阅读说明：本技术 自动变速器润滑油 (Automatic transmission lubricating oil ) 是由 久保浩一 渊正美 中川贵浩 S·萨萨基 S·奥塔 于 2018-11-16 设计创作，主要内容包括：本发明总体上涉及用于自动变速器的润滑油组合物,并且尤其用于使用湿式离合器系统的汽车自动变速器和/或无级变速器的变速器油,特别是包含少量纤维素纤维和/或芳纶纤维的湿纸离合器。(The present invention relates generally to a lubricating oil composition for an automatic transmission, and particularly to a transmission oil for an automatic transmission and/or a continuously variable transmission of an automobile using a wet clutch system, particularly a wet paper clutch containing a small amount of cellulose fibers and/or aramid fibers.)

1. A lubricating oil composition comprising:

a) a major amount of an oil of lubricating viscosity,

b) at least one or more non-post-treated succinimide dispersants,

c)0.01 to 0.5% by weight of phosphoric acid,

d) providing a metal detergent to the composition in an amount of no more than 350ppm metal,

e) at least one or more organophosphorus compounds, wherein

The ratio of nitrogen in the non-post-treated succinimide to phosphorus in the phosphoric acid is 1 to 3.

2. The lubricating oil composition of claim 1, wherein the composition is an automatic transmission or a continuously variable transmission composition.

3. The lubricating oil composition according to claim 2, wherein the automatic transmission or continuously variable transmission is equipped with a wet paper clutch.

4. The lubricating oil composition of claim 3, wherein the wet clutch comprises cellulose fibers and/or aramid fibers.

5. The lubricating oil composition of claim 1, wherein the metal detergent provides 25 to 350ppm by weight calcium to the lubricating oil composition.

6. The lubricating oil composition of claim 1, wherein the one or more non-post-treated succinimide dispersants are present in an amount of 0.3-8 wt.%.

7. The lubricating oil composition of claim 1, wherein the one or more non-post-treated succinimide dispersants is a bis-succinimide.

8. The lubricating oil composition of claim 1, wherein the bissuccinimide is derived from Polyisobutylene (PIB) of 950 molecular weight.

9. The lubricating oil composition of claim 1, wherein the succinimide dispersant is a boronated bis-succinimide derived from 900 to 1500 molecular weight Polyisobutylene (PIB).

10. The lubricating oil composition of claim 1, wherein the organophosphorus compound provides 0.01 to 0.5 wt.% of phosphorus to the lubricating oil composition.

11. The lubricating oil composition of claim 1, wherein the one or more organophosphorus compounds are selected from the group consisting of phosphate amine salts and aromatic hydrogen phosphites.

12. The lubricating oil composition of claim 1, wherein the total phosphorus in the lubricating oil composition is 500ppm or less.

13. A method for improving anti-shudder performance and reducing friction in an internal combustion engine equipped with an automatic transmission or a continuously variable transmission, the method comprising lubricating the transmission with a lubricating oil composition comprising:

a) a major amount of an oil of lubricating viscosity,

b) at least one or more non-post-treated succinimide dispersants,

c)0.01 to 0.5% by weight of phosphoric acid,

d) providing a metal detergent to the composition in an amount of no more than 350ppm metal,

e) at least one or more organophosphorus compounds, wherein

The ratio of nitrogen in the non-post-treated succinimide to phosphorus in the phosphoric acid is 1 to 3.

14. The method according to claim 13, wherein the automatic transmission or the continuously variable transmission is equipped with a wet paper clutch.

15. The method of claim 13, wherein the one or more non-post-treated succinimide dispersants are present in an amount of 0.3-8 wt%.

16. The method of claim 13, wherein the one or more non-post-treated succinimide dispersants is a bis-succinimide.

17. The method of claim 13, wherein the organophosphorus compound provides 0.01 to 0.5 wt.% phosphorus to the lubricating oil composition.

18. The method of claim 13, wherein the one or more organophosphorus compounds are selected from the group consisting of phosphate amine salts and aromatic hydrogen phosphites.

19. The method of claim 13, wherein the total phosphorus in the lubricating oil composition is 500ppm or less.

Technical Field

The present invention relates generally to a lubricating oil composition for an automatic transmission, and particularly to a transmission oil for an automatic transmission and/or a continuously variable transmission of an automobile using a wet clutch system, particularly a wet paper clutch containing a small amount of cellulose fibers and/or aramid fibers.

Background

Automatic transmission lubricating oil, called automatic transmission oil, is generally used to assist smooth running of an automatic transmission that is mounted in an automobile and includes a torque converter, a gear mechanism, a wet clutch, and a hydraulic mechanism.

It is well known that lubricant additives affect the friction properties of wet clutches and steel plates. The additive effects are due to their physical and chemical absorption on the clutch material (e.g., cellulose, aramid (natural and synthetic) fibers, silica and steel plate surfaces). The industry has been pushing the conversion of cellulose rich wet clutch paper for automotive automatic transmissions to aramid wet clutch paper. The ratio of cellulose to aramid is important for the thermal and oxidative stability of the wet clutch. The high aramid wet clutch paper exhibits excellent durability properties. However, aramid fibers are costly.

Furthermore, regulatory changes have led to modern vehicles being required to improve fuel economy and reduce CO₂And (4) discharging to prevent global warming. In addition to improving engine and transmission design, lubricant performance is also needed to address this problem. In the case of an automatic transmission for an automobile, it is required to minimize power loss caused by a torque converter during a start-up time, and a lock-up clutch system has been introduced to improve fuel efficiency. The locking torque converter is installed in a locking wet paper clutch in a torque converter system. Since they can engage the wet clutch after fluid coupling at low speed and in a short time, it is possible to reduce power loss and provide excellent fuel economyOil economy.

In terms of lubrication, it is also important to provide the automatic transmission with a suitable lubricant and to lock up the wet clutch in the transmission. If the lubricant provides poor torque capacity and anti-shudder friction performance, power loss or uncomfortable vibration due to lockup of the wet clutch in the transmission and high noise may occur. Thus, a lubricant for an automatic transmission with a lock-up paper wet clutch system should provide good fuel economy and smooth driving and operating conditions.

The inventors have found a lubricating oil composition that has excellent wet paper clutch friction characteristics, such as anti-shudder performance, and can also maintain excellent wet clutch torque capacity and durability of wet clutch friction characteristics.

