is essentially ZnDTP-free and improves the copper corrosion resistance of the lubricating oil when a high level of molybdenum is used, and a method for improving the copper corrosion resistance of an engine. [Solution] A lubricating oil composition is provided that has a sulfur content of up to 0.4% by weight and a sulfated ash content of up to 0.6% by weight as measured by ASTM D874, and comprises a main amount of base oil, at least 0.02% by weight of a triazole compound, less than about 1.3% by weight of a diphenylamine antioxidant, and at least 900 ppm of molybdenum from a molybdenum-containing compound, and is essentially ZnDTP-free. Also provided is a method for reducing wear and copper corrosion in engines equipped with a diesel particulate filter (DPF) or gasoline particulate filter (GPF) aftertreatment system.

Description

[Background technology]

[0001] Exhaust aftertreatment devices installed in internal combustion engines to comply with emission regulations have proven susceptible to the effects of combustion caused by by-products of the fuel and lubricants used in the engine. Furthermore, certain types of devices are susceptible to one or more of the following: (1) phosphorus from lubricants, (2) sulfur from both fuel and lubricants, and (3) sulfated ash from the combustion of fuel and lubricants. To ensure the durability of various types of aftertreatment devices, special lubricants have been developed that, for example, have relatively low levels of sulfur, phosphorus, and sulfated ash.

[0002] Several challenges exist when formulating automotive engine lubricants that do not inherently contain zinc dialkyldithiophosphate (ZnDTP). ZnDTP is a versatile wear-resistant / antioxidant component that provides good wear and beneficial oxidation protection under harsh conditions. However, ZnDTP contains elements such as zinc, sulfur, and phosphorus, all of which have adverse effects on exhaust gas aftertreatment systems.

[0003] To compensate for the loss of wear resistance and oxidation resistance from ZnDTP, molybdenum-containing lubricant compositions were developed that, while having relatively low levels of sulfated ash, advantageously achieve high wear suppression when used in internal combustion engines. However, the problem encountered when using high levels of molybdenum to compensate for the loss of ZnDTP was the copper corrosion resistance of the lubricant.

[0004] The above problems need to be solved. The original engine manufacturer needed the lubricant to be certified as suitable for engine use by passing the ASTM D6594 test (HTCBT) and the ASTM D130 test (copper strip corrosion test). The challenge with ZnDTP-free oil is to develop a lubricant composition that maintains the wear resistance of conventional automotive lubricants while preventing corrosion and ensuring the durability of various types of aftertreatment devices. The inventors have developed a solution to this problem.

[0005] The inventors have discovered that not all copper corrosion inhibitors can provide sufficient copper corrosion resistance in oils that are high in molybdenum and essentially ZnDTP-free. A specific chemical composition is required. In addition, this chemical composition allows the molybdenum-containing lubricating oil composition of the present invention to achieve high wear suppression performance while simultaneously allowing the use of relatively low levels (or substantially no phosphorus and zinc) content. [Overview of the project]

[0006] This disclosure relates to a lubricating oil composition that generally has a sulfur content of up to 0.4% by weight and a sulfated ash content of up to 0.6% by weight as measured by ASTM D874, and comprises a main amount of base oil, at least 0.02% by weight of a triazole compound, less than about 1.3% by weight of a diphenylamine antioxidant, and at least 900 ppm of molybdenum from a molybdenum-containing compound, and is essentially ZnDTP-free.

[0007] The present invention also provides a method for reducing engine wear and copper corrosion, comprising lubricating an engine with a lubricating oil composition having a sulfur content of up to 0.4% by weight and a sulfated ash content of up to 0.6% by weight as measured by ASTM D874, and comprising a main amount of base oil, at least 0.02% by weight of a triazole compound, less than about 1.3% by weight of a diphenylamine antioxidant, and at least 900 ppm of molybdenum from a molybdenum-containing compound, wherein the lubricating oil composition is essentially ZnDTP-free, and the engine is equipped with a diesel particulate filter (DPF) or gasoline particulate filter (GPF) aftertreatment system. [Modes for carrying out the invention]

[0008] To facilitate understanding of the subject matter disclosed herein, some terms, abbreviations, or other abbreviations used herein are defined below. Any terms, abbreviations, or abbreviations not defined here shall be understood to have the ordinary meanings used by those skilled in the art at the time of filing of this application.

[0009] Definition: In this specification, when the following words and expressions are used, they have the following meanings.

[0010] "Major amount" means more than 50% by weight of the composition.

[0011] "Minor amount" means, with respect to the additives described, that the amount indicated with respect to the total mass of all additives present in the composition, recognized as the active ingredient of one or more additives, is less than 50% by weight of the composition.

[0012] "Active ingredient" or "active substance" refers to an additive material that is not a diluent or solvent.

[0013] All percentages reported are, unless otherwise specified, weight percentages based on the active ingredient (i.e., independent of the carrier or diluent oil).

[0014] The abbreviation "ppm" means what percentage by weight per million based on the total weight of the lubricating oil composition.

[0015] The high temperature high shear (HTHS) viscosity at 150 °C was determined in accordance with ASTM D4683.

[0016] The kinematic viscosity (KV 100 ) at 100 °C was determined in accordance with ASTM D445.

[0017] Metal - The term "metal" refers to an alkali metal, an alkaline earth metal, or a mixture thereof.

[0018] Throughout this specification and the claims, the terms oil-soluble or oil-dispersible are used. Oil-soluble or oil-dispersible means that an amount necessary to provide a desired level of activity or performance can be incorporated by dissolving, dispersing, or suspending it in a lubricating oil. Typically, this means that at least about 0.001% by weight of the material can be incorporated into a lubricating oil composition. For further consideration of the terms oil-soluble and dispersible, and in particular “stable dispersibility,” see U.S. Patent No. 4,320,019. Relevant teachings in this regard are expressly incorporated herein by reference.

[0019] As used herein, the term "sulfated ash" refers to the non-flammable residue resulting from detergents and metal additives in lubricating oils. Sulfated ash can be measured using ASTM Test D874.

[0020] As used herein, the term "Total Base Number" or "TBN" refers to the amount of base equivalent to the number of milligrams of KOH in one gram of sample. Therefore, a higher TBN value reflects an increase in alkalinity, as it indicates a greater amount of alkaline products. TBN was measured using the ASTM D 2896 test.

[0021] The content of boron, calcium, magnesium, molybdenum, phosphorus, sulfur, and zinc was measured according to ASTM D5185.

[0022] All ASTM standards mentioned herein are the latest versions available as of the filing date of this application.

[0023] While various modifications and alternative forms are possible with respect to this disclosure, specific embodiments are described in detail herein. However, the description of specific embodiments herein is not intended to limit this disclosure to any particular form disclosed, but rather to be understood as encompassing all modifications, equivalents, and alternatives that fall within the spirit and scope of the disclosure as defined by the appended claims.

[0024] Not all actions described in the general description or examples are necessarily required, some specific actions may not be necessary, and one or more additional actions may be performed in addition to those described. Furthermore, the order in which actions are listed does not necessarily indicate the order in which they are performed.

[0025] This specification describes benefits, advantages, and solutions to problems relating to specific embodiments. However, any benefits, advantages, solutions, and potentially multiple features that may be induces or make more pronounced benefits, advantages, or solutions should not be construed as material, required, or essential features of any claim, in whole or in part.

[0026] The details and examples of embodiments described herein are intended to provide a general understanding of the structures of various embodiments.

[0027] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variation thereof, encompass the situation of non-exclusive inclusion. For example, a process, method, item, or apparatus that includes a list of features is not necessarily limited to those features, but may include other features not expressly enumerated or other features specific to such process, method, item, or apparatus. Furthermore, unless explicitly stated otherwise, “or” refers to a comprehensive OR, not an exclusive OR. For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0028] The use of “a” or “an” is adopted to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the embodiments of this disclosure. This description should be read as including one or at least one unless it becomes clear that there are other meanings, and singular forms include plural forms, and vice versa. The term “mean” means the mean, geometric mean, or median when referring to a value. The group numbers corresponding to columns in the periodic table of elements use the rules of “New Notation” found in the CRC Handbook of Chemistry and Physics, 81st edition (2000-2001).

