Lubricating oil composition

Abstract

The lubricating oil composition provides improved anti-shudder performance by making an automatic transmission or a continuously variable transmission slippery. The lubricating oil composition includes (a) one or more ashless dispersants and (b) at least one acidic phosphorus compound. When the at least one acidic phosphorus compound is composed only of phosphoric acid, the lubricating oil composition further includes one or more neutral phosphorus compounds. The neutralization rate of the (a) one or more ashless dispersants by the (b) at least one acidic phosphorus compound is 60-100%. The lubricating oil composition further includes at least one friction modifier.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 302,687, filed January 25, 2022, which is incorporated by reference herein in its entirety.

[0002] The present disclosure relates to lubricating oil compositions for automatic transmissions and / or continuously variable transmissions. [Background technology]

[0003] This section is intended to introduce the reader to various aspects of art that may be related to various aspects of the present disclosure, which are described and / or claimed below. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present disclosure. As such, it should be understood that these statements are to be read in this light, and not as admissions of prior art.

[0004] Lubricating oil compositions for automatic transmissions, called automatic transmission fluids, are traditionally used to aid in the smooth operation of the automatic transmission that is located in an automobile and includes a torque converter, a gear mechanism, a wet clutch, and a hydraulic mechanism.

[0005] In general, additives in lubricating oil compositions affect the frictional properties of wet clutches and steel plates. The additive effect is caused by both their physical and chemical absorption into clutch materials, such as cellulose, aramid fibers, silica, and steel plate surfaces. There is an industry movement to change wet clutch papers used in automatic transmissions for automobiles from cellulose-rich to aramid-rich. The ratio of cellulose to aramid is important for the thermal and oxidative stability performance of wet clutches. High aramid wet clutch papers provide excellent durability performance. However, aramid fibers are expensive.

[0006] Furthermore, regulatory changes require modern vehicles to improve fuel economy and reduce emissions. To address this issue, improvements in engine and transmission system design as well as lubricant performance are required. For certain automotive transmissions, power loss caused by the torque converter during starting must be minimized, and lock-up clutch systems are introduced to improve fuel efficiency. Lock-up torque converters are installed in the lock-up wet paper clutch in the torque converter system. They can engage the wet clutch after fluid coupling at lower speeds and for shorter periods of time, reducing power loss and providing better fuel economy.

[0007] On the lubricant side, it is also very important to have a suitable lubricating oil composition for automatic transmissions with lock-up paper wet clutches in the transmission.If the lubricating oil composition reduces torque capacity and anti-vibration friction performance, it will cause power loss due to lock-up of the wet clutches in the transmission or unpleasant vibrations with high noise.Therefore, the lubricating oil composition for automatic transmissions with lock-up paper wet clutch systems should provide both good fuel economy and smooth driving and operating conditions. Summary of the Invention

[0008] A summary of certain embodiments disclosed herein is set forth below. It should be understood that these aspects are presented merely to provide the reader with a brief summary of these specific embodiments, and that these aspects are not intended to limit the scope of the present disclosure. In fact, the present disclosure may encompass a variety of aspects that may not be described below.

[0009] The present inventors have discovered a lubricating oil composition that has excellent wet paper clutch friction properties, such as anti-shudder performance, and is also capable of maintaining excellent wet clutch torque capacity and durability of the wet clutch friction properties.

[0010] In one embodiment, the present disclosure provides a method for producing a 2 to 12 mm 2 The present invention relates to a lubricating oil composition comprising a major amount of an oil of lubricating viscosity having a kinematic viscosity of about 100 / s. The lubricating oil composition comprises (a) one or more ashless dispersants, and (b) at least one acidic phosphorus compound (B1) selected from the group consisting of phosphoric acid, phosphorus compounds having the following structure: [ka] In the formula, R 1 ~R 3 R is independently a C1 to C20 hydrocarbyl group that may optionally contain an ether or thioether moiety. 4 is a hydrogen atom or a C1 to C20 hydrocarbyl group which may optionally contain an ether or thioether moiety.

[0011] R 4 When is a hydrogen atom, the resulting phosphorus compound (B1) is a phosphorous acid which can exist in the tautomeric form: [ka]

[0012] When the at least one acidic phosphorus compound (B1) is composed of phosphoric acid alone, the lubricating oil composition further contains one or more neutral phosphorus compounds (B2) selected from the group consisting of phosphoric acid triesters, phosphites, hydrogen phosphites, thiophosphates, amine salts of acidic phosphoric esters, and amine salts of acidic phosphonates. The neutralization rate of the (a) one or more ashless dispersants by the (b) at least one acidic phosphorus compound (B1) is 60 to 100%. The lubricating oil composition further contains (c) at least one friction modifier (C1) which is a reaction product of a hydrocarbyl-substituted succinic anhydride and a polyamine, and (d) at least one friction modifier (C2) selected from the group of oiliness agents consisting of diols, ethoxylated amines, fatty acid esters, sulfurized fatty acid esters, amides, and alcohols.

[0013] In another aspect, the present disclosure relates to a method for improving anti-shudder performance in an automatic transmission. The method comprises making the transmission slippery with a lubricating oil composition. The lubricating oil composition has a viscosity of 2 to 12 mm at 100° C. 2 The lubricating oil composition comprises a major amount of an oil of lubricating viscosity having a kinematic viscosity of about 100 / s. The lubricating oil composition comprises (a) one or more ashless dispersants, and (b) at least one acidic phosphorus compound (B1) selected from the group consisting of phosphoric acid, phosphorus compounds having the following structure: [ka] In the formula, R 1 ~R 3 R is independently a C1 to C20 hydrocarbyl group that may optionally contain an ether or thioether moiety. 4 is a hydrogen atom or a C1 to C20 hydrocarbyl group which may optionally contain an ether or thioether moiety.

[0014] R 4 When is a hydrogen atom, the resulting phosphorus compound (B1) is a phosphorous acid which may exist in the tautomeric form: [ka]

[0015] When the at least one acidic phosphorus compound (B1) is composed of phosphoric acid alone, the lubricating oil composition further contains one or more neutral phosphorus compounds (B2) selected from the group consisting of phosphoric acid triesters, phosphites, hydrogen phosphites, thiophosphates, amine salts of acidic phosphoric esters, and amine salts of acidic phosphonates. The neutralization rate of the (a) one or more ashless dispersants by the (b) at least one acidic phosphorus compound (B1) is 60 to 100%. The lubricating oil composition further contains (c) at least one friction modifier (C1) which is a reaction product of an alkenyl-substituted succinic anhydride and a polyamine, and (d) at least one friction modifier (C2) selected from the group of oiliness agents consisting of diols, ethoxylated amines, fatty acid esters, sulfurized fatty acid esters, amides, and alcohols. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] definition The following terms are used throughout the present specification and have the following meanings unless otherwise indicated.

[0017] The term "major amount" of base oil refers to an amount of base oil that is at least 40 wt% of the lubricant composition. In some embodiments, a "major amount" of base oil refers to an amount of base oil that is greater than 50 wt%, greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, or greater than 90 wt% of the lubricant composition.

[0018] The term "ashless" in reference to a dispersant in a lubricating oil composition means that the dispersant is substantially free of metals.

[0019] The term "Total Base Number" or "TBN" refers to the level of alkalinity, expressed in mg KOH / g (equivalent to the number of milligrams of KOH required to neutralize 1 gram of product), of an ingredient or composition that indicates its ability to continue to neutralize corrosive acids according to ASTM Standard D2896 or an equivalent procedure. Thus, a high TBN reflects a product that is strongly overbased, and therefore has a large base reserve to neutralize acids.

[0020] The term "Total Acid Number" or "TAN" refers to the level of acidity of an ingredient or composition according to ASTM Standard No. D664 or an equivalent procedure.

[0021] lubricating oil composition The present disclosure generally relates to lubricating oil compositions that provide excellent wet paper clutch friction characteristics, such as anti-shudder performance, and that can maintain excellent wet clutch torque capacity and durability of the wet clutch friction characteristics.

[0022] A lubricating oil composition generally has a viscosity of 2 to 12 mm at 100°C. 2 The lubricating oil composition also includes an oil of lubricating viscosity having a kinematic viscosity of about 100 / s. The lubricating oil composition also includes (a) one or more ashless dispersants, and (b) at least one acidic phosphorus compound (B1) selected from the group consisting of phosphoric acid, phosphorus compounds having the following structure: [ka] In the formula, R 1 ~R 3 R is independently a C1 to C20 hydrocarbyl group that may optionally contain an ether or thioether moiety. 4 is a hydrogen atom or a C1 to C20 hydrocarbyl group which may optionally contain an ether or thioether moiety.

[0023] R 4 When is a hydrogen atom, the resulting phosphorus compound (B1) is a phosphorous acid which may exist in the tautomeric form: [ka]

[0024] When the at least one acidic phosphorus compound (B1) consists solely of phosphoric acid, the lubricating oil composition further contains one or more neutral phosphorus compounds (B2) selected from the group consisting of phosphoric acid triesters, phosphites, hydrogen phosphites, thiophosphates, and their amine salts.

[0025] The neutralization rate of (a) one or more ashless dispersants present in the lubricating oil composition with (b) at least one acidic phosphorus compound (B1) is 60 to 100%.

[0026] The lubricating oil composition further comprises (c) at least one friction modifier (C1) which is a reaction product of a hydrocarbyl-substituted succinic anhydride and a polyamine, and (d) at least one friction modifier (C2) selected from the group of oiliness agents consisting of diols, ethoxylated amines, fatty acid esters, sulfurized fatty acid esters, amides, and alcohols.

[0027] The following sections discuss in detail the components of various embodiments of the lubricating oil composition, provide exemplary lubricating oil compositions, and disclose test results that demonstrate the excellent anti-vibration performance achieved by the lubricating oil compositions.

[0028] Oil of lubricating viscosity The lubricating oil composition disclosed herein generally comprises at least one oil of lubricating viscosity. Any base oil known to those skilled in the art can be used as the oil of lubricating viscosity disclosed herein. Some base oils suitable for preparing the lubricating oil composition 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 DV Brock, Lubrication Engineering, Vol. 43, pages 184-5, (1987), all of which are incorporated herein by reference. Generally, the amount of base oil in the lubricating oil composition may be 70% by weight 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 wt.%, or at least 80 wt.%, and not more than 99 wt.%, or not more than 98.5 wt.%, or not more than 98 wt.%, based on the total weight of the lubricating oil composition.

