CN109679716B

CN109679716B - Composite lithium-based lubricating grease and preparation method thereof

Info

Publication number: CN109679716B
Application number: CN201710969266.0A
Authority: CN
Inventors: 郑会; 苏朔; 龙军; 段庆华; 孙洪伟; 张辉; 何懿峰; 刘中其; 姜靓
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-10-18
Filing date: 2017-10-18
Publication date: 2022-06-28
Anticipated expiration: 2037-10-18
Also published as: CN109679716A

Abstract

The invention provides a composite lithium-based lubricating grease and a preparation method thereof. The composite lithium-based lubricating grease disclosed by the invention comprises the following components by taking the total weight of the lubricating grease as a reference: benzotriazole derivatives, complex lithium-based thickeners, antioxidants and a major amount of lubricating base oil. The composite lithium-based lubricating grease disclosed by the invention has the advantages of lower friction coefficient, excellent extreme pressure wear resistance, excellent oxidation stability, excellent corrosion resistance, excellent antirust performance, excellent colloid stability and excellent mechanical stability, and can be used under severe working conditions such as high temperature, high speed, high load, excessive water and the like.

Description

Composite lithium-based lubricating grease and preparation method thereof

Technical Field

The invention relates to lubricating grease, in particular to composite lithium-based lubricating grease.

Background

The composite lithium-based lubricating grease is high-temperature multi-effect lubricating grease developed in the 60 th of the 20 th century, has a higher dropping point than that of the lithium-based lubricating grease, is more suitable for being used at high temperature, has good multi-effect properties such as good colloid stability, shear stability, water resistance and long service life, and has strong thickening capability on various types of mineral oil and synthetic oil. However, with the development of modern industry, the industrial departments of bearings, automobiles, printing and dyeing, mines, metallurgy, aerospace and the like have more and more rigorous requirements on the oxidation resistance, high and low temperature resistance, extreme pressure abrasion resistance, water resistance, mechanical stability and the like of lubricating grease. The service performance of the base grease often cannot meet the actual requirements.

In recent years, lithium complex grease has been greatly developed at home and abroad. For example, US 3681242, US 3929651, US 3711407 and CN 1052890A, CN 1052891A, CN 1055384A, CN 101705141a report compositions and preparation methods of complex lithium-based grease, some of the complex lithium-based grease is formed by compounding 12-hydroxy lithium stearate with binary acid or boric acid and lithium salt of salicylic acid, and other complex grease is formed by compounding three components; CN 101993769A, CN 101481637A, CN 102358863A has carried out the improvement to the technology of system fat respectively, has reduced manufacturing cost, has shortened saponification time, has promoted production efficiency and maneuverability. CN 101200670A provides a preparation method of complex lithium grease with better comprehensive performance, and has a repair function on damaged bearings through adding nanometer copper powder. CN 101921650A is added into the formula through a surfactant, so that the surfactant and soap molecules form a synergistic effect, and the arrangement mode of the soap molecules and the capability of solidifying base oil are improved.

With the increasing increase of the parameters of power, speed, precision and the like of modern mechanical equipment, the working load is higher and higher, the service environment is more and more severe, so that the abrasion and the service life of mechanical parts are greatly influenced, and in order to improve the lubricating performance of lubricating grease and prolong the service life of the equipment, an anti-friction agent is required to be added into the lubricating grease to reduce the frictional resistance between frictional surfaces and prevent the abrasion and the scuffing of materials.

Disclosure of Invention

The invention provides a composite lithium-based lubricating grease and a preparation method thereof.

Specifically, the present invention relates to the following aspects.

1. The composite lithium-based lubricating grease comprises the following components by taking the total weight of the lubricating grease as a reference: benzotriazole derivatives, a composite lithium-based thickening agent, an antioxidant and a main amount of lubricating base oil, wherein the benzotriazole derivatives have a structure shown in a general formula (I):

in the general formula (I), the radical R' is selected from C_1-25Hydrocarbyl radical, C_3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), or is selected from C_1-20Hydrocarbyl and C_3-20A linear or branched heteroalkyl radical, preferably selected from C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl, C_10-25Straight-chain or branched alkynyl, C_10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), more preferably C_10-25A linear or branched alkyl group; n is selected from integers from 0 to 10, preferably from integers from 0 to 5, more preferably 0; n radicals R₀Are the same or different from each other and are each independently selected from C_1-10Straight or branched alkylene, preferably independently selected from C_2-5A linear or branched alkylene group; n +2 groups A, which may be the same or different from each other, are each independently selected from the group consisting of hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2), C _1-25The hydrocarbon group and the hydrocarbon group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500) are preferably independently selected from the group consisting of hydrogen, the group represented by the formula (I-1), the group represented by the formula (I-2), and C_1-6Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25The linear or branched alkenyl group and the polyisobutenyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500) are preferably each independently selected from the group consisting of hydrogen, the group represented by the formula (I-1), the group represented by the formula (I-2) and C_1-4A linear or branched alkyl group, preferably each independently selected from hydrogen, a group represented by formula (I-1) and a group represented by formula (I-2), provided that at least one of the n +2 groups A is a group represented by formula (I-1) and at least one of the n +2 groups A is a group represented by formula (I-2); when at least one of said groups A is C_10-25Straight chainOr branched alkyl, C_10-25When the alkenyl group is a linear or branched alkenyl group or a hydrocarbon group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), the group R' may also be hydrogen,