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in which this disclosure pertains. Materials, methods, and examples are for illustrative purposes only and are not intended to limit the scope of this disclosure. Many details relating to specific materials and processing practices, beyond what is described herein, are conventional and can be found in texts and other sources within the lubricants and petroleum and gas industries.

[0030] This specification and its examples are not intended to serve as a comprehensive and exhaustive description of all elements and features of formulations, compositions, apparatus and systems that use the structures or methods described herein. Furthermore, separate embodiments may be combined into a single embodiment, and conversely, for brevity, various features described in the context of a single embodiment may be provided separately or in any partial combination. Additionally, any values ​​listed within a range include all values ​​within that range. Many other embodiments may become apparent to those skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure to enable structural substitutions, logical substitutions, or other modifications without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative rather than restrictive.

[0031] Triazole compounds All species containing a triazole moiety are useful in the compositions according to this disclosure.

[0032] The compositions of this disclosure typically contain about 0.02 to about 1.0 weight percent of triazole, but may also contain about 0.02 to 0.08 weight percent, 0.02 to 0.07 weight percent, 0.02 to 0.06 weight percent, or 0.02 to about 0.5 weight percent of the triazole compound. In some embodiments, the compositions of the present invention contain 1 weight percent or less, 0.75 weight percent or less, or even 0.5 weight percent or less of the triazole compound. In some embodiments, the compositions of the present invention contain at least 0.02 weight percent, 0.03 weight percent, 0.04 weight percent, 0.05 weight percent, 0.07 weight percent, or even 0.1 weight percent of triazole. The triazole compound may be substituted with a hydrocarbyl moiety.

[0033] The triazoles of this disclosure may have MWs of approximately 70 to approximately 1000 g / mol, approximately 70 to approximately 950 g / mol, approximately 70 to approximately 900 g / mol, approximately 70 to approximately 850 g / mol, approximately 70 to approximately 800 g / mol, approximately 70 to approximately 750 g / mol, approximately 70 to approximately 700 g / mol, approximately 70 to approximately 650 g / mol, approximately 70 to approximately 600 g / mol, approximately 70 to approximately 550 g / mol, or approximately 70 to approximately 500 g / mol.

[0034] In one embodiment, the triazole of the present disclosure does not contain an active sulfur group.

[0035] Alkyl and aryl derivatives of triazoles are preferred. The most preferred is tolyltriazole. These may be substituted or unsubstituted.

[0036] As used herein, the terms “hydrocarbon,” “hydrocarbyl,” or “hydrocarbon-based” mean that the parts described have primarily hydrocarbon properties within the context of this disclosure. These include parts that are essentially pure hydrocarbons, i.e., parts containing only carbon and hydrogen. They may also include parts that contain substituents or atoms that do not alter the primary hydrocarbon properties of the part. Such substituents may include halos, alkoxys, nitros, and so on. These parts may also contain heteroatoms. Suitable heteroatoms will be obvious to those skilled in the art and will include, for example, sulfur, nitrogen, oxygen, and phosphorus. Thus, while maintaining the properties of the primary hydrocarbon within the context of the invention, these parts may also contain atoms other than carbon that are present in a chain or ring otherwise composed of carbon atoms. For example, alkyl and aryl groups are hydrocarbyl groups.

[0037] As an example, triazole compounds can be substituted with monocyclic or multicyclic aryl moieties, such as substituted or unsubstituted aryl moieties containing covalent rings. Non-limiting examples of substituted aromatic moieties containing covalent rings include biphenyl, 1,1′-binaphthyl, p,p′-vitryl, and biphenylenyl. As another example, the aryl moiety may contain multiple fused rings. Non-limiting examples of aryl moieties containing multiple fused rings include naphthyl, anthryl, pyrenyl, phenantrenyl, and phenalenyl. As yet another example, the aryl moiety may contain a monocyclic ring covalently bonded to the triazole. Non-limiting examples of aryl moieties containing a monocyclic ring covalently bonded to the triazole include phenyl. As yet another example, the aryl moiety may contain a monocyclic ring condensed to the triazole. Non-limiting examples of aryl moieties containing a monocyclic ring condensed to the triazole include benzotriazole and tolyltriazole.

[0038] The substituted triazoles of the present invention can be prepared by condensing basic triazoles with aldehydes and amines via their acidic -NH groups. In some embodiments, the substituted triazole is the reaction product of a triazole, an aldehyde, and an amine. Suitable triazoles that can be used to prepare the substituted triazoles of the present disclosure include triazole, alkyl-substituted triazole, benzotriazole, tolyltriazole, or other aryltriazoles. Suitable aldehydes include reactive equivalents such as formaldehyde and formalin. Suitable amines include primary or secondary amines. In some embodiments, the amine is a secondary amine and further a branched amine. In yet another embodiment, the amine is a beta-branched amine, such as bis-2-ethylhexylamine.

[0039] The triazoles of the present disclosure have the following structure:

Chemical formula

[0040] In one example, the triazole may have the following structure (IX) or (X):

Chemical formula

[0041] Molybdenum-containing compounds Organic molybdenum compounds contain at least a molybdenum atom, a carbon atom, and a hydrogen atom, but may also contain a sulfur atom, a phosphorus atom, a nitrogen atom, and / or an oxygen atom. Suitable organic molybdenum compounds include various organic molybdenum complexes such as molybdenum dithiocarbamate, molybdenum dithiophosphate, and molybdenum carboxylate, molybdenum esters, molybdenamines, and molybdenamides, which can be obtained by reacting molybdenum oxide or ammonium molybdate with a fat, glyceride, fatty acid, or fatty acid derivative (e.g., esters, amines, amides). The term "fatty" refers to a carbon chain having 10 to 22 carbon atoms, usually a linear carbon chain.

[0042] Molybdate esters prepared by the methods disclosed in U.S. Patent No. 4,889,647 and U.S. Patent No. 6,806,241B2. A commercially available example is MOLYVAN® 855 additive manufactured by RT Vanderbilt Company, Inc.

[0043] Molybdenum dithiocarbamate (MoDTC) has the following structure (XI): [ka] [In the formula, R 1 , R 2 , R 3 and R 4 These are linear or branched alkyl groups having 4 to 18 carbon atoms (for example, 8 to 13 carbon atoms) independently of each other. This is an organic molybdenum compound represented by [formula].

[0044] The preparation of these compounds is well known in the literature and in U.S. Patents 3,356,702 and 4,098,705, which are incorporated herein by reference. Examples of commercially available products include MOLYVAN® 807, MOLYVAN® 822, and MOLYVAN® 2000 manufactured by RTVanderbilt Company Inc., SAKURA-LUBE® 165 and SAKURA-LUBE® 515 manufactured by ADEKA CORPORATION, and Naugalube® MolyFM manufactured by Chemtura Corporation.

[0045] As taught by U.S. Patents No. 5,888,945 and No. 6,010,987, trinuclear dialkyldithiocarbamate molybdenum is also known in the art, and these patents are incorporated herein by reference. The existence of trinuclear molybdenum compounds, preferably having the formulas Mo3S4(dtc)4 or Mo3S7(dtc)4 [wherein dtc represents an independently selected diorganodithiocarbamate ligand comprising an independently selected organic group, and the ligand has a sufficient number of carbon atoms among all organic groups of the ligand of the compound] and mixtures thereof makes the compounds soluble or dispersible in lubricating oils.

