Friction modifier for automatic transmission fluids

Abstract

A lubricating oil composition is disclosed. The composition comprises: an oil with a main amount of lubricating viscosity; one or more ashless dispersants; at least one phosphorus-containing anti-wear additive, wherein at least one phosphorus-containing anti-wear additive is a phosphorus-containing acid, a phosphate ester, a phosphite ester, a thiophosphate ester, or an amine salt thereof; at least one friction modifier, wherein at least one friction modifier is a diol, an ethoxylated amine, a fatty acid ester, or an alcohol; and a nitrogen-containing friction modifier having the following structural formula. [Formula 1] TIFF2026512485000019.tif37165 (wherein R1 and R2 are independently branched C10-C25 hydrocarbyl groups)

Description

[Technical Field]

[0001] This disclosure relates to a lubricating oil composition for automatic transmissions. [Background technology]

[0002] Regarding wet clutch paper used in automotive automatic transmissions, there is a trend in the industry to switch from wet clutch paper with a high cellulose content to wet clutch paper with a high aramid content. In particular, wet clutches can transmit power through mechanical and fluid coupling by fitting together paper wet friction plates immersed in a lubricant. Paper wet friction plates typically feature composite materials containing cellulose and reinforcing fibers such as aramid. The ratio of cellulose to aramid is important for the thermal stability and oxidation stability performance of the wet clutch.

[0003] Lubricant additives can significantly impact the performance of wet clutches. The effects of these additives are caused by both their physical and chemical absorption into the clutch material, such as cellulose, aramid (natural and synthetic) fibers, silica, and the steel plate surface. High-aramid wet clutch paper offers superior durability. However, aramid fibers are expensive.

[0004] Without sufficient wear-resistant and friction-modifying additives, the engine may experience power loss, unpleasant vibrations, and / or noise due to the lock-up of the wet clutch in the transmission. [Overview of the project]

[0005] A summary of certain embodiments disclosed herein is provided below. It should be understood that these embodiments are presented merely to provide the reader with a brief overview of these particular embodiments, and that they are not intended to limit the scope of this disclosure. In fact, this disclosure may encompass a variety of embodiments not shown below.

[0006] In one embodiment, the present disclosure relates to a lubricating oil composition comprising: (a) an oil having a major amount of lubricating viscosity; (b) one or more ashless dispersants; (c) at least one phosphorus-containing anti-wear additive, wherein at least one phosphorus-containing anti-wear additive is a phosphorus-containing acid, a phosphate ester, a phosphite ester, a thiophosphate ester, or an amine salt thereof; (d) at least one friction modifier, wherein at least one friction modifier is a diol, an ethoxylated amine, a fatty acid ester, or an alcohol; (e) a nitrogen-containing friction modifier having the following structural formula; [ka] (In the formula, R 1 and R 2 (This is independently a branched C10-C25 hydrocarbyl group).

[0007] In another aspect, the disclosure relates to a method for improving vibration resistance, the method being: The present invention comprises lubricating a transmission using a lubricating oil composition, wherein the lubricating oil composition comprises the following components: (a) an oil having a major amount of lubricating viscosity; (b) one or more ashless dispersants; (c) at least one phosphorus-containing anti-wear additive, wherein at least one phosphorus-containing anti-wear additive is a phosphorus-containing acid, a phosphate ester, a phosphite ester, a thiophosphate ester, or an amine salt thereof; (d) at least one friction modifier, wherein at least one friction modifier is a diol, an ethoxylated amine, a fatty acid ester, or an alcohol; (e) a nitrogen-containing friction modifier having the following structural formula; [ka] (In the formula, R 1 and R 2 (This is independently a branched C10-C25 hydrocarbyl group). [Modes for carrying out the invention]

[0008] definition The following terms are used throughout this specification and, unless otherwise indicated, have the following meanings:

[0009] The term “major amount” of base oil refers to an amount of base oil that is at least 40% by weight of the lubricating oil composition. In some embodiments, “major amount” of base oil refers to an amount of base oil that is more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or more than 90% by weight of the lubricating oil composition.

[0010] The term "ash-free" in reference to dispersants in lubricating oil compositions means that the dispersant is substantially free of metal.

[0011] The term "Total Base Number" or "TBN" refers to the alkalinity level of an ingredient or composition, expressed in mg KOH / g (equivalent to the number of milligrams of KOH required to neutralize 1 g of the product), indicating its ability to continue neutralizing corrosive acids, according to ASTM Standard D2896 or an equivalent procedure. The term "Total Acid Number" or "TAN" refers to the acidity level of an ingredient or composition, according to ASTM Standard D664 or an equivalent procedure.

[0012] This disclosure generally relates to a lubricating oil composition that provides excellent wet paper clutch friction characteristics, such as vibration resistance, and can maintain excellent wet clutch torque capacity and durability of wet clutch friction characteristics.

[0013] Lubricating oil compositions generally have a viscosity of 2-12 mm at 100°C. 2It contains oil with a lubricating viscosity having a kinematic viscosity of / s. The lubricating oil composition also contains one or more ashless dispersants, at least one phosphorus-containing antiwear additive, where at least one phosphorus-containing antiwear additive is a phosphorus-containing acid, a phosphoric acid ester, a phosphorous acid ester, a thiophosphoric acid ester, or an amine salt thereof, at least one friction modifier, where at least one friction modifier is a diol, an ethoxylated amine, a fatty acid ester, or an alcohol, and a nitrogen-containing friction modifier having a structural formula represented by the following formula (I) (where R 1 and R 2 are independently branched C10-C25 hydrocarbyl groups).

Chemical formula

[0014] As used herein, "branched-chain" means that the hydrocarbyl group contains at least one tertiary carbon.

[0015] Formula 1 can be prepared, for example, by reacting diethylenetriamine (DETA) with a branched-chain carboxylic acid. In some embodiments, the hydrocarbyl group is fully saturated. [[ID=二十]]

[0016] Suitable branched-chain carboxylic acids include, for example, 2-butyloctanoic acid, 3-butyloctanoic acid, 4-butyloctanoic acid, 2-hexyldecanoic acid, 3-hexyldecanoic acid, 4-hexyldecanoic acid, 2-octyldodecanoic acid, 3-octyldodecanoic acid, 4-octyldodecanoic acid, 5-octyldodecanoic acid, and the like. Some suitable branched carboxylic acids may be commercially available. These include gelselic acid (e.g., ISOCARB 16, ISOCARB 20) commercially available from Sasol (Houston, TX).

[0017] In some embodiments, Formula 1 (where R 1 and R 2These are independently branched hydrocarbyl groups, each having a total of 10 to 25 carbon atoms. These can undergo a simple condensation reaction to form, for example, an imidazoline represented by formula 1A. [ka]

[0018] The following sections provide detailed descriptions of the components of various embodiments of the lubricating oil composition, offer exemplary lubricating oil compositions, and disclose test results demonstrating the excellent friction and vibration resistance achieved by the lubricating oil composition.

[0019] Lubricating viscosity of oil The lubricating oil compositions disclosed herein generally contain at least one oil with a lubricating viscosity. Any base oil known to those skilled in the art can be used as an oil with a lubricating viscosity disclosed herein. Several base oils suitable for preparing lubricating oil compositions are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer Chapters 1 and 2 (1996); and A. Sequeria, Jr., “Lubricant Base Oil and Wax Processing,” New York, Marcel Decker, Chapter 6, (1994); and DVBrock, Lubrication Engineering, Vol. 43, pages 184-5, (1987), all of which are incorporated herein by reference. Generally, the amount of base oil in a lubricating oil composition may be 70% to 99.5% by weight based on the total weight of the lubricating oil composition. In some embodiments, the amount of base oil in the lubricating oil composition is at least 75% by weight, or at least 80% by weight, and 99% by weight or less, or 98.5% by weight or less, or 98% by weight or less, based on the total weight of the lubricating oil composition.