Summary of The Invention

According to one embodiment of the present invention, there is provided a lubricating oil composition comprising:

i) a major amount of an oil of lubricating viscosity,

ii) at least one or more non-post-treated succinimide dispersants,

iii)0.01 to 0.5% by weight of phosphoric acid,

iv) a metal detergent which provides no more than 350ppm of metal to the composition, v) at least one or more organophosphorus compounds, wherein

The ratio of nitrogen in the non-post-treated succinimide to phosphorus in the phosphoric acid is 1 to 3.

According to another embodiment of the present invention, there is provided a method for improving anti-shudder performance and reducing friction in an internal combustion engine equipped with an automatic transmission or a continuously variable transmission, the method comprising lubricating the transmission with a lubricating oil composition comprising:

i) a major amount of an oil of lubricating viscosity,

ii) at least one or more non-post-treated succinimide dispersants,

iii)0.01 to 0.5% by weight of phosphoric acid,

iv) providing no more than 350ppm metal of a metal detergent to the composition,

v) at least one or more organophosphorus compounds, wherein

The ratio of nitrogen in the non-post-treated succinimide to phosphorus in the phosphoric acid is 1 to 3.

Detailed Description

Defining:

the following terms will be used throughout the specification and, unless otherwise indicated, will have the following meanings.

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

In the description that follows, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used. They may vary by 1%, 2%, 5%, or sometimes 10% to 20%.

The term "total base number" or "TBN" refers to the level of alkalinity in an oil sample that indicates the ability of the composition to continue to neutralize corrosive acids according to ASTM standard No. d2896 or equivalent procedures. This test measures the change in conductivity and the result is expressed as mgKOH/g (milliequivalents of KOH required to neutralize 1 gram of product). Thus, a high TBN reflects an over-based product, and therefore, a higher base reserve to neutralize the acid.

The term "PIB" refers to polyisobutylene.

Oil of lubricating viscosity

The lubricating oil compositions disclosed herein typically comprise at least one oil of lubricating viscosity. Any base oil known to those skilled in the art may be used as the oil of lubricating viscosity disclosed herein. Some base oils suitable for use in preparing lubricating oil compositions have been described in Mortier et al, "Chemistry and Technology of lubricating oils", "2 nd edition, London, Springer, chapters 1 and 2 (1996); and a. sequenria, jr., "lube Base Oil and paraffin Processing (lubricating Base Oil and Wax Processing)," new york, Marcel Decker, chapter 6, (1994); and d.v. brock, Lubrication Engineering (Lubrication Engineering), volume 43, pages 184-5 (1987), all of which are incorporated herein by reference. Generally, the amount of base oil in the lubricating oil composition can be from about 70 to about 99.5 wt.%, based on the total weight of the lubricating oil composition. In some embodiments, the amount of base oil in the lubricating oil composition is from about 75 to about 99 wt.%, from about 80 to about 98.5 wt.%, or from about 80 to about 98 wt.%, based on the total weight of the lubricating oil composition.

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 prepared from the polymerization of at least one alpha olefin (e.g., ethylene), such as polyalphaolefins or PAOs, or oils prepared from hydrocarbon synthesis processes using carbon monoxide and hydrogen, such as the fischer-tropsch process. In certain embodiments, the base oil comprises less than about 10 wt% of one or more heavy fractions, based on the total weight of the base oil. Heavy fraction means a lubricating oil fraction having a viscosity of at least about 20cSt at 100 ℃. In certain embodiments, the viscosity of the heavy fraction is at least about 25cSt or at least about 30cSt at 100 ℃. In further embodiments, the amount of the one or more heavy fractions in the base oil is less than about 10 wt.%, less than about 5 wt.%, less than about 2.5 wt.%, less than about 1 wt.%, or less than about 0.1 wt.%, based on the total weight of the base oil. In other embodiments, the base oil does not comprise heavy fractions.

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 ℃ of about 1.5 centistokes (cSt) to about 20cSt, about 2 centistokes (cSt) to about 20cSt, or about 2cSt to about 16 cSt. The kinematic viscosity of the base oil or lubricating oil compositions disclosed herein can be measured according to astm d 445, which is incorporated herein by reference.

In other embodiments, the base oil is or comprises a base stock or blend of base stocks. In further embodiments, the base stock is made using a variety of different processes including, but not limited to, distillation, solvent refining, hydrotreating, oligomerization, esterification, and re-refining. In some embodiments, the base stock comprises a re-refined stock. In other embodiments, the rerefined stock should be substantially free of materials introduced by manufacture, contamination, or previous use.

In some embodiments, the base oil comprises one or more base oils in one or more of groups I-V, as specified in American Petroleum Institute (API) publication 1509, 14 th edition, 12 months 1996 (i.e., API base oil interchange guidelines for passenger car engine oils and diesel engine oils), which is incorporated herein by reference. The API guidelines define base stocks as lubricant components that can be manufactured using a number of different processes. Group I, II and III base oils are mineral oils, each having specific ranges of saturated hydrocarbon content, sulfur content, and viscosity index. Group IV basestocks are Polyalphaolefins (PAOs). Group V base stocks include all other base oils not included in group I, II, III or IV.

In some embodiments, the base oil comprises one or more base stocks of group I, II, III, IV, V or combinations thereof. In other embodiments, the base oil comprises one or more base stocks of group II, III, IV or combinations thereof. In further embodiments, the base oil comprises one or more base oils of group II, III, IV, or combinations thereof, wherein the base oil has a kinematic viscosity at 100 ℃ of from about 1.5 centistokes (cSt) to about 20cSt, from about 2cSt to about 20cSt, or from about 2cSt to about 16 cSt. In some embodiments, the base oil is a group II base oil.

The base oil may be selected from natural oils of lubricating viscosity, synthetic oils of lubricating viscosity, and mixtures thereof. In some embodiments, the base oil includes a base stock obtained by isomerization of synthetic and slack waxes, as well as a hydrocracked base stock produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude. In other embodiments, base oils of lubricating viscosity include natural oils, such as animal oils, vegetable oils, mineral oils (e.g., liquid petroleum oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types and solvent-treated or acid-treated mineral oils), oils derived from coal or shale, and combinations thereof. Some non-limiting examples of animal oils include bone oil, lanolin, fish oil, lard, dolphin oil, seal oil, shark oil, tallow oil, and whale oil. Some non-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 meadow foam oil. Such oils may be partially or fully hydrogenated.