[0046] Molybdenum dithiophosphate (MoDTP) has the following structure (XII): [ka] [In the formula, R 5 , R 6 , R 7 , and R 8 These are linear or branched alkyl groups having 4 to 18 carbon atoms (for example, 8 to 13 carbon atoms) independently of each other. This is an organic molybdenum compound represented by [formula].

[0047] Molybdenum carboxylic acid is described in U.S. Patent RE (Reissue) No. 38,929 and U.S. Patent No. 6,174,842, and is therefore incorporated herein by reference. Molybdenum carboxylic acid can be derived from any oil-soluble carboxylic acid. Typical carboxylic acids include naphthenic acid, 2-ethylhexanoic acid, and linolenic acid. Commercial suppliers of carboxylates produced from these particular acids are MOLYBDENUM NAP-ALL, MOLYBDENUM HEX-CEM, and MOLYBDENUM LIN-ALL, respectively. The manufacturer of these products is OMG OM Group.

[0048] Ammonium molybdate is prepared by acid-base reactions with oil-soluble amines in the presence of an acidic molybdenum source such as molybdenum trioxide, molybdic acid, ammonium molybdate, or ammonium thiomolybdate, and optionally a sulfur source such as sulfur, inorganic sulfides, polysulfides, or carbon disulfide. Preferred amine compounds are polyamine dispersants, which are commonly used in engine oil compositions. Examples of such dispersants are succinimide and Mannich-type dispersants. Preparations of these can be found in U.S. Patents 4,259,194, 4,259,195, 4,265,773, 4,265,843, 4,727,387, 4,283,295, and 4,285,822.

[0049] In one embodiment, the molybdenamine is a molybdenum-succinimide complex. Suitable molybdenum-succinimide complexes are described, for example, in U.S. Patent No. 8,076,275. These complexes are formed with an acidic molybdenum compound and have structure (XIII) or (XIV): [ka] [In the formula, R is C 24 ~C 350 (For example, C 70 ~C 128) is an alkyl or alkenyl group, where R′ is a linear or branched alkylene group having 2 to 3 carbon atoms, x is 1 to 11, and y is 1 to 10. It is prepared by a process involving the reaction of a polyamine represented by with an alkyl or alkenyl succinimide or a mixture thereof.

[0050] The molybdenum compounds used in the preparation of molybdenum-succinimide complexes are acidic molybdenum compounds or salts of acidic molybdenum compounds. "Acidic" means that the molybdenum compound will react with basic nitrogen compounds, as measured by ASTM D664 or D2896. Generally, acidic molybdenum compounds are hexavalent. Representative examples of suitable molybdenum compounds include molybdenum trioxide, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, as well as other molybdenum salts, such as hydrogen salts (e.g., sodium hydrogen molybdate), MoOCl4, MoO2Br2, Mo2O3Cl6, etc.

[0051] Succinimides that can be used to prepare molybdenum-succinimid complexes are disclosed in numerous references and are well known in the art. Certain basic types of succinimides and related materials included in the technical term “succinimide” are taught in U.S. Patents 3,172,892, 3,219,666 and 3,272,746. The term “succinimide” is understood in the art to include many chemical species such as amides, imides, and amidines that may be formed. However, the main product is succinimide, and the term is generally accepted to mean the product of the reaction of alkyl or alkenyl-substituted succinic acid or its anhydride with a nitrogen-containing compound. Preferred succinimides are prepared by reacting polyisobutenyl succinic anhydride, which has about 70 to 128 carbon atoms, with a polyalkylene polyamine selected from triethylenetetramine, tetraethylenepentamine, and mixtures thereof.

[0052] The molybdenum-succinimide complex can be post-treated with a sulfur source at appropriate pressure and a temperature not exceeding 120°C to provide a molybdenum-succinimide sulfide complex. The sulfidation process can be carried out for approximately 0.5 to 5 hours (e.g., 0.5 to 2 hours). Suitable sulfur sources include elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, and the formula R2S. x [In the formula, R is hydrocarbyl (e.g., C1~C 10 Organic polysulfides represented by [alkyl(C1-C1) and x is at least 3] 10 Examples include mercaptans, inorganic sulfides and inorganic polysulfides, thioacetamides, and thiourea.

[0053] The lubricating oil composition of the present invention is provided from one or more oil-soluble or dispersed oil-stable molybdenum-containing compounds and contains, based on the total mass of the composition, at least about 800 ppm, at least about 850 ppm, at least about 900 ppm, at least about 950 ppm, at least about 1000 ppm, at least about 1050 ppm, and at least about 1100 ppm of molybdenum. In one embodiment, the lubricating oil composition of the present invention is provided from one or more oil-soluble or dispersed oil-stable molybdenum-containing compounds and contains, based on the total mass of the composition, at least about 800 ppm to about 2000 ppm, at least about 900 ppm to about 1500 ppm, at least about 900 ppm to about 1400 ppm, at least about 900 ppm to about 1300 ppm, at least about 900 ppm to about 1200 ppm, and at least about 900 ppm to about 1100 ppm of molybdenum.

[0054] In one embodiment, the oil-soluble or dispersed oil-stable molybdenum-containing compound is present in the lubricating oil composition of the present invention such that the weight ratio of sulfur to molybdenum in the lubricating oil composition is about 4:1 or less. In another embodiment, the weight ratio of sulfur to molybdenum in the lubricating oil composition is less than about 3:1. In yet another embodiment, the weight ratio of sulfur to molybdenum in the lubricating oil composition is about 0.5:1 to about 4:1. In yet another embodiment, the weight ratio of sulfur to molybdenum in the lubricating oil composition is about 1:1 to about 4:1. In yet another embodiment, the weight ratio of sulfur to molybdenum in the lubricating oil composition is about 1:1 to about 3:1. In yet another embodiment, the weight ratio of sulfur to molybdenum in the lubricating oil composition is about 1:1 to about 2.5:1.

[0055] sulfur-containing compounds Generally, the sulfur level in the lubricating oil composition of the present invention, based on the total weight of the lubricating oil composition, is about 4000 ppm or less, for example, levels of about 100-4000 ppm, 100-3000 ppm, 100-2500 ppm, 100-2400 ppm, 100-2300 ppm, 100-2200 ppm, 100-2100 ppm, 100-2000 ppm, 100-1900 ppm, 100-1800 ppm, 100-1700 ppm, and 100-1600 ppm.

[0056] The sulfur content may be derived from elemental sulfur or sulfur-containing compounds. Sulfur or sulfur-containing compounds may be intentionally added to the lubricating oil composition, or they may be present in one or more base oils or additives for the lubricating oil composition. In one embodiment, the main amount of sulfur in the lubricating oil composition comes from active sulfur compounds, i.e., more than 50%. "Active sulfur" means a sulfur compound that has wear-resistant activity and preferably corrosion-resistant properties. The sulfur-containing compound may be an inorganic sulfur compound or an organic sulfur compound. The sulfur-containing compound may be a compound containing one or more groups such as sulfamoyl, sulfenamoyl, sulfeno, sulfide, sulfinamoyl, sulfino, sulfinyl, sulfonio, sulfonyldioxy, sulfate, thio, thiocarbamoyl, thiocarbonyl, thiocarbonylamino, thiocarboxy, thiocyanate, thioformyl, thioxo, thioketone, thioaldehyde, or thioester. Sulfur may also be present in heterogroups or compounds containing carbon atoms and sulfur atoms (and, optionally, other heteroatoms such as oxygen or nitrogen) in the chain or ring. Preferred sulfur-containing compounds include dihydrocarbyl sulfides and polysulfides, e.g., alkyl or alkenyl sulfides and polysulfides, sulfurized fatty acids or their esters, ashless dithiophosphates, cyclic organosulfur compounds, polyisobutylthiothion compounds, ashless dithiocarbamates, and mixtures thereof.

