Lubricating oil composition

Abstract

To provide a lubricating oil composition for an internal combustion engine including a lubricant additive that provides improved performance advantages, and a method for lubricating the internal combustion engine.SOLUTION: A lubricating oil composition is provided which comprises: (a) greater than 50 wt.% of a base oil of lubricating viscosity, selected from the group consisting of API Group I, II, III, IV, and V oils and mixtures thereof; (b) 0.1 to 20 wt.% of an alkyl-substituted hydroxyaromatic carboxylic acid, wherein an alkyl-substituent of the alkyl-substituted hydroxyaromatic carboxylic acid has 12 to 40 carbon atoms; and (c) a metal detergent wherein the lubricant composition is a monograde lubricant composition meeting specifications of SAE J300 revised January 2015 requirements for SAE 20, 30, 40, 50, or 60 monograde engine oils, and the TBN as measured by ASTM D2896 is in a range of 5 to 200 mg KOH / g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a lubricating oil composition containing an ashless alkyl-substituted hydroxyaromatic carboxylic acid. [Background technology]

[0002] Lubricants are typically formulated with metal detergent additives. However, excessive overbasic detergents present in marine diesel lubricants, for example, can create excessively basic sites, potentially destabilizing unused micelles of overbasic detergent containing insoluble metal salts. This destabilization can lead to the formation of deposits of insoluble metal salts in ash formation, which then adhere to the cylinder walls and other engine components.

[0003] Therefore, it is desirable to include a lubricating additive that provides improved performance advantages without contributing to the additional concentration of overbasic metal detergents.

[0004] This disclosure aims to achieve improved lubricant performance by using ashless alkyl-substituted hydroxyaromatic carboxylic acids. [Overview of the project]

[0005] In one embodiment, a lubricating oil composition is provided, comprising (a) a base oil having a lubricating viscosity of more than 50% by weight, and (b) 0.1 to 20% by weight of an alkyl-substituted hydroxyaromatic carboxylic acid, wherein the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid has 12 to 40 carbon atoms, and is a monograde lubricating oil composition that satisfies the specifications of SAE J300, which is the January 2015 revised requirement for SAE 20, 30, 40, 50, or 60 monograde engine oil, and has a TBN of 5 to 200 mg KOH / g as measured by ASTM D2896.

[0006] In another embodiment, a method for lubricating an internal combustion engine is provided, which includes supplying the internal combustion engine with a lubricating oil composition disclosed herein. Furthermore, [1] to

[13] below all represent one embodiment or aspect of the present invention. [1] A lubricating oil composition comprising (a) a base oil having a lubricating viscosity of more than 50% by weight, and (b) 0.1 to 20% by weight of an alkyl-substituted hydroxyaromatic carboxylic acid, wherein the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid has 12 to 40 carbon atoms, and the composition is a monograde lubricating oil composition that satisfies the specifications of SAE J300, which is the January 2015 revised requirement for SAE 20, 30, 40, 50, or 60 monograde engine oil, and has a TBN of 5 to 200 mg KOH / g as measured by ASTM D2896. [2] The lubricating oil composition according to [1], wherein the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid is a residue derived from an alpha-olefin having 14 to 28 carbon atoms per molecule. [3] The lubricating oil composition according to [1], wherein the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid is a residue derived from an alpha-olefin having 20 to 24 carbon atoms per molecule. [4] The lubricating oil composition according to [1], wherein the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid is a residue derived from an alpha-olefin having 20 to 28 carbon atoms per molecule. [5] The lubricating oil composition according to any one of [2], [3], and [4], wherein the alpha-olefin is a normal alpha-olefin, an isomerized normal alpha-olefin, or a mixture thereof. [6] The lubricating oil composition according to [1], wherein the amount of alkyl-substituted hydroxybenzoic acid is in the range of 1.0 to 5.0% by weight of the lubricating oil composition. [7] The lubricating oil composition according to [1], wherein the lubricating oil composition has TBN in one of the ranges of 5-10 mg KOH / g, 15-150 mg KOH / g, 20-80 mg KOH / g, 30-100 mg KOH / g, 30-80 mg KOH / g, 60-100 mg KOH / g, and 60-150 mg KOH / g. [8] The lubricating oil composition according to [1] further comprises one or more of the following: metal cleaner, dispersant, anti-wear agent, antioxidant, friction modifier, corrosion inhibitor, rust inhibitor, deemulsifier, anti-foaming agent, viscosity modifier, pour point depressant, nonionic surfactant, and thickener. [9] A method for lubricating an internal combustion engine, comprising supplying the lubricating oil composition described in [1] to the internal combustion engine.

[10] The method according to [9], wherein the internal combustion engine is a compression ignition engine.

[11] <00001十一>

[12] The method according to

[10] , wherein the compression ignition engine is a two-stroke engine that operates at 200 rpm or less.

[13] The method according to

[10] , wherein the compression ignition engine uses residual fuel, marine residual fuel, low-sulfur marine residual fuel, marine distillate fuel, low-sulfur marine distillate fuel, high-sulfur fuel, or gaseous fuel.

Mode for Carrying Out the Invention

[0007] preface In this specification, the following words and expressions, when used, have the meanings ascribed below.

[0008] "Major amount" means more than 50% by weight of the composition.

[0009] "Minor amount" means less than 50% by weight of the composition.

[0010] It should be noted that there seems to be an error in the original text where "十一" appears in . It is translated as "十一" here as there is no clear indication of how to correct it. If this is a misprint, it needs to be corrected in the original for a more accurate translation. As used herein and in the claims, “alpha-olefin” refers to an olefin having a carbon-carbon double bond between the first and second carbon atoms of the longest continuous chain of carbon atoms. Unless otherwise specified, the term “alpha-olefin” includes both straight-chain and branched-chain alpha-olefins. In the case of branched-chain alpha-olefins, the branching may be at position 2 (vinylidene) and / or position 3 or higher relative to the olefin double bond. As always used herein and in the claims, the term “vinylidene” refers to an alpha-olefin having a branch at position 2 relative to the olefin double bond. Alpha-olefins are most often mixtures of isomers and often mixtures of compounds with various numbers of carbon atoms: C6, C8, C 10 , C 12 , C 14 Low molecular weight alpha-olefins, such as alpha-olefins, are mostly 1-olefins. 16 -C 18 or C 20 -C 24 In high molecular weight olefin cuts such as those mentioned above, the proportion of double bonds isomerized either internally or at the vinylidene position increases.

[0011] "Normal alpha-olefin" refers to a linear aliphatic monoolefin having a carbon-carbon double bond between the first and second carbon atoms. Note that "normal alpha-olefin" is not synonymous with "linear alpha-olefin," as the term "linear alpha-olefin" may include linear olefin compounds having a double bond between the first and second carbon atoms.

[0012] "Isomerized olefins" or "isomerized normal alpha olefins" refer to olefins obtained by isomerizing an olefin. Generally, isomerized olefins have double bonds at different positions than their starting olefins and may also have different properties.

[0013] "TBN" refers to the total base number measured by ASTM D2896.

[0014] "KV" 100 means the kinematic viscosity at 100 °C measured by ASTM D445.

[0015] "Weight percent" (wt%) means the percentage that the indicated component, compound, or substituent represents in the total weight of the composition, unless otherwise specified.

[0016] All percentages reported are wt% on an active ingredient basis (i.e., regardless of carrier or diluent oil), unless otherwise specified. The diluent oil of the lubricant additive can be any suitable base oil (e.g., Group I base oil, Group II base oil, Group III base oil, Group IV base oil, Group V base oil, or mixtures thereof).