In some embodiments, synthetic oils of lubricating viscosity include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs and homologs thereof, and the like. In other embodiments, synthetic oils include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof, where the terminal hydroxyl groups may be modified by esterification, etherification, etc. In another embodiment, the synthetic oil comprises an ester of a dicarboxylic acid with a plurality of alcohols. In certain embodiments, the synthetic oil comprises a blend of C₅-C₁₂Esters of monocarboxylic acids with polyols and polyol ethers. In another embodiment, the synthetic oil comprises trialkyl phosphate oils, such as tri-n-butyl phosphate and tri-iso-butyl phosphate.

In some embodiments, synthetic oils of lubricating viscosity include silicon-based base oils (e.g., polyalkyl-, polyaryl-, polyalkoxy-, polyaryloxy-siloxane oils and silicate oils). In other embodiments, the synthetic oil comprises a liquid ester of a phosphorus-containing acid, a polymeric tetrahydrofuran, a polyalphaolefin, and the like.

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

In another embodiment, the base oil comprises a poly-alpha-olefin (PAO). Typically, the poly-alpha-olefin may be derived from an alpha-olefin having from about 1.5 to about 30, from about 2 to about 20, or from about 2 to about 16 carbon atoms. Non-limiting examples of suitable poly-alpha-olefins include those derived from octene, decene, mixtures thereof, and the like. The viscosity of these poly-alpha-olefins may be from about 1.5 to about 15, from about 1.5 to about 12, or from about 1.5 to about 8 centistokes at 100 ℃. In some cases, the poly-alpha-olefins may be used with other base oils, such as mineral oils.

In another embodiment, the base oil comprises a polyalkylene glycol or polyalkylene glycol derivative, wherein the terminal hydroxyl groups of the polyalkylene glycol can be modified by esterification, etherification, acetylation, and the like. 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, and the like), mono-and polycarboxylates 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.

In another embodiment, the base oil comprises any ester of a dicarboxylic acid (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butanol, hexanol, dodecanol, 2-ethylhexanol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Non-limiting examples of such esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the like.

In another embodiment, the base oil comprises hydrocarbons produced by a fischer-tropsch process. The fischer-tropsch process produces hydrocarbons from a gas containing hydrogen and carbon monoxide using a fischer-tropsch catalyst. These hydrocarbons may require further processing for use as base oils. For example, hydrocarbons may be dewaxed, hydroisomerized, and/or hydrocracked using methods known to those skilled in the art.

In another embodiment, the base oil comprises an unrefined oil, a refined oil, a rerefined oil, or a mixture thereof. Unrefined oils are those obtained directly from a natural or synthetic source without further purification 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 treated by one or more purification methods to improve one or more properties. Many such purification methods are known to those skilled in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like. Rerefined oils are obtained by applying processes to refined oils similar to those used to obtain refined oils. Such rerefined oils are also known as reclaimed or reprocessed oils and are often additionally processed by processes involving the removal of spent additives and oil breakdown products.

Nitrogen-containing ashless succinimide dispersants

In one aspect, one or more nitrogen-containing ashless succinimide dispersants are present in the lubricating oil composition. In one aspect, the one or more nitrogen-containing ashless succinimide dispersants are non-post-treated dispersants.

Typical examples of nitrogen-containing ashless dispersants include alkenyl or alkyl succinimides derived from polyolefins and derivatives thereof. Succinimides may be obtained by reaction between a succinic anhydride substituted with a high molecular weight alkenyl or alkyl group and a polyalkylene polyamine containing an average of 3 to 10 (preferably 4 to 7) nitrogen atoms per molecule. In one aspect, the high molecular weight alkenyl or alkyl groups are preferably polyolefins having a number average molecular weight of about 900 to 5000, with polybutene being particularly advantageous. In one aspect, the high molecular weight alkenyl or alkyl group is preferably a polyolefin having a number average molecular weight of 900 to 4000, 900 to 3500, 900 to 3000, 900 to 2500, 900 to 2000, 900 to 1500, 900 to 1000, 90 to 1000, 1000.

In some aspects, a chlorination method in which chlorine is used is utilized in the step of obtaining polybutenyl succinic anhydride by a reaction between polybutene and maleic anhydride. However, with this method, although the reactivity is good, a large amount of chlorine (e.g., about 2000ppm) remains in the final succinimide product. On the other hand, if a thermal reaction involving no chlorine is used, the amount of residual chlorine in the final product can be kept at a very low level (e.g., below 40 ppm). Moreover, it is advantageous to use polybutene (at least about 50% of which has a methylvinylidene structure) with high reactivity, which can be improved even by a thermal reaction method, as compared with conventional polybutene (mainly having a β -olefin structure). If the reactivity is high, unreacted polybutene is less in the dispersant, and thus a dispersant having a high concentration of the active ingredient (succinimide) can be obtained. Therefore, it is preferable to produce the succinimide by first obtaining polybutenyl succinic anhydride by a thermal reaction using highly reactive polybutene, and then reacting the polybutenyl succinic anhydride with a polyamine. The succinimide may be used in the form of a so-called modified succinimide by further reacting with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate, organic acid, or the like. Boron-containing alkenyl (or alkyl) succinimides obtained by reaction with boric acid or a boron compound are particularly advantageous in terms of thermal and oxidative stability. The succinimide has mono-, di-and polytypes depending on the number of imide structures per molecule, but as the succinimide used for the purpose of the present invention, a di-type is preferable.

Other examples of nitrogen-containing ashless dispersants include polymeric succinimide dispersants derived from an ethylene- α -olefin copolymer (e.g., one having a molecular weight of 1000 to 15,000), and alkenyl benzylamine-based ashless dispersants.

Particularly preferred nitrogen-containing ashless dispersants are mono-and di-alkyl or alkenyl succinimides derived from the reaction of alkyl or alkenyl succinic acids or anhydrides or alkylene polyamines. These compounds are generally considered to have the formula (I)

Wherein R is₁Essentially hydrocarbon chains having a molecular weight of about 450-3000, i.e., R₁Is a hydrocarbon chain, preferably an alkenyl group, containing from about 30 to about 200 carbon atoms; alk is an alkylene chain of 2 to 10, preferably 2 to 6, carbon atoms, R₂，R₃And R₄Is selected from C₁-C₄Alkyl or alkoxy or hydrogen, preferably hydrogen, and x is an integer from 0 to 10, preferably from 0 to 3;

or formula (II)

Wherein R is₅And R₇Are all essentially hydrocarbon chains having a molecular weight of about 450-₅And R₇Is a hydrocarbon chain, preferably an olefinic chain, containing from about 30 to about 200 carbon atoms; alk is an alkylene chain of 2 to 10, preferably 2 to 6, carbon atoms, R₆Is selected from C₁-C₄Alkyl or alkoxy or hydrogen, preferably hydrogen, and y is an integer from 0 to 10, preferably from 0 to 3. In one embodiment, R₁，R₅And R₇Is a polyisobutyl group.