[0020] In certain embodiments, the base oil is or comprises any natural or synthetic lubricating base oil fraction. Some non-limiting examples of synthetic oils include oils such as polyalphaolefins or PAOs prepared from the polymerization of at least one alpha-olefin, such as ethylene, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gas, such as the Fischer-Tropsch process. In certain embodiments, the base oil comprises one or more heavy fractions in less than 10% by weight based on the total weight of the base oil. A heavy fraction refers to a lubricating oil fraction having a viscosity of at least 20 cSt at 100°C. In certain embodiments, the heavy fraction has a viscosity of at least 25 cSt, or at least 30 cSt, at 100°C. As an example, the heavy fraction may have a viscosity ranging from 20 cSt, 25 cSt, or 30 cSt at 100°C to a maximum of 25 cSt, 30 cSt, or 35 cSt. In further embodiments, the amount of one or more heavy fractions in the base oil is less than 10% by weight, less than 5% by weight, less than 2.5% by weight, less than 1% by weight, or less than 0.1% by weight, based on the total weight of the base oil. Furthermore, in even more embodiments, the base oil does not contain any heavy fractions.

[0021] In certain embodiments, the lubricating oil composition comprises a base oil with a primary lubricating viscosity. In some embodiments, the base oil has a kinematic viscosity of at least 1.5 centistokes (cSt) or at least 2 centistokes (cSt) at 100°C and 20 cSt or less, or 16 cSt or less. The kinematic viscosity of the base oils or lubricating oil compositions disclosed herein may be measured according to ASTM D 445 (incorporated herein by reference).

[0022] In other embodiments, the base oil is a base stock or a blend of base stocks, or comprises the same. In further embodiments, the base stock is produced using a variety of different processes, including but not limited to distillation, solvent purification, hydrogenation, oligomerization, esterification, and repurification. In some embodiments, the base stock comprises repurified stock. In further embodiments, the repurified stock is substantially free of substances introduced through production, contamination, or prior use.

[0023] In some embodiments, the base oil comprises one or more base stocks in one or more groups I through V as specified in American Petroleum Institute (API) Publication 1509, Fourteen Edition, December, 1996 (i.e., API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils), which is incorporated herein by reference. The API guidelines define base stock as a lubricating component that may be manufactured using a variety of different processes. Base stocks of groups I, II, and III are mineral oils, each having a specific range of saturated mass, sulfur content, and viscosity index. Base stocks of group IV are polyalphaolefins (PAOs). Base stocks of group V comprise all other base stocks not included in groups I, II, III, or IV.

[0024] In some embodiments, the base oil comprises one or more base stocks from groups I, II, III, IV, V, or combinations thereof. In other embodiments, the base oil comprises one or more base stocks from groups II, III, IV, or combinations thereof. In further embodiments, the base oil comprises one or more base stocks from groups II, III, IV, or combinations thereof, wherein the base oil has a kinematic viscosity of at least 1.5 centistokes (cSt) or at least 2 cSt at 100°C, and 20 cSt or less, or 16 cSt or less. In some embodiments, the base oil is a mixture of base oils from group II and base oils from group III.

[0025] The base oil may be selected from the group consisting of natural oils of lubricating viscosity, synthetic oils of lubricating viscosity, and mixtures thereof. In some embodiments, the base oil may be a base stock obtained by isomerization of synthetic waxes and slack waxes, as well as a hydrocracking base stock produced by hydrocracking (rather than solvent extraction) the aromatic and polar components of the crude product. In other embodiments, the base oil may be a natural oil, e.g., animal oils, vegetable oils, mineral oils (e.g., liquid petroleum and paraffinic, naphthenic, or mixed paraffinic-naphthenic type solvent-treated or acid-treated mineral oils), oils derived from coal or shale, and combinations thereof. Some non-limiting examples of animal oils include bone oil, lanolin, fish oil, lard, dolphin oil, seal oil, shark oil, tallow oil, and whale oil. Some non-exclusive examples of vegetable oils include castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil, hemp oil, linseed oil, tung oil, oyster oil, jojoba oil, and meadowfoam oil. Such oils may be partially or completely hydrogenated.

[0026] In some embodiments, synthetic oils of lubricating viscosity include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and copolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, and their derivatives, analogs, and homologs. In other embodiments, synthetic oils include alkylene oxide polymers, interpolymers, copolymers, and their derivatives, the terminal hydroxyl groups of which may be modified by esterification, etherification, etc. In further embodiments, synthetic oils include esters of dicarboxylic acids with various alcohols. In certain embodiments, synthetic oils include C5-C 12 Examples include monocarboxylic acids and esters produced from polyols and polyol ethers. In further embodiments, examples of synthetic oils include tri-alkyl phosphate ester oils, such as tri-n-butyl phosphate and tri-iso-butyl phosphate.

[0027] In some embodiments, examples of synthetic oils with lubricating viscosity include silicone-based oils (e.g., polyalkyl-, polyaryl-, polyalkoxy-, polyaryloxysiloxane oils, and silicate oils). In other embodiments, examples of synthetic oils include liquid esters of phosphorus-containing acids, polymer tetrahydrofurans, and polyalphaolefins.

[0028] Base oils derived from the hydrogen isomerization of waxes may also be used alone or in combination with the aforementioned natural and / or synthetic base oils. Such wax isomerized oils are produced by hydrogen isomerizing natural or synthetic waxes or mixtures thereof on a hydrogen isomerization catalyst.

[0029] In further embodiments, the base oil comprises poly-alpha-olefin (PAO). Generally, the poly-alpha-olefin may be derived from alpha-olefins having 2-30, 2-20, or 2-16 carbon atoms. Non-limiting examples of suitable poly-alpha-olefins include those derived from octene, decene, or mixtures thereof. These poly-alpha-olefins may have a viscosity of at least 1.5 centistokes at 100°C and 15 centistokes or less, or 12 centistokes or less, or 8 centistokes or less. In some examples, the poly-alpha-olefin may be used with other base oils such as mineral oil, synthetic esters, or alkylated naphthalene base oils.

[0030] In further embodiments, the base oil comprises a polyalkylene glycol or a polyalkylene glycol derivative, where the terminal hydroxyl groups of the polyalkylene glycol may be modified by esterification, etherification, acetylation, etc. Non-limiting examples of suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyisopropylene glycol, and combinations thereof. Non-limiting examples of suitable polyalkylene glycol derivatives include ethers of polyalkylene glycols (e.g., methyl ether of polyisopropylene glycol, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol, etc.), mono and polycarboxylic acid esters of polyalkylene glycols, and combinations thereof. In some examples, the polyalkylene glycol or polyalkylene glycol derivative may be used with other base oils, such as poly-alpha-olefins and mineral oils.

[0031] In further embodiments, the base oil may be any of the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Non-limiting 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, and 2-ethylhexyl diester of linoleic acid dimer.

[0032] In further embodiments, the base oil may be hydrocarbons prepared by the Fischer-Tropsch process. The Fischer-Tropsch process uses a Fischer-Tropsch catalyst to prepare hydrocarbons from a gas containing hydrogen and carbon monoxide. These hydrocarbons may require further processing to be useful as base oils. For example, hydrocarbons may be dewaxed, hydrogen-isomerized, and / or hydrocracked using processes known to those skilled in the art.

[0033] In further embodiments, the base oil may be unrefined oil, refined oil, re-refined oil, or a mixture thereof. Unrefined oil is obtained directly from a natural or synthetic source without further refining. Non-limiting examples of unrefined oil include shale oil obtained directly from a dry distillation operation, petroleum obtained directly from primary distillation, and ester oil obtained directly from an esterification process and used without further processing. Refined oil is similar to unrefined oil unless the former has been further processed by one or more refining processes to improve one or more properties. Many such refining processes are known to those skilled in the art, such as solvent extraction, secondary extraction, acid or base extraction, filtration, and leaching. Re-refined oil is obtained by applying a process similar to that used to obtain refined oil to refined oil. Such re-refined oil is also known as recycled or reprocessed oil and may often be further processed by processes relating to the removal of spent additives and oil decomposition products.

[0034] Ashless dispersant The lubricating oil composition comprises at least one ashless dispersant (A). According to exemplary embodiments, the lubricating oil composition comprises one or more nitrogen-containing ashless succinimide dispersants. According to specific embodiments, one or more nitrogen-containing ashless succinimide dispersants are non-post-treatment dispersants.