[0057] Examples of dihydrocarbyl sulfides or polysulfides include formula XV: R 9 -S b -R 10 (XV) [In the formula, R 9 and R 10 They are the same or different, C1~C 20 alkyl groups, alkenyl groups or cyclic alkyl groups, C6-C 20 Aryl group, C7~C 20 Alkylaryl group, or C7-C 20 [Represents an arylalkyl group, where b is an integer between 1 and 7] There are compounds represented by R. 9 and R10 When each of the alkyl groups is an alkyl group, the compound is called an alkyl sulfide. In formula VIII, R 9 and R 10 Examples of groups represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, cyclohexyl, phenyl, naphthyl, tolyl, xylyl, benzyl, and phenethyl.

[0058] One class of ashless dithiophosphates suitable for use in this specification is formula XVI: [ka] [In the formula, R 11 and R 12 [These are independently alkyl groups having 3 to 8 carbon atoms.] This includes (commercially sold by RT Vanderbilt Co., Inc. as VANLUBE® 7611M).

[0059] Another class of ashless dithiophosphates suitable for use herein includes dithiophosphate esters of carboxylic acids, such as those commercially available from Ciba Geigy Corp as IRGALUBE® 63.

[0060] Another class of ashless dithiophosphates suitable for use herein includes triphenylphosphorothionates, such as those commercially available from Ciba Geigy Corp as IRGALUBE® TPPT.

[0061] Suitable polyisobutylthiothion compounds include those with formula XVII: [ka] [In the formula, R 13is hydrogen or methyl, X is sulfur or oxygen, m is an integer from 1 to 9, n is 0 or 1, and when n is 0, R 13 It is methyl, and when n is 1, R 13 [is hydrogen] This includes compounds represented by [formula]. Examples of these polyisobutylthiothion compounds are disclosed, for example, in U.S. Patent Application Publication No. 20050153850, which is incorporated herein by reference.

[0062] In a preferred embodiment, the sulfur compound for use in the lubricating oil composition of the present invention is of formula XVIII: [ka]

[0063] [In the formula, R 13 , R 14 , R 15 , and R 16 These are identical or different aliphatic hydrocarbyl groups having 1 to 13 carbon atoms, and R 17 This is an alkylene group having 1 to 8 carbon atoms. The bisdithiocarbamate compound is represented by . The bisdithiocarbamate of formula XI is a known compound, described in U.S. Patent No. 4,648,985, which is incorporated herein by reference. The aliphatic hydrocarbyl group having 1 to 13 carbon atoms may be a branched or linear alkyl group having 1 to 13 carbon atoms. A preferred bisdithiocarbamate compound for use herein is methylenebis(dibutyldithiocarbamate), which is commercially available under the trademark Vanlube® 7723 (RT Vanderbilt Co., Inc.).

[0064] In one embodiment, the sulfur compound for use in the lubricating oil composition of the present invention is an ashless thiocarbamate compound described in U.S. Patent Publication No. 20140045737 and U.S. Patent Publication No. 20170260475, both of which are incorporated herein by reference.

[0065] In some embodiments, the lubricating oil composition of the present invention is substantially free of phosphorus-containing substances. In some embodiments, the level of phosphorus in the lubricating oil composition of the present invention is, based on the total weight of the lubricating oil composition, about 0.01% to about 0.12% by weight, about 0.01% to about 0.10% by weight, about 0.01% to about 0.08% by weight, and about 0.01% to about 0.06% by weight. In one embodiment, the lubricating oil composition of the present invention is substantially free of zinc dialkyldithiophosphate.

[0066] In one embodiment, the level of sulfated ash produced by the lubricating oil composition of the present invention is about 0.60% by weight or less, as determined by ASTM D 874, for example, a sulfated ash level of about 0.10 to about 0.60% by weight, as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil composition of the present invention is about 0.50% by weight or less, as determined by ASTM D 874, for example, a sulfated ash level of about 0.10 to about 0.50% by weight, as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil composition of the present invention is about 0.40% by weight or less, as determined by ASTM D 874, for example, a sulfated ash level of about 0.10 to about 0.40% by weight, as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil composition of the present invention is about 0.30% by weight or less, as determined by ASTM D 874, for example, a level of sulfated ash of about 0.10 to about 0.30% by weight, as determined by ASTM D 874.

[0067] Diphenylamine antioxidant The lubricating oil composition of the present invention may contain an amine antioxidant. In one embodiment, the antioxidant is a diphenylamine antioxidant. Examples of diphenylamine antioxidants include monoalkylated diphenylamines, dialkylated diphenylamines, trialkylated diphenylamines, and mixtures thereof. Some of these include butyldiphenylamine, dibutyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, nonyldiphenylamine, dinonyldiphenylamine, t-butyl-t-octyldiphenylamine, bisnonylated diphenylamine, bisoctylated diphenylamine, and phenyl-α-naphthylamine, alkyl or arylalkyl-substituted phenyl-α-naphthylamines, alkylated p-phenylenediamine, tetramethyl-diaminodiphenylamine, and the like.

[0068] In some embodiments, the diphenylamine antioxidant is present in weight % less than 1.3, less than 1.2, less than 1.0, or less than 0.90 based on the total weight of the lubricating oil composition. In some embodiments, the diphenylamine antioxidant is present in weight % about 0.20 to about 1.30, about 0.20 to about 1.20, about 0.20 to about 1.10, about 0.20 to about 1.00, about 0.30 to about 0.90, about 0.60 to about 0.90, or about 0.70 to about 0.90 based on the total weight of the lubricating oil composition. In one embodiment, the formulation does not contain the diphenylamine antioxidant.

[0069] Boron-containing compounds Representative examples of at least one oil-soluble or dispersed oil-stable boron-containing compound for use in the lubricating oil composition of the present invention include borooxide dispersants, borooxide friction modifiers, dispersed alkali metal or mixed alkali metal or alkaline earth metal borates, borooxide epoxides, boric acid esters, borooxide fatty amines, borooxide amides, borooxide sulfonates, borooxide salicylates, and mixtures thereof.

[0070] Examples of boron dispersants include, but are not limited to, basic nitrogen boron compounds selected from the group consisting of carboxylic acid ester copolymers having one or more further polar functional groups, such as succinimide, carboxylic acid amide, hydrocarbyl monoamine, hydrocarbyl polyamine, Mannich base, phosphonoamide, thiophosphonamide and phosphoramide, thiazole, e.g., 2,5-dimercapto-1,3,4-thiadiazole, mercaptobenzothiazole and its derivatives, triazole, e.g., alkyltriazole and benzotriazole, amine, amide, imine, imide, hydroxyl, carboxyl, etc., for example, products prepared by copolymerization of monomers of the above functional groups with long-chain alkyl acrylates or methacrylates, and mixtures thereof. Preferred boron dispersants are succinimide derivatives of boron, such as polyisobutenyl succinimide boron.

[0071] Examples of boro-based friction modifiers include, but are not limited to, fatty boro-based epoxides, alkoxylated fatty boro-based amines, glycerol boro-based esters, and mixtures thereof.

[0072] Hydrated particulate alkali metal borates are well known in the art and commercially available. Representative examples of hydrated particulate alkali metal borates and methods for their preparation are disclosed, for example, in U.S. Patents 3,313,727; 3,819,521; 3,853,772; 3,907,601; 3,997,454; 4,089,790; 6,737,387 and 6,534,450, the contents of which are incorporated herein by reference. Hydrated alkali metal borates can be represented by the formula: M2O·mB2O3·nH2O, where M is an alkali metal with an atomic number in the range of about 11 to about 19, such as sodium and potassium, m is a number (both integer and decimal) in the range of about 2.5 to about 4.5, and n is a number in the range of about 1.0 to about 4.8. Hydrated sodium borate is preferred. Hydrated borate particles generally have an average particle size of less than approximately 1 micron.