in the general formula (I-1) and the general formula (I-2), the group R₅And R₆Are the same or different from each other and are each independently selected from C_1-20Hydrocarbyl (especially C)_1-20Straight or branched alkyl), preferably each independently selected from C _1-15Straight or branched alkyl, more preferably each independently selected from C_3-12A linear or branched alkyl group; the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom, preferably both groups X are sulfur atoms and both groups Y are oxygen atoms; the two radicals R' are identical or different from each other and are each independently selected from hydrogen and C_1-20Hydrocarbyl, preferably independently selected from hydrogen and C_1-20Straight or branched chain alkyl, more preferably each independently selected from hydrogen and C_1-6Straight or branched chain alkyl, more preferably both hydrogen; radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C_1-20Hydrocarbyl, preferably independently selected from hydrogen and C_1-10Straight or branched alkyl, more preferably R₁And R₄Are each hydrogen, R₂And R₃One of them is C_1-10Straight or branched alkyl (preferably C)_1-6Linear or branched alkyl), the other being hydrogen, the linear or branched heteroalkyl meaning that the carbon chain structure of the linear or branched alkyl is selected from-O-, -S-and-NR- (wherein the group R is selected from H and C) by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) of_1-4Straight-chain or branched alkyl, preferably selected from H and methyl).

2. A grease according to any one of the preceding aspects, wherein the benzotriazole derivative is selected from the following specific compounds or mixtures of any two or more thereof:

3. A complex lithium grease comprises the following components by taking the total weight of the grease as a reference: a benzotriazole derivative, a complex lithium-based thickener, an antioxidant, and a major amount of a lubricating base oil, the benzotriazole derivative being produced by a method comprising the step of reacting a phosphorus compound represented by formula (I-A), an amine compound represented by formula (I-B), and a benzotriazole compound represented by formula (I-C) in the presence of an aldehyde represented by formula (I-D),

wherein the radical R' is selected from C_1-25Hydrocarbyl radical, C_3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), or is selected from C_1-20Hydrocarbyl and C_3-20A linear or branched heteroalkyl radical, preferably selected from C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl, C_10-25Straight-chain or branched alkynyl, C_10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), more preferably C_10-25A linear or branched alkyl group; n is selected from an integer from 0 to 10, preferably from an integer from 0 to 5, more preferably 0; n radicals R₀Are the same or different from each other and are each independently selected from C_1-10Straight or branched alkylene, preferably independently selected from C_2-5A linear or branched alkylene group; n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C _1-25The hydrocarbyl group and the hydrocarbyl group with the number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500) are preferably respectively and independently selected from hydrogen and C_1-6Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25The linear or branched alkenyl group and the polyisobutenyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500) are preferably each independently selected from hydrogen and C_1-4Straight-chain or branched alkyl, with the proviso that at least two of the n +2 groups A' represent hydrogen; when at least one of said groups A' is C_10-25Straight or branched alkyl, C_10-25The group R' may also be hydrogen when it is a linear or branched alkenyl group or a hydrocarbyl group having a number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500); radical R₅And R₆Are the same or different from each other and are each independently selected from C_1-20Hydrocarbyl (especially C)_1-20Straight or branched alkyl), preferably each independently selected from C_1-15Straight or branched alkyl, more preferably each independently selected from C_3-12A linear or branched alkyl group; the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom, preferably both groups X are sulfur atoms and both groups Y are oxygen atoms; the radical R' is selected from hydrogen and C_1-20Hydrocarbyl, preferably selected from hydrogen and C_1-20Straight or branched alkyl, more preferably selected from hydrogen and C _1-6Straight or branched alkyl, more preferably hydrogen; radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C_1-20Hydrocarbyl, preferably independently selected from hydrogen and C_1-10Straight or branched alkyl, more preferably R₁And R₄Are each hydrogen, R₂And R₃One of them is C_1-10Straight or branched alkyl (preferably C)_1-6Linear or branched alkyl), the other being hydrogen, the linear or branched heteroalkyl meaning that the carbon chain structure of the linear or branched alkyl is selected from-O-, -S-and-NR- (wherein the group R is selected from H and C) by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) of_1-4Straight-chain or branched alkyl, preferably selected from H and methyl).