[0017] lubricating oil composition The lubricating oil composition of the present disclosure comprises (a) a base oil having a lubricating viscosity of more than 50 wt% and (b) 0.1 to 20 wt% of an alkyl-substituted hydroxyaromatic carboxylic acid, wherein the alkyl-substituted group of the alkyl-substituted hydroxyaromatic carboxylic acid has 12 to 40 carbon atoms. The lubricating oil composition is a monograde lubricating oil composition that meets the specifications of SAE J300, which are the January 2015 revised requirements for SAE 20, 30, 40, 50, or 60 monograde engine oils, and has a TBN of 5 to 200 mg KOH / g as measured by ASTM D2896.

[0018] The lubricating oil composition is a monograde lubricating oil composition that meets the specifications of SAE J300, which are the January 2015 revised requirements for SAE 20, 30, 40, 50, or 60 monograde engine oils. The kinematic viscosity of SAE 20 oil is 6.9 to <9.3 mm 2 / s at 100 °C. The kinematic viscosity of SAE 30 oil is 9.3 to <12.5 mm 2 / s at 100 °C. The kinematic viscosity of SAE 40 oil is 12.5 to <16.3 mm 2 / s at 100 °C. The kinematic viscosity of SAE 50 oil is 16.3 to <21.9 mm2 The value is / s. The kinematic viscosity of SAE60 oil is 21.9 to <26.1 mm at 100°C. 2 It is / s.

[0019] In some embodiments, the lubricating oil composition is suitable for use as a marine cylinder lubricant (MCL). Marine cylinder lubricants are typically manufactured in accordance with SAE30, SAE40, SAE50, or SAE60 monograde specifications to provide a sufficiently thick lubricating film on the cylinder liner wall at high temperatures. Typically, TBN in marine diesel cylinder lubricants is 15-200 mg KOH / g (for example, 15-150 mg KOH / g, 15-60 mg KOH / g, 20-200 mg KOH / g, 20-150 mg KOH / g, 20-120 mg KOH / g, 20-80 mg KOH / g, 30-200 mg KOH / g, 30-150 mg KOH / g, 30-120 mg KOH / g, 30-100 mg KOH / g, 30-80 mg KOH / g, 60-200 mg KOH / g, 60-150 mg KOH / g, 60-120 mg KOH / g, 60-100 mg KOH / g, 60-80 mg KOH / g, 80-200 mg KOH / g, 80-150 mg KOH / g, 80-150 mg The range is 120 KOH / g, 120-200 mg KOH / g, or 120-150 mg KOH / g.

[0020] In some embodiments, this lubricating oil composition is suitable for use as a marine system oil. Marine system oil lubricants are typically manufactured in SAE20, SAE30, or SAE40 monograde specifications. The viscosity of marine system oils is set at such a relatively low level because the viscosity of the system oil may increase during use, and engine designers set viscosity increase limits to prevent operational problems. Typically, the TBN of marine system oil lubricants is in the range of 5 to 12 mg KOH / g (e.g., 5 to 10 mg KOH / g, or 5 to 9 mg KOH / g).

[0021] In some embodiments, this lubricating oil composition is suitable for use as a trunk piston engine oil (TPEO) for marine engines. Marine TPEO lubricants are typically manufactured to SAE 30 or SAE 40 monograde specifications. Typically, the TBN of marine TPEO lubricants ranges from 10 to 60 mg KOH / g (e.g., 10 to 30 mg KOH / g, 20 to 60 mg KOH / g, 20 to 40 mg KOH / g, 30 to 60 mg KOH / g, or 30 to 55 mg KOH / g).

[0022] Lubricating viscosity of oil Lubricating viscosity oils can be selected from any of the base oils in Groups I through V, as specified in the American Petroleum Institute (API) Base Oil Interoperability Guidelines (API 1509). The five base oil groups are summarized in Table 1. [Table 1]

[0023] Groups I, II, and III are mineral oil process stocks. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinic unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatic compounds, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but they can also be naturally occurring oils such as vegetable oils. It should be noted that while Group III base oils are derived from mineral oil, the rigorous processing these fluids undergo results in physical properties very similar to some true synthetic oils such as PAO. Therefore, oils derived from Group III base oils are sometimes referred to as synthetic fluids in the industry.

[0024] The base oils used in the disclosed lubricating oil compositions may be mineral oils, animal oils, vegetable oils, synthetic oils, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrotapping, hydrofinishing, unrefined, refined, and refined oils, and mixtures thereof.

[0025] Unrefined oils are derived from natural, mineral, or synthetic sources and undergo little to no refining. Refined oils are similar to unrefined oils except that they undergo one or more refining steps, which may improve one or more properties. Examples of appropriate refining techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, and leaching. Oils refined to edible quality may or may not be useful. Edible oils are sometimes called white oils. In some embodiments, lubricating oil compositions do not contain edible oils or white oils.

[0026] Refined oils are also known as recycled oils or reprocessed oils. These oils are obtained in the same way as refined oils using the same or similar processes. Often, these oils are further processed by techniques for removing spent additives and oil degradation products.

[0027] Mineral oils may include oils obtained by drilling or from plants and animals, or any mixture thereof. Such oils include castor oil, lard, olive oil, peanut oil, corn oil, soybean oil, linseed oil, and liquid petroleum-based oils, as well as mineral lubricants such as paraffinic, naphthenic, or paraffinic-naphthenic mixtures, which are solvent-treated or acid-treated. Such oils can be partially or completely hydrogenated as needed. Oils derived from coal or shale may also be useful.

[0028] Useful synthetic lubricants include hydrocarbon oils such as polymerized, oligomerized, or crosspolymerized olefins (e.g., polybutylene, polypropylene, propylene / isobutylene copolymers); trimers or oligomers of poly(1-hexene), poly(1-octene), and 1-decene, e.g., poly(1-decene), such materials are often called α-olefins, and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs or mixtures thereof. Polyalphaolefins are usually hydrogenated materials.

[0029] Other synthetic lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decanephosphonic acid), or high molecular weight tetrahydrofurans. Synthetic oils can be produced by the Fischer-Tropsch reaction and are usually hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure, as well as by other gas-to-liquid oils.

[0030] The base oils used in the useful lubricating formulations described herein are any of the various oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof. In one embodiment, the base oil is a Group II base oil or a blend of two or more different base oils (e.g., a mixture of Group I and Group II base oils). In another embodiment, the base oil is a Group I base oil or a blend of two or more different Group I base oils. Suitable Group I base oils include any light overhead cut from a vacuum distillation column, such as light neutral, medium neutral, and heavy neutral base stocks. The base oil may also include bottom fractions such as residual base oil stock or bright stock. Bright stock is a highly refined and dewaxed high-viscosity base oil conventionally produced from residual stock or bottom fractions. Bright stock is 180 mm at 40°C. 2 kinematic viscosity exceeding / s (for example, 250 mm) 2 / s exceeding, or 500-1100mm 2 It may have a range of / s.

[0031] The base oil constitutes the main component of the lubricating oil composition of this disclosure and is present in an amount exceeding 50% by weight (e.g., at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 90% by weight) based on the total weight of the composition. The base oil is measured at 100°C and is 2-40 mm 2 Having a kinematic viscosity of / s is convenient.

[0032] Ashless alkyl-substituted hydroxyaromatic carboxylic acids The alkyl-substituted hydroxyaromatic carboxylic acids of this disclosure will be present in the lubricating oil composition in small amounts compared to the lubricating viscosity of the oil. The concentration of the alkyl-substituted hydroxyaromatic carboxylic acids in the lubricating oil of this disclosure may range from 0.1 to 20% by weight or more (e.g., 0.25 to 15% by weight, 0.5 to 10% by weight, 0.75 to 5% by weight, or 1 to 5% by weight, or 2 to 5% by weight) based on the total weight of the lubricating oil.