In one embodiment, the actual reaction product of the alkylene or alkenylene succinic acid or anhydride and the alkylene polyamine will comprise a mixture of compounds including mono-and bis-succinimides. The mono-alkenyl succinimide and di-alkenyl succinimide produced may depend on the charged molar ratio of polyamine to succinic acid groups and the particular polyamine used. Polyamine to succinic acid group addition molar ratio of about 1: 1 can produce predominantly monoalkenylsuccinimides. Polyamine to succinic acid group addition molar ratio of about 1: 2 can produce the main dienylsuccinimide. Examples of succinimide dispersants include those described in, for example, U.S. Pat. Nos. 3172892, 4234435 and 6165235, which are incorporated herein by reference in their entirety.

In one embodiment, the polyolefins from which the substituents are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms, typically 2 to 6 carbon atoms. The amine reacted with the succinic acylating agent to form the carboxylic dispersant composition may be a monoamine or polyamine.

In a preferred aspect, the alkenyl succinimide may be prepared by reacting a polyalkylene succinic anhydride with an alkylene polyamine. Polyalkylene succinic anhydrides are the reaction products of polyolefins, preferably polyisobutylene, with maleic anhydride. Such polyalkylene succinic anhydrides may be prepared using conventional polyisobutenes, or high-methylvinylidene polyisobutenes. Thermal, chlorination, free radical, acid catalysis or any other method may be used in this preparation. Examples of suitable polyalkylene succinic anhydrides are thermal PIBSA (polyisobutenyl succinic anhydride), which is described in U.S. patent No. 3361673; chlorinated PIBSA, described in U.S. patent No. 3172892; a mixture of hot and chlorinated PIBSA, described in U.S. patent No. 3912764; high succinic acid ratio PIBSA, described in U.S. patent No. 4234435; poly PIBSA, described in U.S. patent nos. 5112507 and 5175225; high succinic acid ratio poly-PIBSA, described in U.S. patent nos. 5565528 and 5616668; free radical PIBSA, described in U.S. patent nos. 5286799, 5319030 and 5625004; PIBSA made from high methylvinylidene polybutene, described in U.S. patent nos. 4152499, 5137978 and 5137980; high succinic ratio PIBSA made from high methylvinylidene polybutene, described in european patent application publication No. ep 355895; terpolymer PIBSA, described in U.S. patent No. 5792729; sulfonic acid PIBSA, described in U.S. patent No.5777025 and european patent application publication No. ep542380; and purified PIBSA, described in U.S. patent No.5523417 and european patent application publication No. ep 602863. The disclosures of each of these documents are incorporated herein by reference in their entirety. The polyalkylene succinic anhydride is preferably polyisobutenyl succinic anhydride. In a preferred embodiment, the polyalkylene succinic anhydrides are polyisobutenyl succinic anhydrides derived from polyisobutene having a number average molecular weight of 1200 or less, preferably a number average molecular weight of 400 to 1200, preferably 500 to 1100, 550 to 1100, 600 to 1100, 650 to 1100, 700 to 1100, 750 to 1100, 800 to 1000, 850 to 1000, 900 to 1000 and 950 to 1000.

Preferred polyalkyleneamines for the preparation of succinimides are of the formula (III):

wherein z is an integer from 0 to 10 and Alk is an alkylene group of 2 to 10, preferably 2 to 6, carbon atoms, R₈，R₉And R₁₀Is selected from C₁-C₄Alkyl or alkoxy or hydrogen, preferably hydrogen, and z is an integer from 0 to 10, preferably from 0 to 3.

Alkylene amines include primarily methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines and cyclic and higher homologs of such amines, such as piperazine and aminoalkyl-substituted piperazines. Specific examples thereof are ethylenediamine, triethylenetetramine, propylenediamine, decamethylenediamine, octamethylenediamine, di (heptamethylene) triamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di (trimethylene) triamine, 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 homologues, for example obtained from the condensation of two or more of the above-mentioned alkylene amines, are also useful.

Ethylene amines are particularly useful. They are described in more detail in the title "Ethylene Amines", Encyclopedia of Chemical Technology, Kirk-Othmer, Vol.5, pp.898-905 (Interscience publishers, New York, 1950). The term "ethyleneamine" is used in a generic sense to refer to a class of polyamines which conform to the formula (IV):

H₂N(CH₂CH₂NH)_αH

formula IV

Wherein 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, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.

The individual alkenyl succinimides used in the alkenyl succinimide compositions of the present invention may be prepared by conventional methods, as disclosed, for example, in U.S. patent nos. 2992708; 3018250, respectively; 3018291, respectively; 3024237, respectively; 3100673, respectively; 3172892, respectively; 3202678, respectively; 3219666, respectively; 3272746, respectively; 3361673, respectively; 3381022, respectively; 3912764, respectively; 4234435, respectively; 4612132, respectively; 4747965, respectively; 5112507, respectively; 5241003, respectively; 5266186, respectively; 5286799, respectively; 5319030, respectively; 5334321, respectively; 5356552, respectively; 5716912, the disclosure of which is hereby incorporated by reference in its entirety for all purposes.

Also included in the term "alkenyl succinimide" are post-treated succinimides such as disclosed in U.S. patent nos. 4612132 to Wollenberg et al; U.S. Pat. No.4746446 to Wollenberg et al, which relates to the post-treatment of borate esters or ethylene carbonate; and the like, as well as other post-processing methods, each of which is incorporated herein by reference in its entirety. Preferably the carbonate treated alkenyl succinimide is a polybutene succinimide derived from polybutene having a molecular weight of 450-. Preferably it is prepared by reacting a mixture of a polybutylenesuccinic acid derivative, an unsaturated acidic reagent copolymer of an unsaturated acidic reagent and an olefin, and a polyamine under reactive conditions, as taught in U.S. patent No.5716912, which is incorporated herein by reference.