[0029] 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 a hydrocarbon synthesis procedure using carbon monoxide and hydrogen gas, such as the Fischer-Tropsch process. In certain embodiments, the base oil comprises less than 10 wt.% of one or more heavy fractions, based on the total weight of the base oil. 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 to up to 25 cSt, 30 cSt, or 35 cSt at 100° C. In further embodiments, the amount of one or more heavy fractions in the base oil is less than 10 wt%, less than 5 wt%, less than 2.5 wt%, less than 1 wt%, or less than 0.1 wt%, based on the total weight of the base oil. In yet further embodiments, the base oil is free of heavy fractions.

[0030] In certain embodiments, the lubricating oil composition comprises a major amount of a base oil of lubricating viscosity. In some embodiments, the base oil has a kinematic viscosity at 100° C. of at least 1.5 centistokes (cSt) or at least 2 centistokes (cSt) and no more than 20 cSt, or no more than 16 cSt. The kinematic viscosity of the base oil or lubricating oil composition disclosed herein can be measured according to ASTM D445, which is incorporated herein by reference.

[0031] In other embodiments, the base oil is or comprises a base stock or a blend of base stocks. In further embodiments, the base stocks are produced using a variety of different processes, including, but not limited to, distillation, solvent refining, hydrotreating, oligomerization, esterification, and rerefining. In some embodiments, the base stock comprises a rerefined stock. In further embodiments, the rerefined stock is substantially free of materials introduced by manufacture, contamination, or previous use.

[0032] In some embodiments, the base oil comprises one or more of the base stocks in one or more of Groups I-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 stocks as lubricating components that may be produced using a variety of different processes. Groups I, II, and III base stocks are mineral oils, each having a specific range of saturates, sulfur content, and viscosity index. Group IV base stocks are polyalphaolefins (PAOs). Group V base stocks include all other base stocks not included in Groups I, II, III, or IV.

[0033] In some embodiments, the base oil comprises one or more base stocks in Group I, II, III, IV, V, or combinations thereof. In other embodiments, the base oil comprises one or more base stocks in Group II, III, IV, or combinations thereof. In further embodiments, the base oil comprises one or more base stocks in Group II, III, IV, or combinations thereof, wherein the base oil has a kinematic viscosity at 100° C. of at least 1.5 centistokes (cSt), or at least 2 cSt, and no more than 20 cSt, or no more than 16 cSt. In some embodiments, the base oil is a mixture of a Group II base oil and a Group III base oil.

[0034] 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 includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extraction) the aromatic and polar components of crude oil. In other embodiments, the base oil of lubricating viscosity includes natural oils, such as animal oils, vegetable oils, mineral oils (e.g., liquid petroleum oils and paraffinic, naphthenic, or mixed paraffinic-naphthenic 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 oil, dolphin oil, seal oil, shark oil, tallow oil, and whale oil. Some non-limiting 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, oiticica oil, jojoba oil, and meadowfoam oil. Such oils may be partially or fully hydrogenated.

[0035] 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 derivatives, analogs and congeners thereof. In other embodiments, synthetic oils include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof, where the terminal hydroxyl groups can be modified by esterification, etherification, and the like. In further embodiments, synthetic oils include esters of dicarboxylic acids with various alcohols. In certain embodiments, synthetic oils include C 5 ~C 12 Included are esters made from monocarboxylic acids and polyols and polyol ethers. In a further embodiment, the synthetic oils include trialkyl phosphate ester oils, such as tri-n-butyl phosphate and tri-iso-butyl phosphate.

[0036] In some embodiments, synthetic oils of lubricating viscosity include silicon-based oils (e.g., polyalkyl-, polyaryl-, polyalkoxy-, polyaryloxy-siloxane oils and silicate oils), hi other embodiments, synthetic oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.

[0037] Base oils derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforementioned natural and / or synthetic base oils. Such wax isomerate oils are produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.

[0038] In further embodiments, the base oil comprises a poly-alpha-olefin (PAO). Generally, the poly-alpha-olefin may be derived from an alpha-olefin having 2 to 30, 2 to 20, or 2 to 16 carbon atoms. Non-limiting examples of suitable poly-alpha-olefins include those derived from octene, decene, mixtures thereof, and the like. These poly-alpha-olefins may have a viscosity at 100° C. of at least 1.5 centistokes and no more than 15 centistokes, or no more than 12 centistokes, or no more than 8 centistokes. In some examples, the poly-alpha-olefins may be used with other base oils, such as mineral oils, synthetic esters, or alkylated naphthalene base oils.

[0039] In further embodiments, the base oil comprises a polyalkylene glycol or a polyalkylene glycol derivative, wherein the terminal hydroxyl group 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 cases, the polyalkylene glycol or polyalkylene glycol derivative may be used with other base oils, such as poly-alpha-olefins and mineral oils.

[0040] In further embodiments, the base oil includes 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 azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, etc.

[0041] In a further embodiment, the base oil comprises hydrocarbons prepared by the Fischer-Tropsch process, in which a Fischer-Tropsch catalyst is used to prepare hydrocarbons from a gas containing hydrogen and carbon monoxide. These hydrocarbons may require further processing to be used as base oils. For example, the hydrocarbons may be dewaxed, hydroisomerized, and / or hydrocracked using methods known to those skilled in the art.

[0042] In further embodiments, the base oil comprises unrefined oil, refined oil, re-refined oil, or mixtures thereof. Unrefined oils are those obtained directly from natural or synthetic sources without further refining treatment. Non-limiting examples of unrefined oils include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process and used without further treatment. Refined oils are similar to unrefined oils, except that the former have been further treated by one or more refining processes to improve one or more properties. Many such refining processes, such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, are known to those skilled in the art. Re-refined oils are obtained by applying processes to refined oils similar to those used to obtain refined oils. Such re-refined oils are also known as reclaimed or reprocessed oils, and are often further treated by processes aimed at removing spent additives and oil breakdown products.

[0043] Ashless Dispersant The lubricating oil composition comprises at least one ashless dispersant (A). According to an exemplary embodiment, the lubricating oil composition comprises one or more nitrogen-containing ashless succinimide dispersant(s). According to a particular embodiment, the one or more nitrogen-containing ashless succinimide dispersants are non-post-treated dispersants.

[0044] Typical examples of nitrogen-containing ashless dispersants include hydrocarbyl succinimides, such as alkenyl or alkyl succinimides derived from polyolefins, and derivatives thereof. Succinimides can be obtained by reacting succinic anhydrides substituted with high molecular weight alkenyl or alkyl groups with polyalkylene polyamines containing an average of at least 3 or 4 nitrogen atoms per molecule and no more than 7 or 10 nitrogen atoms per molecule. In one embodiment, the high molecular weight alkenyl 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 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 no more than 4000, or no more than 3000, or no more than 2000, or no more than 1050. For example, the polyolefin may have a number average molecular weight of 1000.

[0045] In some embodiments, chlorine is utilized in the step of obtaining polybutenyl succinic anhydride by the reaction between polybutene and maleic anhydride, a chlorination method. However, although this method has good reactivity, a large amount of chlorine (e.g., 2000 ppm) remains in the final succinimide product. On the other hand, when a thermal reaction not involving 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). In addition, compared with conventional polybutenes (mainly those having β-olefin structures), the use of highly reactive polybutenes (those having at least 50% methylvinylidene structures) is advantageous in that the reactivity is also increased by the thermal reaction method. When the reactivity is high, the amount of unreacted polybutene in the dispersant is reduced, and therefore a dispersant containing a high concentration of 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 to produce succinimide by reacting this polybutenyl succinic anhydride with a polyamine. Succinimides can be used in a form called modified succinimide by further reacting with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate, organic acid, etc. The boron-containing alkenyl (or alkyl) succinimide obtained by reacting with boric acid or a boron compound is particularly advantageous in terms of thermal stability and oxidation stability. Succinimides include mono-type, bis-type, tris-type, and poly-type according to the number of imide structures per molecule, and the bis-type is usually used as the succinimide in lubricating oil compositions.

[0046] Other examples of nitrogen-containing ashless dispersants include polymeric succinimide dispersants derived from ethylene-α-olefin copolymers (eg, those having a molecular weight of 1000 to 15,000), and alkenyl benzyl amine-based ashless dispersants.

[0047] Exemplary nitrogen-containing ashless dispersants are the mono and bis alkyl or alkenyl succinimides derived from the reaction of alkyl or alkenyl succinic acids or anhydrides with alkylene polyamines. These compounds are generally considered to have the formula (I): [ka] In the formula, R 1 is a substantially hydrocarbon chain having a molecular weight of 500 to 3000, i.e., R 1 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; R 2 , R 3 and R 4 is C 1 ~C 4 or hydrogen, typically hydrogen, and x is an integer from 0 to 10, typically 0 to 3; or may be considered to have the formula (II): [ka] In the formula, R 5 and R 7 are both essentially hydrocarbon chains having a molecular weight of 500 to 3000, i.e., R 5 and R 7 are each a hydrocarbyl chain, such as an alkenyl chain, containing from 30 to 220 carbon atoms; Alk is an alkylene chain of from 2 to 10, usually from 2 to 6, carbon atoms; R 6 is C 1 ~C 4 or hydrogen, typically hydrogen; and y is an integer from 0 to 10, typically 0 to 3. 1 , R 5 and R 7 is a polyisobutyl group.

[0048] In some embodiments, R 2 or R6 is part of a cyclic ring, the cyclic ring containing two or more nitrogen atoms.

[0049] In one embodiment, the actual reaction product of the alkylene or alkenylene succinic acid or anhydride with the alkylene polyamine will include a mixture of compounds including monosuccinimides and bissuccinimides. The monoalkenyl succinimides and bisalkenyl succinimides produced may depend on the molar charge ratio of the polyamine to the succinic acid groups and the particular polyamine used. A 1:1 molar charge ratio of the polyamine to the succinic acid groups may produce primarily monoalkenyl succinimides. A 1:2 molar charge ratio of the polyamine to the succinic acid groups may produce primarily bisalkenyl succinimides. Examples of succinimide dispersants include those described in, for example, U.S. Pat. Nos. 3,172,892, 4,234,435, and 6,165,235, which are incorporated herein by reference in their entireties.