[0033] One embodiment of this disclosure has the following structure (1): [ka] Regarding alkyl-substituted hydroxyaromatic carboxylic acids represented by, In the formula, the carboxylic acid group may be in the ortho, meta, or para position relative to the hydroxyl group, or a mixture thereof. 1 This is an alkyl substituent having 12 to 40 carbon atoms (for example, 14 to 28 carbon atoms, 14 to 18 carbon atoms, 18 to 30 carbon atoms, 20 to 28 carbon atoms, or 20 to 24 carbon atoms).

[0034] The alkyl substituent of an alkyl-substituted hydroxyaromatic carboxylic acid may be a residue derived from an alpha-olefin having 12 to 40 carbon atoms. In one embodiment, the alkyl substituent is a residue derived from an alpha-olefin having 14 to 28 carbon atoms. In one embodiment, the alkyl substituent is a residue derived from an alpha-olefin having 14 to 18 carbon atoms. In one embodiment, the alkyl substituent is a residue derived from an alpha-olefin having 20 to 28 carbon atoms. In one embodiment, the alkyl substituent is a residue derived from an alpha-olefin having 20 to 24 carbon atoms. In one embodiment, the alkyl substituent of an alkyl-substituted hydroxyaromatic carboxylic acid is a monomer selected from propylene, butylene, or a mixture thereof. 12 ~C 40These are residues derived from olefins containing oligomers. Examples of such olefins include propylene tetramers, butylene trimers, isobutylene oligomers (e.g., polyisobutylene), and tetramer dimers. The olefins used may be linear, isomerized linear, branched, or partially branched linear. The olefins may be mixtures of linear olefins, mixtures of isomerized linear olefins, mixtures of branched olefins, mixtures of partially branched linear olefins, or any of the aforementioned mixtures. Alpha-olefins may be normal alpha-olefins, isomerized normal alpha-olefins, or mixtures thereof.

[0035] In one embodiment, where the alkyl substituent is a residue derived from the isomerized alphaolefin, the alphaolefin may have an isomerization level (I) of 0.1 to 0.4 (e.g., 0.1 to 0.3, or 0.1 to 0.2). The isomerization level (I) is, 1 This can be determined by 1H NMR spectroscopy and represents the relative amount of methyl groups (-CH3) (chemical shift 0.30-1.01 ppm) bonded to methylene skeleton groups (-CH2-) (chemical shift 1.01-1.38 ppm), as shown by the following formula: I = m / (m+n) Defined by, In the formula, m is a methyl group having a chemical shift of 0.30±0.03 to 1.01±0.03 ppm. 1 This is an 1H NMR integral, where n is the methylene group having a chemical shift of 1.01±0.03 to 1.38±0.10 ppm. 1 This is an H NMR integral.

[0036] In one embodiment, the alkyl-substituted hydroxyaromatic carboxylic acid has the following structure (2): [ka] It can be represented by, In the formula, R 1 This is as described above in this specification.

[0037] In one embodiment, the alkyl-substituted hydroxyaromatic carboxylic acid is a hydroxyaromatic compound (e.g., phenol) and a β-branched primary alcohol (e.g., C) as described in U.S. Patent No. 8,704,006. 12 -C 40 It originates from alkyl-substituted hydroxyaromatic compounds, which are alkylation products of Guerbet-type alcohols.

[0038] In one embodiment, the alkyl-substituted hydroxyaromatic carboxylic acid is derived from a renewable source of alkylphenol compounds, such as distilled cashew nut shell liquid (CNSL) or hydrogenated CNSL. Distilled CNSL is a mixture of metahydrocarbyl-substituted phenols, where the hydrocarbyl groups are linear and unsaturated, and includes cardanol. Catalytic hydrogenation of distilled CNSL produces a mixture of metahydrocarbyl-substituted phenols, mainly rich in 3-pentadecylphenol.

[0039] Alkyl-substituted hydroxyaromatic carboxylic acids can be prepared by methods known in the art, such as those described in U.S. Patents 8,030,258 and 8,993,499. Process for preparing alkyl-substituted hydroxyaromatic carboxylic acids

[0040] The alkyl-substituted hydroxyaromatic carboxylic acids of this disclosure can be prepared by any process known to those skilled in the art for producing alkyl-substituted hydroxyaromatic carboxylic acids. For example, a process for preparing an alkyl-substituted hydroxyaromatic carboxylic acid may include (a) alkylating a hydroxyaromatic compound with an olefin to produce an alkyl-substituted hydroxyaromatic compound; (b) reacting the alkyl-substituted hydroxyaromatic compound with an alkali metal base to produce an alkali metal salt of the alkyl-substituted hydroxyaromatic compound; (c) carboxylating the alkali metal salt of the alkyl-substituted hydroxyaromatic compound with a carboxylating agent (e.g., CO2) to produce an alkali metal alkyl-substituted hydroxyaromatic carboxylate; and (d) acidifying the alkali metal alkyl-substituted hydroxyaromatic carboxylate with an aqueous solution of an acid strong enough to produce an alkyl-substituted hydroxyaromatic carboxylic acid.

[0041] (A) Alkylation Alkylation can be carried out by introducing a hydrocarbon feed containing a hydroxyaromatic compound or a mixture of hydroxyaromatic compounds, an olefin or a mixture of olefins, and an acid catalyst into a reaction zone under constant stirring. The resulting mixture is held in the alkylation zone under alkylation conditions for a sufficient time to allow for substantial conversion of the olefin to a hydroxyaromatic alkylate (e.g., at least 70% mol% of the olefin reacted). After the desired reaction time, the reaction mixture can be removed from the alkylation zone and fed into a liquid-liquid separator to separate the hydrocarbon product from the acid catalyst, which can then be recycled back into the reactor in a closed loop. The hydrocarbon product can be further processed to remove excess unreacted hydroxyaromatic and olefin compounds from the desired alkylate product. Excess hydroxyaromatic compounds can also be recycled back into the reactor.

[0042] Suitable hydroxyaromatic compounds include monocyclic hydroxyaromatic compounds and polycyclic hydroxyaromatic compounds comprising one or more aromatic moieties, such as one or more benzene rings, which are optionally fused together or otherwise connected via alkylene bridges. Exemplary hydroxyaromatic compounds include phenol, cresol, and naphthol. In one embodiment, the hydroxyaromatic compound is phenol. In one embodiment, the hydroxyaromatic compound is naphthol.

[0043] The olefins used may be linear, isomerized linear, branched, or partially branched linear. The olefins may be mixtures of linear olefins, mixtures of isomerized linear olefins, mixtures of branched olefins, mixtures of partially branched linear olefins, or any of the aforementioned mixtures. In some embodiments, the olefins are normal alpha olefins, isomerized normal alpha olefins, or mixtures thereof.

[0044] In some embodiments, the olefin is a mixture of normal alpha-olefins selected from olefins having 12 to 40 carbon atoms per molecule (e.g., 14 to 28 carbon atoms per molecule, 14 to 18 carbon atoms per molecule, 18 to 30 carbon atoms per molecule, 20 to 28 carbon atoms per molecule, 20 to 24 carbon atoms per molecule). In some embodiments, the normal alpha-olefin is isomerized using at least one solid or liquid catalyst.

[0045] In another embodiment, the olefin is a monomer selected from propylene, butylene, or a mixture thereof. 12 ~C 40 It contains one or more olefins, including oligomers. Generally, one or more olefins are monomers selected from propylene, butylene, or mixtures thereof. 12 ~C 40It will likely contain a major amount of oligomers. Examples of such olefins include propylene tetramers and butylene trimers. As will be readily apparent to those skilled in the art, other olefins may exist. For example, C 12 ~C 40 Other olefins that can be used in addition to the oligomers include linear olefins, cyclic olefins, branched olefins other than propylene oligomers such as butylene or isobutylene oligomers, arylalkylenes, and mixtures thereof. Suitable linear olefins include 1-hexene, 1-nonene, 1-decene, 1-dodecene, and mixtures thereof. Particularly suitable linear olefins can be obtained from processes such as ethylene oligomerization or wax cracking, C 16 ~C 30 These are high molecular weight normal alpha-olefins, such as normal alpha-olefins. Suitable cyclic olefins include cyclohexene, cyclopentene, cyclooctene, and mixtures thereof. Suitable branched-chain olefins include butylene dimers or trimers or high molecular weight isobutylene oligomers, and mixtures thereof. Suitable arylalkylenes include styrene, methylstyrene, 3-phenylpropene, 2-phenyl-2-butene, and mixtures thereof.