In one embodiment, the dispersant system comprises from 1 to 20 wt.%, preferably from 1 to 15 wt.%, preferably from 1 to 10 wt.%, preferably from 1 to 8 wt.%, preferably from 1 to 6 wt.%, preferably from 1 to 5 wt.%, preferably from 1 to 4.4 wt.%, preferably from 1 to 4 wt.%, preferably from 1 to 3 wt.%, preferably from 1.5 to 4.0 wt.%, preferably from 1.5 to 3.5 wt.%, preferably from 1.5 to 3.0 wt.%, preferably from 2.0 to 3.0 wt.%, based on the weight of the lubricating oil composition.

In another embodiment, the non-post treated dispersant is a non-post treated succinimide dispersant. In other embodiments, the non-post-treated succinimide dispersant is present in the lubricating oil composition at 0.3 to 8 wt.%, 0.3 to 5 wt.%, 0.3 to 4.4 wt.%, 0.5 to 3.0 wt.%, 0.6 to 2.0 wt.%.

The individual alkenyl succinimides used in the alkenyl succinimide compositions of the present invention may be prepared by conventional methods, for example, as described in U.S. Pat. Nos.2,992,708; 3,018,250, respectively; 3,018,291, respectively; 3,024,237, respectively; 3,100,673, respectively; 3,172,892; 3,202,678, respectively; 3,219,666; 3,272,746; 3,361,673, respectively; 3,381,022; 3,912,764, respectively; 4,234,435; 4,612,132, respectively; 4,747,965, respectively; 5,112,507, respectively; 5,241,003, respectively; 5,266,186, respectively; 5,286,799, respectively; 5,319,030, respectively; 5,334,321, respectively; 5,356,552; 5,716,912, the disclosure of which is incorporated herein by reference in its entirety for all purposes.

Post-treated succinimides are also included in the term "alkenyl succinimides", for example, in Wollenberg, et al, U.S. Pat. Nos. 4,612,132; wollenberg, et al, U.S. Pat. No.4,746,446; as well as other post-treatment methods disclosed herein involving borate or ethylene carbonate, which are all incorporated herein by reference in their entirety. Preferably, the carbonate-treated alkenyl succinimide is a polybutene succinimide derived from polybutene having a molecular weight of 450 to 3000, preferably 600 to 2500, preferably 700 to 2500, preferably 800 to 2500, preferably 900 to 2500, more preferably 900 to 2400, and preferably 900 to 2300 and mixtures of these molecular weights. Preferably, it is prepared by reacting a mixture of a polybutylenesuccinic acid derivative, an unsaturated acidic reagent copolymer of an unsaturated acidic reagent and an olefin with a polyamine under reaction conditions, such as taught in U.S. Pat. No.5,716,912, which is incorporated herein by reference.

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

In one aspect, boron is present in an amount less than 500, less than 450, less than 400, less than 350, less than 300, less than 250, less than 200, less than 150, less than 100, wt. ppm of the lubricating oil composition.

Phosphoric acid/phosphorous acid

In one embodiment, inorganic phosphoric acid or phosphorous acid is present in the lubricating oil composition. In another embodiment, the acid is phosphoric acid.

In one embodiment, the inorganic phosphoric or phosphorous acid is present in the solution in an amount of 75 to 90 weight percent.

In one embodiment, the inorganic phosphoric or phosphorous acid is present in an amount of 0.01 to 1.0 wt.% of the lubricating oil composition. In other embodiments, the inorganic phosphoric acid or phosphorous acid is present in the lubricating oil composition in an amount of 0.01 to 0.5 wt.%, 0.01 to 0.1 wt.%, 0.01 to 0.08 wt.%, 0.01 to 0.07 wt.%, 0.01 to 0.06 wt.%, 0.02 to 0.06 wt.%, 0.03 to 0.05 wt.%.

In one embodiment, the nitrogen to phosphorus of phosphoric acid ratio of the non-post-treated succinimide in the lubricating oil composition is from 1.0 to 10.0. In other embodiments, the nitrogen/phosphorus ratio in the lubricating oil composition of the present invention is from 1.0 to 8.0, from 1.0 to 6.0, from 1.0 to 5.0, from 1.0 to 4.0, from 1.0 to 3.5, from 1.0 to 3.0, from 1.0 to 2.5, from 1.5 to 1.5, from 1.5 to 2.0.

In one embodiment, the total phosphorus content in the lubricating oil composition is 500ppm or less.

Metal detergent

In one embodiment, the lubricating oil composition comprises a metal detergent compound. Non-limiting examples of suitable metal detergents include sulfurized or unsulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfurized or unsulfurized metal salts of polyhydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxyaromatic sulfonates, sulfurized or unsulfurized 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 detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates, and combinations thereof. The metal may be any metal suitable for making sulfonate, phenate, salicylate, or phosphonate detergents. Non-limiting examples of suitable metals include alkaline earth metals, basic metals, and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, and the like.

Some suitable detergents have been described in Mortier et al, "Chemistry and Technology of Lubricants", 2 nd edition, London, Springer, Chapter 3, pages 75-85 (1996); and Leslie R.Rudnick, "scientific Additives: Chemistry and Applications", New York, Marcel Dekker, Chapter 4, pp 113-136 (2003), the contents of which are incorporated herein by reference.

Typically, the amount of metal detergent is about 0.001 wt.% to about 5 wt.%, about 0.01 wt.% to about 3 wt.%, about 0.01 wt.% to about 2 wt.%, about 0.01 wt.% to about 1 wt.%, about 0.02 wt.% to about 0.5 wt.%, about 0.02 wt.% to about 0.4 wt.%, or about 0.03 wt.% to about 0.3 wt.%, based on the total weight of the lubricating oil composition.

In one embodiment, the metal detergent is a calcium sulfonate detergent with a TBN of 420mg KOH/gm and a calcium content of 16 wt.%.

In another embodiment, the calcium in the lubricating oil composition is present in an amount of no more than 350wt. In other embodiments, calcium in the lubricating oil composition is present in an amount of 25 to 350, 30 to 340, 34 to 337wt.

Friction modifiers

As the friction modifier contained in the lubricating oil composition of the present invention, various known friction modifiers can be used, but low molecular weight C is preferred₆To C₃₀A hydrocarbon-substituted succinimide, a fatty acid amide, or a polyol. The friction modifier may be used alone or in combination. In some aspects, the friction modifier is present in the lubricating oil composition in an amount of 0.01 to 5 wt.%. In other aspects, the friction modifier is present in the lubricating oil composition in an amount of 0.01 to 3.0, 0.01 to 2.0 wt.%, 0.01 to 1.5, 0.01 to 1.0.