[0035] Typical examples of nitrogen-containing ashless dispersants include hydrocarbyl succinimides such as alkenyl succinimides or alkyl succinimides derived from polyolefins, and their derivatives. Succinimides can be obtained by reacting succinic anhydride substituted with a high molecular weight alkenyl group or alkyl group with a polyalkylene polyamine containing at least an average of 3 or 4 nitrogen atoms per molecule and 7 or 10 or fewer nitrogen atoms per molecule. In one embodiment, the high molecular weight alkenyl group or alkyl group is typically a polyolefin having a number average molecular weight of about 500 to 5000, with polyisobutene being particularly preferred. In one embodiment, the high molecular weight alkenyl group or alkyl group is typically a polyolefin having a number average molecular weight of at least 500, or at least 700, or at least 800, or at least 900, or at least 950, and 4000 or less, or 3000 or less, or 2000 or less, or 1050 or less. For example, a polyolefin may have a number average molecular weight of 1000.

[0036] In some embodiments, chlorine is used in the step of obtaining polybutenyl succinic anhydride by reaction between polybutene and maleic anhydride. However, although this method is highly reactive, a large amount of chlorine (e.g., 2000 ppm) remains in the final succinimide product. On the other hand, when a thermal reaction that does not involve chlorine is used, the amount of residual chlorine in the final product can be kept at a very low level (e.g., 40 ppm or less). Furthermore, using highly reactive polybutene (at least 50% having a methylvinylidene structure) compared to conventional polybutene (mainly having a β-olefin structure) is advantageous in that the reactivity is also increased by the thermal reaction method. When the reactivity is high, there is less unreacted polybutene in the dispersant, and therefore a dispersant containing a high concentration of the active ingredient (succinimide) can be obtained. Therefore, it is possible to first obtain polybutenyl succinic anhydride by a thermal reaction using highly reactive polybutene, and then produce succinimide by reacting this polybutenyl succinic anhydride with a polyamine. Succinimide can be used in modified forms called modified succinimides by further reacting with boric acid, alcohols, aldehydes, ketones, alkylphenols, cyclic carbonates, organic acids, etc. Boron-containing alkenyl (or alkyl) succinimides obtained by reaction with boric acid or boron compounds are particularly advantageous in terms of thermal and oxidative stability. Succinimides are classified into mono, bis, tris, and poly types according to the number of imide structures per molecule, but the bis type is typically used as succinimide in lubricating oil compositions.

[0037] Other examples of nitrogen-containing ashless dispersants include high-molecular-weight succinimide dispersants derived from ethylene-α-olefin copolymers (e.g., those with molecular weights of 1,000 to 15,000), and alkenylbenzylamine-based ashless dispersants.

[0038] Exemplary nitrogen-containing ashless dispersants are mono and bis alkylsuccinimides or alkenylsuccinimides derived from the reaction of alkylsuccinic acid or alkenylsuccinic acid or anhydride with alkylene polyamines. These compounds generally have the formula (I): [ka]

[0039] (wherein R1 is a substantially hydrocarbon chain having a molecular weight of 500 to 3000, i.e., R1 is a hydrocarbyl chain containing 40 to 200 carbon atoms, e.g., an alkenyl radical; Alk is an alkylene chain of 2 to 10 or 2 to 6 carbon atoms; R2, R3 and R4 are selected from C1-C4 alkyl or alkoxy or alkylamine or hydrogen, typically hydrogen; x is an integer from 0 to 10, typically 0 to 3; optionally, two nitrogen atoms may constitute part of a cyclic structure); Alternatively, it is thought to have equation II: [ka] (In the formula, R5 and R7 are both substantially hydrocarbon chains having molecular weights of 500 to 3000, i.e., R5 and R7 are hydrocarbyl chains such as alkenyl chains containing 30 to 220 carbon atoms, respectively; Alk is an alkylene chain of 2 to 10, typically 2 to 6 carbon atoms; R6 is selected from C1-C4 alkyl or alkoxy or alkylamine or hydrogen, typically hydrogen; y is an integer of 0 to 10, typically 0 to 3; optionally, two nitrogen atoms may constitute part of a cyclic structure). In one embodiment, R1, R5 and R7 are polyisobutyl groups.

[0040] In one embodiment, the actual reaction product of alkylene succinic acid or alkenylene succinic acid or anhydride with an alkylene polyamine may include a mixture of compounds containing monosuccinimide and bissuccinimide. The resulting monoalkenylsuccinimide and bisalkenylsuccinimide may depend on the molar charge ratio of the polyamine to the succinic acid groups and the specific polyamine used. A molar charge ratio of 1:1 of the polyamine to the succinic acid groups may primarily produce monoalkenylsuccinimide. A molar charge ratio of 1:2 of the polyamine to the succinic acid groups may primarily produce bisalkenylsuccinimide. Examples of succinimide dispersants include, for example, those described in U.S. Patents 3,172,892, 4,234,435, and 6,165,235, which are incorporated herein in whole by reference.

[0041] In one embodiment, the substituent-derived polyalkene is typically a homopolymer and interpolymer of polymerizable olefin monomers having 2 to 16 carbon atoms, usually 2 to 6 carbon atoms. The amine reacted with the succinic acid acylating agent to form the carboxylic acid dispersant composition may be a monoamine or a polyamine.

[0042] In one aspect of this disclosure, alkenyl succinimide may be prepared by reacting a polyalkylene succinic anhydride with an alkylene polyamine. Polyalkylene succinic anhydride is a reaction product of a polyalkylene (typically polyisobutene) with maleic anhydride. Conventional polyisobutene or high-methylvinylidene polyisobutene may be used to prepare such polyalkylene succinic anhydride. This preparation may be carried out using heat, chlorination, free radicals, acid catalysts, or any other process. Suitable examples of polyalkylene succinic anhydrides include: thermal PIBSA (polyisobutenyl succinic anhydride) described in U.S. Patent No. 3,361,673; chlorinated PIBSA described in U.S. Patent No. 3,172,892; mixtures of thermal PIBSA and chlorinated PIBSA described in U.S. Patent No. 3,912,764; high succinic acid ratio PIBSA described in U.S. Patent No. 4,234,435; and those described in U.S. Patents No. 5,112,507 and No. 5,175,225. PolyPIBSA; high succinic acid ratio PolyPIBSA as described in U.S. Patent Nos. 5,565,528 and 5,616,668; free radical PIBSA as described in U.S. Patent Nos. 5,286,799, 5,319,030 and 5,625,004; PIBSA manufactured from high methylvinylidene polybutene as described in U.S. Patent Nos. 4,152,499, 5,137,978 and 5,137,980; European Patent Application Publication No. EP These include high succinic acid ratio pibsa produced from high methylvinylidene polybutene as described in U.S. Patent No. 355,895; terpolymer pibsa as described in U.S. Patent No. 5,792,729; sulfonic acid pibsa as described in U.S. Patent No. 5,777,025 and European Patent Application Publication No. EP 542,380; and purified pibsa as described in U.S. Patent No. 5,523,417 and European Patent Application Publication No. EP 602,863. The disclosures of each of these documents are incorporated herein by reference in their entirety. Polyalkylene succinic anhydrides are typically polyisobutenyl succinic anhydrides.In one exemplary embodiment, the polyalkylene succinic anhydride is a polyisobutenyl succinic anhydride derived from polyisobutylene having a number average molecular weight of at least 500, or at least 600, or at least 700, or at least 800, or at least 900, and 1400 or less, or 1300 or less, or 1200 or less, or 1100 or less, or 1000 or less.

[0043] A typical polyalkyleneamine used to prepare succinimide is of formula (III): [ka] (In the formula, z is an integer from 0 to 10, Alk is an alkylene radical of 2 to 10 carbon atoms, typically 2 to 6, and R8, R9 and R 10 (where z is selected from C1-C4 alkyl, alkoxy, or alkylamine or hydrogen, typically hydrogen, and z is an integer between 0 and 10, typically between 0 and 3).

[0044] Examples of alkyleneamines include methyleneamine, ethyleneamine, butyleneamine, propyleneamine, pentyleneamine, hexyleneamine, heptyleneamine, octyleneamine, other polymethyleneamines, and cyclic and higher-order homologs of amines such as piperazines and aminoalkyl-substituted piperazines. These are specifically exemplified by ethylenediamine, triethylenetetraamine, propylenediamine, decamethyldiamine, octamethylenediamine, diheptamethylenetriamine, tripylenetetraamine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, ditrimethylenetriamine, 2-heptyl-3-(2-aminopropyl)-imidazoline, 4-methylimidazoline, N,N-dimethyl-1,3-propanediamine, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)-piperazine, 1,4-bis(2-aminoethyl)piperazine, and 2-methyl-1-(2-aminobutyl)piperazine. Higher-order homologs obtained by condensing two or more of the alkyleneamines exemplified above are equally useful.