[0073] Examples of borooxide epoxides include those obtained from the reaction product of one or more boron compounds with at least one epoxide. Suitable boron compounds include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boric acid, boric acid, tetraboric acid and metaboric acid, boronamides, and various esters of boric acid. Epoxides are generally aliphatic epoxides having about 8 to about 30 carbon atoms, preferably about 10 to about 24 carbon atoms, more preferably about 12 to about 20 carbon atoms. Suitable aliphatic epoxides include dodecene oxide, hexadecene oxide, and mixtures thereof. Mixtures of epoxides, such as commercially available mixtures of epoxides having about 14 to about 16 carbon atoms or about 14 to about 18 carbon atoms, can also be used. Epoxide borooxides are commonly known and, for example, are described in U.S. Patent No. 4,584,115.

[0074] Examples of borate esters include those obtained by reacting one or more of the boron compounds disclosed above with one or more alcohols having appropriate lipophilicity. Typically, the alcohols will contain 6 to about 30 carbon atoms, preferably 8 to about 24 carbon atoms. Methods for producing the borate esters described above are well known in the art. Borate esters may also be boro-phospholipids. Representative examples of borate esters include those having structures shown in formulas XIX to XXI: [ka] (In the formula, each R is independently C1-C 12 It is a linear or branched alkyl group, R 1 is hydrogen or C1-C 12 (It is a linear or branched alkyl group.)

[0075] Examples of borolipid amines include borolipid amines obtained by reacting one or more of the boron compounds disclosed above with one or more fatty amines, for example, amines having about 14 to about 18 carbon atoms. Borolipid amines can be prepared by reacting an amine with a boron compound at a temperature in the range of about 50 to about 300°C, preferably in the range of about 100 to about 250°C, and in which the ratio of the equivalent weight of the amine to the equivalent weight of the boron compound is about 3:1 to about 1:3.

[0076] Examples of boroamides include boroamides obtained from reaction products of linear or branched saturated or unsaturated monohydric aliphatic acids having 8 to about 22 carbon atoms, urea, and boric acid compounds and mixtures thereof with polyalkylene polyamines.

[0077] Examples of boro oxide sulfonates include (a) (i) at least one of an oil-soluble sulfonic acid or an alkaline earth sulfonate or a mixture thereof, in the presence of a hydrocarbon solvent; (ii) at least one source of an alkaline earth metal; (iii) at least one source of boron; and (iv) a perbasic acid other than the boron source reacted with the boron source at a temperature between 0 and less than 10 mole percent; and (b) an alkaline earth metal boro oxide sulfonate obtained by heating the reaction product of (a) to a temperature higher than the distillation temperature of the hydrocarbon solvent and distilling the hydrocarbon solvent and water from the reaction. Suitable alkaline earth metal boro oxide sulfonates include, for example, those disclosed in U.S. Patent Application Publication No. 20070123437, the contents of which are incorporated herein by reference.

[0078] Examples of salicylate boroides include (a) at least one of oil-soluble salicylic acid or alkaline earth salicylate or a mixture thereof in the presence of a hydrocarbon solvent; (ii) at least one source of alkaline earth metal; (iii) at least one source of boron; and (iv) reacting a boron source with a perbasic acid other than the boron source at a rate of 0 to less than 10 mole percent; and (b) alkaline earth metal salicylates obtained by heating the reaction product of (a) to a temperature higher than the distillation temperature of the hydrocarbon solvent and distilling the hydrocarbon solvent and water from this reaction.

[0079] The lubricating oil composition of the present invention contains more than about 400 ppm of boron based on the total mass of the composition, which is provided from one or more oil-soluble or dispersed oil-stable boron-containing compounds. In one embodiment, the lubricating oil composition of the present invention contains at least about 500 ppm of boron based on the total mass of the composition, which is provided from one or more oil-soluble or dispersed oil-stable boron-containing compounds. In another embodiment, the lubricating oil composition of the present invention contains at least about 600 ppm of boron based on the total mass of the composition, which is provided from one or more oil-soluble or dispersed oil-stable boron-containing compounds. In yet another embodiment, the lubricating oil composition of the present invention contains at least about 700 ppm of boron based on the total mass of the composition, which is provided from one or more oil-soluble or dispersed oil-stable boron-containing compounds. In other embodiments, the lubricating oil composition of the present invention is provided from one or more oil-soluble or dispersed oil-stable boron-containing compounds and contains boron in amounts of approximately 400 ppm to approximately 2000 ppm, approximately 500 ppm to approximately 1500 ppm, approximately 600 ppm to approximately 1500 ppm, approximately 600 ppm to approximately 1200 ppm, approximately 600 ppm to approximately 1000 ppm, approximately 600 ppm to approximately 900 ppm, approximately 700 ppm to approximately 900 ppm, and approximately 750 ppm to approximately 900 ppm, based on the total mass of the composition.

[0080] Other lubricant additives The lubricating oil compositions of this disclosure may also contain other conventional additives that can impart or improve any desired properties of the lubricating oil composition in which these additives are dispersed or dissolved. Any additives known to those skilled in the art may be used in the lubricating oil compositions disclosed herein. Several suitable additives are described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd edition, London, Springer (1996); and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker (2003), both of which are incorporated herein by reference. For example, lubricating oil compositions can be blended with antioxidants, anti-wear agents, metal cleaners, rust inhibitors, dehazing agents, deemulsifiers, metal deactivators, friction modifiers, pour point depressants, antifoaming agents, cosolvents, corrosion inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents, and mixtures thereof. Various additives are known and commercially available. These additives or similar compounds can be used in the preparation of the lubricating oil compositions of this disclosure by conventional blending procedures.

[0081] The lubricating oil composition of the present invention may contain one or more detergents. Metal-containing or ash-forming detergents function as detergents that reduce or remove deposits, and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally contain a polar head with a long hydrophobic tail. The polar head contains a metal salt of an acidic organic compound. The salt may contain a substantially stoichiometric amount of metal, in which case they are usually described as normal or neutral salts. Large amounts of metal bases can be incorporated by reacting excess metal compounds (e.g., oxides or hydroxides) with an acidic gas (e.g., carbon dioxide).

[0082] The cleaning agents that can be used include oil-soluble neutral and overbasic sulfonates, phenates, sulfide phenates, thiophosphonates, salicylates, and naphthenates, as well as metals, particularly alkali or alkaline earth metals, such as barium, sodium, potassium, lithium, calcium, and magnesium, and other oil-soluble carboxylates. The most commonly used metals are calcium and magnesium, both of which can be present in cleaning agents used in lubricants, as well as mixtures of calcium and / or magnesium with sodium. The lubricating oil composition of the present invention may contain one or more friction modifiers that can reduce friction between moving parts. All friction modifiers known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers include fatty carboxylic acids, derivatives of fatty carboxylic acids (e.g., alcohols, esters, borate esters, amides, metal salts, etc.), mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids, mono-, di- or tri-alkyl substituted phosphoric acids or derivatives of phosphonic acids (e.g., esters, amides, metal salts, etc.), mono-, di- or tri-alkyl substituted amines, mono- or di-alkyl substituted amides, and combinations thereof. In some embodiments, examples of friction modifiers include, but are not limited to, friction modifiers obtained from reaction products of nitrogen-containing compounds selected from the group consisting of alkoxylated fatty amines; fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, glycerol borooxide esters; and fatty imidazolines disclosed in U.S. Patent No. 6,372,696 (the contents of which are incorporated herein by reference); fatty acid esters of C4-C75, or C6-C24, or C6-C20, and ammonia and alkanolamines, and mixtures thereof. The amount of friction modifier may vary in the range of about 0.01% to about 10% by weight, about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight, based on the total weight of the lubricating oil composition.

[0083] The lubricating oil composition of the present invention may contain an additional organic antioxidant in an amount of 0.1 to 3% by weight. In addition to the diarylamines mentioned above, the antioxidant may be a hindered phenol antioxidant.