4. The production process according to any one of the preceding aspects, wherein the reaction time of the reaction is 0.1 to 24 hours, preferably 0.5 to 6 hours, and the reaction temperature of the reaction is 0 to 250 ℃, preferably 60 to 120 ℃.

5. The production process according to any one of the preceding aspects, wherein the molar ratio of the phosphorus compound represented by the formula (I-A) to the amine compound represented by the formula (I-B) is 1: 0.1 to 10, preferably 1: 0.6 to 1.5; the molar ratio of the phosphorus compound represented by the formula (I-A) to the benzotriazole compound represented by the formula (I-C) is 1: 0.1 to 10, preferably 1: 0.6 to 1.5; the molar ratio of the phosphorus compound represented by the formula (I-A) to the aldehyde represented by the formula (I-D) is 1: 1 to 10, preferably 1: 2 to 4.

6. A grease according to any one of the preceding aspects, wherein the benzotriazole derivative comprises from 0.01% to 10% (preferably from 0.1% to 5%) of the total mass of the grease; the composite lithium-based thickener accounts for 5-35% (preferably 10-20%) of the total mass of the lubricating grease; the antioxidant accounts for 0.1-10% (preferably 0.5-2%) of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.

7. The lubricating grease according to any one of the preceding aspects, wherein the complex lithium-based thickener is formed by reacting a mixed acid with lithium hydroxide. The mixed acid is a mixture of high molecular acid and low molecular acid, the high molecular acid is C12-C25 fatty acid and/or hydroxy fatty acid, and can be one or more of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid, and stearic acid and/or 12-hydroxystearic acid are preferred; the low molecular acid is C2-C11 organic acid, and can be one or more of acetic acid, propionic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid and terephthalic acid, and preferably C5-C11 organic dicarboxylic acid. The preferred molar ratio of the high molecular acid to the low molecular acid is 1: 0.1-1; the lubricating base oil is one or more of mineral oil, vegetable oil and synthetic oil, and preferably has a kinematic viscosity of 5-60mm at 100 deg.C ²A lubricating base oil having a kinematic viscosity at 100 ℃ of from 10 to 30mm is most preferred²A lubricating base oil per second; the vegetable oil can be one or more of castor oil, rapeseed oil, peanut oil and soybean oil; the synthetic oil may be one or more of poly alpha-olefin oil, ester oil, fluorine oil and silicone oil.

The antioxidant is selected from one or more of amine type antioxidant, phenol type antioxidant, ester type antioxidant and thiophenol ester type antioxidant, preferably amine type antioxidant, and for example, one or more of diphenylamine, diisooctyldiphenylamine, β -naphthylamine, N-phenyl- α -naphthylamine, N-phenyl- β -naphthylamine, N-isopropyl-N '-phenyl-p-phenylenediamine, N-cyclohexyl-N' -phenyl-p-phenylenediamine, N '-di- β -naphthyl-p-phenylenediamine and N, N' -di-sec-butyl-p-phenylenediamine may be used.

In the grease composition of the present invention, the content of each component can be calculated according to the amount of the fed material. Wherein the content of the composite lithium-based thickener is 100% × (weight of high molecular lithium salt + weight of low molecular lithium salt)/total weight of the grease.

8. The preparation method of the lithium complex grease in any one of the preceding aspects comprises the following steps: the composite lithium-based thickening agent and the lubricating base oil are uniformly mixed, are refined at the constant temperature of 180-230 ℃, are cooled, are added with the benzotriazole derivative and the antioxidant, and are ground into grease. The refining time is preferably 5 to 25 minutes.

The preparation method of the preferred compound lithium grease comprises the following steps: mixing and heating part of base oil, high molecular acid and low molecular acid, heating to 85-95 ℃, adding an aqueous solution of lithium hydroxide for saponification, heating to 190-210 ℃ after the reaction is completed, performing high-temperature refining, adding the rest base oil, cooling to 100-120 ℃, adding the benzotriazole derivative and the antioxidant, and grinding into grease. The amount of water in the aqueous solution of lithium hydroxide is generally 0.1 to 10 times by weight the amount of lithium hydroxide, so that the saponification reaction proceeds smoothly. The amount of the partial base oil and the rest base oil is respectively 50-75% and 25-50% of the total amount of the base oil. The temperature of the saponification reaction is preferably 85 to 95 ℃, and the time of the saponification reaction is preferably 0.2 to 1.5 hours.