[0045] Ethylene amines are particularly useful. They are described in some detail under the heading “Ethylene Amines” in the Encyclopedia of Chemical Technology, Kirk-Othmer, Vol. 5, pp. 898–905 (Interscience Publishers, New York, 1950). The term “ethylene amine” is used in a general sense to refer primarily to a class of polyamines conforming to formula (IV): H2N(CH2CH2NH) α H (IV) (wherein α is an integer between 1 and 10). In one embodiment, α is an integer between 3 and 5. Therefore, it includes, for example, ethylenediamine, diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine, pentaethylenehexamine, and the like.

[0046] It should be understood that the polyamines used herein often refer to mixtures of polyamine products. For example, triethylenetetramine (TETA), commercially available from Huntsman, is described as a mixture of linear TETA, branched TETA, BIS aminoethylpiperazine (BIS AEP), and N-[(2-aminoethyl)2-aminoethyl]piperazine) or PEEDA. [ka] [ka] [ka] [ka]

[0047] The individual alkenylsuccinimides used in the alkenylsuccinimid compositions are incorporated herein by reference, all of which are disclosed in whole for all purposes, as specified in U.S. Patent Nos. 2,992,708; 3,018,250; 3,018,291; 3,024,237; 3,100,673; 3,172,892; 3,202,678; 3,219,666; 3,272,746; and 3,361. It can be prepared by conventional processes as disclosed in No. 673; No. 3,381,022; No. 3,912,764; No. 4,234,435; No. 4,612,132; No. 4,747,965; No. 5,112,507; No. 5,241,003; No. 5,266,186; No. 5,286,799; No. 5,319,030; No. 5,334,321; No. 5,356,552; and No. 5,716,912.

[0048] The term “alkenyl succinimide” also includes post-processed succinimides such as post-processing processes involving borates or ethylene carbonate, as disclosed by Wollenberg, et al., U.S. Patent No. 4,612,132; Wollenberg, et al., U.S. Patent No. 4,746,446, etc., each of which is incorporated herein by reference as a whole. Carbonate-treated alkenyl succinimides are typically polyisobutene succinimides derived from polyisobutene having a molecular weight of at least 500, or at least 900, or at least 1,300, or at least 2,000 and no more than 3,000, or no more than 2,500, no more than 2,400, or no more than 2,300.

[0049] In one embodiment, the dispersant system is present in an amount of at least 1% by weight, or at least 1.5% by weight, or at least 2.0% by weight, and 20% by weight or less, or 15% by weight or less, or 10% by weight or less, or 5.0% by weight or less, or 4.0% by weight or less, or 3.0% by weight or less, based on the total weight of the lubricating oil composition, for example, in an amount of 1.0 to 3.0% by weight.

[0050] In another embodiment, the untreated dispersant is an untreated succinimide dispersant. In yet another embodiment, the untreated succinimide dispersant is present in an amount of at least 0.3% by weight, or at least 0.5% by weight, or at least 0.6% by weight, and 8% by weight or less, or 5% by weight or less, or 4% by weight or less, or 3.0% by weight or less, or 2.0% by weight or less, based on the total weight of the lubricating oil composition.

[0051] The individual alkenylsuccinimides used in the alkenylsuccinimid compositions are incorporated herein by reference, all of which are disclosed in whole for all purposes, as specified in U.S. Patent Nos. 2,992,708; 3,018,250; 3,018,291; 3,024,237; 3,100,673; 3,172,892; 3,202,678; 3,219,666; 3,272,746; and 3,361. It can be prepared by conventional processes as disclosed in No. 673; No. 3,381,022; No. 3,912,764; No. 4,234,435; No. 4,612,132; No. 4,747,965; No. 5,112,507; No. 5,241,003; No. 5,266,186; No. 5,286,799; No. 5,319,030; No. 5,334,321; No. 5,356,552; and No. 5,716,912.

[0052] The term “alkenylsuccinimide” also includes post-processed succinimides such as other post-processing processes, as well as post-processing processes involving borates or ethylene carbonate, as disclosed by, for example, U.S. Patent No. 4,612,132, U.S. Patent No. 4,746,446, each of which is incorporated herein by reference as a whole. Typically, carbonate-treated alkenylsuccinimides are polybutenesuccinimides derived from polyisobutene having a molecular weight of at least 500, or at least 600, or at least 800, or at least 900, and 3000 or less, or 2500 or less, or 2300 or less.

[0053] According to exemplary embodiments, each nitrogen-containing ashless succinimide dispersant has a number average molecular weight of at least 500, at least 750, or at least 850, or at least 1000, and 1800 or less, or 1700 or less, or 1600 or less, or 1500 or less, or 1400 or less, or 1350 or less.

[0054] Each nitrogen-containing ashless succinimide dispersant typically contains at least 25 mg KOH / g or at least 30 mg KOH / g, and TBN of 55 mg KOH / g or less or 50 mg KOH / g or less.

[0055] The nitrogen content of each nitrogen-containing ashless succinimide dispersant in the exemplary embodiment is in the range of 1.0% to 3.0% by weight, based on the total weight of the nitrogen-containing ashless succinimide dispersant.

[0056] In one embodiment, the dispersant is not post-treated. In another embodiment, the dispersant is post-treated with a boron compound.

[0057] According to exemplary embodiments, one or more nitrogen-containing ashless succinimide dispersants include boron-containing dispersants. The boron content of these nitrogen-containing ashless succinimide dispersants is in the range of 0.1% to 2.0% by weight, based on the total weight of the nitrogen-containing ashless succinimide dispersants.

[0058] According to an exemplary embodiment, one or more nitrogen-containing ashless succinimide dispersants comprise two dispersants. The first dispersant is a boron-modified polyisobutenyl succinimide having a polyisobutene number-average molecular weight of 1300, a nitrogen content of 1.95% by weight, a boron content of 0.63% by weight, and a TBN of 46 mg KOH / g. The second dispersant is a polyisobutenyl succinimide having a polyisobutene number-average molecular weight of 1000, a nitrogen content of 1.93% by weight, and a TBN of 35 mg KOH / g.

[0059] The lubricating oil composition typically contains less than 0.3% by weight of sulfated ash, or 0.1% by weight or less of sulfated ash, based on the total weight of the lubricating oil composition.

[0060] Phosphorus-containing wear-resistant additive The lubricating oil composition further comprises at least one phosphorus-containing wear-resistant additive compound. Various different phosphorus-containing wear-resistant additive compounds can be used in the lubricating oil composition. However, according to exemplary embodiments, the lubricating oil composition comprises at least one phosphorus-containing wear-resistant additive, which is a phosphorus-containing acid, a phosphorus ester, a phosphorous acid ester, a thiophosphate ester, or an amine salt thereof. In some embodiments, the phosphorus-containing acid is phosphoric acid or phosphorous acid.

[0061] phosphoric acid The phosphoric acid in the lubricating oil composition is typically an 85% by weight solution of inorganic phosphoric acid H3PO4. According to an exemplary embodiment, the phosphoric acid (85% by weight solution) contains phosphorus in an amount of at least 20.0% by weight, or at least 25.0% by weight, and 32.0% by weight or less, or 30.0% by weight or less, based on the total weight of the phosphoric acid.

[0062] According to an exemplary embodiment, the phosphoric acid (85% by weight solution) has a total acid number (TAN) of at least 850 mg KOH / g or at least 950 mg KOH / g, and 1050 mg KOH / g or less or 1000 mg KOH / g or less.

[0063] In one embodiment, phosphoric acid (85% by weight solution) is present in an amount of 0.01% to 1.0% by weight based on the total weight of the lubricating oil composition. In other embodiments, phosphoric acid is present in an amount of at least 0.01% by weight, or at least 0.02% by weight, or at least 0.03% by weight, and 0.5% by weight or less, or 0.6% by weight or less, or 0.7% by weight or less, or 1.0% by weight or less, based on the total weight of the lubricating oil composition.