[0050] In one embodiment, the polyalkenes from which the substituents are derived are typically homopolymers and interpolymers of polymerizable olefin monomers having from 2 to 16 carbon atoms, usually from 2 to 6 carbon atoms. The amines reacted with the succinic acylating agent to form the carboxylic dispersant composition can be monoamines or polyamines.

[0051] In one aspect of the present disclosure, alkenyl succinimides may be prepared by reacting polyalkylene succinic anhydrides with alkylene polyamines. Polyalkylene succinic anhydrides are the reaction products of polyalkylenes (usually polyisobutenes) with maleic anhydride. Conventional polyisobutenes or high methylvinylidene polyisobutenes may be used to prepare such polyalkylene succinic anhydrides. The preparation may use thermal, chlorination, free radical, acid catalysis, or any other process. Examples of suitable polyalkylene succinic anhydrides are thermal PIBSA (polyisobutenyl succinic anhydride) as described in U.S. Pat. No. 3,361,673; chlorinated PIBSA as described in U.S. Pat. No. 3,172,892; mixtures of thermal and chlorinated PIBSA as described in U.S. Pat. No. 3,912,764; high succinic acid ratio PIBSA as described in U.S. Pat. No. 4,234,435; and those described in U.S. Pat. Nos. 5,112,507 and 5,175,225. high succinic acid ratio PolyPIBSA as described in U.S. Pat. Nos. 5,565,528 and 5,616,668; free radical PIBSA as described in U.S. Pat. Nos. 5,286,799, 5,319,030 and 5,625,004; PIBSA made from high methylvinylidene polybutene as described in U.S. Pat. Nos. 4,152,499, 5,137,978 and 5,137,980; High succinic acid ratio PIBSA made from high methylvinylidene polybutene, as described in U.S. Pat. No. 355 895; terpolymer PIBSA, as described in U.S. Pat. No. 5,792,729; sulfonic acid PIBSA, as described in U.S. Pat. No. 5,777,025 and European Patent Application Publication No. EP 542 380; and purified PIBSA, as described in U.S. Pat. No. 5,523,417 and European Patent Application Publication No. EP 602 863. The disclosure of each of these documents is incorporated herein by reference in its entirety. Polyalkylene succinic anhydride is usually polyisobutenyl succinic anhydride.In an 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 not more than 1400, or not more than 1300, or not more than 1200, or not more than 1100, or not more than 1000.

[0052] Typical polyalkyleneamines used to prepare succinimides are of formula (III): [ka] where z is an integer from 0 to 10, Alk is an alkylene radical of 2 to 10, typically 2 to 6, carbon atoms, and R 8 , R 9 and R 10 is C 1 ~C 4 is selected from alkyl, alkoxy, alkylamine or hydrogen, typically hydrogen; z is an integer from 0 to 10, typically 0 to 3.

[0053] The alkylene amines include primarily methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines, as well as cyclic and higher homologues of amines such as piperazine and aminoalkyl substituted piperazines. They are specifically exemplified by ethylenediamine, triethylenetetraamine, propylenediamine, decamethyldiamine, octamethylenediamine, diheptamethylenetriamine, tripropylenetetraamine, 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 homologs obtained by condensing two or more of the above-exemplified alkyleneamines are also useful.

[0054] Ethylene amines are particularly useful. They are described in some detail in the Encyclopedia of Chemical Technology, Kirk-Othmer, Vol. 5, pp. 898-905 (Interscience Publishers, New York, 1950) under the heading "Ethylene Amines". The term "ethylene amine" is used in a general sense to refer to a class of polyamines which largely conform to the formula (IV): [ka] where α is an integer from 1 to 10. In one embodiment, α is an integer from 3 to 5. Thus, it includes, for example, ethylenediamine, diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine, pentaethylenehexamine, and the like.

[0055] It should be understood that polyamines as used herein often include 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]

[0056] Specific alkenyl succinimides used in the alkenyl succinimide composition may be selected from the group consisting of those disclosed in U.S. Pat. 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; 3,361; and the like, the disclosures of which are all incorporated herein by reference in their entirety for all purposes. ,673; 3,381,022; 3,912,764; 4,234,435; 4,612,132; 4,747,965; 5,112,507; 5,241,003; 5,266,186; 5,286,799; 5,319,030; 5,334,321; 5,356,552; and 5,716,912.

[0057] Also included within the scope of the term "alkenyl succinimide" are post-treated succinimides such as those involving borate or ethylene carbonate as disclosed by Wollenberg, et al., U.S. Pat. No. 4,612,132; Wollenberg, et al., U.S. Pat. No. 4,746,446, each of which is incorporated herein by reference in its entirety, as well as other post-treatment processes. 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.

[0058] In one embodiment, the dispersant system is present in an amount of at least 1 wt.%, or at least 1.5 wt.%, or at least 2.0 wt.%, and not more than 20 wt.%, or not more than 15 wt.%, or not more than 10 wt.%, or not more than 5.0 wt.%, or not more than 4.0 wt.%, or not more than 3.0 wt.%, for example, 1.0 to 3.0 wt.%, based on the total weight of the lubricating oil composition.

[0059] In another embodiment, the non-post-treated dispersant is a non-post-treated succinimide dispersant, hi other embodiments, the non-post-treated succinimide dispersant is present in an amount of at least 0.3 wt%, or at least 0.5 wt%, or at least 0.6 wt%, and not more than 8 wt%, or not more than 5 wt%, or not more than 4 wt%, or not more than 3.0 wt%, or not more than 2.0 wt%, based on the total weight of the lubricating oil composition.

[0060] Specific alkenyl succinimides used in the alkenyl succinimide composition may be selected from the group consisting of those disclosed in U.S. Pat. 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; 3,361; and the like, the disclosures of which are all incorporated herein by reference in their entirety for all purposes. ,673; 3,381,022; 3,912,764; 4,234,435; 4,612,132; 4,747,965; 5,112,507; 5,241,003; 5,266,186; 5,286,799; 5,319,030; 5,334,321; 5,356,552; and 5,716,912.

[0061] Also included within the scope of the term "alkenyl succinimide" are post-treated succinimides such as those disclosed, for example, in U.S. Pat. No. 4,612,132, U.S. Pat. No. 4,746,446, each of which is incorporated herein by reference in its entirety, as well as other post-treatment processes involving borates or ethylene carbonate. Typically, carbonate-treated alkenyl succinimides are polybutene succinimides derived from polyisobutene having a molecular weight of at least 500, or at least 600, or at least 800, or at least 900, and no more than 3000, or no more than 2500, or no more than 2300.

[0062] According to exemplary embodiments, the nitrogen-containing ashless succinimide dispersants each have a number average molecular weight of at least 500, at least 750, or at least 850, or at least 1000, and no more than 1800, or no more than 1700, or no more than 1600, or no more than 1500, or no more than 1400, or no more than 1350.

[0063] Each nitrogen-containing ashless succinimide dispersant typically has a TBN of at least 25 mg KOH / g or at least 30 mg KOH / g and no more than 55 mg KOH / g or no more than 50 mg KOH / g.

[0064] The nitrogen content of each nitrogen-containing ashless succinimide dispersant according to the exemplary embodiment ranges from 1.0% to 3.0% by weight, based on the total weight of the nitrogen-containing ashless succinimide dispersant.

[0065] In one embodiment the dispersant is not post-treated, hi another embodiment the dispersant is post-treated with a boron compound.

[0066] According to an exemplary embodiment, the one or more nitrogen-containing ashless succinimide dispersant(s) comprises a boron-containing dispersant having a boron content in the range of 0.1% to 2.0% by weight based on the total weight of the nitrogen-containing ashless succinimide dispersant.

[0067] According to an exemplary embodiment, the one or more nitrogen-containing ashless succinimide dispersants include two dispersants: a first dispersant is a boron-modified polyisobutenyl succinimide having a polyisobutene number average molecular weight of 1300, a nitrogen content of 1.95 wt%, a boron content of 0.63 wt%, and a TBN of 46 mg KOH / g; and a second dispersant is a polyisobutenyl succinimide having a polyisobutene number average molecular weight of 1000, a nitrogen content of 1.93 wt%, and a TBN of 35 mg KOH / g.

[0068] The lubricating oil composition typically contains less than 0.3 weight percent sulfated ash, or 0.1 weight percent or less sulfated ash, based on the total weight of the lubricating oil composition.

[0069] Phosphorus Compounds The lubricating oil composition further comprises at least one phosphorus compound. A variety of different phosphorus compounds can be used in the lubricating oil composition. However, according to an exemplary embodiment, the lubricating oil composition comprises at least one acidic phosphorus compound (B1) selected from phosphoric acid, or a phosphorus compound of the following structure, or a combination thereof: [ka] In the formula, R 1 ~R 3 independently, C may optionally contain an ether or thioether moiety; 1 ~C 20 R is a hydrocarbyl group. 4 R is a hydrogen atom or a C1-C20 hydrocarbyl group that may optionally contain an ether or thioether moiety. 4 When is a hydrogen atom, the resulting phosphorus compound (B1) is a phosphorous acid which may exist in the tautomeric form: [ka]

[0070] According to an exemplary embodiment, when the acidic phosphorus compound (B1) consists solely of phosphoric acid, the lubricating oil composition further contains one or more neutral phosphorus compounds (B2) selected from phosphoric acid triesters, phosphites, hydrogen phosphites, thiophosphates, amine salts of acidic phosphoric esters, and amine salts of acidic phosphonic esters.

[0071] phosphoric acid The phosphoric acid in the lubricating oil composition is usually inorganic phosphoric acid H 3 PO 4 According to an exemplary embodiment, the phosphoric acid (85 wt. % solution) contains phosphorus in an amount of at least 20.0 wt. %, or at least 25.0 wt. %, and not more than 32.0 wt. %, or not more than 30.0 wt. %, based on the total weight of the phosphoric acid.

[0072] According to an exemplary embodiment, the phosphoric acid (85 wt. % solution) has a total acid number (TAN) of at least 850 mg KOH / g or at least 950 mg KOH / g and no greater than 1050 mg KOH / g or no greater than 1000 mg KOH / g.

[0073] In one embodiment, the phosphoric acid (85 wt % solution) is present in an amount of 0.01 wt % to 1.0 wt %, based on the total weight of the lubricating oil composition, hi other embodiments, the phosphoric acid is present in an amount of at least 0.01 wt %, or at least 0.02 wt %, or at least 0.03 wt %, and not more than 0.5 wt %, or not more than 0.6 wt %, or not more than 0.7 wt %, or not more than 1.0 wt %, based on the total weight of the lubricating oil composition.