(FM1) succinimide friction modifier:

in one aspect of the invention, the friction modifier of the invention is a bissuccinimide.

In one aspect of the invention, the bis-succinimide friction modifier of the invention is an alkenyl substituted succinimide represented by formula (V) or a post-treated derivative thereof:

wherein each R₁And R₁' independently is an alkenyl group having a branched structure at the β -position represented by the following formula (VI)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 or a 5-8 membered heterocyclic group, x is an integer of 1 to 6, and y is an integer of 0 to 20:

wherein each R₃And R₄Is an aliphatic hydrocarbon group and R₃And R₄Is in the range of 3 to 45, provided that R is₃Carbon atom number ratio R of₄More than 3 carbon atoms or R₃Carbon atom number ratio R of₄The number of carbon atoms of (2) is less than 1.

In another aspect, the invention resides in a friction modifier comprising an alkenyl-substituted succinimide of the following formula (VII):

wherein each R₁And R₁' is independently an alkenyl group having a branched structure at the β -position derived from a dimer of a single linear α -olefin having 3 to 24 carbon atoms, and Q is a residue of an alkylene-polyamine having 1 to 20 carbon atoms and containing an amino group at least at each terminal thereof.

The friction modifier provided by the present invention is effective for imparting improved friction properties to lubricating oil compositions, as evidenced by increased coefficient of friction and extended coefficient of friction stability. Therefore, the lubricating oil composition containing the friction modifier of the invention can make an automatic transmission device not judder for a relatively long time.

The friction modifier of the invention may be an alkenyl-substituted succinimide itself represented by the above formula (V) or (VII). In addition, the friction modifier may be a post-treated alkenyl-substituted succinimide obtained by post-treating the alkenyl-substituted succinimide with a known post-treating agent such as boric acid, phosphoric acid, carboxylic acid, or ethylene carbonate.

(FM2) ethoxylated amines

In one aspect of the invention, the friction modifier of the invention is an ethoxylated amine.

R-N(C2H4OH)2 (VIII)

In the general formula (VIII), R represents hydrogen, an alkyl group or an alkenyl group. Mixtures of compounds having different alkyl or alkenyl groups may also be used. The alkyl or alkenyl group may be straight or branched and is preferably from 8 to 22 carbon atoms.

(FM3) polyol:

in one aspect of the present invention, the polyol of the present invention is a diol compound represented by the following formula (IX).

In the general formula (IX), R represents hydrogen, an alkyl group or an alkenyl group. Mixtures of compounds having different alkyl or alkenyl groups may also be used. The alkyl or alkenyl group may be straight-chain or branched, and the preferred number is 10 to 30 carbon atoms.

Phosphorus compounds

The phosphorus compounds may be those employed as antiwear agents in lubricating oil compositions. Examples of the phosphorus compound include phosphoric acid, phosphoric acid esters, phosphorous acid esters, thiophosphoric acid and thiophosphoric acid esters. Also useful are amine salts of phosphates and phosphites.

Examples of the phosphate esters include triaryl phosphate, trialkyl aryl alkyl (phosphatyl) phosphate, triaryl alkyl phosphate, and trienyl phosphate. Specific examples include triphenyl phosphate, tricresyl phosphate, benzyl diphenyl phosphate, ethyl diphenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, ditolyl phenyl phosphate, ethyl phenyl diphenyl phosphate, di (ethylphenyl) phenyl phosphate, propyl phenyl diphenyl phosphate, di (propylphenyl) phenyl phosphate, triethyl phenyl phosphate, tripropyl phenyl phosphate, butylphenyl diphenyl phosphate, di (butylphenyl) phenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri (2-ethylhexyl) phosphate, tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate, tristearyl phosphate, and triolenyl phosphate.

Examples of the acid phosphate ester include 2-ethylhexyl acid phosphate ester, ethyl acid phosphate ester, butyl acid phosphate ester, oleyl acid phosphate ester, tetracosanoic acid phosphate ester, isodecyl acid phosphate ester, lauryl acid phosphate ester, tridecyl acid phosphate ester, stearyl acid phosphate ester and isostearyl acid phosphate ester.

Examples of phosphites include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (nonylphenyl) phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, trioleyl phosphite, dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, distearyl hydrogen phosphite and diphenyl hydrogen phosphite. Among these phosphates, tricresyl phosphate and triphenyl phosphate are preferable.

Examples of amines that form amine salts with phosphate esters include mono-substituted amines, di-substituted amines, and tri-substituted amines. Examples of mono-substituted amines include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, and benzylamine. Examples of disubstituted amines include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine, benzyl monoethanolamine, phenyl monoethanolamine, and tolyl monopropanolamine. Examples of tri-substituted amines include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, triolefinylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl monopropanolamine, dioctylmonoethanolamine, dihexylmonopropanolamine, dibutyl monopropanolamine, oleyldiethanolamine, stearyldipropanolamine, lauryl diethanolamine, octyldiethanolamine, butyldiethanolamine, benzyldiethanolamine, phenyldiethanolamine, tolyldipropanolamine, ditolylethanolamine, triethanolamine and tripropanolamine.

Examples of phosphorothioates include alkyltrithioates, aryl or alkylaryl phosphorothioates, and zinc dialkyldithiophosphates. Among them, lauryl trithiophosphite, triphenyl thiophosphate, and zinc dilauryl dithiophosphate are particularly preferable.

These extreme pressure agents may be used alone or in combination of two or more, and are generally used in an amount of 0.01 to 10 mass%, preferably 0.05 to 5 mass%, based on the total amount of the power transmitting fluid composition, for example, from the viewpoint of balance between effect and cost.

In one embodiment, the phosphorus compound is a phosphate amine salt compound, an aromatic hydrogen phosphate ester compound, or a combination thereof.

In one aspect, the amine phosphate salt is present in the lubricating oil composition at 0.01 to 0.5, 0.02 to 0.3, 0.02 to 0.2, 0.03 to 0.02, 0.04 to 0.02, 0.05 to 0.18, 0.05 to 0.15 wt.%.