[0064] Phosphite In some embodiments, the lubricating oil composition may contain phosphorous acid, (HO)2PO, and / or its tautomer phosphonic acid. The tautomer forms are shown below: [ka]

[0065] Acidic phosphate esters In certain embodiments, the phosphorus-containing wear-resistant additive compound may include an acidic monophosphate ester or an acidic diphosphate ester. Examples of phosphate esters include mono- and / or diaryl phosphates, mono- and / or dialkyl phosphates, mono- and / or alkyl-aryl phosphates, mono- and / or aryl-alkyl phosphates, and mono- and / or dialkenyl phosphates. Specific examples include mono- and / or diphenyl phosphates, mono- and / or dicresyl phosphates, benzylphenyl phosphates, ethylphenyl phosphates, mono- and / or dibutyl phosphates, ethylbutyl phosphates, cresylphenyl phosphates, ethylphenylphenyl phosphates, propylphenylphenyl phosphates, phosphoric acid, diethylphenyl phosphates, dipropylphenyl phosphates, butylphenylphenyl phosphates, dibutylphenyl phosphates, dihexyl phosphates, di(2-ethylhexyl) phosphates, dioctyl phosphates, didecyl phosphates, dilauryl phosphates, dimyristyl phosphates, dipalmityl phosphates, distearyl phosphates, and dioleyl phosphates.

[0066] The thioether bond may be contained in the alkyl group. Examples of phosphate esters containing thioether include mono- and / or dialkyl thiophosphate, mono- and / or di-butylthioethyl phosphate, mono- and / or di-hexylthioethyl phosphate, mono- and / or dioctylthioethyl phosphate, mono- and / or di-decylthioethyl phosphate, mono- and / or di-dodecylthioethyl phosphate, and mono- and / or di-hexadecylthioethyl phosphate.

[0067] According to exemplary embodiments, each acidic monophosphate and / or diphosphate ester has a phosphorus content of 3.0% to 20.0% by weight and a sulfur content of 5.0% to 15.0% by weight, based on the total weight of the phosphate ester.

[0068] The lubricating oil composition may contain phosphorus in an amount of at least 0.01% by weight, or at least 0.02% by weight, or at least 0.03% by weight, and 0.20% by weight or less, or 0.1% by weight or less, or 0.08% by weight or less, based on the total weight of the lubricating oil composition.

[0069] Neutral phosphate ester Examples of phosphate esters include triaryl phosphate, trialkyl phosphate, trialkylaryl phosphate, triarylalkyl phosphate, and trialkenyl phosphate. Specific examples include triphenyl phosphate, tricresyl phosphate, benzyl diphenyl phosphate, ethyl diphenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, dicresyl phosphate, ethylphenyl diphenyl phosphate, di(ethylphenyl)phenyl phosphate, propylphenyl diphenyl phosphate, di(propylphenyl)phenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl diphenyl phosphate, di(butylphenyl)phenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri(2-ethylhexyl) phosphate, trioctyl phosphate, tridecyl phosphate, trilauryl phosphate, trimiristyl phosphate, tripalmystyl phosphate, tripalmystyl phosphate, tristearyl phosphate, and trioleyl phosphate.

[0070] Phosphite esters Examples of phosphite esters include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri(nonylphenyl) phosphite, tri(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, and trioleyl phosphite.

[0071] The thioether bond may be contained in the alkyl group. Examples of thioether-containing phosphite esters include trialkyl thiophosphite, tributylthioethyl thiophosphite, trihexylthioethyl thiophosphite, trioctylthioethyl thiophosphite, tridecylthioethyl thiophosphite, tridodecylthioethyl thiophosphite, and trihexadecylthioethyl thiophosphite.

[0072] According to exemplary embodiments, each phosphite ester has a phosphorus content of 3.0% to 15.0% by weight. If the phosphite ester contains a thioether bond, the phosphite ester has a sulfur content of 5.0% to 25.0% by weight based on the total weight of the phosphite ester.

[0073] Hydrogen phosphite In certain embodiments, hydrogen phosphite is a dialkyl hydrogen phosphite or a diphenyl hydrogen phosphite, with dialkyl hydrogen phosphite being preferred, but the present invention is not limited to these. Examples of dibutyl hydrogen phosphite, dipentyl hydrogen phosphite, dihexyl hydrogen phosphite, dioctyl hydrogen phosphite, di-2 ethylhexyl hydrogen phosphite, didecyl hydrogen phosphite, dilauryl hydrogen phosphite, dioctadecyl hydrogen phosphite, and diphenyl hydrogen phosphite.

[0074] The thioether bond may be contained in the alkyl group. Examples of hydrogen phosphite esters containing a thioether include dialkyl hydrogen phosphite, dibutylthioethyl hydrogen phosphite, dihexylthioethyl hydrogen phosphite, dioctylthioethyl hydrogen phosphite, didecylthioethyl hydrogen phosphite, didodecylthioethyl hydrogen phosphite, and dihexadecylthioethyl hydrogen phosphite.

[0075] According to exemplary embodiments, each hydrogen phosphite has a phosphorus content of 3.0% to 15.0% by weight. In embodiments in which the hydrogen phosphite contains a thioether bond, the hydrogen phosphite has a sulfur content of 5.0% to 25.0% by weight based on the total weight of the hydrogen phosphite.

[0076] Thiophosphate ester Specific examples of thiophosphate esters include dithiophosphate trialkyls, such as dithiophosphate tripropyl, dithiophosphate tributyl, dithiophosphate tripentyl, dithiophosphate trihexyl, and dithiophosphate trioctyl, as well as dithiophosphoryl alkylene alkyl carboxylates 0,0-dialkyl, such as Irgalube 63 (manufactured by BASF Corporation), Vanlube 727, and Vanlube 7611 (manufactured by Vanderbilt Co., Ltd.).

[0077] Amine salt Specific examples of amine salts include amine salts of acidic phosphate esters or amine salts of acidic phosphite esters. Examples of such amine salts include amine salts of mono-hexyl phosphate, di-hexyl phosphate, mono-2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, mono-octyl phosphate, di-octyl thiophosphate, mono-octyl thiophosphate, di-octyl thiophosphate, mono-decyl phosphate, mono-dodecyl phosphate, di-dodecyl phosphate, mono-octadecyl phosphate, and di-octadecyl phosphate.

[0078] The amine used to produce the amine salt may be represented as R5R6R7N. R5, R6, and R7 are independently saturated or unsaturated aliphatic, aromatic, or aromaliphatic hydrocarbons having 1 to 20 carbon atoms, or hydrogen. If the group is a hydrocarbon, it may be a linear or branched chain.

[0079] In certain embodiments, the amine salt may be represented by formula (V): [ka] (In the formula, R8 is C9-C 22 Hydrocarbil, R9 and R 10 Each of these is independently a C1-C4 hydrocarbil, and R 11 is C 10 -C 20 Hydrocarbil, R 12 is hydrogen or C 10 -C 20 (It is a hydrocarbyl.) Examples of such amine salts are described in U.S. Patent No. 5,552,068, which is incorporated herein by reference in its entirety.

[0080] According to exemplary embodiments, each amine salt has a phosphorus content of 3.0% to 15.0% by weight and a nitrogen content of 0.5% to 5.0% by weight, based on the total weight of the amine salt.

[0081] Exemplary phosphorus compounds In exemplary embodiments, one or more phosphorus-containing anti-wear additive compounds are present in an amount of 0.01% to 3.0% by weight based on the total weight of the lubricating oil composition. In other embodiments, one or more phosphorus-containing anti-wear additive compounds are present in an amount of at least 0.01% by weight, or at least 0.02% by weight, or at least 0.03% by weight, and 1.0% by weight or less, or 0.5% by weight or less, or 0.3% by weight or less, or 0.2% by weight or less, based on the total weight of the lubricating oil composition.

[0082] Friction modifier Various known friction modifiers can be used as friction modifiers in the lubricating oil compositions of this disclosure. Friction modifiers can bring about improvements in frictional performance in the lubricating oil composition, such as those demonstrated by an increase or decrease in the coefficient of friction and an extension of the stability of the coefficient of friction. Therefore, lubricating oil compositions containing friction modifiers can protect automatic transmissions from vibration for a relatively long period of time.

[0083] According to certain embodiments, the friction modifier of the lubricating oil composition includes a diol. For example, the lubricating oil composition may include a diol compound having the following formula (IX): [ka] (wherein R represents hydrogen, an alkyl group, or an alkenyl group). It is also possible to use mixtures of compounds having different alkyl or alkenyl groups. The alkyl or alkenyl group may be linear or branched and may typically contain 10 to 30 carbon atoms.