[0074] Acid monophosphate or diphosphate esters In certain embodiments, the phosphorus compound may include an acid monophosphate or diphosphate ester. Examples of phosphate esters include mono- and / or di-aryl phosphates, mono- and / or di-alkyl phosphates, mono- and / or alkyl-aryl phosphates, mono- and / or aryl-alkyl phosphates, and mono- and / or di-alkenyl phosphates. Specific examples include mono- and / or di-phenyl phosphates, mono- and / or di-cresyl phosphates, benzylphenyl phosphates, ethylphenyl phosphates, mono- and / or di-butyl phosphates, ethylbutyl phosphates, cresylphenyl phosphates, ethyl-phenylphenyl phosphates, propyl-phenylphenyl phosphates, phosphoric acid, di-ethylphenyl phosphates, di-propyl-phenyl phosphates, butylphenylphenyl phosphates, di-butylphenyl phosphates, di-hexyl phosphates, di-(2-ethylhexyl) phosphates, di-octyl phosphates, di-decyl phosphates, di-lauryl phosphates, di-myristyl phosphates, di-palmityl phosphates, di-stearyl phosphates, and di-oleyl phosphates.

[0075] The thioether bond may be contained in the alkyl group. Examples of phosphate esters containing thioether include mono- and / or di-alkyl thiophosphates, mono- and / or di-butylthioethyl phosphates, mono- and / or di-hexylthioethyl phosphates, mono- and / or di-octylthioethyl phosphates, mono- and / or di-decylthioethyl phosphates, mono- and / or di-dodecylthioethyl phosphates, and mono- and / or di-hexadecylthioethyl phosphates.

[0076] According to an exemplary embodiment, each acid 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 esters.

[0077] The lubricating oil composition may contain phosphorus in an amount of at least 0.01 wt.%, or at least 0.02 wt.%, or at least 0.03 wt.%, and not more than 0.20 wt.%, or not more than 0.1 wt.%, or not more than 0.08 wt.%, based on the total weight of the lubricating oil composition.

[0078] 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 phenyl phosphate, ethyl phenyl diphenyl phosphate, di(ethylphenyl)phenyl phosphate, propyl phenyl diphenyl phosphate, di(propylphenyl)phenyl phosphate, triethyl phenyl phosphate, tripropyl phenyl phosphate, butyl phenyl diphenyl phosphate, di(butylphenyl)phenyl phosphate, tributyl phenyl phosphate, trihexyl phosphate, tri(2-ethylhexyl) phosphate, trioctyl phosphate, tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate, tristearyl phosphate, and trioleyl phosphate.

[0079] Phosphite esters Examples of phosphites 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.

[0080] The thioether linkage may be contained in the alkyl group. Examples of phosphites containing thioether include tri-alkyl thiophosphites, tri-butylthioethyl phosphite, tri-hexylthioethyl phosphite, tri-octylthioethyl phosphite, tri-decylthioethyl phosphite, tri-dodecylthioethyl phosphite, and tri-hexadecylthioethyl phosphite.

[0081] According to an exemplary embodiment, each phosphite has a phosphorus content of 3.0% to 15.0% by weight. If the phosphite contains a thioether linkage, the phosphite has a sulfur content of 5.0% to 25.0% by weight, based on the total weight of the phosphite.

[0082] Hydrogen phosphite In certain embodiments, the hydrogen phosphite is a di-alkyl hydrogen phosphite, a hydrogen di-phenyl ester, and the hydrogen dialkyl-phenyl ester is preferred, but the present invention is not limited thereto. Examples of hydrogen phosphite di-esters include di-butyl hydrogen phosphite, di-pentyl hydrogen phosphite, di-hexyl hydrogen phosphite, di-octyl hydrogen phosphite, di-2-ethylhexyl hydrogen phosphite, di-decyl hydrogen phosphite, di-lauryl hydrogen phosphite, di-octadecyl hydrogen phosphite, di-phenyl hydrogen phosphite, etc.

[0083] The thioether linkage may be contained in the alkyl group. Examples of hydrogen phosphites containing thioether include di-alkyl hydrogen thiophosphites, di-butylthioethyl hydrogen phosphite, di-hexylthioethyl hydrogen phosphite, di-octylthioethyl hydrogen phosphite, di-decylthioethyl hydrogen phosphite, di-dodecylthioethyl hydrogen phosphite, and di-hexadecylthioethyl hydrogen phosphite.

[0084] According to an exemplary embodiment, each hydrogen phosphite has a phosphorus content of 3.0% to 15.0% by weight. In embodiments in which the hydrogen phosphite contains thioether linkages, the hydrogen phosphite has a sulfur content of 5.0% to 25.0% by weight, based on the total weight of the phosphite.

[0085] Amine Salts As noted above, according to an exemplary embodiment, when the acidic phosphorus compound (B1) consists solely of phosphoric acid, the lubricating oil composition further contains one or more neutral phosphorus compounds (B2) which may comprise an amine salt of an acidic phosphoric acid ester or an amine salt of an ester of acidic phosphorous acid. Examples of such amine salts include the amine salt of mono-hexyl phosphate, the amine salt of di-hexyl phosphate, the amine salt of mono-2-ethyl-hexyl phosphate, the amine salt of di-2-ethylhexyl phosphate, the amine salt of mono-octyl phosphate, the amine salt of di-octyl phosphate, the amine salt of mono-octyl thiophosphate, the amine salt of di-octyl thiophosphate, the amine salt of mono-decyl phosphate, the amine salt of mono-dodecyl phosphate, the amine salt of di-dodecyl phosphate, the amine salt of mono-octadecyl phosphate, and the amine salt of di-octadecyl phosphate.

[0086] The amine used to prepare the amine salt is R 5 R 6 R 7 N. R 5 , R 6 and R 7are independently a saturated or unsaturated aliphatic, aromatic, or araliphatic hydrocarbon having 1 to 20 carbon atoms, or hydrogen. When the group is a hydrocarbon, it may be a straight chain structure or branched chain.

[0087] In certain embodiments, the amine salt may be represented by formula (V): [ka] In the formula, R 8 is C 9 ~C 22 is hydrocarbyl, R 9 and R 10 are each independently C 1 ~C 4 is hydrocarbyl, R 11 is C 10 ~C 20 is hydrocarbyl, R 12 is hydrogen or C 10 ~C 20 Examples of such amine salts are described in U.S. Patent No. 5,552,068, which is incorporated herein by reference in its entirety.

[0088] According to an exemplary embodiment, 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.

[0089] Exemplary Phosphorus Compounds According to exemplary embodiments, the one or more neutral phosphorus compound(s) (B2) are present in an amount of 0.01 wt.% to 3.0 wt.%, based on the total weight of the lubricating oil composition. In other embodiments, the one or more neutral phosphorus compound(s) (B2) are present in an amount of at least 0.01 wt.%, or at least 0.02 wt.%, or at least 0.03 wt.%, and not more than 1.0 wt.%, or not more than 0.5 wt.%, or not more than 0.3 wt.%, or not more than 0.2 wt.%, based on the total weight of the lubricating oil composition.

[0090] According to an exemplary embodiment, the lubricating oil composition comprises inorganic phosphorus acid H 3 PO 4 Contains inorganic phosphate H 3 PO 4 (85 wt % solution) has a phosphorus content of 27.0 wt % based on the total weight of inorganic phosphoric acid and a total acid number (TAN) of 973 mg KOH / g. In this embodiment, the lubricating oil composition further comprises one or more neutral phosphorus compounds (B2) selected from phosphate esters, phosphites, hydrogen phosphites, thiophosphate esters, amine salts of acid phosphate esters, and amine salts of esters of acid phosphorous acid.

[0091] According to one embodiment, the lubricating oil composition comprises a mixture of phosphites, specifically monoalkyl phosphites containing thioether alkyl groups (acidic phosphorus compounds), and dialkyl phosphites containing thioether alkyl groups. The mixture of mono / dialkyl phosphites containing thioether alkyl groups has a phosphorus content of 8.0 wt. % and a sulfur content of 8.4 wt. % based on the total weight of the mixture, and a TAN of 111 mg KOH / g.

[0092] According to another exemplary embodiment, a lubricating oil composition comprises diphenyl hydrogen phosphite having a phosphorus content of 13.3 wt. %, based on the total weight of the diphenyl hydrogen phosphite.

[0093] In another exemplary embodiment, the lubricating oil composition includes an amine phosphate, such as an amine salt of a phosphoric acid alkyl ester, in one embodiment, the amine phosphate salt has a phosphorus content of 8.2 wt. % and a nitrogen content of 1.8 wt. % based on the total weight of the alkyl amine salt.

[0094] According to an exemplary embodiment, at least one phosphorus compound of the lubricating oil composition is an inorganic phosphorus acid H in combination with a mixture of mono / dialkyl phosphite esters containing thioether alkyl groups. 3 PO 4 According to another exemplary embodiment, the lubricating oil composition comprises inorganic phosphate H 3 PO4 and a mixture of mono / dialkyl phosphites containing thioether alkyl groups, diphenyl hydrogen phosphite, and an alkylamine salt of an alkyl phosphate ester. According to another exemplary embodiment, the at least one phosphorus compound of the lubricating oil composition comprises only a mixture of mono / dialkyl phosphites containing thioether alkyl groups. According to yet another exemplary embodiment, the lubricating oil composition comprises a mixture of mono / dialkyl phosphites containing thioether alkyl groups, diphenyl hydrogen phosphite, and an alkylamine salt of an alkyl phosphate ester. According to another exemplary embodiment, the lubricating oil composition comprises inorganic H phosphate. 3 PO 4 , diphenyl hydrogen phosphite, and alkylamine salts of alkyl phosphate esters.