[0046] Any suitable reactor configuration can be used in the reactor zone. These include batch and continuous stirred-tank reactors, reactor riser configurations, and boiling or fixed-bed reactors.

[0047] Alkylation can be carried out at temperatures between 15°C and 200°C, at a pressure sufficient to keep a significant portion of the feed in the liquid phase. Typically, a pressure of 0–150 psig is sufficient to maintain the feed and product in the liquid phase.

[0048] The residence time in the reactor is sufficient to convert a significant portion of the olefin into the alkylate product. The required time can range from 30 seconds to approximately 300 minutes. A more precise residence time can be determined by those skilled in the art using a batch-type stirred reactor to measure the kinetics of the alkylation process.

[0049] At least one hydroxyaromatic compound or a mixture of hydroxyaromatic compounds and an olefin can be injected separately into the reaction zones or mixed before injection. Both single and multiple reaction zones can be used by injecting the hydroxyaromatic compounds and olefins into one, some, or all of the reaction zones. It is not necessary to maintain the same process conditions in the reaction zones.

[0050] The hydrocarbon feed for the alkylation process may include a mixture of hydroxyaromatic compounds and a mixture of olefins, such that the molar ratio of hydroxyaromatic compounds to olefins is 0.5:1 to 50:1 or greater. If the molar ratio of hydroxyaromatic compounds to olefins is greater than 1:1, there is an excess of hydroxyaromatic compounds. Preferably, an excess of hydroxyaromatic compounds is used to increase the reaction rate and improve the selectivity of the product. If an excess of hydroxyaromatic compounds is used, the excess unreacted hydroxyaromatic compounds in the reactor effluent can be separated (e.g., by distillation) and recycled back into the reactor.

[0051] Typically, alkyl-substituted hydroxyaromatic compounds include a mixture of monoalkyl-substituted isomers. The alkyl group in alkyl-substituted hydroxyaromatic compounds is typically bonded to the hydroxyl group primarily at the ortho and para positions of the hydroxyaromatic compound. In one embodiment, the alkylation product may consist of 1-99% ortho isomers and 99-1% para isomers. In another embodiment, the alkylation product may consist of 5-70% ortho isomers and 95-30% para isomers.

[0052] Acidic alkylation catalysts are strong acid catalysts such as Brønsted acids or Lewis acids. Useful strong acid catalysts include hydrofluoric acid, hydrochloric acid, hydrobromic acid, perchloric acid, nitric acid, sulfuric acid, trifluoromethanesulfonic acid, fluorosulfonic acid, AMBERLYST® 36 sulfonic acid (available from The Dow Chemical Company), nitric acid, aluminum trichloride, aluminum tribromide, boron trifluoride, antimony pentachloride, and mixtures thereof. Acidic ionic liquids can be used as an alternative to the strong acid catalysts commonly used in alkylation processes.

[0053] (B) Neutralization Alkyl-substituted hydroxyaromatic compounds are neutralized with an alkali metal base (e.g., an oxide or hydroxide of lithium, sodium, or potassium). Neutralization occurs in the presence of a light solvent (e.g., toluene, xylene isomers, light alkylbenzenes, etc.), which can form an alkali metal salt of the alkyl-substituted hydroxyaromatic compound. In one embodiment, the solvent forms an azeotropic mixture with water. In another embodiment, the solvent may be a monoalcohol such as 2-ethylhexanol. In this case, 2-ethylhexanol is removed by distillation before carboxylation. The purpose of introducing the solvent is to facilitate the removal of water.

[0054] Neutralization is carried out at a high enough temperature to remove moisture. Neutralization can be performed under a slight vacuum to require lower reaction temperatures.

[0055] In one embodiment, xylene is used as the solvent, and the reaction is carried out at a temperature of 130°C to 155°C under an absolute pressure of approximately 80 kPa.

[0056] In another embodiment, 2-ethylhexanol is used as the solvent. Since the boiling point of 2-ethylhexanol (184°C) is significantly higher than that of xylene (140°C), neutralization is carried out at a temperature of at least 150°C.

[0057] To complete the distillation of water, the pressure can be gradually reduced below atmospheric pressure. In one embodiment, the pressure is reduced to 7 kPa or less.

[0058] By performing the operation at a sufficiently high temperature and gradually decreasing the pressure in the reactor below atmospheric pressure, the formation of alkali metal salts of alkyl-substituted hydroxyaromatic compounds can be carried out without the need to add a solvent, forming an azeotropic mixture with the water formed during this reaction. For example, the temperature is raised to 200°C, and then the pressure is gradually reduced below atmospheric pressure. Preferably, the pressure is reduced to 7 kPa or less.

[0059] Water removal can occur over a period of at least one hour (for example, at least three hours).

[0060] The amount of reagent may correspond to a molar ratio of 0.5:~1.2:1 (e.g., 0.9:1~1.05:1) between the alkali metal base and the alkyl-substituted hydroxyaromatic compound, and a weight / weight ratio of 0.1:1~5:1 (e.g., 0.3:1~3:1) between the solvent and the alkyl-substituted hydroxyaromatic compound.

[0061] (C) Carboxylation The carboxylation step is carried out by simply bubbling carbon dioxide (CO2) into the reaction medium resulting from the previous neutralization step, until at least 50 mol% of the starting alkali metal salt of the alkyl-substituted hydroxyaromatic compound is converted to an alkali metal alkyl-substituted hydroxyaromatic carboxylate (measured as hydroxybenzoic acid by potentiometric measurement).

[0062] At least 50 mol% (e.g., at least 75 mol%, or at least 85 mol%) of the starting alkali metal salt of the alkyl-substituted hydroxyaromatic compound is converted to an alkali metal alkyl-substituted hydroxyaromatic carboxylate using CO2 for 1 to 8 hours at a temperature of 110°C to 200°C under a pressure of 0.1 to 1.5 MPa.

[0063] In one variant using potassium salts, the temperature may be between 125°C and 165°C (e.g., 130°C and 155°C), and the pressure may be between 0.1 and 1.5 MPa (e.g., 0.1 and 0.4 MPa).

[0064] In another variant using sodium salts, the temperature may be lower in the direction, ranging from 110°C to 155°C (e.g., 120°C to 140°C), and the pressure may be 0.1 to 2.0 MPa (e.g., 0.3 to 1.5 MPa).

[0065] Carboxylation is usually carried out in a diluent such as a hydrocarbon or alkylate (e.g., benzene, toluene, xylene, etc.). In this case, the weight ratio of the solvent to the alkali metal salt of the alkyl-substituted hydroxyaromatic compound may be in the range of 0.1:1 to 5:1 (e.g., 0.3:1 to 3:1).

[0066] In another variant, no solvent is used. In this case, carboxylation is carried out in the presence of a diluent oil to avoid materials that are too viscous. The weight ratio of the diluent oil to the alkali metal salt of the alkyl-substituted hydroxyaromatic compound may be in the range of 0.1:1 to 2:1 (e.g., 0.2:1 to 1:1, or 0.2:1 to 0.5:1).