[0084] Examples of hindered phenol antioxidants include 2,6-di-t-butyl-p-cresol, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-methylenebis(6-t-butyl-o-cresol), 4,4′-isopropylidenebis(2,6-di-t-butylphenol), 4,4′-bis(2,6-di-t-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), 4,4′-thiobis(2-methyl-6-t-butylphenol), and 2,2-thio-diethylenebis[3-(3 This includes, but is not limited to, commercial products such as Irganox L135® (BASF), Naugalube 531® (Chemtura), and Ethanox 376® (SI Group).

[0085] Lubricating viscous oil Lubricating oils (sometimes called "base stock" or "base oil") are the main liquid component of lubricants, and are blended with additives and, in some cases, other oils to produce the final lubricant (or lubricant composition). Base oils are useful for producing concentrates and from which lubricant compositions are made, and can be selected from natural and synthetic lubricants and combinations thereof.

[0086] Natural oils include animal and vegetable oils, liquid petroleum, and hydrogenated, refined, solvent-treated mineral lubricants of the paraffinic, naphthenic, and mixed paraffinic-naphthenic types. Lubricating oils derived from coal or shale are also useful base oils.

[0087] Synthetic lubricants include hydrocarbon oils, such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, alkylated naphthalene); polyphenols (e.g., biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides, as well as their derivatives, analogs and homologs.

[0088] Other suitable types of synthetic lubricants include esters of dicarboxylic acids (e.g., malonic acid, alkylmalonic acid, alkenylmalonic acid, succinic acid, alkylsuccinic acid and alkenylsuccinic acid, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelaate, diisodecyl azelaate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting 1 mole of sebacate with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0089] Furthermore, esters useful as synthetic oils include C5-C 12This also includes monocarboxylic acids and polyols, as well as those made from polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

[0090] Base oils may also be derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are produced from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons usually require further processing to be useful as base oils. For example, the hydrocarbons may be subjected to hydrogen isomerization, hydrocracking and hydrogen isomerization, dewaxing, or hydrogen isomerization and dewaxing using processes known to those skilled in the art.

[0091] The lubricating oil compositions of the present invention may use unrefined oil, refined oil, and re-refined oil. Unrefined oil is obtained directly from natural or synthetic raw materials without further refining. For example, shale oil obtained directly from retort operations, petroleum obtained directly from distillation, or ester oil obtained directly from an esterification process and used without further processing are unrefined oils. Refined oil is similar to unrefined oil except that it has been further processed in one or more refining steps to improve one or more properties. Many such refining techniques, such as distillation, solvent extraction, acid or base extraction, filtration, and osmosis, are known to those skilled in the art.

[0092] Refined oil is obtained by a process similar to that used to obtain refined oil, which is applied to refined oil that has already been used. Such refined oil is also known as recycled oil or reprocessed oil and is often further processed by technologies used to obtain approval for used additives and oil-cleared products.

[0093] Therefore, the base oils that can be used in the manufacture of this lubricating oil composition may be selected from any of the base oils in Groups I to V specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509). The above base oil groups are summarized in Table 1 below. [Table 1]

[0094] Suitable base oils for use in this specification are any of the types corresponding to API Group II, Group III, Group IV, and Group V oils, or combinations thereof, preferably Group III to Group V oils due to their exceptional volatility, stability, viscosity, and cleanliness.

[0095] The lubricating oil for use in the lubricating oil compositions of this disclosure, also called the base oil, is typically present in a major amount, for example, more than 50% by weight, preferably more than about 70% by weight, more preferably about 80 to about 99.5% by weight, and most preferably about 85 to about 98% by weight, based on the total weight of the composition. As used herein, the term “base oil” is understood to mean a base stock or blend of base stocks that is a lubricating component manufactured by a single manufacturer (regardless of the source or location of the manufacturer) toward the same specifications, conforming to the specifications of the same manufacturer, and identified by a unique formula, product identification number, or both. The base oil for use herein may be a known or hereafter discovered lubricating oil used in the formulation of lubricating oil compositions for any such application, such as functional fluids such as engine oil, marine cylinder oil, hydraulic oil, gear oil, and transmission fluid. Furthermore, the base oils used herein may, as necessary, include viscosity index improvers, such as high molecular weight alkyl methacrylates, olefin copolymers, such as ethylene-propylene copolymers or styrene-butadiene copolymers, and mixtures thereof. The topology of the viscosity modifier may include, but is not limited to, linear, branched, hyperbranched, star-shaped, or comb-shaped topologies.

[0096] As those skilled in the art will readily understand, the viscosity of base oils varies depending on the application. Therefore, the viscosity of base oils used herein is typically in the range of about 2 centistokes to about 2000 centistokes (cSt) at 100°C (C). Generally, base oils used as engine oils individually have a kinematic viscosity range of about 2 cSt to about 30 cSt at 100°C, preferably about 2 cSt to about 20 cSt, preferably about 2 cSt to about 18 cSt, preferably about 3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt, and by selecting or blending according to the desired end application and additives in the finished oil, the desired grade of engine oil can be achieved. For example, lubricating oil compositions with SAE viscosity grades such as 0W, 0W-8, 0W-12, 0W-16, 0W-20, 0W-26, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, and 40 can be obtained.

[0097] Preferably, the lubricating oil composition may have a total base number (TBN) of 4 to 12 mg KOH / g (e.g., 5 to 12 mg KOH / g, 6 to 12 mg KOH / g, 6 to 10 mg KOH / g, 6 to 8 mg KOH / g).

[0098] Generally, the concentration of each additive in a lubricating oil composition may range from approximately 0.001% to approximately 20% by weight, approximately 0.01% to approximately 15% by weight, or approximately 0.1% to approximately 10% by weight, approximately 0.005% to approximately 5% by weight, or approximately 0.1% to approximately 2.5% by weight, based on the total weight of the lubricating oil composition at the time of use. Furthermore, the total amount of additives in the lubricating oil composition may range from approximately 0.001% to approximately 20% by weight, approximately 0.01% to approximately 10% by weight, or approximately 0.1% to approximately 5% by weight, based on the total weight of the lubricating oil composition.

[0099] In the preparation of lubricating oil formulations, it is common practice to introduce additives in the form of 10-80% by weight of active ingredient concentrates in hydrocarbon oils, such as mineral lubricants, or other suitable solvents.

[0100] Typically, these concentrates can be diluted with 3 to 100 parts by weight, or for example 5 to 40 parts by weight, of lubricating oil per 1 part by weight of the additive package, when forming the final lubricant, such as crankcase motor oil. The purpose of the concentrates is, of course, to make the handling of various materials easier and more manageable, and to facilitate dissolution or dispersion in the final blend.

[0101] Process for preparing a lubricating oil composition The lubricating oil compositions disclosed herein can be prepared by any method known to those skilled in the art for producing lubricating oils. In some embodiments, the base oil can be blended or mixed with the additive compounds described herein. Any mixing or dispersion apparatus known to those skilled in the art can be used to blend, mix or solubilize the components. Blending, mixing or solubilization can be carried out in blenders, stirrers, dispersers, mixers (e.g., planetary mixers and double planetary mixers), homogenizers (e.g., Gaulin homogenizers and Rannie homogenizers), mills (e.g., colloidal mills, ball mills and sand mills) or any other mixing or dispersion apparatus known in the art.

[0102] In some embodiments, the lubricating oil compositions disclosed herein may be suitable for use as motor oil (i.e., engine oil or crankcase oil) in compression-ignition or spark-ignition internal combustion engines, particularly direct-injection, boosted engines. In addition to being particularly effective in improving copper corrosion and reducing wear performance in high-durability compression-ignition engines equipped with aftertreatment devices such as diesel particulate filters (DPFs), the lubricating oil compositions may be particularly effective in improving copper corrosion and reducing wear performance in spark-ignition engines equipped with gasoline particulate filters (GPFs).