[0095] Neutralization rate An important feature of the lubricating oil composition of the present disclosure is the neutralization of at least one ashless dispersant (A) by at least one acidic phosphorus compound (B1), herein represented by the neutralization rate and / or the initial pH of the composition. For example, in some embodiments, a polyamine is bound to the dispersant, and it has been found that the basic nitrogen of this polyamine adsorbs to the oxide film on the metal surface, reducing the effectiveness of the anti-wear agent, or to the paper material of the wet clutch, reducing the effectiveness of the FM. The effectiveness of the oiliness agent is also adversely affected. By appropriately controlling the amount of basic amine, the effectiveness of additives such as anti-wear agents, oiliness agents, and FMs can be significantly changed. On the other hand, if the oil is overly neutralized with acid and the oil becomes strongly acidic, rust and corrosion can occur. Therefore, it is desirable for the oil to be in the appropriate range (pH=6-9). The neutralization rate is the proportion of at least one ashless dispersant (A) that is neutralized by at least one acidic phosphorus compound (B1).

[0096] The neutralization ratio of a lubricating oil composition is calculated by dividing the total acid number (TAN) of the acidic phosphorus compound(s) by the total base number of the ashless dispersant(s). TAN is the total TAN provided by the combination of one or more acidic phosphorus compounds, and TBN is the combined TBN of one or more ashless dispersants. TAN is measured by the method of ASTM D664; TBN is measured by the method of ASTM D4739. As a non-limiting example, the neutralization ratio can be determined according to the following steps: (a) measuring the base number of each dispersant (A) according to ASTM D4739; (b) measuring the acid number of each acidic phosphorus compound (B1) according to ASTM D664; and (c) multiplying the values ​​determined for (a) and (b) by the weight percent amount of each component added to the formulation to calculate the total base number from the dispersant (A) and the total acid number from the acidic phosphorus compound (B1). The percentage of the total base number of the dispersant that can be neutralized by the total acid number of the acidic phosphorus compound is calculated by dividing the total base number by the total acid number and multiplying by 100.

[0097] According to exemplary embodiments, the lubricating oil composition has a neutralization rate of at least 60% or at least 75% and not more than 120%, or not more than 100%. A neutralization rate of 60 to 100% means that between 60 percent and 100 percent of the ashless dispersant(s) is neutralized by the acidic phosphorus compound(s).

[0098] Initial pH (i-pH) according to ASTM D664 As mentioned above, the initial pH (i-pH) of the composition can be used to represent the neutralization of at least one ashless dispersant (A) by at least one acidic phosphorus compound (B1). The i-pH may be determined, for example, by mixing the dispersant (A in Table 1) with the acidic phosphorus compound (B1 in Table 1) at a temperature of 50-80°C for 30 minutes and allowing the resulting mixture to return to room temperature in the same manner as for a normal blend. The degree to which the mixture is neutralized can be understood by looking at the i-pH measured by potentiometric titration method of ASTM D664. A mixture of the dispersant (A in Table 1) and the acidic phosphorus compound(s) (B1 in Table 1) was dissolved in a mixed solvent of toluene, 2-propanol, and water, and the acidity (or basicity) was measured with a pH meter before titration. The first pH value indicated by the pH meter before titration is the i-pH. This value represents the acidity (or basicity) of the mixture. This i-pH measurement is often used in the general market for lubricant maintenance, as well as to ascertain the acidity (or basicity) of such mixtures. It is often used as a method to determine the degree of deterioration (oxidation) of used oil. According to an exemplary embodiment, the pH is at least 4 and less than 10, between 4 and 9.5, or between 4.5 and 9.5.

[0099] As mentioned above, the at least one acidic phosphorus compound (B1) is selected from phosphoric acid, or a phosphorus compound of the following structure, or a combination thereof: [ka] In the formula, R 1 ~R 3 R is independently a C1 to C20 hydrocarbyl group that may optionally contain an ether or thioether moiety. 4 is a hydrogen atom or a C1 to C20 hydrocarbyl group which may optionally contain an ether or thioether moiety.

[0100] R 4 When is a hydrogen atom, the resulting phosphorus compound (B1) is a phosphorous acid which may exist in the tautomeric form: [ka]

[0101] The at least one ashless dispersant (A) comprises one or more nitrogen-containing ashless succinimide dispersant(s).

[0102] Friction modifiers Various known friction modifiers may be used as friction modifiers in the lubricating oil compositions of this disclosure.

[0103] The friction modifier may include a reaction product of a hydrocarbyl succinic acid or anhydride with a polyamine. According to certain embodiments, the actual reaction product of a hydrocarbyl succinic acid or anhydride with a polyamine may include a mixture of compounds including monosuccinimides and bissuccinimides. The monosuccinimides and bissuccinimides produced may depend on the molar charge ratio of the polyamine to the succinic acid groups and the particular polyamine used. A molar charge ratio of the polyamine to the succinic acid groups of about 1:1 may produce primarily monosuccinimides. A molar charge ratio of the polyamine to the succinic acid groups of about 1:2 may produce primarily bissuccinimides. According to certain embodiments, the friction modifier includes a low molecular weight C6-C30 hydrocarbyl substituted succinimide.

[0104] According to another exemplary embodiment, the friction modifier of the lubricating oil composition is a bissuccinimide. The bissuccinimide friction modifier may be a hydrocarbyl-substituted succinimide or a subsequently processed derivative represented by the following formula (VI): [ka]

[0105] In the formula, R 1 and R 1 R ′ is independently a hydrocarbyl group having a branched structure represented by the following formula (VII) at the β-position; 2is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an alkylamine, or a 5- to 8-membered heterocyclic group; x is an integer of 1 to 6; and y is an integer of 0 to 20: [ka] In the formula, R 3 and R 4 Each of R is an aliphatic hydrocarbyl group; 3 The number of carbon atoms in R 4 or R 3 The number of carbon atoms in R 4 The number of carbon atoms in R is one less than the number of carbon atoms in 3 and R 4 The total number of carbon atoms in the compound is in the range of 3 to 30.

[0106] In some embodiments, R 2 is part of a cyclic ring, the cyclic ring containing two or more nitrogen atoms.

[0107] According to another embodiment, the friction modifier comprises an alkenyl-substituted succinimide or a subsequently treated derivative of formula (VIII): [ka]

[0108] In the formula, R 1 and R 1 Each of the ' is independently a hydrocarbyl group having a branched structure at the β-position derived from a dimer of a single linear β-olefin having 3 to 24 carbon atoms, and Q is a residue of a polyamine having 1 to 20 carbon atoms.

[0109] Friction modifiers can provide improved friction performance to lubricating oil compositions, as evidenced by increased coefficient of friction and extended coefficient of friction stability, and thus lubricating oil compositions containing friction modifiers can protect automatic transmissions from shudder for relatively long periods of time.

[0110] According to another embodiment, the friction modifier comprises a post-treated alkenyl-substituted succinimide obtained by post-treating an alkenyl-substituted succinimide with a known post-treating agent, such as boric acid, phosphoric acid, carboxylic acid, or ethylene carbonate.

[0111] According to certain embodiments, the friction modifier of the lubricating oil composition comprises a diol. For example, the lubricating oil composition may comprise a diol compound having the following formula (IX): [ka] In the formula, R represents hydrogen, an alkyl group, or an alkenyl group. It is also possible to use a mixture of compounds having different alkyl or alkenyl groups. The alkyl or alkenyl groups can be either linear or branched and usually contain from 10 to 30 carbon atoms.

[0112] According to another embodiment, the friction modifier of the lubricating oil composition comprises an ethoxylated amine. The ethoxylated amine may have the following formula (X): [ka] In the formula, R represents hydrogen, an alkyl group, or an alkenyl group. It is also possible to use a mixture of compounds having different alkyl or alkenyl groups. The alkyl or alkenyl groups can be either linear or branched and usually contain from 8 to 22 carbon atoms.

[0113] According to certain embodiments, the friction modifier of the lubricating oil composition comprises a fatty acid ester, a fatty acid amide, a fatty acid amide of a low molecular weight amino acid, and / or an alcohol. 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.

[0114] According to an exemplary embodiment, the lubricating oil composition comprises a combination of at least one friction modifier (C1) which is a reaction product of a hydrocarbyl-substituted succinic anhydride and a polyamine, and at least one friction modifier (C2) selected from a diol, an ethoxylated amine, a fatty acid ester, and an alcohol.

[0115] Each friction modifier is typically present in an amount of 0.01 wt.% to 3 wt.% 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 wt.% to 5 wt.% based on the total weight of the lubricating oil composition. In exemplary embodiments, the friction modifiers are present in an amount of at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, and no more than 4.0 wt.%, or no more than 3.0 wt.%, or no more than 2.0 wt.%, based on the total weight of the lubricating oil composition.

[0116] Other Additives Optionally, the lubricating oil composition may further comprise at least one additive or modifier (hereinafter referred to as "additive") capable of imparting or improving any desired property of the lubricating oil composition. Any additive known to a person skilled in the art may be used in the lubricating oil composition disclosed herein. Some 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, the at least one additive may be selected from the group consisting of antioxidants, antiwear agents, surfactants, rust inhibitors, demulsifiers, multifunctional additives, viscosity index improvers, pour point depressants, antifoam agents, metal deactivators, corrosion inhibitors, lubricity improvers, thermal stability improvers, anti-fog additives, anti-icing agents, dyes, markers, static dissipative agents, biocides, and combinations thereof. The additives may also include friction modifiers and dispersants in addition to those friction modifiers and dispersants described above.

[0117] The concentration of each additive in the lubricating oil composition, when used, is typically at least 0.001 wt%, or at least 0.01 wt%, or at least 0.1 wt%, individually, and not more than 15 wt%, or not more than 10 wt%, or not more than 8 wt%, based on the total weight of the lubricating oil composition. Furthermore, the total amount of the additives combined in the lubricating oil composition is typically at least 0.001 wt%, or at least 0.1 wt%, or at least 1 wt%, and not more than 20 wt%, or not more than 15 wt%, or not more than 10 wt%, for example, from 9 wt% to 10 wt%, based on the total weight of the lubricating oil composition.

[0118] In one embodiment, the lubricating oil composition contains a metal surfactant compound. Some non-limiting examples of suitable metal surfactants include sulfurized or non-sulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfurized or non-sulfurized metal salts of multiple hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or non-sulfurized alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of alkyl or alkenyl polyacids, and chemical and physical mixtures thereof. Other non-limiting examples of suitable metal surfactants include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates, and combinations thereof. The metal can be any metal suitable for making sulfonate, phenate, salicylate, or phosphonate surfactants. 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.

[0119] Some suitable surfactants 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.