[0067] (D) Acidification Next, the alkali metal alkyl-substituted hydroxyaromatic carboxylate produced above is brought into contact with at least one acid capable of converting the alkali metal alkyl-substituted hydroxyaromatic carboxylate to an alkyl-substituted hydroxyaromatic carboxylic acid. Such acids are well known in the art to acidify the aforementioned alkali metal salts. Typically, hydrochloric acid or an aqueous sulfuric acid solution is used.

[0068] Other performance additives The lubricating oil formulations of this disclosure may further contain one or more other commonly used lubricating oil performance additives. Such optional components include detergents (e.g., metal detergents), dispersants, anti-wear agents, antioxidants, friction modifiers, corrosion inhibitors, rust inhibitors, demulsifiers, anti-foaming agents, viscosity modifiers, pour point depressants, nonionic surfactants, and thickeners. Some of these are described in more detail below.

[0069] Cleansing agent Detergents are additives that reduce the formation of deposits on pistons, such as high-temperature varnish and lacquer deposits in engines. They typically have acid-neutralizing properties and can keep finely divided solids suspended. Most detergents are based on metal "soaps," which are metal salts of acidic organic compounds.

[0070] Detergents generally contain a polar head with a long hydrophobic tail, the polar head containing a metal salt of an acidic organic compound. The salt may contain substantially stoichiometric amounts of metal, in which case it is usually described as a normal or neutral salt and may typically have 0 to <100 mg KOH / g of TBN in 100% active mass. Large amounts of metal base can be included by the reaction of excess metal compounds, such as oxides or hydroxides, with acidic gases such as carbon dioxide.

[0071] The resulting overbasic detergent contains a neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle. Such an overbasic detergent may have TBN of 100 mg KOH / g or more (e.g., 200-500 mg KOH / g or more) in 100% active mass.

[0072] Suitable cleaning agents include oil-soluble neutral and overbasic sulfonates, phenates, sulfide phenates, thiophosphonates, salicylates, and naphthenates, as well as other oil-soluble carboxylates of metals, particularly alkali metals or alkaline earth metals (e.g., lithium, sodium, potassium, calcium, and magnesium). The most commonly used metals are Ca and Mg, and mixtures of Ca and / or Mg with Na, both of which may be present in the cleaning agents used in the lubricating composition. Cleaning agents can be used in various combinations.

[0073] The cleaning agent may be present in the lubricating oil composition at a concentration of 0.5 to 20% by weight.

[0074] Dispersant During engine operation, oil-insoluble oxidation byproducts are generated. Dispersants help keep these byproducts in solution and reduce their deposition on metal surfaces. Dispersants are well known as ashless dispersants because they do not contain metals that form ash before being mixed into the lubricant composition and typically do not contribute to any ash content when added to the lubricant. Ashless dispersants are characterized by polar groups bonded to relatively high molecular weight or heavy hydrocarbon chains. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. An example of an N-substituted long-chain alkenyl succinimide is polyisobutylene succinimide, which has a number-average molecular weight of polyisobutylene substituents in the range of 500 to 5000 daltons (e.g., 900 to 2500 daltons). Succinimide dispersants and their preparations are disclosed, for example, in U.S. Patents 4,234,435 and 7,897,696. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamine).

[0075] In some embodiments, the lubricant composition comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number-average molecular weight in the range of 500 to 5000 daltons (e.g., 900 to 2500 daltons). Polyisobutylene succinimide can be used alone or in combination with other dispersants.

[0076] The dispersant can also be post-treated by conventional methods involving reaction with one of various agents. These agents include boron compounds (e.g., boric acid) and cyclic carbonates (ethylene carbonates).

[0077] Another class of dispersants includes Mannich bases. Mannich bases are materials formed by the condensation of high molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in detail in U.S. Patent No. 3,634,515.

[0078] Another class of dispersants includes high molecular weight esters prepared by the reaction of hydrocarbyl acylating agents with polyhydric aliphatic alcohols such as glycerol, pentaerythritol, or sorbitol. Such materials are described in detail in U.S. Patent No. 3,381,022.

[0079] Another class of dispersants includes high molecular weight ester amides.

[0080] The dispersant can be present in the lubricating oil composition at a concentration of 0.1 to 10% by weight.

[0081] wear-resistant agent Anti-wear agents reduce friction and excessive wear and are typically based on compounds containing sulfur, or phosphite, or both. Of particular note are dihydrocarbyl dithiophosphate metal salts, where the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, copper, or zinc. Zinc dihydrocarbyl dithiophosphate (ZDDP) is an oil-soluble salt of dihydrocarbyl dithiophosphate, and is given the following formula: Zn[SP(S)(OR)(OR')]2 It can be expressed as, In the formula, R and R' can be the same or different hydrocarbyl radicals containing 1 to 18 (e.g., 2 to 12) carbon atoms. To obtain oil solubility, the total number of carbon atoms in dithiophosphate (i.e., R and R') is generally 5 or more.

[0082] The anti-wear agent can be present in the lubricating oil composition at a concentration of 0.1 to 6% by weight.

[0083] Antioxidants Antioxidants slow down the oxidative degradation of the base oil during use. Such degradation can lead to deposits on metal surfaces, the presence of sludge, or an increase in the viscosity of the lubricant.

[0084] Useful antioxidants include hindered phenols. Hindered phenol antioxidants often contain secondary and / or tertiary butyl groups as sterically hindered groups. The phenol group may be further substituted with hydrocarbyl groups (typically linear or branched alkyl) and / or crosslinking groups bonded to a second aromatic group. Examples of hindered phenol antioxidants include 2,6-di-tert-butylphenol, 2,6-di-tert-butylcresol, 2,4,6-tri-tert-butylphenol, 2,6-di-alkylphenolpropionate derivatives, and bisphenols such as 4,4'-bis(2,6-di-tert-butylphenol) and 4,4'-methylene-bis(2,6-di-tert-butylphenol).

[0085] Alkylphenol sulfides and their alkali and alkaline earth metal salts are also useful as antioxidants.

[0086] Non-phenolic antioxidants that can be used include aromatic amine antioxidants such as diarylamines and alkylated diarylamines. Specific examples of aromatic amine antioxidants include phenyl-α-naphthylamine, 4,4'-dioctyldiphenylamine, butylated / octylated diphenylamine, nonylated diphenylamine, and octylated phenyl-α-naphthylamine.

[0087] Antioxidants can be present in the lubricating oil composition at a concentration of 0.01 to 5% by weight.

[0088] Friction modifier A friction modifier is any material that can alter the coefficient of friction of a surface lubricated by a lubricant or fluid containing such material. Suitable friction modifiers include fatty amines, esters such as glycerol borate esters, fatty phosphates, fatty acid amides, fatty epoxides, fatty borate epoxides, alkoxylated fatty amines, alkoxylated fatty borate amines, metal salts of fatty acids, or fatty imidazolines, and condensation products of carboxylic acids and polyalkylene polyamines. As used herein, the term “fatty” in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain. Molybdenum compounds are also known as friction modifiers. Friction modifiers can be present in 0.01 to 5% by weight of the lubricating oil composition.

[0089] Rust inhibitor Rust inhibitors generally protect lubricated metal surfaces from chemical attack by water or other contaminants. Suitable rust inhibitors include suitable nonionic rust inhibitors, and may include nonionic polyoxyalkylene agents (e.g., polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate); stearic acid and other fatty acids; dicarboxylic acids; metal soaps; fatty acid amine salts; metal salts of bisulfonic acids; partial carboxylic acid esters of polyhydric alcohols; phosphate esters; (short-chain) alkenyl succinic acid, its partial esters and nitrogen-containing derivatives; and synthetic alkali sulfonates (e.g., metal dinonylnaphthalene sulfonate). Such additives may be present in 0.01 to 5% by weight of the lubricating oil composition.

[0090] Deemulsifier Deemulsifiers facilitate oil-water separation of lubricating oil compositions exposed to water or steam. Suitable deemulsifiers include trialkyl phosphates, as well as various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof. Such additives can be present in the lubricating oil composition at a concentration of 0.01 to 5% by weight.