[0084] According to other embodiments, the friction modifier of the lubricating oil composition includes an ethoxylated amine. The ethoxylated amine may have the following formula (VII): RN(C2H4OH)2(VII) (wherein R represents hydrogen, an alkyl group, or an alkenyl group). It is also possible to use mixtures of compounds having different alkyl or alkenyl groups. The alkyl or alkenyl group may be linear or branched and may typically contain 8 to 22 carbon atoms.

[0085] According to certain embodiments, the friction modifier of the lubricating oil composition includes fatty acid esters, fatty acid amides, fatty acid amides of low molecular weight amino acids, and / or alcohols. Examples of fatty acid esters include those disclosed in U.S. Patent No. 3,933,659, which is incorporated herein by reference in its entirety.

[0086] Each friction modifier is typically present in an amount of 0.01% to 3% by weight based on the total weight of the lubricating oil composition. The total amount of friction modifiers present in the lubricating oil composition is typically 0.01% to 5% by weight based on the total weight of the lubricating oil composition. In exemplary embodiments, the friction modifier is present in an amount of at least 0.01% by weight, or at least 0.05% by weight, or at least 0.1% by weight, and 4.0% by weight or less, or 3.0% by weight or less, or 2.0% by weight or less, based on the total weight of the lubricating oil composition.

[0087] Other additives Optionally, the lubricating oil composition may further contain at least one additive or modifier (hereinafter referred to as "additive") which can impart or improve any desired properties of the lubricating oil composition. Any additive known to those skilled in the art can 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). In some embodiments, at least one additive can be selected from the group consisting of antioxidants, anti-wear agents, cleaning agents, rust inhibitors, anti-emulsifiers, multi-functional additives, viscosity index improvers, pour point depressants, anti-foaming agents, metal deactivators, corrosion inhibitors, lubricity improvers, thermal stability improvers, anti-fogging additives, anti-icing agents, dyes, markers, antistatic agents, biocides, and combinations thereof. The additive may also include friction modifiers and dispersants in addition to the friction modifiers and dispersants described above.

[0088] The concentration of each additive in the lubricating oil composition, when used, is typically at least 0.001% by weight, or at least 0.01% by weight, or at least 0.1% by weight, and 15% by weight or less, or 10% by weight or less, or 8% by weight or less, based on the total weight of the lubricating oil composition. Furthermore, the combined total amount of additives in the lubricating oil composition is typically at least 0.001% by weight, or at least 0.1% by weight, or at least 1% by weight, and 20% by weight or less, or 15% by weight or less, or 10% by weight or less, for example, 9% to 10% by weight, based on the total weight of the lubricating oil composition.

[0089] In one embodiment, the lubricating oil composition contains a metal cleaning compound. Some non-limiting examples of suitable metal cleaning agents include sulfurized or non-sulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, boro oxide sulfonates, sulfurized or non-sulfurized metal salts of multiple hydroxyalkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or non-sulfurized alkyl or alkenyl naphthenates, metal salts of alkanic acids, metal salts of alkyl or alkenyl polyacids, and chemical and physical mixtures thereof. Other non-limiting examples of suitable metal cleaning agents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates, and combinations thereof. The metal may be any metal suitable for the manufacture of sulfonate, phenate, salicylate, or phosphonate cleaning agents. Non-limiting examples of suitable metals include alkaline earth metals, alkali metals, and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, etc.

[0090] Several suitable cleaning agents are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 3, pages 75-85 (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 4, pages 113-136 (2003) (both of which are incorporated herein by reference).

[0091] Generally, the amount of metal cleaner is approximately 0.001% to 0.5% by weight, approximately 0.01% to 0.3% by weight, approximately 0.01% to 0.2% by weight, approximately 0.01% to 0.1% by weight, approximately 0.02% to 0.5% by weight, approximately 0.02% to 0.4% by weight, or approximately 0.03% to 0.3% by weight, based on the total weight of the lubricating oil composition.

[0092] In one embodiment, the metal cleaner is a calcium sulfonate or calcium salicylate cleaner containing 50-450 mg KOH / gm of TBN and 1.0-20% by weight of calcium.

[0093] In another embodiment, calcium is present in the lubricating oil composition at a concentration of 300 ppm by weight or less. In yet another embodiment, calcium is present in the lubricating oil composition at concentrations of 25-300, 30-250, and 34-250 ppm by weight.

[0094] According to some embodiments, the lubricating oil composition comprises at least one antioxidant capable of reducing or preventing the oxidation of the lubricating viscosity oil or base oil. Any antioxidant known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable antioxidants include amine antioxidants (e.g., alkyldiphenylamine, phenyl-alpha-naphthylamine, alkyl or aralkyl-substituted phenyl-alpha-naphthylamine, alkylated p-phenylenediamine, tetramethyl-diaminodiphenylamine, etc.), phenolic antioxidants (e.g., 2-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2 Examples of antioxidants include 6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 4,4'-methylenebis-(2,6-di-tert-butylphenol), 4,4'-thiobis(6-di-tert-butyl-o-cresol), sulfur-based antioxidants (e.g., dilauryl-3,3'-thiodipropionate, sulfur-phenol-based antioxidants, etc.), phosphorus-based antioxidants (e.g., phosphates, etc.), zinc dithiophosphate, oil-soluble copper compounds, and combinations thereof. The amount of antioxidant may vary from at least 0.01% by weight, or at least 0.05% by weight, or at least 0.1% by weight, and 10% by weight or less, or 5% by weight or less, or 3% by weight or less, based on the total weight of the lubricating oil composition. Several suitable antioxidants are described in Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 1, pages 1-28 (2003) (incorporated herein by reference).

[0095] The lubricating oil composition may optionally contain at least one pour point depressant that can lower the pour point of the lubricating oil composition. Any pour point depressant known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable pour point depressants include polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di(tetra-paraffinphenol)phthalates, condensates of tetra-paraffinphenol, condensates of chlorinated paraffin and naphthalene, and combinations thereof. In some embodiments, examples of pour point depressants include ethylene-vinyl acetate copolymers, condensates of chlorinated paraffin and phenol, and polyalkylstyrene. The amount of pour point depressant may vary from at least 0.01% by weight, or at least 0.05% by weight, or at least 0.1% by weight, and 10% by weight or less, or 5% by weight or less, or 3% by weight or less, based on the total weight of the lubricating oil composition. Several suitable pour point depressants are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 187-189 (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 11, pages 329-354 (2003) (both of which are incorporated herein by reference).

[0096] The lubricating oil composition may further contain at least one anti-foaming agent or defoamer. Any anti-foaming agent or defoamer known to those skilled in the art may be used in the lubricating oil composition. Not limited examples of suitable defoamers include silicone oil or polydimethylsiloxane, fluorosilicone, alkoxylated fatty acids, polyethers (e.g., polyethylene glycol), branched polyvinyl ether, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines, and combinations thereof. In some embodiments, examples of defoamers include glycerol monostearate, polyglycol palmitate, trialkyl monothiophosphate, esters of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, or glycerol dioleate. The amount of defoamer may vary from at least 0.0001% by weight, or at least 0.0005% by weight, or at least 0.001% by weight and 1% by weight or less, or 0.5% by weight or less, or 0.1% by weight or less, based on the total weight of the lubricating oil composition. Several suitable antifoaming agents are described by reference in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 190–193 (1996), which are incorporated herein by reference.

[0097] The lubricating oil composition may optionally contain at least one corrosion inhibitor capable of reducing corrosion. Any corrosion inhibitor known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable corrosion inhibitors include dodecyl succinic acid half-esters or amides, phosphate esters, thiophosphates, alkylimidazolines, sarcosine, benzotriazoles, thiadiazoles, and combinations thereof. The amount of corrosion inhibitor may vary from at least 0.001% by weight, or at least 0.005% by weight and 5% or less by weight, or 1% or less by weight, or 0.5% or less by weight, based on the total weight of the lubricating oil composition. Several suitable corrosion inhibitors are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 193-196 (1996), which is incorporated herein by reference.