[0120] Generally, the amount of metal surfactant is from about 0.001% to about 0.5% by weight, from about 0.01% to about 0.3% by weight, from about 0.01% to about 0.2% by weight, from about 0.01% to about 0.1% by weight, from about 0.02% to about 0.5% by weight, from about 0.02% to about 0.4% by weight, or from about 0.03% to about 0.3% by weight, based on the total weight of the lubricating oil composition.

[0121] In one embodiment, the metal surfactant is a calcium sulfonate or calcium salicylate surfactant with a TBN of 50-450 mg KOH / gm and a calcium content of 1.0-20 wt. %.

[0122] In another embodiment, calcium is present at up to 300 ppm by weight of the lubricating oil composition, hi other embodiments, calcium is present at from 25 to 300, 30 to 250, or 34 to 250 ppm by weight of the lubricating oil composition.

[0123] According to some embodiments, the lubricating oil composition includes at least one antioxidant capable of reducing or preventing oxidation of the oil of lubricating viscosity 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-based antioxidants (e.g., alkyldiphenylamines, phenyl-alpha-naphthylamines, alkyl or aralkyl substituted phenyl-alpha-naphthylamines, alkylated p-phenylenediamines, tetramethyl-diaminodiphenylamines, etc.), phenol-based antioxidants (e.g., 2-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2, 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), etc.), sulfur-based antioxidants (e.g., dilauryl-3,3'-thiodipropionate, sulfurized phenol-based antioxidants, etc.), phosphorus-based antioxidants (e.g., phosphites, etc.), zinc dithiophosphates, oil-soluble copper compounds, and combinations thereof. The amount of antioxidant may vary from at least 0.01 wt%, or at least 0.05 wt%, or at least 0.1 wt%, and not more than 10 wt%, or not more than 5 wt%, or not more than 3 wt%, based on the total weight of the lubricating oil composition. Some suitable antioxidants are described in Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 1, pages 1-28 (2003), which is incorporated herein by reference.

[0124] The lubricating oil composition may optionally include at least one pour point depressant capable of lowering 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-paraffin phenol) phthalate, condensates of tetra-paraffin phenol, condensates of chlorinated paraffins with naphthalene, and combinations thereof. In some embodiments, the pour point depressant includes ethylene-vinyl acetate copolymers, condensates of chlorinated paraffins with phenols, polyalkylstyrenes, and the like. The amount of pour point depressant may vary from at least 0.01 wt%, or at least 0.05 wt%, or at least 0.1 wt%, and not more than 10 wt%, or not more than 5 wt%, or not more than 3 wt%, based on the total weight of the lubricating oil composition. Some 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.

[0125] The lubricating oil composition may further comprise at least one antifoaming agent or defoamer. Any antifoaming agent or defoamer known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable defoamers include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated fatty acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines, and combinations thereof. In some embodiments, the defoamer comprises 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 wt%, or at least 0.0005 wt%, or at least 0.001 wt%, and not more than 1 wt%, or not more than 0.5 wt%, or not more than 0.1 wt%, based on the total weight of the lubricating oil composition. Some suitable antifoaming agents are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996), which is incorporated herein by reference.

[0126] The lubricating oil composition may optionally include 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 half esters or amides of dodecyl succinic acid, phosphate esters, thiophosphates, alkyl imidazolines, sarcosines, benzotriazoles, thiadiazoles, and combinations thereof. The amount of corrosion inhibitor may vary from at least 0.001 wt.%, or at least 0.005 wt.%, and not more than 5 wt.%, or not more than 1 wt.%, or not more than 0.5 wt.%, based on the total weight of the lubricating oil composition. Some 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.

[0127] The lubricating oil composition disclosed herein may optionally contain at least one extreme pressure (EP) agent that can prevent the seizure 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 composition. In general, extreme pressure agents are compounds that can chemically bond with metals to form a surface film that prevents the welding of asperities on opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters and alpha-olefins, functionally substituted dihydrocarbyl polysulfides, thialdehydes, thiaketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, polysulfide olefin products, amine salts of phosphates or thiophosphates, and combinations thereof. The amount of extreme pressure agent may vary from at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, and not more than 5 wt.%, or not more than 3 wt.%, or not more than 1 wt.%, based on the total weight of the lubricating oil composition. Some suitable extreme pressure agents are described in Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 8, pages 223-258 (2003), which is incorporated herein by reference.

[0128] In one embodiment, the lubricating oil composition does not contain a sulfur-based extreme pressure agent.

[0129] The lubricating oil composition disclosed herein may optionally include at least one rust inhibitor capable of inhibiting corrosion of ferrous metal surfaces. Any rust inhibitor known to one skilled in the art may be used in the lubricating oil composition. 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 made from tall oil fatty acid, oleic acid, linoleic acid, etc.), alkenyl succinic acids in which the alkenyl group contains 10 or more carbon atoms (e.g., tetrapropenyl succinic acid, tetradecenyl succinic acid, hexadecenyl succinic acid, etc.), long chain alpha, omega-dicarboxylic acids having molecular weights in the range of 600 to 3000 daltons, and combinations. The amount of rust inhibitor may vary from at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, and not more than 10 wt.%, or not more than 5 wt.%, or not more than 3 wt.%, based on the total weight of the lubricating oil composition.

[0130] Other non-limiting examples of suitable rust inhibitors include non-ionic polyoxyethylene surfactants such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octylstearyl 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 heavy sulfonic acids, partial carboxylic acid esters of polyhydric alcohols, and phosphoric acid esters.

[0131] In some embodiments, the lubricating oil composition comprises at least one multifunctional additive. Some non-limiting examples of suitable multifunctional additives include sulfurized oxymolybdenum dithiocarbamates, sulfurized oxymolybdenum organophosphorodithioates, oxymolybdenum monoglycerides, oxymolybdenum diethylate amides, amine-molybdenum complex compounds, and sulfur-containing molybdenum complex compounds.

[0132] In certain embodiments, the lubricating oil composition comprises at least one viscosity index improver. Some non-limiting examples of suitable viscosity index improvers include polymethacrylic acid type polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.

[0133] In some embodiments, the lubricating oil composition includes at least one metal deactivator. Some non-limiting examples of suitable metal deactivators include disalicylidene propylene diamine, triazole derivatives, thiadiazole derivatives, and mercaptobenzimidazole.

[0134] The additives disclosed herein may be in the form of an additive concentrate having two or more additives. The additive concentrate may include a suitable diluent, such as a hydrocarbon oil of suitable viscosity. Such a diluent may 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, carboxylic acid esters (especially diester oils), and combinations thereof. In some embodiments, the diluent is a light hydrocarbon oil, both natural or synthetic. In general, the diluent oil may have a viscosity of 13 centistokes to 35 centistokes at 40°C.

[0135] In general, it is desirable for the diluent to readily solubilize the lubricating oil soluble additive and provide an oil additive concentrate that is readily soluble in the oil of lubricating viscosity, oil stock or fuel. Additionally, it is desirable for the diluent not to introduce any undesirable properties, including, for example, high volatility and high viscosity, as well as impurities such as heteroatoms, into the oil of lubricating viscosity and ultimately into the finished lubricating oil or fuel.

[0136] According to certain embodiments, the lubricating oil composition comprises an oil soluble additive concentrate composition comprising an inert diluent, the oil soluble additive concentrate composition being present in an amount of at least 2.0 wt. %, or at least 10 wt. %, and not more than 90 wt. %, or not more than 50 wt. %, based on the total weight of the lubricating oil composition. EXAMPLES

[0137] The following examples are presented to demonstrate the embodiments of the present disclosure, and are not intended to limit the present disclosure to the specific embodiments shown.Unless otherwise indicated, all parts and percentages are by weight.When numerical ranges are given, it should be understood that embodiments outside the ranges given may still fall within the scope of the present disclosure.The specific details described in each example should not be interpreted as necessary features of the present disclosure.

[0138] Lubricating oil compositions of the present invention and comparative lubricating oil compositions were prepared from the following components and additives and evaluated for antiwear performance: Exemplary lubricating oil compositions include a succinimide dispersant, acidic and neutral phosphorus additives (optional in some comparative examples), friction modifiers (optional in some comparative examples), other lubricating oil additives (surfactants, antioxidants, metal deactivators, seal swell additives, antifoam agents, and viscosity modifiers), and a base oil.

[0139] Table 1 lists each lubricating oil composition including the amount (wt %) of each component. The examples of the present invention are non-limiting examples of lubricating oil compositions. The following specific components are present in the lubricating oil compositions of Table 1:

[0140] Dispersant A is a boron-modified polyisobutenyl succinimide with a polyisobutylene number average molecular weight of 1,300 (nitrogen (N): 1.95 wt %, boron (B): 0.63 wt %, TBN: 46 mg KOH / g).

[0141] Dispersant B is a polyisobutenyl succinimide having a polyisobutylene number average molecular weight of 1000 (nitrogen (N): 1.93 wt %, TBN: 35 mg KOH / g).

[0142] Dispersant C is a polyisobutenyl succinimide having a polyisobutene number average molecular weight of 550 (nitrogen (N): 1.93 wt %, TBN: 33 mg KOH / g).

[0143] Dispersant D is a polyisobutenyl succinimide having a polyisobutene number average molecular weight of 1000 (nitrogen (N): 2.13 wt %, TBN: 26 mg KOH / g).

[0144] Phosphorus compound 1 is inorganic phosphate H 3 PO 4 (85 wt% solution, phosphorus (P): 27.0 wt%, TAN: 973 mg KOH / g).

[0145] Phosphorus compound 2 is a mixture of mono / dialkyl phosphites containing thioether alkyl groups (P: 8.0 wt %, sulfur (S): 8.4 wt %, TAN: 111 mg KOH / g).

[0146] The phosphorus compound 3 is diphenyl hydrogen phosphite (P: 13.3% by weight).

[0147] The phosphorus compound 4 is a monoalkylamine salt of a dialkyl phosphate ester (P: 8.2% by weight, N: 1.8% by weight).

[0148] The phosphorus compound 5 is di-lauryl hydrogen phosphite (P: 7.24% by weight).

[0149] Friction modifier 1 is C 20It is a reaction product of alkenyl-substituted succinic anhydride and diethylenetriamine (N: 4.6% by weight).

[0150] Friction modifier 2 is an ethoxylated monoalkylamine (N: 4.1 wt %).

[0151] Friction modifier 3 is C 16 Diol / C 18 It is a mixture of diols.

[0152] Other additives present in the lubricating oil composition include a mixture of surfactants, antioxidants, metal deactivators, antifoam agents, seal swell agents, and viscosity modifiers.