[0091] Anti-foaming agent Antifoaming agents delay the formation of stable foam. Silicones and organic polymers are typical antifoaming agents. For example, polysiloxanes such as silicone oil, or polydimethylsiloxanes, provide foam-suppressing properties. Further antifoaming agents include copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate. Such additives can be present in the lubricating oil composition at a concentration of 0.001 to 1% by weight.

[0092] Viscosity modifier Viscosity modifiers provide lubricants with operability at both high and low temperatures. These additives impart shear stability at high temperatures and acceptable viscosity at low temperatures. Suitable viscosity modifiers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene polymers, styrene / maleate copolymers, styrene-butadiene copolymers, styrene-isoprene polymers, alphaolefin-maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, and hydrated alkenylaryl conjugated diene copolymers. Such additives can be present in the lubricating oil composition at a concentration of 0.1 to 15% by weight.

[0093] Pour point depressant Pour point depressants lower the minimum temperature at which a fluid can flow or be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyacrylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkyl fumarates, vinyl esters of fatty acids, and allyl vinyl ethers. Such additives can be present in the lubricating oil composition at a concentration of 0.01 to 1% by weight.

[0094] Nonionic surfactants Nonionic surfactants such as alkylphenols may improve the handling of asphaltenes during engine operation. Examples of such materials include alkylphenols having alkyl substituents from linear or branched alkyl groups having 9 to 30 carbon atoms. Other examples include alkylbenzenols, alkylnaphthols, and alkylphenol aldehyde condensates, in which the aldehyde is formaldehyde, resulting in a methylene-crosslinked alkylphenol condensate. Such additives can be present in the lubricating oil composition at concentrations of 0.1 to 20% by weight.

[0095] Thickening agent Lubricants can be thickened using thickeners such as polyisobutylene (PIB) and polyisobutenyl succinic anhydride (PIBSA). PIB and PIBSA are commercially available materials from several manufacturers. PIB can be used in the manufacture of PIBSA and is typically a viscous, oil-miscible liquid with a weight-average molecular weight in the range of 1000-8000 daltons (e.g., 1500-6000 daltons) and a kinematic viscosity of 2000-6000 mmHg at 100°C. 2 The range is / s. Such additives can be present in 1 to 20% by weight of the lubricating oil composition.

[0096] Use of lubricating oil composition The lubricant composition may be effective as engine oil or crankcase lubricant for spark-ignition and compression-ignition internal combustion engines, including automobile and truck engines, two-stroke cycle engines, aircraft piston engines, marine diesel engines, and fixed-gas engines.

[0097] An internal combustion engine can be a two-stroke or four-stroke engine.

[0098] In one embodiment, the internal combustion engine is a marine diesel engine. The marine diesel engine may be a medium-speed four-stroke compression ignition engine with a speed of 250 to 1100 rpm, or a low-speed crosshead two-stroke compression ignition engine with a speed of 200 rpm or less (for example, 10 to 200 rpm, or 60 to 200 rpm).

[0099] Marine diesel engines can be lubricated with marine diesel cylinder lubricant (usually for two-stroke engines), system oil (usually for two-stroke engines), or crankcase lubricant (usually for four-stroke engines).

[0100] The term "marine" does not limit engines to those used in water-borne vessels, but also includes engines for other industrial applications, such as auxiliary power generators for primary propulsion and stationary land-based power generators, as understood in the art.

[0101] In some embodiments, the internal combustion engine may be fueled with residual fuel, marine residual fuel, low-sulfur marine residual fuel, marine distillate fuel, low-sulfur marine distillate fuel, or high-sulfur fuel.

[0102] "Residual fuel" is defined as having at least 2.5% by weight (e.g., at least 5% by weight, or at least 8% by weight) of carbon residue and a viscosity of 14.0 mm at 50°C, as determined by ISO 10370:2014. 2 This refers to flammable materials in large marine engines exceeding 1 / s, such as marine residual fuel as defined in ISO 8217:2017 ("Petroleum products - Fuels (Class F) - Marine fuel specifications"). Residual fuel is mainly the non-boiling fraction of crude oil distillation. Depending on the pressure and temperature of the refinery's distillation process, as well as the type of crude oil, a small amount of potentially boiling diesel fuel remains in the non-boiling fraction, resulting in various grades of residual fuel.

[0103] "Marine residual fuel" refers to fuel that meets the specifications for marine residual fuel as defined in ISO 8217:2017. "Low sulfur marine residual fuel" refers to fuel that conforms to the specifications for marine residual fuel as defined in ISO 8217:2017, and further contains 1.5% by weight or less of sulfur, or even 0.5% by weight or less, relative to the total weight of the fuel. This fuel is a residual product of the distillation process.

[0104] Distillate fuel consists of petroleum fractions of crude oil separated at refineries by boiling or "distillation" processes. "Marine distillate fuel" is fuel that meets the specifications for marine distillate fuel as defined in ISO 8217:2017. "Low sulfur marine distillate fuel" is fuel that meets the specifications for marine spill fuel as defined in ISO 8217:2017 and further contains 0.1% by weight or less, 0.05% by weight or less, or even 0.005% by weight or less of sulfur relative to the total weight of the fuel, and this fuel is the distillation cut of the distillation process.

[0105] "High-sulfur fuel" refers to fuel that contains more than 1.5% by weight of sulfur relative to its total weight.

[0106] Internal combustion engines may also be operated on “gaseous fuels” such as methane-dominant fuels (e.g., natural gas), biogas, liquefied gas gas, or liquefied natural gas gas (LNG).

[0107] example The following examples are intended to be non-restrictive.

[0108] Test method The Black Sludge Deposit (BSD) test is used to evaluate the ability of lubricants to deal with unstable unburned asphaltenes in residual fuel oil. This test measures the tendency of lubricant to deposit on test paper by applying oxidative thermal strain to a mixture of heavy oil and lubricant. A sample of the lubricant composition is mixed with a specific amount of residual fuel to form the test mixture. The test mixture is pumped as a thin film onto metal test paper, controlled for a set time (12 hours) at the test temperature (200°C) during the test. The oil-fuel test mixture is recycled back into the sample container. After the test, the test paper is cooled, washed, and dried. The weight of the test plate is then measured. In this way, the weight of the deposit remaining on the test plate is measured and recorded as the change in the weight of the test plate. Improvement in sludge treatment is demonstrated by a smaller weight of deposit remaining on the test plate.

[0109] Sediment control is measured by the Komatsu Hot Tube (KHT) test, which uses a heated glass tube. Through this glass tube, a sample of lubricant, approximately 5 mL of the total sample, is pumped with an airflow of 10 mL / min, typically at 0.31 mL / hour for an extended period, e.g., 16 hours. At the end of the test, the glass tube is evaluated for the sediment on a scale from 1.0 (very heavy varnish) to 10 (no varnish). Test results are reported in multiples of 0.5. If the glass tube is completely clogged with sediment, the test result is recorded as "clogged." Clogged sediment is below a 1.0 rating (in this case, the lacquer is very thick and dense, but fluid flow is still possible). The test is performed at 310°C and is described in SAE Technical Paper 840262.

[0110] The oxidation stability of lubricants is evaluated using the Modified Institute of Petroleum Test Method 48 (MIP-48). In this test, two samples of the lubricant are heated for a set period of time. Nitrogen is passed through one of the test samples, and air is passed through the other. The two samples are then cooled, and the viscosity of each sample is determined. The viscosity increase due to oxidation of each lubricant composition is calculated by subtracting the kinematic viscosity at 100°C of the nitrogen-blown sample from the kinematic viscosity at 100°C of the air-blown sample, and dividing the difference in this subtraction by the kinematic viscosity at 100°C of the nitrogen-blown sample. Better stability against viscosity increase due to oxidation is demonstrated by a lower viscosity increase.