[0098] The lubricating oil compositions disclosed herein may optionally contain at least one extreme pressure (EP) agent capable of preventing seizing of sliding metal surfaces under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art may be used in the lubricating oil compositions. Generally, extreme pressure agents are compounds that can chemically combine with metals to form a surface film that prevents welding of irregularities on opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure additives include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent phosphorus acids, sulfurized olefins, dihydrocarbyl polysulfides, Diels-Alder sulfide adducts, dicyclopentadiene sulfides, sulfurized or cosulfurized mixtures of fatty acid esters and monounsaturated olefins, fatty acids, cosulfurized blends of fatty acid esters and alpha-olefins, functionally substituted dihydrocarbyl polysulfides, thiaaldehydes, thiaketones, epithio compounds, sulfur-containing acetal derivatives, cosulfurized blends of terpenes and acyclic olefins, polysulfide olefin products, amine salts of phosphate esters or thiophosphate esters, and combinations thereof. The amount of extreme pressure additive may vary from at least 0.01% by weight, or at least 0.05% by weight, or at least 0.1% by weight, and 5% by weight or less, or 3% by weight or less, or 1% by weight or less, based on the total weight of the lubricating oil composition. Several suitable extreme pressure additives are described in Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 8, pages 223-258 (2003) (incorporated herein by reference).

[0099] In one embodiment, the lubricating oil composition does not contain a sulfur-based extreme pressure agent.

[0100] The lubricating oil compositions disclosed herein may optionally contain at least one rust inhibitor capable of inhibiting corrosion of ferrous metal surfaces. Any rust inhibitor known to those skilled in the art may be used in the lubricating oil compositions. Non-limiting examples of suitable rust inhibitors include oil-soluble monocarboxylic acids (e.g., 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid, etc.), oil-soluble polycarboxylic acids (e.g., those produced from tall oil fatty acids, oleic acid, linoleic acid, etc.), alkenyl succinic acids containing 10 or more carbon atoms in the alkenyl group (e.g., tetrapropenyl succinic acid, tetradecenyl succinic acid, hexadecenic acid, etc.), long-chain alpha,omega-dicarboxylic acids having molecular weights in the range of 600 to 3000 daltons, and combinations thereof. The amount of rust inhibitor may vary from at least 0.01% by weight, or at least 0.05% by weight, or at least 0.1% by weight, and 10% by weight or less, or 5% by weight or less, or 3% by weight or less, based on the total weight of the lubricating oil composition.

[0101] Other non-limiting examples of suitable rust inhibitors include, for example, nonionic polyoxyethylene surfactants such as 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. Further non-limiting examples of suitable rust inhibitors include stearic acid and other fatty acids, dicarboxylic acids, metal soaps, fatty acid amine salts, metal salts of bisulfonic acids, partially carboxylic acid esters of polyhydric alcohols, and phosphate esters.

[0102] In some embodiments, the lubricating oil composition includes at least one multifunctional additive. Some non-limiting examples of suitable multifunctional additives include oxymolybdenum dithiocarbamates, oxymolybdenum organophosphorus dithioates, oxymolybdenum monoglycerides, oxymolybdenum diethylate amides, amine-molybdenum complex compounds, and sulfur-containing molybdenum complex compounds.

[0103] In certain embodiments, the lubricating oil composition includes at least one viscosity index improver. Some non-limiting examples of suitable viscosity index improvers include polymethacrylate polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant-type viscosity index improvers.

[0104] In some embodiments, the lubricating oil composition includes at least one metal deactivator. Some non-limiting examples of suitable metal deactivators include disalicylidenepropylenediamine, triazole derivatives, thiadiazole derivatives, and mercaptobenzimidazole.

[0105] The additives disclosed herein may be in the form of additive concentrates having two or more additives. The additive concentrate may contain a suitable diluent, for example, a hydrocarbon oil of a suitable viscosity. Such diluents can be selected from the group consisting of natural oils (e.g., mineral oils), synthetic oils, and combinations thereof. Some non-limiting examples of mineral oils include paraffinic oils, naphthenic oils, asphaltic oils, and combinations thereof. Some non-limiting examples of synthetic base oils include polyolefin oils (especially hydrogenated-alpha-olefin oligomers), alkylated aromatics, polyalkylene oxides, aromatic ethers, and carboxylic acid esters (especially diester oils), and combinations thereof. In some embodiments, the diluent is a light hydrocarbon oil (both natural and synthetic). Generally, the diluent oil can have a viscosity of 13 centistokes to 35 centistokes at 40°C.

[0106] Generally, it is desirable that the diluent readily solubilizes lubricating oil-soluble additives and provides an oil additive concentrate that is readily soluble in lubricating viscosity oil, oil stock, or fuel. Furthermore, it is desirable that the diluent does not ultimately introduce any undesirable properties, including, for example, high volatility and high viscosity, as well as impurities such as heteroatoms, into the lubricating viscosity oil, and consequently into the finished lubricating oil or fuel.

[0107] According to a particular embodiment, the lubricating oil composition comprises an oil-soluble additive concentrate composition containing an inert diluent, wherein the oil-soluble additive concentrate composition is present in an amount of at least 2.0% by weight or at least 10% by weight, and 90% by weight or less or 50% by weight or less, based on the total weight of the lubricating oil composition. [Examples]

[0108] The following embodiments are provided to demonstrate embodiments of the Disclosure and are not intended to limit the Disclosure to any specific embodiment shown. Unless otherwise indicated, parts and proportions are all on a weight basis. Where a range of numbers is given, it should be understood that embodiments outside that range may still be included within the scope of the Disclosure. Specific details described in each embodiment should not be construed as essential features of the Disclosure.

[0109] Lubricant sample Lubricant samples (i.e., baseline, comparative example, and embodiment of the invention) were evaluated for frictional performance. Each sample contained a friction modifier, a succinimide dispersant, and a phosphorus-containing anti-wear additive. The samples were blended with a mixture containing base oils from groups II and III.

[0110] Friction modifier A 211.7 g of diethylenetriamine (2 mol) and 1056.1 g of 2-hexyldecanoic acid (4.1 mol) were placed in a 2.0 L glass reactor under nitrogen. The mixture was heated to 180°C for 1 hour. The reaction temperature was increased to 190°C and a vacuum was applied. After 2 hours, the temperature was again increased to 200°C and the mixture was held for a further 2.5 hours. The nitrogen content of the final product was 6.72% by weight.

[0111] Dispersant Dispersant 1 is a boron-modified polyisobutenyl bis-succinimide with a number-average molecular weight of 1,300 (N: 1.95% by weight, B: 0.63% by weight).

[0112] Dispersant 2 is polyisobutenyl bis-succinimide with a number-average molecular weight of 950 (N: 1.93% by weight).

[0113] Phosphorus-containing wear-resistant additive Phosphorus compound 1 is inorganic phosphoric acid H3PO4 (P: 27.0% by weight).

[0114] The phosphorus compound 2 is diphenyl hydrogen phosphite (P: 13.3% by weight).

[0115] Phosphorus compound 3 is a monoalkylamine salt of a dialkyl phosphate ester (P: 8.2% by weight, N: 1.8% by weight).

[0116] Friction modifier Friction modifier 1 is an ethoxylated monoalkylamine, which is commercially available from Nouryon under the trademark name Ethomeen® T / 12 (N: 4.1% by weight).

[0117] Friction modifier 2 is a mixture of C16 / C18 diols.

[0118] Friction modifier 3 is a reaction product of C20 alkenyl-substituted succinic anhydride and diethylenetriamine (N: 4.6% by weight).

[0119] The sample also includes other lubricating additives, including cleaning agents(s), antioxidants(s), metal deactivators(s), anti-foaming agents(s), seal swelling agents(s), and viscosity modifiers(s).

[0120] JASO SAE #2 friction test Dynamic and static friction tests, as well as JASO SAE #2 friction tests, are performed using an SAE No. 2 testing machine in accordance with the "Test Method for Friction of Automotive and Automotive Automatic Transmission Fluids" (as defined in JASO M348.2002). friction material FZ127-24-Y12, steel plate (FZ132-8Y2) Dynamic friction measurement Moment of inertia of the inertia disc: 0.343 kgm, oil temperature: 100°C. Rotation speed: 3,600 rpm, surface pressure of friction plate: 785 MPa Test cycle: 30 seconds / cycle, Number of tests: 5,000 cycles Static friction measurement Rotation speed: 0.7 rpm, oil temperature: 100°C. Surface pressure of the friction plate: 785 MPa Test period: 3 minutes after rotation begins Test cycles: After 1, 5, 10, 20, 50, 100, 200, 500, 1000, 2000, 3000, 4000, and 5000 cycles.