[0153] Table 1 also lists the results of several tests performed on the inventive and comparative lubricant compositions.

[0154] The TBN measurements above were obtained according to ASTM D4739, and the TAN measurements were obtained according to ASTM D664. The neutralization ratios for each exemplary lubricating oil composition are listed in Table 1. The neutralization ratios were calculated as above using the TBN and TAN values ​​measured using ASTM D4739 and ASTM D664, respectively. The i-pH for the mixtures of A (ashless dispersant(s)) and B1 (acidic phosphorus compound(s)) shown in Table 1 is measured according to ASTM D664 as above. The other tests listed were performed as described herein.

[0155] Wet clutch vibration resistance test The wet clutch vibration resistance performance test was carried out according to the method of JASO M349-2012. More specifically, the durability of vibration resistance performance was measured by a low speed friction device according to the "Road Vehicle Test Method for Vibration Resistance of Automatic Transmission Fluids" described in JASO M-349:2012.

[0156] Tests were conducted using friction plates containing cellulose and / or aramid fibers and steel plates as defined in JASO M-349:2012 as friction materials. Approximately 150 mL of lubricating oil was applied to the friction plates and steel plates. The break-in conditions consisted of pressing the friction plate and steel plate together at a contact pressure of 1 MPa and a lubricating oil temperature of 80°C. The sliding speed of the friction plate along the steel plate was 0.6 m / s, and the sliding time during break-in was 30 minutes. The durability test conditions included pressing the friction plate and steel plate together at a contact pressure of 1 MPa and a lubricating oil temperature of 120°C. The sliding speed of the friction plate along the steel plate was 0.9 m / s, the sliding time was 30 minutes, the rest time was 1 minute, and the performance measurement interval during the durability test was 6 hours. A positive value of the friction coefficient (dμ / dV) indicates vibration resistance performance. The vibration resistance duration was the same as the method described in JASO M349-12. The vibration resistance duration measures the duration required for the friction characteristic (dμ / dv) to reach a negative value at a clutch sliding speed of 0.3 m / s or 0.9 m / s at an oil temperature of 40° C. or 80° C. A longer duration indicates better vibration resistance performance. As illustrated by the data in Table 1 below, the compositions 1 to 10 of the examples of the present invention provide significantly longer vibration resistance duration (198 to 612 hours) compared to the comparative compositions (0 to 38 hours).

[0157] JASO SAE #2 friction test The JASO SAE #2 friction test is a dynamic and static friction test conducted using an SAE No. 2 testing machine in accordance with the "Friction Test Method for Automotive and Automotive Automatic Transmission Fluids" defined in JASO M348.2002 2012. The following parameters were used in this test:

[0158] Friction material plate: FZ127-24-Y12, steel plate (FZ132-8Y2).

[0159] Dynamic friction measurement: moment of inertia of inertia disc: 0.343 kgm. Oil temperature: 100°C, rotation: 3,600 rpm, surface pressure of friction plate: 785 MPa. Test cycle: 30 seconds / cycle, number of tests: 5,000 cycles.

[0160] Static friction measurement: Rotation: 0.7 rpm. Oil temperature: 100°C, friction plate surface pressure: 785 MPa. Test period: 3 seconds after rotation starts. Test cycles: after 1, 5, 10, 20, 50, 100, 200, 500, 1000, 2000, 3000, 4000, and 5000 cycles.

[0161] Measurements: Static friction coefficient (μs) at maximum torque generated when starting rotation at 0.7 rpm, and static friction coefficient (μt) after 2 seconds.

[0162] The transmission torque capacity was evaluated by the values ​​of μt at 50, 500, and 5000 cycles. [Table 1-1] [Table 1-2] [Table 2-1] [Table 2-2]

[0163] As shown in Table 1, Comparative Examples 1 and 2 show poor friction properties and vibration resistance performance due to low neutralization of the basic dispersant. In contrast, Examples 1 and 2 of the present invention, which contain sufficient acidic components (phosphorus compounds 1 and 2), effectively neutralize the basic dispersant to provide excellent vibration resistance performance. Example 6 of the present invention, which has a neutralization rate of almost 100%, shows good results in both the SAE#2 friction test and the LVFA vibration resistance test.

[0164] Inventive Example 5 illustrates the need for adding a neutral phosphorus compound when only inorganic acid is used to neutralize the dispersant (see Comparative Example 3). When an organic phosphorus acid is used, good friction properties and anti-shudder performance are observed without the need for additional phosphorus compounds, as shown in Inventive Examples 3 and 4. Friction modifiers are also a key ingredient to provide sufficient performance, as illustrated by the significant difference in friction and anti-shudder lifetime between Inventive Example 5 and Comparative Examples 4 and 5.

[0165] Inventive Examples 7-10 also demonstrate that the additive combinations described herein are similarly effective in low viscosity base oil formulations. An additional top treat of friction modifiers was shown to further improve anti-shudder performance at the low viscosity baseline. Inventive Examples 11-16 demonstrate that alternative dispersant types and combinations are also effective in anti-shudder evaluations.

[0166] Additional explanation The following non-limiting clauses are provided as further explanation of various exemplary embodiments of the present invention.

[0167] Embodiment 1. A lubricating oil composition having a viscosity of 2 to 12 mm at 100°C. 2 (a) one or more ashless dispersants; and (b) at least one acidic phosphorus compound (B1) selected from the group consisting of phosphoric acid, phosphorus compounds having the following structure: [ka] In the formula, R 1 ~R 3 are independently a C1 to C20 hydrocarbyl group that may optionally contain an ether or thioether moiety; R 4is a hydrogen atom or a C1-C20 hydrocarbyl group which may optionally contain an ether moiety or a thioether moiety; when the at least one acidic phosphorus compound (B1) consists solely of phosphoric acid, the lubricating oil composition further contains one or more neutral phosphorus compounds (B2) selected from the group consisting of triphosphates, phosphites, hydrogen phosphites, thiophosphates, and amine salts thereof, and (a) the neutralization ratio of the one or more ashless dispersants with (b) the at least one acidic phosphorus compound (B1) is 60 to 100; the lubricating oil composition also contains (c) at least one of the friction modifiers (C1), wherein the friction modifier is a reaction product of an alkenyl-substituted succinic anhydride and a polyamine; and (d) at least one friction modifier (C2) selected from the group of oiliness agents consisting of diols, ethoxylated amines, fatty acid esters, sulfurized fatty acid esters, amides, and alcohols.

[0168] Embodiment 2. The lubricating oil composition of embodiment 1, comprising phosphorus in an amount of 0.01 wt.% to 0.20 wt.%, based on the total weight of the lubricating oil composition.

[0169] Embodiment 3. The lubricating oil composition of any of the preceding embodiments, comprising less than 0.3 wt. % sulfated ash, based on the total weight of the lubricating oil composition.

[0170] Embodiment 4. The lubricating oil composition according to any of the preceding embodiments, wherein the neutralization rate is 60 to 100%.

[0171] Embodiment 5. The lubricating oil composition of any of the preceding embodiments, wherein the at least one acidic phosphorus compound (B1) comprises a mixture of mono / dialkyl phosphite esters containing thioether alkyl groups.

[0172] Embodiment 6. The lubricating oil composition of any of the preceding embodiments, wherein the at least one acidic phosphorus compound (B1) further comprises phosphoric acid.

[0173] Embodiment 7. The lubricating oil composition of any of the preceding embodiments, further comprising diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and alkylamine salts of alkyl phosphoric acid esters as the one or more neutral phosphorus compounds (B2).

[0174] Embodiment 8. The lubricating oil composition of any of the preceding embodiments, wherein the at least one acidic phosphorus compound (B1) comprises only phosphoric acid, and the one or more neutral phosphorus compounds (B2) comprise diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and alkylamine salts of phosphoric acid alkyl esters.

[0175] Embodiment 9. The lubricating oil composition of any of the preceding embodiments, wherein the one or more ashless dispersants comprise polyisobutenyl succinimide; the at least one acidic phosphorus compound (B1) comprises at least one of phosphoric acid and a mixture of mono / dialkyl phosphites containing thioether alkyl groups; the one or more neutral phosphorus compounds (B2), when present, comprise diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and / or alkylamine salts of alkyl phosphate esters; the friction modifier (C1) comprises the reaction product of a C20 alkenyl-substituted succinic anhydride and diethylenetriamine; and the at least one friction modifier (C2) comprises an ethoxylated monoalkylamine and / or a mixture of a C16 diol and a C18 diol.

[0176] Embodiment 10. The lubricating oil composition of any of the preceding embodiments, wherein the base oil comprises a mixture of a Group II base oil and a Group III base oil; and the lubricating oil composition further comprises at least one of a surfactant, an antioxidant, a metal deactivator, an antifoam agent, a seal swell agent, and a viscosity modifier.

[0177] Embodiment 11. The lubricating oil composition of any of the preceding embodiments, wherein the mixture of A and B1 has an initial pH (i-pH) as determined by ASTM D664 of 4 to 10.

[0178] A lubricating oil composition according to any of the preceding embodiments, wherein the initial pH (i-pH) determined by ASTM D664 of the mixture of Embodiment 12.A and B1 is 4.5 to 9.5.

[0179] Embodiment 13. A method for improving vibration resistance performance, which includes making the transmission slippery with a lubricating oil composition, wherein the lubricating oil composition comprises a major amount of oil having a lubricating viscosity with a kinematic viscosity of 2 to 12 mm 2 / s at 100 °C, (a) one or more ashless dispersants, and (b) at least one acidic phosphorus compound (B1) selected from the group consisting of phosphoric acid, phosphorus compounds of the following structure, and combinations thereof; [Chemical formula] In the formula, R 1 ~R 3 are each independently a C1-C20 hydrocarbyl group which may optionally contain an ether moiety or a thioether moiety; R 4 is a hydrogen atom, or a C1-C20 hydrocarbyl group which may optionally contain an ether moiety or a thioether moiety; when the at least one acidic phosphorus compound (B1) is composed of only phosphoric acid, the lubricating oil composition further comprises one or more neutral phosphorus compounds (B2) selected from the group consisting of phosphate esters, phosphite esters, hydrogen phosphite esters, thiophosphate esters, and amine salts thereof; the neutralization rate of (a) the one or more ashless dispersants by (b) the at least one acidic phosphorus compound (B1) is 60 to 100%; the lubricating oil composition also comprises (c) at least one of the friction modifiers (C1) wherein the friction modifier is a reaction product of an alkenyl-substituted succinic anhydride and a polyamine; and (d) at least one friction modifier (C2) selected from the group of oiliness agents consisting of diols, ethoxylated amines, fatty acid esters, sulfurized fatty acid esters, amides, and alcohols.