In another aspect, the combination of the amine phosphate ester salt and the aromatic hydrogen phosphate ester compound is present in the lubricating oil composition at 0.01 to 0.5, 0.02 to 0.3, 0.02 to 0.2, 0.03 to 0.2, 0.04 to 0.2, 0.05 to 0.20 wt.%.

In one embodiment, the total phosphorus in the lubricating oil composition is 500ppm or less. In one embodiment, the total phosphorus in the lubricating oil composition is 450, 425, 400ppm or less.

In one embodiment, the total phosphorus in the lubricating oil composition is from 450 to 50, 450 to 100, 450 to 150, 400 to 50, 400 to 100, 400 to 150 ppm.

In one embodiment, the lubricating oil composition comprises a sulfur-based extreme pressure agent. In another embodiment, the lubricating oil composition does not comprise a sulfur-based extreme pressure agent.

Other additives

Optionally, the lubricating oil composition may further comprise at least one additive or modifier (hereinafter "additive") which may impart or improve any desirable property of the lubricating oil composition. Any additive known to those skilled in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives have been described in Mortier et al, "chemistry and Technology of Lubricants," 2 nd 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 additive may be selected from the group consisting of antioxidants, anti-wear agents, detergents, rust inhibitors, demulsifiers, friction modifiers, multifunctional additives, viscosity index improvers, pour point depressants, foam inhibitors, metal deactivators, dispersants, corrosion inhibitors, lubricity improvers, thermal stability improvers, anti-haze additives, icing inhibitors, dyes, markers, static dissipative agents, biocides, and combinations thereof. Generally, when used, the concentration of each additive in the lubricating oil composition can be from about 0.001 wt.% to about 15 wt.%, from about 0.01 wt.% to about 10 wt.%, or from about 0.1 wt.% to about 8 wt.%, based on the total weight of the lubricating oil composition. In addition, the total amount of additives in the lubricating oil composition can be about 0.001 wt.% to about 20 wt.%, about 0.01 wt.% to about 10 wt.%, or about 0.1 wt.% to about 8 wt.%, based on the total weight of the lubricating oil composition.

Optionally, the lubricating oil compositions disclosed herein may further comprise an antioxidant, which may reduce or prevent oxidation of the 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., alkyldiphenylamine, phenyl- α -naphthylamine, alkyl-or aralkyl-substituted phenyl- α -naphthylamine, alkylated p-phenylenediamine, tetramethyl-diaminodiphenylamine, etc.), phenolic antioxidants (e.g., 2-tert-butylphenol, 4-methyl-2, 6-di-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, 2, 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 phenolic antioxidants, etc.), phosphorus-based antioxidants (e.g., phosphites, etc.), zinc dithiophosphates, oil-soluble copper compounds, and combinations thereof. The amount of antioxidant may vary within the following ranges: from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition. Some suitable antioxidants have been described in leslie r.rudnick, "lube Additive: chemistry and Applications, "New York, MarcelDekker, Chapter 1, pages 1-28 (2003), which is incorporated herein by reference.

The lubricating oil compositions disclosed herein may optionally comprise a pour point depressant, which may lower the pour point of the lubricating oil composition. Any pour point depressant known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable pour point depressants include polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di (tetra-paraffinphenol) phthalate (di (tetra-paraffinphenol) phthalate), condensates of tetra-paraffinphenol (condensates of tetra-paraffinphenol), condensates of chlorinated paraffins with naphthalene, and combinations thereof. In some embodiments, the pour point depressant comprises ethylene-vinyl acetate copolymers, condensates of chlorinated paraffins and phenols, polyalkylstyrenes, and the like. The amount of pour point depressant may vary within the following ranges: from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition. Some suitable pour point depressants have been described in Mortier et al, "Chemistry and Technology of Lubricants," 2 nd edition, London, Springer, Chapter 6, pages 187-189 (1996); and Leslie R.Rudnick, "LubricantAdditives: chemistry and Applications, New York, Marcel Dekker Chapter 11, page 329-354 (2003), which are all incorporated herein by reference.

The lubricating oil compositions disclosed herein may optionally contain foam inhibitors or defoamers, which can disrupt foam in the oil. Any foam inhibitor 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 glycol), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines, and combinations thereof. In some embodiments, the defoamer comprises glycerol monostearate/salt, polyglycol palmitate/salt, trialkyl monothiophosphate ester/salt, an ester of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate/salt, or glycerol dioleate/salt. The amount of defoamer may vary within the following ranges: from about 0.0001 wt.% to about 1 wt.%, from about 0.0005 wt.% to about 0.5 wt.%, or from about 0.001 wt.% to about 0.1 wt.%, based on the total weight of the lubricating oil composition. Some suitable antifoams have been described in Mortier et al, "Chemistry and technology of Lubricants," 2 nd edition, London, Springer, Chapter 6, pp 190-193 (1996), which is incorporated herein by reference.

The lubricating oil compositions disclosed herein may optionally comprise corrosion inhibitors, which may reduce 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, thiophosphate esters, alkyl imidazolines, sarcosines, benzotriazoles, thiadiazoles, and combinations thereof. The amount of corrosion inhibitor may vary within the following ranges: from about 0.001 wt.% to about 5 wt.%, from about 0.005 wt.% to about 1 wt.%, or from about 0.005 wt.% to about 0.5 wt.%, based on the total weight of the lubricating oil composition. Some suitable corrosion inhibitors have been described in Mortier et al, "Chemistry and Technology of Lubricants," 2 nd edition, London, Springer, Chapter 6, pages 193-196 (1996), which is incorporated herein by reference.

The lubricating oil compositions disclosed herein may optionally comprise an Extreme Pressure (EP) agent that can prevent the sliding metal surface from seizing under extreme pressure conditions. Any extreme pressure agent known to those of ordinary skill in the art may be used in the lubricating oil composition. Generally, the extreme pressure agent is a compound capable of chemically bonding with a metal to form a surface film that prevents seizure under high load against micro-stabs in the metal surface. 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, mixtures of sulfurized or co-sulfurized fatty acid esters with monounsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters, and alpha-olefins, functionally substituted dihydrocarbyl polysulfides, thiaaldehydes, thiaketones, cyclic sulfur compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, and polysulfide olefin products, amine salts of phosphoric or thiophosphoric esters, and combinations thereof. The amount of the extreme pressure agent may vary from about 0.01 wt.% to about 5 wt.%, from about 0.05 wt.% to about 3 wt.%, or from about 0.1 wt.% to about 1 wt.%, based on the total weight of the lubricating oil composition. Some suitable extreme pressure agents have been described in Leslier R.Rudnick, "Lunbrict Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 8, page 223-.