[0103] The following examples are provided to illustrate embodiments of the Disclosure, but are not intended to limit the Disclosure to any specific embodiment described. Unless otherwise indicated, all parts and percentages are by weight. All numerical values ​​are approximate. Where numerical ranges are given, it should be understood that embodiments outside those ranges may still be included within the scope of the Disclosure. The specific details described in each example should not be construed as essential features of the Disclosure.

[0104] It should be understood that various modifications can be made to the embodiments disclosed herein. Therefore, the above description should not be construed as limiting, but merely as an example of preferred embodiments. For example, the functions described above and realized as the best mode for operating the disclosure are for illustrative purposes only. Other combinations and methods can be implemented by those skilled in the art without departing from the scope and spirit of the disclosure. Furthermore, those skilled in the art should anticipate other modifications within the claims and spirit of the claims appended herein.

[0105] example The following examples are for illustrative purposes only and do not limit the scope of this disclosure in any way. Unless otherwise specified, all weight percents are expressed on an additive basis, including an appropriate amount of diluent oil.

[0106] Formulation A The low-phosphorus lubricant composition was prepared by blending the following components together to obtain an SAE 10W-30 viscosity grade formulation: (1) Regarding the boron content, a combination of 760 ppm boro oxide dispersant (5.2% by weight in the finished oil based on additives), potassium hydrated borate (0.556% by weight in the finished oil), and sulfonate borooxide (3 mmol / kg in the finished oil), with a total base number (TBN) of 160 on an additive basis. (2) Regarding the molybdenum content, a molybdenum succinimide complex with 1200 ppm. (3) 2.6% by weight of a dispersant. (4) A total of 14 mmol / kg of one or more detergents. (5) 1.31% by weight of alkylated diphenylamine antioxidant. (6) 1% by weight of a hindered phenol antioxidant. (7) 0.7% by weight of ashless dithiocarbamate (8) 0.5% by weight of a pour point depressant. (9) 3.0% by weight of a dispersant viscosity index improver. (10) A defoaming agent with a silicon content of 10 ppm. (11) The remainder was a diluent consisting of approximately 70% by weight of Group III base oil and approximately 30% by weight of Group II base oil.

[0107] Corrosion inhibitor A The copper corrosion inhibitor (metal deactivator) A was IRGAMET® 39, a tolyltriazole derivative available from BASF. Its chemical name is 1-[bis(2-ethylhexyl)aminomethyl]-4-methylbenzotriazole.

[0108] Corrosion inhibitor B The copper corrosion inhibitor B was DURAPHOS® TLP, a phosphite available from the Rhodia Group. Its chemical name is trilauryl phosphite.

[0109] Corrosion inhibitor C The copper corrosion inhibitor C was HITEC® 4313, an ashless dialkylthiadiazole available from Afton Chemical. Its chemical name is 2,5-bis(octyldisulfanyl)-1,3,4-thiadiazole.

[0110] Corrosion inhibitor D The copper corrosion inhibitor D was HITEC® 4312, an ashless dialkylthiadiazole derivative available from Afton Chemical. Its chemical name is 2,5-dimercapto-1,3,4-thiadiazole derivative.

[0111] Corrosion inhibitor E The copper corrosion inhibitor E was Vanlube® RI-A, an alkyl succinic acid half-acid ester derivative available from RT Vanderbilt.

[0112] Corrosion inhibitor F The copper corrosion inhibitor F was Amine(amine)O, which is N-β-hydroxyethyl oleylimidazoline available from BASF.

[0113] Corrosion inhibitor G The copper corrosion inhibitor G was Kemguard® CI-4083, a hydroxyethylimidazoline concentrate available from Kemira.

[0114] Corrosion inhibitor H The copper corrosion inhibitor H was Cobratec® TT-100, a mixture of 5-methyl and 4-methyl-1H-benzotriazole (i.e., tolyltriazole) available from PMC Specialties Group.

[0115] Corrosion inhibitor I Copper corrosion inhibitor I contains 2(3H)-benzothiazole thion, available from RT Vanderbilt. 12 -C 14 The compound in question was Vanlube® 601E, a tert-alkyl compound.

[0116] Example 1 The lubricating oil was blended in the same manner as in formulation A, except that 0.85% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.02% by weight of corrosion inhibitor A was added.

[0117] Example 2 The lubricating oil was blended in the same manner as in formulation A, except that 0.85% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.03% by weight of corrosion inhibitor A was added.

[0118] Example 3 The lubricating oil was blended in the same manner as in formulation A, except that 0.85% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.04% by weight of corrosion inhibitor A was added.

[0119] Example 4 The lubricating oil was blended in the same manner as in formulation A, except that 0.85% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.05% by weight of corrosion inhibitor A was added.

[0120] Example 5 The lubricating oil was blended in the same manner as in formulation A, except that, with respect to the molybdenum content, 1000 ppm of molybdenum succinimide complex and 0.42% by weight of ashless dithiocarbamate were used, and 0.02% by weight of corrosion inhibitor A was added.

[0121] Example 6 The lubricating oil was blended in the same manner as in formulation A, except that 0.85% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.07% by weight of corrosion inhibitor A was added.

[0122] Example 7 The lubricating oil was blended in the same manner as in formulation A, except that 0.85% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.10% by weight of corrosion inhibitor A was added.

[0123] Example 8 The lubricating oil was blended in the same manner as in formulation A, except that 0.85% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.15% by weight of corrosion inhibitor A was added.

[0124] Example 9 The lubricating oil was blended in the same manner as in formulation A, except that 0.75% by weight of diphenylamine antioxidant was used and 0.05% by weight of corrosion inhibitor A was added.

[0125] Example 10 The lubricating oil was blended in the same manner as in formulation A, except that 0.75% by weight of diphenylamine antioxidant and 0.75% by weight of potassium hydrated borate were used, and 0.05% by weight of corrosion inhibitor A was added. As a result, the boron content in the formulation increased from 760 ppm to 890 ppm.

[0126] Example 11 The lubricating oil was blended in the same manner as in formulation A, except that 0.75% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.05% by weight of corrosion inhibitor A was added. As a result, the sulfur content in the formulation decreased from 2400 ppm to 1600 ppm.

[0127] Example 12 The lubricating oil was blended in the same manner as in formulation A, except that 0.75% by weight of diphenylamine antioxidant, 0.75% by weight of potassium hydrated borate, and 0.42% by weight of ashless dithiocarbamate were used, and 0.05% by weight of corrosion inhibitor A was added. As a result, the boron content in the formulation increased from 760 ppm to 890 ppm, and the sulfur content in the formulation decreased from 2400 ppm to 1600 ppm.

[0128] Example 13 The lubricating oil was blended in the same manner as in formulation A, except that 0.75% by weight of diphenylamine antioxidant and 0.42% by weight of ashless dithiocarbamate were used, and 0.05% by weight of corrosion inhibitor H was added. As a result, the sulfur content in the formulation decreased from 2400 ppm to 1600 ppm.

[0129] Comparative Example 1 Formula A was duplicated.

[0130] Comparative Example 2 The lubricating oil was blended in the same manner as in formulation A, except that 0.02% by weight of corrosion inhibitor A was added.

[0131] Comparative Example 3 The lubricating oil was blended in the same manner as in the case of formulation A, except that 0.03% by weight of corrosion inhibitor A was added.

[0132] Comparative Example 4 The lubricating oil was blended in the same manner as in formulation A, except that 0.04% by weight of corrosion inhibitor A was added.

[0133] Comparative Example 5 The lubricating oil was blended in the same manner as in formulation A, except that 0.05% by weight of corrosion inhibitor A was added.

[0134] Comparative Example 6 The lubricating oil was blended in the same manner as in formulation A, except that 0.5% by weight of corrosion inhibitor B was added.