[0121] measurement The static friction coefficient (μs) at the maximum torque generated when the rotation starts at 0.7 rpm, and the static friction coefficient (μt) after 2 seconds.

[0122] Transmission torque capacity was evaluated by the μt values ​​at 50, 500, and 5000 cycles.

[0123] Wet clutch vibration resistance test JASO M349-2012 The durability of vibration resistance was determined using a low-speed friction tester, in accordance with the "Automotive - Test Method for Vibration Resistance of Automatic Transmission Fluids" described in JASO M-349:2012. In this test, a positive value for the friction coefficient (dμ / dV) indicates vibration resistance. Details of the test conditions are described below. friction material Cellulose disc / steel plate; paper disc / steel plate Oil amount Approximately 150 mL Conditions Surface pressure: 1 MPa Oil temperature: 80℃ Sliding speed: 0.6 m / s Skiing time: 30 minutes Durability test conditions Surface pressure: 1 MPa Oil temperature: 120℃ Sliding speed: 0.9 m / s Slip time: 30 minutes Pause time: 1 minute Performance measurement time interval: 6 hours

[0124] Vibration resistance duration was determined by measuring the duration required for dμ / dV to reach a negative value. A longer duration indicates better vibration resistance. [Table 1]

[0125] The results of the LVFA vibration resistance test demonstrate that friction modifier A of the present invention (a reaction product of 2-hexyldecanoic acid and diethylenetriamine) functions as well as the alkenyl succinimide friction modifier. In comparison, the baseline formulation had a relatively short vibration resistance duration.

[0126] For the sake of brevity, this specification explicitly discloses only certain ranges. However, ranges from any lower bound can be combined with any upper bound to enumerate ranges not explicitly described, and similarly, ranges from any lower bound can be combined with any other lower bound to enumerate ranges not explicitly described, and similarly, ranges from any upper bound can be combined with any other upper bound to enumerate ranges not explicitly described. Furthermore, ranges include all points or individual values ​​between their endpoints, even if they are not explicitly listed. Thus, all points or individual values, combined with any other point or individual value, or any other lower or upper bound, can function as their own lower or upper bounds, enumerating ranges not explicitly described.

[0127] Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever there is a transitional phrase “comprising” before a composition, element, or group of elements, it is understood that the description of that composition, element, or group of elements also assumes the same composition or group of elements that is preceded by the transitional phrase “essentially consists of,” “consists of,” “selected from a group consisting of,” or “is,” and vice versa.

[0128] As used herein, the terms "a" and "the" are understood to include both singular and plural forms.

[0129] Various terms are defined above. To the extent that a term used in a claim is not defined above, the broadest definition given to that term by experts in the relevant art should be provided, as reflected in at least one printed publication or issued patent. Furthermore, all patents, test methods, and other documents cited in this application shall be fully incorporated by reference, to the extent that such disclosure does not conflict with this application and in all jurisdictions where such incorporation is permitted.

[0130] The above description of the Disclosure is illustrative and illustrative. Furthermore, while the Disclosure illustrates and describes only preferred embodiments, as stated above, the Disclosure is applicable in a variety of other combinations, modifications, and environments, and it should be understood that changes or modifications are possible within the scope of the concepts expressed herein to match the art or knowledge of the above teachings and / or related art. Although the above is directed toward embodiments of the Disclosure, other further embodiments of the Disclosure can be devised without departing from its basic scope, the scope of which will be determined by the claims that follow.

[0131] Where combinations, subsets, or groups of elements (for example, combinations of components in a composition or combinations of steps in a method) are disclosed, even if specific references to various individual and collective combinations and permutations of these elements are not explicitly disclosed, each is understood to be specifically intended and described herein.

[0132] The embodiments described herein are intended to further illustrate the best known modes for carrying out the invention and to enable those skilled in the art to utilize the disclosure with various modifications necessary for a particular use or application in such or other embodiments. Therefore, the description is not intended to limit the embodiments disclosed herein. Furthermore, the appended claims are intended to be interpreted as encompassing alternative embodiments.

Claims

1. A lubricating oil composition: (a) A main amount of oil with lubricating viscosity, (b) One or more ashless dispersants, (c) at least one phosphorus-containing wear-resistant additive, wherein the at least one phosphorus-containing wear-resistant additive is a phosphorus-containing acid, a phosphate ester, a phosphite ester, a thiophosphate ester, or an amine salt thereof, (d) at least one friction modifier, wherein the at least one friction modifier is a diol, an ethoxylated amine, a fatty acid ester, or an alcohol, (e) The following structure: 【Chemistry 1】 (In the formula, R １ and R ２ (This is independently a branched C10-C25 hydrocarbyl group.) The lubricating oil composition comprising a nitrogen-containing friction modifier having [a specific characteristic].

2. The lubricating oil composition according to claim 1, wherein phosphorus is contained in an amount of 0.01% to 0.20% by weight based on the total weight of the lubricating oil composition.

3. The lubricating oil composition according to claim 1, wherein the friction modifier of (e) is present in an amount of 0.01% to 1.0% by weight based on the total weight of the lubricating oil composition.

4. The lubricating oil composition according to claim 1, wherein the friction modifier of (e) is present in an amount of 0.25% to 0.75% by weight based on the total weight of the lubricating oil composition.

5. The lubricating oil composition according to claim 1, wherein one or more ashless dispersants include a polyisobutenyl succinimide dispersant.

6. The lubricating oil composition according to claim 5, wherein the polyisobutenyl group has a number average molecular weight of about 900 to about 1400.

7. The lubricating oil composition according to claim 1, wherein the nitrogen-containing friction modifier is a reaction product of 2-hexyldecanoic acid and diethylenetriamine.

8. The lubricating oil composition according to claim 1, wherein the phosphorus-containing acid is phosphoric acid or phosphorous acid.

9. The lubricating oil composition according to claim 1, wherein the branched hydrocarbyl group comprises at least one tertiary carbon.

10. The lubricating oil composition according to claim 1, wherein at least one of the branched hydrocarbyl groups is derived from octyldodecanoic acid or hexyldecanoic acid.

11. A method for improving vibration resistance, The lubricating oil composition makes the transmission slippery, and the lubricating oil composition is (a) A main amount of oil with lubricating viscosity, (b) One or more ashless dispersants, (c) at least one phosphorus-containing wear-resistant additive, wherein the at least one phosphorus-containing wear-resistant additive is a phosphorus-containing acid, a phosphate ester, a phosphite ester, a thiophosphate ester, or an amine salt thereof, (d) at least one friction modifier, wherein the at least one friction modifier is a diol, an ethoxylated amine, a fatty acid ester, or an alcohol, (e) The following structure: 【Chemistry 2】 (In the formula, R １ and R ２ (This is independently a branched C10-C25 hydrocarbyl group.) The method comprising a nitrogen-containing friction modifier having [a specific characteristic].

12. The method according to claim 11, wherein the lubricating oil composition contains phosphorus in an amount of 0.01% to 0.20% by weight based on the total weight of the lubricating oil composition.

13. The method according to claim 11, wherein the friction modifier of (e) is present in an amount of 0.01% to 1.0% by weight based on the total weight of the lubricating oil composition.

14. The method according to claim 11, wherein the friction modifier of (e) is present in an amount of 0.25% to 0.75% by weight based on the total weight of the lubricating oil composition.

15. The method according to claim 11, wherein the one or more ashless dispersants include a polyisobutenyl succinimide dispersant.

16. The method according to claim 15, wherein the polyisobutenyl group has a number average molecular weight of about 900 to about 1400.

17. The method according to claim 11, wherein the nitrogen-containing friction modifier is a reaction product of 2-hexyldecanoic acid and diethylenetriamine.

18. The method according to claim 1, wherein the phosphorus-containing acid is phosphoric acid or phosphorous acid.

19. The method according to claim 11, wherein the branched hydrocarbyl group comprises at least one tertiary carbon.

20. The method according to claim 11, wherein at least one of the branched hydrocarbyl groups is derived from octyldodecanoic acid or hexyldecanoic acid.

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