[0111] Examples 1-5 A series of 40BN trunk piston engine oil lubricants formulated with Group I base oils were prepared with ashless alkyl-substituted hydroxyaromatic carboxylic acids and conventional additives such as overbasic alkylhydroxybenzoate calcium detergent ("Ca detergent"), zinc dialkyldithiophosphate (ZDDP), and anti-foaming agents. Comparative lubricants were prepared without the use of ashless alkyl-substituted hydroxyaromatic carboxylic acids. These lubricants were evaluated for sludge treatment, deposit control, and viscosity increase and base number (BN) decrease due to oxidation.

[0112] Overbasic alkylhydroxybenzoate calcium cleaning agent is C 20 ~C 28 It has alkyl substituents derived from a linear n-alphaolefin and was prepared according to the method described in Example 1 of U.S. Patent Application Publication 2007 / 0027043. On an as-received basis, the additive contained 12.5% ​​by weight of Ca and about 33% by weight of diluent oil, with a TBN of about 350 mg KOH / g and a basicity index of about 7.2. On an active ingredient basis, the TBN of this additive is about 520 mg KOH / g.

[0113] Ashless alkyl-substituted hydroxyaromatic carboxylic acids are C 20 -C 24C derived from isomerized n-alphaolefin 20 -C 24 This is an oil concentrate of hydrocarbyl-substituted hydroxyaromatic salicylic acid. The concentrate contained approximately 25.0% by weight of diluted oil.

[0114] The results are summarized in Table 2. The weight percentages reported for the additives in Table 2 are based on their condition as received. [Table 2]

[0115] As is clear from the results shown in Table 2, trunk piston engine lubricant compositions containing ashless alkyl-substituted hydroxyaromatic carboxylic acids (Examples 1-5) showed remarkably little black sludge formation in marine residual fuel, improved deposit control, and improved stability against viscosity increase and BN decrease due to oxidation compared to lubricant compositions without ashless alkyl-substituted hydroxyaromatic carboxylic acids (Comparative Example A).

[0116] Examples 6-10 A series of 40BN trunk piston engine oil lubricants formulated with Group II base oils were prepared, as described in Examples 1-5, including ashless alkyl-substituted hydroxyaromatic carboxylic acids and conventional additives such as overbasic alkylhydroxybenzoate calcium detergents, dialkyldithiophosphate zinc (ZDDP), and anti-foaming agents. Comparative lubricants were prepared without the use of ashless alkyl-substituted hydroxyaromatic carboxylic acids. The lubricants were evaluated for sludge treatment, deposit control, and viscosity increase and BN reduction due to oxidation. The results are summarized in Table 3. The weight percentages reported for the additives in Table 3 are based on their as-is condition. [Table 3]

[0117] As is clear from the results shown in Table 3, the trunk piston engine lubricating oil compositions (Examples 6 to 10) containing ashless alkyl-substituted hydroxyaromatic carboxylic acids have surprisingly little black sludge formation in marine residual fuels, improved deposit control, and better stability against viscosity increase and BN decrease based on oxidation than the lubricating oil composition (Comparative Example B) not containing ashless alkyl-substituted hydroxyaromatic carboxylic acids.

[0118] Example 11 A series of 140 BN marine cylinder lubricants formulated with Group I base oils were prepared by including ashless alkyl-substituted hydroxyaromatic carboxylic acids and conventional additives such as overbased calcium sulfonate detergents, overbased calcium sulfide phenate detergents, bis-succinimide dispersants, and anti-foaming agents. The comparative lubricant was prepared without using ashless alkyl-substituted hydroxyaromatic carboxylic acids. The lubricants were evaluated for sludge treatment, deposit control, and viscosity increase and base number (BN) decrease based on oxidation.

[0119] The ashless alkyl-substituted hydroxyaromatic carboxylic acid is an oil concentrate of C20-C24 hydrocarbyl-substituted hydroxyaromatic salicylic acid derived from C20-C24 isomerized normal alpha olefins. The additive contained about 25.0 wt% diluent oil.

[0120] The results are summarized in Table 4. The weight percentages of the additives reported in Table 4 are based on the as-received state.

Table 4

[0121] As is clear from the results shown in Table 4, the marine cylinder lubricant (Example 11) containing ashless alkyl-substituted hydroxyaromatic carboxylic acids had surprisingly less black sludge formation in marine residual fuels than the lubricating oil composition (Comparative Example C) not containing ashless alkyl-substituted hydroxyaromatic carboxylic acids.

[0122] Example 12 A series of 12BN trunk piston engine oil lubricants formulated with Group I base oils were prepared, as described in Examples 1–5, including ashless alkyl-substituted hydroxyaromatic carboxylic acids and conventional additives such as overbasic alkylhydroxybenzoate calcium detergent ("calcium detergent"), zinc dialkyldithiophosphate (ZDDP), and anti-foaming agents. Comparative lubricants were prepared without the use of ashless alkyl-substituted hydroxyaromatic carboxylic acids. The lubricants were evaluated for sludge treatment, deposit control, and viscosity increase and base number (BN) decrease due to oxidation.

[0123] The overbasic alkylhydroxybenzoate calcium detergent had alkyl substituents derived from linear C20-C28 n-alphaolefins and was prepared according to the method described in Example 1 of U.S. Patent Application Publication 2007 / 0027043. As obtained, the additive contained 12.5% ​​by weight of Ca and about 33% by weight of diluent oil, with a TBN of about 350 mg KOH / g and a basicity index of about 7.2. On an active ingredient basis, the TBN of this additive was about 520 mg KOH / g.

[0124] The ashless alkyl-substituted hydroxyaromatic carboxylic acid is an oil concentrate of C20-C24 hydrocarbyl-substituted hydroxyaromatic salicylic acid derived from C20-C24 isomerized n-alphaolefin. This additive contained approximately 25.0% by weight of diluted oil.

[0125] The results are summarized in Table 5. The weight percentages reported for the additives in Table 5 are based on their condition as received. [Table 5]

[0126] As is clear from the results shown in Table 5, the trunk piston engine lubricant composition containing ashless alkyl-substituted hydroxyaromatic carboxylic acid (Example 12) showed remarkably little black sludge formation in marine residual fuel, improved deposit control, and improved stability against viscosity increase and BN decrease due to oxidation compared to the lubricant composition without ashless alkyl-substituted hydroxyaromatic carboxylic acid (Comparative Example D).

[0127] Example 13 A series of 50BN trunk piston engine oil lubricants formulated with Group I base oils were prepared, as described in Examples 1-5, including ashless alkyl-substituted hydroxyaromatic carboxylic acids and conventional additives such as overbasic alkylhydroxybenzoate calcium detergent ("calcium detergent"), zinc dialkyldithiophosphate (ZDDP), and anti-foaming agents. Comparative lubricants were prepared without the use of ashless alkyl-substituted hydroxyaromatic carboxylic acids. The lubricants were evaluated for sludge treatment, deposit control, and viscosity increase and base number (BN) decrease due to oxidation.

[0128] The overbasic alkylhydroxybenzoate calcium detergent had alkyl substituents derived from linear C20-C28 n-alphaolefins and was prepared according to the method described in Example 1 of U.S. Patent Application Publication 2007 / 0027043. As obtained, the additive contained 12.5% ​​by weight of Ca and about 33% by weight of diluent oil, with a TBN of about 350 mg KOH / g and a basicity index of about 7.2. On an active ingredient basis, the TBN of this additive was about 520 mg KOH / g.

[0129] The ashless alkyl-substituted hydroxyaromatic carboxylic acid is an oil concentrate of C20-C24 hydrocarbyl-substituted hydroxyaromatic salicylic acid derived from C20-C24 isomerized n-alphaolefin. This additive contained approximately 25.0% by weight of diluted oil.