[0135] Comparative Example 7 The lubricating oil was blended in the same manner as in formulation A, except that 0.15% by weight of corrosion inhibitor C was added.

[0136] Comparative Example 8 The lubricating oil was blended in the same manner as in formulation A, except that 0.05% by weight of corrosion inhibitor D was added.

[0137] Comparative Example 9 The lubricating oil was blended in the same manner as in formulation A, except that 0.05% by weight of corrosion inhibitor E was added.

[0138] Comparative Example 10 The lubricating oil was blended in the same manner as in formulation A, except that 0.05% by weight of corrosion inhibitor F was added.

[0139] Comparative Example 11 The lubricating oil was blended in the same manner as in formulation A, except that 0.05% by weight of corrosion inhibitor G was added.

[0140] Comparative Example 12 The lubricating oil was blended in the same manner as in formulation A, except that 0.05% by weight of corrosion inhibitor I was added.

[0141] ASTM D6594 HTCBT (High Temperature Corrosion Bench Test) The ASTM D6594 HTCBT test is used to test diesel engine lubricants to examine their tendency to corrode various metals, particularly lead and copper alloys commonly used in cam followers and bearings. Four metal test pieces—copper (Cu), lead (Pb), tin (Sn), and phosphor bronze—are immersed in a measured amount of engine oil. Air (5 L / hour) is blown into the oil at a high temperature (170°C) for a set period (168 hours). Once the test is complete, the copper test piece and the stressed oil are examined to detect corrosion and corrosion products, respectively. The concentrations of copper, lead, and tin in the new and stressed oil, as well as the changes in each metal concentration, are recorded. To pass, the lead concentration should not exceed 120 ppm, and the copper concentration should not exceed 20 ppm. A copy of this test method is available from ASTM International, located at 100 Barr Harbor Drive, PO Box 0700, West Conshohocken, PA 19428-2959, and is incorporated herein for all purposes. The results of HTCHT are shown in Tables 2 and 3 below.

[0142] Copper strip corrosion test - ASTM D130 Crude oil contains sulfur compounds, most of which are removed during refining. However, some of the sulfur compounds remaining in petroleum products may be corrosive to various metals, and this corrosivity is not necessarily directly related to the total sulfur content. The effect can vary depending on the chemical type of sulfur compounds present. The copper strip corrosion test is designed to assess the relative corrosivity of petroleum products. In this test, a polished copper strip is immersed in a specific volume of the test sample and heated under temperature and time conditions specific to the class of the test material. At the end of the heating period, the copper strip is removed, cleaned, and its color and discoloration level are evaluated against the ASTM copper strip corrosion standard summarized below (Table 2). [Table 2]

[0143] The corrosion properties of Examples 1-13 and Comparative Examples 1-12 were evaluated using both HTCBT and copper strip corrosion tests. These results are shown in Tables 3-7. It is clear that Examples 1-13 demonstrated superior performance against copper corrosion compared to Comparative Examples 1-12. For the purposes of this test, a value of less than 30 for copper is exceptionally good. [Table 3] [Table 4] [Table 5] [Table 6] [Table 7]

Claims

1. It has a sulfur content of up to 0.4% by weight and a sulfated ash content of up to 0.6% by weight, as measured by ASTM D874. a. Main amount of base oil, b. At least 0.02% by weight of a triazole compound, c. A diphenylamine antioxidant in an amount of less than approximately 1.3% by weight, and d. At least 900 ppm of molybdenum from molybdenum-containing compounds A lubricating oil composition containing, which is essentially free of ZnDTP.

2. The composition according to claim 1, further comprising an oil-soluble or oil-dispersible boron-containing compound.

3. The composition according to claim 2, wherein the boron-containing compound is present in an amount of boron of at least about 500 ppm based on the total weight of the composition.

4. The composition according to claim 3, wherein the boron-containing compound is present in an amount of boron of about 500 ppm to about 1500 ppm based on the total weight of the composition.

5. The composition according to claim 1, wherein the sulfur content is about 0.01% by weight to about 0.4% by weight, based on the total weight of the composition.

6. The composition according to claim 1, wherein the molybdenum-containing compound is present in an amount of molybdenum of about 900 to 1500 ppm based on the total weight of the composition.

7. The composition according to claim 1, wherein the composition has a sulfur-to-molybdenum weight ratio of 4:1 or less.

8. The composition according to claim 7, wherein the composition has a sulfur-to-molybdenum weight ratio of 0.5:1 to 4:

1.

9. The composition according to claim 1, wherein the triazole compound is present in a proportion of about 0.02% by weight to about 1.0% by weight based on the total weight of the lubricating oil composition.

10. The composition according to claim 1, wherein the sulfated ash is present in a proportion of about 0.01% by weight to about 0.60% by weight based on the total weight of the lubricating oil composition.

11. The composition according to claim 1, wherein the diphenylamine antioxidant is present in a proportion of about 0.20% to about 1.30% by weight, based on the total weight of the lubricating oil composition.

12. The composition according to claim 1, wherein the lubricating oil does not contain a diphenylamine antioxidant.

13. The composition according to claim 1, wherein phosphorus is present in a proportion of about 0.01% to about 0.12% by weight, based on the total weight of the lubricating oil composition.

14. A method for improving the copper corrosion resistance of an engine, (i) Having a sulfur content of up to 0.4% by weight and a sulfated ash content of up to 0.6% by weight as measured by ASTM D874, a. Main amount of base oil, b. At least 0.02% by weight of a triazole compound, c. A diphenylamine antioxidant in an amount of less than approximately 1.3% by weight, and d. At least 900 ppm of molybdenum from molybdenum-containing compounds A lubricating oil composition comprising, Lubricating the engine with a lubricating oil composition that is essentially free of ZnDTP, and (ii) To operate the engine Includes, The above method, wherein the engine is equipped with a diesel particulate filter (DPF) aftertreatment system.

15. A method for improving the copper corrosion resistance of an engine, (i) Having a sulfur content of up to 0.4% by weight and a sulfated ash content of up to 0.6% by weight as measured by ASTM D874, a. Main amount of base oil, b. At least 0.02% by weight of a triazole compound, c. A diphenylamine antioxidant in an amount of less than approximately 1.3% by weight, and d. At least 900 ppm of molybdenum from molybdenum-containing compounds A lubricating oil composition comprising, Lubricating the engine with a lubricating oil composition that is essentially free of ZnDTP, and (ii) To operate the engine Includes, The above method, wherein the engine is equipped with a gasoline particulate filter (GPF) aftertreatment system.

16. A method for improving copper corrosion resistance in an engine while simultaneously reducing wear, (i) Having a sulfur content of up to 0.4% by weight and a sulfated ash content of up to 0.6% by weight as measured by ASTM D874, a. Main amount of base oil, b. At least 0.02% by weight of a triazole compound, c. A diphenylamine antioxidant in an amount of less than approximately 1.3% by weight, and d. At least 900 ppm of molybdenum from molybdenum-containing compounds A lubricating oil composition comprising, Lubricating the engine with a lubricating oil composition that is essentially free of ZnDTP, and (ii) To operate the engine Includes, The above method, wherein the engine is equipped with a diesel particulate filter (DPF) aftertreatment system.

17. A method for improving copper corrosion resistance in an engine while simultaneously reducing wear, (i) Having a sulfur content of up to 0.4% by weight and a sulfated ash content of up to 0.6% by weight as measured by ASTM D874, a. Main amount of base oil, b. At least 0.02% by weight of a triazole compound, c. A diphenylamine antioxidant in an amount of less than approximately 1.3% by weight, and d. At least 900 ppm of molybdenum from molybdenum-containing compounds A lubricating oil composition comprising, Lubricating the engine with a lubricating oil composition that is essentially free of ZnDTP, and (ii) To operate the engine Includes, The above method, wherein the engine is equipped with a gasoline particulate filter (GPF) aftertreatment system.

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