In one embodiment, the lubricating oil composition does not comprise a sulfur-based extreme pressure agent.

The lubricating oil compositions disclosed herein may optionally contain rust inhibitors, which can inhibit corrosion of ferrous metal surfaces. Any rust inhibitor known to those 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, beeswax acid, etc.), oil-soluble polycarboxylic acids (e.g., those produced from tall oil fatty acids, oleic acid, linoleic acid, etc.), alkenylsuccinic acids in which the alkenyl group contains 10 or more carbon atoms (e.g., tetrapropenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, etc.); long chain alpha, omega-dicarboxylic acids having a molecular weight of 600-. The amount of rust inhibitor may vary within the following ranges: from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition.

Other non-limiting examples of suitable rust inhibitors include nonionic polyoxyethylene surfactants such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ethers, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octylstearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate/salt, polyoxyethylene sorbitol monooleate/salt, and polyethylene glycol monooleate/salt. Additional 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.

In some embodiments, the lubricating oil composition comprises at least a multifunctional additive. Some non-limiting examples of suitable polyfunctional additives include oxymolybdenum dithiocarbamate sulfide, oxymolybdenum dithiophosphate sulfide, oxymolybdenum monoglyceride, oxymolybdenum diethylate, amine-molybdenum complex compounds, and sulfur-containing molybdenum complex compounds.

In certain embodiments, the lubricating oil composition comprises at least a viscosity index improver. Some non-limiting examples of suitable viscosity index improvers include polymethacrylate/salt type polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.

In some embodiments, the lubricating oil composition comprises at least a metal deactivator. Some non-limiting examples of suitable metal deactivators include bis-salicylidene propylenediamine, triazole derivatives, thiadiazole derivatives, and mercaptobenzimidazole.

The additives disclosed herein may be in the form of an additive concentrate having more than one additive. The additive concentrate may contain a suitable diluent, such as a hydrocarbon oil of suitable viscosity. Such diluents may be selected from natural oils (e.g., mineral oils), synthetic oils, and combinations thereof. Some non-limiting examples of mineral oils include paraffinic base oils, naphthenic base oils, asphaltic base oils, and combinations thereof. Some non-limiting examples of synthetic base oils include polyolefin oils (particularly hydrogenated alpha-olefin oligomers), alkylated aromatic hydrocarbon oils, polyalkylene oxides, aromatic ethers, and carboxylic acid esters (particularly diester oils) and combinations thereof. In some embodiments, the diluent is a light hydrocarbon oil, which is natural or synthetic. Typically, the diluent oil may have a viscosity of about 13 centistokes to about 35 centistokes at 40 ℃.

In general, it is desirable that the diluent readily solubilizes the lubricating oil soluble additives of the present invention and provide an oil additive concentrate that is readily soluble in lubricant base stocks or fuels. In addition, it is desirable that the diluent does not introduce any undesirable characteristics into the lubricant base stock, including, for example, high volatility, high viscosity, and impurities such as heteroatoms, and thus is not ultimately introduced into the final lubricant or fuel.

The present invention further provides an oil soluble additive concentrate composition comprising an inert diluent and from 2.0 to 90 wt%, preferably from 10 to 50 wt%, based on the total weight of the concentrate, of an oil soluble additive composition of the present invention.

The following examples illustrate exemplary embodiments of the invention, but are not intended to limit the invention to the specific embodiments described. Unless indicated to the contrary, all parts and percentages are by weight. All numerical values are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the invention. The specific details described in each embodiment should not be construed as essential features of the invention.

Examples

Dispersant 1 non-post-treated bissuccinimide derived from MW 950 PIB, N2.0 wt%.

Dispersant 2 boronated bissuccinimide derived from MW 950 PIB.

Dispersant 3 boronated bissuccinimide derived from MW 1300 PIB.

Phosphoric acid 85% by weight H₃PO₄And P was 27% by weight.

Detergent, calcium sulfonate, TBN 420 and calcium 16 wt%.

Friction modifier 1(FM1) bis-succinimide friction modifier.

Friction modifier 2(FM2) ethoxylated amine.

Friction modifier 3(FM3) polyol.

Phosphorus Compound 1(P1) amine salt of phosphoric acid ester.

Phosphorus compound 2(P2) aromatic Hydrophosphites

Base oil group 2 base oil.

Antioxidant, mixture of phenolic and aminic antioxidants.

And the corrosion inhibitor is thiadiazole or triazole.

The sealing expanding agent is ester type sealing expanding agent.

VII dispersed Polymethacrylate (PMA)

Lubricating oil compositions were prepared according to inventive examples 1 to 4 and comparative examples 1 to 5, and are summarized in table 1.

TABLE 1

N¹Nitrogen from non-post-treated succinimide

P²Phosphorus derived from phosphoric acid

The wet clutch anti-shudder performance of inventive examples 1 to 4 and comparative examples 1 to 5 was evaluated using the JASO M349-2012 test procedure. The results are in table 2 below.

Anti-jitter performance test JASO M349-2012 of wet clutch

Durability of anti-shudder performance by low speed friction equipment according to the description in JASO M-349: "roadways-Test method for anti-shredder performance of automatic transmission fluids" assay 2012. The details of the test method are described below.

O test conditions

■ Friction Material: cellulose disc/steel plate

■ oil dosage: about 150mL

Run-in conditions

■ contact pressure: 1MPa of

■ oil temperature: 80 deg.C

■ sliding speed: 0.6m/s

■ slip time: 30 minutes

O μ -V Performance test conditions

■ contact pressure: 1MPa of

■ oil temperature: 40, 80, 120 ℃ C

■ sliding speed: continuously increasing and decreasing between 0m/s and 1.5m/s

O durability test conditions

■ contact pressure: 1MPa of

■ oil temperature: 120 deg.C

■ sliding speed: 0.9m/s

■ time: 30 minutes

■ stop time: 1 minute

■ Performance measurement time: mu-V characteristics are tested from 0 hours every 24 hours (or 6 hours if necessary, e.g. due to clutch failure)

■ Note that: the anti-jitter performance was evaluated by measuring the time period for which d μ/dV at 0.9m/s reached 0. The longer the measurement period, the better the anti-jitter performance.

TABLE 2 anti-jitter Performance results