[0130] The results are summarized in Table 6. The weight percentages reported for the additives in Table 6 are based on their condition as received. [Table 6]

[0131] As is clear from the results shown in Table 6, the trunk piston engine lubricant composition containing ashless alkyl-substituted hydroxyaromatic carboxylic acid (Example 13) showed remarkably little black sludge formation in marine residual fuel, improved deposit control, and improved stability against viscosity increase and BN decrease due to oxidation compared to the lubricant composition without ashless alkyl-substituted hydroxyaromatic carboxylic acid (Comparative Example E).

[0132] Examples 14-17 A series of 40BN trunk piston engine oil lubricants formulated with Group I base oils were prepared, as described in Examples 1-5, including ashless alkyl-substituted hydroxyaromatic carboxylic acids and conventional additives such as overbasic alkylhydroxybenzoate calcium detergent ("calcium detergent"), zinc dialkyldithiophosphate (ZDDP), and anti-foaming agents. Comparative lubricants were prepared without the use of ashless alkyl-substituted hydroxyaromatic carboxylic acids. The lubricants were evaluated for sludge treatment, deposit control, and viscosity increase and base number (BN) decrease due to oxidation.

[0133] The overbasic alkylhydroxybenzoate calcium detergent had alkyl substituents derived from linear C20-C28 n-alphaolefins and was prepared according to the method described in Example 1 of U.S. Patent Application Publication 2007 / 0027043. As obtained, the additive contained 12.5% ​​by weight of Ca and about 33% by weight of diluent oil, with a TBN of about 350 mg KOH / g and a basicity index of about 7.2. On an active ingredient basis, the TBN of this additive was about 520 mg KOH / g.

[0134] Ashless alkyl-substituted hydroxyaromatic carboxylic acids are oil concentrates of C20-C24 hydrocarbyl-substituted hydroxyaromatic salicylic acid derived from C20-C24 isomerized n-alphaolefin (containing 25.0% by weight of diluent oil), C20-C28 hydrocarbyl-substituted hydroxyaromatic salicylic acid derived from C20-C28 n-alphaolefin (containing 25.0% by weight of diluent oil), C14-C16-C18 hydrocarbyl-substituted hydroxyaromatic salicylic acid derived from C14-C16-C18 n-alphaolefin (containing approximately 20.0% by weight of diluent), or C20-C24 hydrocarbyl-substituted naphthoic acid derived from C20-C24 isomerized n-alphaolefin (containing approximately 20.0% by weight of diluent oil).

[0135] The results are summarized in Table 7. The weight percentages reported for the additives in Table 7 are based on their condition as received. [Table 7]

[0136] As is clear from the results shown in Table 7, trunk piston engine lubricant compositions containing ashless alkyl-substituted hydroxyaromatic carboxylic acids (Examples 14-17) showed remarkably less black sludge formation in marine residual fuel, improved deposit control, and improved stability against viscosity increase and BN reduction due to oxidation compared to lubricant compositions without ashless alkyl-substituted hydroxyaromatic carboxylic acids (Comparative Example A).

[0137] Example 18 A series of 7BN system oils formulated with Group I base oils were prepared with ashless alkyl-substituted hydroxyaromatic carboxylic acids, zinc dialkyldithiophosphate (ZDDP), and conventional additives such as anti-foaming agents. These samples also contained two types of calcium detergents, an overbasic calcium sulfonate detergent and an overbasic calcium sulfide phenate detergent, and a bissuccinimide dispersant. Comparative lubricants were prepared without the use of ashless alkyl-substituted hydroxyaromatic carboxylic acids. The lubricants were evaluated for sludge treatment, deposit control, and viscosity increase and base number (BN) decrease due to oxidation.

[0138] The ashless alkyl-substituted hydroxyaromatic carboxylic acid is an oil concentrate of C20-C24 hydrocarbyl-substituted hydroxyaromatic salicylic acid derived from C20-C24 isomerized n-alphaolefin. This additive contained approximately 25.0% by weight of diluted oil.

[0139] The results are summarized in Table 8. The weight percentages of additives reported in Table 8 are based on the condition in which they were obtained. [Table 8]

[0140] As is clear from the results shown in Table 8, the system oil containing ashless alkyl-substituted hydroxyaromatic carboxylic acid (Example 18) showed remarkably less black sludge formation in marine residual fuel, improved deposit control, and improved stability against viscosity increase and BN decrease due to oxidation compared to the lubricating oil composition without ashless alkyl-substituted hydroxyaromatic carboxylic acid (Comparative Example F).

Claims

1. A lubricating oil composition comprising (a) a base oil with a lubricating viscosity selected from oils of API Group I, Group II, Group III, Group IV, and Group V and mixtures thereof, in greater than 50% by weight, and (b) an alkyl-substituted hydroxyaromatic carboxylic acid comprising 0.1 to 20% by weight of an alkyl-substituted hydroxyaromatic carboxylic acid having 12 to 40 carbon atoms in the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid and represented by the following structure (1), and an overbasic metal detergent, wherein the lubricating oil composition satisfies the specifications of SAE J300, which is the January 2015 revised requirement for SAE 20, 30, 40, 50, or 60 monograde engine oils, and the TBN measured by ASTM D2896 is 5 to 200 mg KOH / g; 【Chemistry 1】 In the formula, the carboxylic acid group may be in the ortho, meta, or para position relative to the hydroxyl group, or a mixture thereof, and R1 is an alkyl substituent having 12 to 40 carbon atoms.

2. The lubricating oil composition according to claim 1, wherein the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid is a residue derived from an alpha-olefin having 14 to 28 carbon atoms per molecule.

3. The lubricating oil composition according to claim 1, wherein the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid is a residue derived from an alpha-olefin having 20 to 24 carbon atoms per molecule.

4. The lubricating oil composition according to claim 1, wherein the alkyl substituent of the alkyl-substituted hydroxyaromatic carboxylic acid is a residue derived from an alpha-olefin having 20 to 28 carbon atoms per molecule.

5. The lubricating oil composition according to any one of claims 2, 3, and 4, wherein the alpha-olefin is a normal alpha-olefin, an isomerized normal alpha-olefin, or a mixture thereof.

6. The lubricating oil composition according to claim 1, wherein the amount of alkyl-substituted hydroxybenzoic acid is in the range of 1.0 to 5.0% by weight of the lubricating oil composition.

7. The lubricating oil composition according to claim 1, wherein the lubricating oil composition has TBN in one of the ranges of 5 to 10 mg KOH / g, 15 to 150 mg KOH / g, 20 to 80 mg KOH / g, 30 to 100 mg KOH / g, 30 to 80 mg KOH / g, 60 to 100 mg KOH / g, and 60 to 150 mg KOH / g.

8. The lubricating oil composition according to claim 1, further comprising one or more of the following: dispersant, anti-wear agent, antioxidant, friction modifier, corrosion inhibitor, rust inhibitor, deemulsifier, anti-foaming agent, viscosity modifier, pour point depressant, nonionic surfactant, and thickener.

9. A method for lubricating an internal combustion engine, comprising supplying the lubricating oil composition described in claim 1 to the internal combustion engine.

10. The method according to claim 9, wherein the internal combustion engine is a compression ignition engine.

11. The method according to claim 10, wherein the compression ignition engine is a four-stroke engine operating at 250 to 1100 rpm.

12. The method according to claim 10, wherein the compression ignition engine is a two-stroke engine that operates at 200 rpm or less.

13. The method according to claim 10, wherein the compression ignition engine is a residual fuel, marine residual fuel, low-sulfur marine residual fuel, marine distillate fuel, low-sulfur marine distillate fuel, high-sulfur fuel, or gaseous fuel.

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