[0180] Embodiment 14. The method of the preceding embodiment 13, wherein the lubricating oil composition comprises phosphorus in an amount of 0.01 wt.% to 0.20 wt.%, based on the total weight of the lubricating oil composition.

[0181] Embodiment 15. The method of any of the preceding embodiments, wherein the lubricating oil composition comprises sulfated ash in an amount less than 0.3 wt.%, based on the total weight of the lubricating oil composition.

[0182] Embodiment 16. The method of any of the preceding embodiments, wherein the neutralization rate of the lubricating oil composition is from 60 to 100%.

[0183] Embodiment 17. The method of any of the preceding embodiments, wherein the at least one acidic phosphorus compound (B1) comprises at least one of phosphoric acid and a mixture of mono / dialkyl phosphite esters containing thioether alkyl groups, and the one or more neutral phosphorus compounds (B2) comprise at least one of diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and alkylamine salts of phosphoric acid alkyl esters.

[0184] Embodiment 18. The method of any of the preceding embodiments, wherein the transmission is an automatic transmission or a continuously variable transmission.

[0185] Embodiment 19. The method of any of the preceding embodiments, wherein the transmission includes a wet clutch system.

[0186] Embodiment 20. The method of any of the preceding embodiments, wherein the friction material used in the wet clutch system is a paper material containing cellulose and / or aramid fibers.

[0187] Embodiment 21. The method of any of the preceding embodiments, wherein the one or more ashless dispersants comprise polyisobutenyl succinimide; the at least one acidic phosphorus compound (B1) comprises at least one of phosphoric acid and a mixture of mono / dialkyl phosphite esters containing thioether alkyl groups; the one or more neutral phosphorus compounds (B2), when present, comprise diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and / or alkylamine salts of phosphoric acid alkyl esters; the friction modifier (C1) comprises the reaction product of a C20 alkenyl-substituted succinic anhydride and diethylenetriamine; and the at least one friction modifier (C2) comprises at least one of an ethoxylated monoalkylamine and a mixture of a C16 diol and a C18 diol.

[0188] Embodiment 22. The method of any of the preceding embodiments, wherein the base oil of the lubricating oil composition comprises a mixture of a Group II base oil and a Group III base oil; and the lubricating oil composition further comprises at least one of a surfactant, an antioxidant, a metal deactivator, an antifoam agent, a seal swell agent, and a viscosity modifier.

[0189] While the particular embodiments described above are shown by way of example, it should be understood that these embodiments are susceptible to various modifications and alternative forms and can also be used in any suitable combination. It should be further understood that the claims are not intended to be limited to the particular forms disclosed, but rather are intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure.

Claims

1. 1. A lubricating oil composition comprising: 2-12mm at 100℃ ２ a major amount of oil of lubricating viscosity having a kinematic viscosity of 0.1 g / s; (a) one or more ashless dispersants; (b) at least one acidic phosphorus compound (B1) selected from the group consisting of phosphoric acid, phosphorus compounds of the following structure, and combinations thereof; 【Chemistry 1】 In the formula, R １ ~R ３ is independently a C1-C20 hydrocarbyl group that may optionally contain an ether or thioether moiety; R ４ is a hydrogen atom or a C1-C20 hydrocarbyl group which may optionally contain an ether or thioether moiety; When the at least one acidic phosphorus compound (B1) consists solely of phosphoric acid, the lubricating oil composition further contains one or more neutral phosphorus compounds (B2) selected from the group consisting of phosphates, phosphites, hydrogen phosphites, thiophosphates, and amine salts thereof; (a) the neutralization rate of said one or more ashless dispersants with (b) said at least one acidic phosphorus compound (B1) is 60 to 100%; The lubricating oil composition also comprises (c) at least one friction modifier (C1), wherein the friction modifier is a reaction product of an alkenyl-substituted succinic anhydride and a polyamine; (d) at least one friction modifier (C2) selected from the group of oiliness agents consisting of diols, ethoxylated amines, fatty acid esters, sulfurized fatty acid esters, amides, and alcohols.

2. 10. The lubricating oil composition of claim 1, comprising phosphorus in an amount of 0.01 to 0.20 wt %, based on the total weight of the lubricating oil composition.

3. 10. The lubricating oil composition of claim 1, comprising less than 0.3 weight percent sulfated ash, based on the total weight of the lubricating oil composition.

4. 2. The lubricating oil composition according to claim 1, wherein the neutralization rate is from 75 to 100%.

5. 2. The lubricating oil composition of claim 1, wherein the at least one acidic phosphorus compound (B1) comprises a mixture of mono / dialkyl phosphites containing thioether alkyl groups.

6. 6. The lubricating oil composition of claim 5, wherein the at least one acidic phosphorus compound (B1) further comprises phosphoric acid.

7. 2. The lubricating oil composition of claim 1, wherein the one or more neutral phosphorus compounds (B2) include diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and alkylamine salts of alkyl phosphate esters.

8. 2. The lubricating oil composition of claim 1, wherein the at least one acidic phosphorus compound (B1) comprises only phosphoric acid and the one or more neutral phosphorus compounds (B2) comprise diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and alkylamine salts of alkyl phosphoric acid esters.

9. 2. The lubricating oil composition of claim 1, wherein the one or more ashless dispersants comprise polyisobutenyl succinimide; the at least one acidic phosphorus compound (B1) comprises at least one of phosphoric acid and a mixture of mono / dialkyl phosphites containing thioether alkyl groups; the one or more neutral phosphorus compounds (B2), when present, comprise diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and / or alkylamine salts of alkyl phosphate esters; the friction modifier (C1) comprises the reaction product of a C20 alkenyl-substituted succinic anhydride and diethylenetriamine; and the at least one friction modifier (C2) comprises an ethoxylated monoalkylamine and / or a mixture of a C16 diol and a C18 diol.

10. 10. The lubricating oil composition of claim 9, wherein the oil of lubricating viscosity comprises a mixture of a Group II base oil and a Group III base oil; and the lubricating oil composition further comprises at least one of a surfactant, an antioxidant, a metal deactivator, an antifoam agent, a seal swell agent, and a viscosity modifier.

11. 2. The lubricating oil composition of claim 1, wherein the mixture of A and B1 has an initial pH (i-pH) of 4 to 10 as determined by ASTM D664.

12. 2. The lubricating oil composition of claim 1, wherein the mixture of A and B1 has an initial pH (i-pH) of 4.5 to 9.5 as determined by ASTM D664.

13. A method for improving vibration resistance, comprising the steps of: making the transmission slippery with a lubricating oil composition, the lubricating oil composition comprising: 2-12mm at 100℃ ２ a major amount of oil of lubricating viscosity having a kinematic viscosity of 0.1 g / s; (a) one or more ashless dispersants; (b) at least one acidic phosphorus compound (B1) selected from the group consisting of phosphoric acid, phosphorus compounds of the following structure, and combinations thereof; 【Chemistry 2】 In the formula, R １ ~R ３ is independently a C1-C20 hydrocarbyl group that may optionally contain an ether or thioether moiety; R ４ is a hydrogen atom or a C1-C20 hydrocarbyl group which may optionally contain an ether or thioether moiety; When the at least one acidic phosphorus compound (B1) consists solely of phosphoric acid, the lubricating oil composition further contains one or more neutral phosphorus compounds (B2) selected from the group consisting of phosphates, phosphites, hydrogen phosphites, thiophosphates, and amine salts thereof; (a) the neutralization rate of said one or more ashless dispersants with (b) said at least one acidic phosphorus compound (B1) is 60 to 100%; The lubricating oil composition also comprises (c) at least one friction modifier (C1), wherein the friction modifier is a reaction product of an alkenyl-substituted succinic anhydride and a polyamine; (d) at least one friction modifier (C2) selected from the group of oiliness agents consisting of diols, ethoxylated amines, fatty acid esters, sulfurized fatty acid esters, amides, and alcohols.

14. The method of claim 13, wherein the lubricating oil composition comprises phosphorus in an amount of 0.01 wt % to 0.20 wt %, based on the total weight of the lubricating oil composition.

15. 14. The method of claim 13, wherein the lubricating oil composition comprises sulfated ash in an amount less than 0.3 weight percent, based on the total weight of the lubricating oil composition.

16. The method of claim 13, wherein the neutralization rate of the lubricating oil composition is from 75 to 100%.

17. 14. The method of claim 13, wherein the at least one acidic phosphorus compound (B1) comprises at least one of phosphoric acid and a mixture of mono / dialkyl phosphite esters containing thioether alkyl groups, and the one or more neutral phosphorus compounds (B2) comprise at least one of diphenyl hydrogen phosphite, di-lauryl hydrogen phosphite, and alkylamine salts of phosphoric acid alkyl esters.

18. 14. The method of claim 13, wherein the transmission is an automatic transmission or a continuously variable transmission.

19. The method of claim 18 , wherein the transmission includes a wet clutch system.

20. 20. The method of claim 19, wherein the friction material used in the wet clutch system is a paper material containing cellulose and / or aramid fibers.

21. 14. The method of claim 13, wherein the one or more ashless dispersants comprise polyisobutenyl succinimide; the at least one acidic phosphorus compound (B1) comprises at least one of phosphoric acid and a mixture of mono / dialkyl phosphite esters containing thioether alkyl groups; the one or more neutral phosphorus compounds (B2), when present, comprise diphenyl hydrogen phosphite, and / or an alkylamine salt of an alkyl phosphate ester; the friction modifier (C1) comprises the reaction product of a C20 alkenyl-substituted succinic anhydride and diethylenetriamine; and the at least one friction modifier (C2) comprises at least one of an ethoxylated monoalkylamine and a mixture of a C16 diol and a C18 diol.

22. 14. The method of claim 13, wherein the base oil of the lubricating oil composition comprises a mixture of a Group II base oil and a Group III base oil; and the lubricating oil composition further comprises at least one of a surfactant, an antioxidant, a metal deactivator, an antifoam agent, a seal swell agent, and a viscosity modifier.

Images