The composite lithium-based lubricating grease disclosed by the invention has the advantages of lower friction coefficient, excellent extreme pressure wear resistance, excellent oxidation stability, excellent corrosion resistance, excellent antirust performance, excellent colloid stability and excellent mechanical stability, and can be used under severe working conditions such as high temperature, high speed, high load, excessive water and the like.

Technical effects

The benzotriazole derivative according to the present invention does not contain a metal element, is less likely to generate ash and deposits, and is an environmentally friendly lubricant additive.

The benzotriazole derivatives according to the present invention exhibit significantly improved antiwear properties and extreme pressure properties as compared with lubricating oil additives of the prior art, and are effective in improving the antiwear properties and load bearing capacity of lubricating oils.

The benzotriazole derivative according to the present invention, in a preferred embodiment, further exhibits excellent thermal oxidation stability (thermal stability) while exhibiting excellent anti-wear properties. Which is not simultaneously possessed by the lubricating oil additives of the prior art.

The benzotriazole derivatives according to the present invention, in preferred embodiments, further exhibit excellent anti-corrosion properties while exhibiting excellent anti-wear properties. Which is not simultaneously possessed by the lubricating oil additives of the prior art.

According to the benzotriazole derivative of the present invention, in a preferred embodiment, while exhibiting excellent anti-wear properties, it further exhibits excellent rust inhibitive properties. Which is not simultaneously possessed by the lubricating oil additives of the prior art.

According to the benzotriazole derivative of the present invention, in a preferred embodiment, it further exhibits excellent friction reducing properties while exhibiting excellent abrasion resistance. Which is not simultaneously possessed by the lubricating oil additives of the prior art.

The preparation method of the benzotriazole derivative has the characteristics of simple process, no waste gas emission, less waste water, safety, environmental protection and the like.

Detailed Description

The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.

All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or a synonym thereof, directed to a material, substance, method, step, device, or component, the subject matter from which the heading is derived encompasses those conventionally used in the art as presented in the present application, but also includes those not currently in use, but which would become known in the art to be suitable for a similar purpose.

In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.

In the context of the present invention, the term "halogen" refers to fluorine, chlorine, bromine or iodine.

In the context of the present invention, the term "hydrocarbyl" has the meaning conventionally known in the art and includes straight or branched chain alkyl, straight or branched chain alkenyl, straight or branched chain alkynyl, cycloalkyl, cycloalkenyl, aryl, or combinations thereof. As the hydrocarbon group, a linear or branched alkyl group, a linear or branched alkenyl group, an aryl group, or a combination thereof is preferable. Specific examples of the hydrocarbon group include C_1-30The hydrocarbon group is more specifically C_1-30Straight or branched alkyl, C_2-30Straight-chain or branched alkenyl, C_3-20Cycloalkyl radical, C_3-20Cycloalkenyl radical, C_6-20Aryl or a combination thereof.

In the context of the present specification as C_1-4Straight or branched chain alkanesExamples of the group include methyl, ethyl and propyl groups, and C is_2-4Examples of the straight-chain or branched alkenyl group include a vinyl group, an allyl group, and an propenyl group.

In the context of the present invention, the term "linear or branched heteroalkyl" refers to a linear or branched alkyl having a carbon chain structure selected from the group consisting of-O-, -S-and-NR- (wherein the radical R is selected from the group consisting of H and C) by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) _1-4Straight-chain or branched alkyl, preferably selected from H and methyl). It is preferable from the viewpoint of structural stability that, when plural, any two of the hetero groups are not directly bonded to each other. It is apparent that the hetero group is not at the end of the carbon chain of the linear or branched alkyl group or the linear or branched heteroalkyl group. It is expressly stated here that, although the interruptions may be present (for example by a heterogroup-NR-and R represents C)_1-4Linear or branched alkyl) may result in the linear or branched heteroalkyl group having a different total number of carbon atoms than the linear or branched alkyl group, but for convenience, the number of carbon atoms in the linear or branched heteroalkyl group prior to the interruption is still used to refer to the number of carbon atoms in the linear or branched heteroalkyl group after the interruption.

In the context of the present specification, the number average molecular weight Mn is determined by Gel Permeation Chromatography (GPC), unless otherwise specified.

In the context of the present specification, any reference to Gel Permeation Chromatography (GPC) or measurement conditions of a GPC profile, unless otherwise specified, is: the instrument adopts a Waters 2695 type gel permeation chromatographic analyzer of the Waters company in America, tetrahydrofuran is adopted as a mobile phase, the flow rate is 1mL/min, the temperature of a chromatographic column is 35 ℃, the outflow time is 40min, and the mass fraction of a sample is 0.16-0.20%.

Finally, unless otherwise explicitly indicated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless not otherwise generally recognized by those of skill in the art.

The invention firstly relates to a benzotriazole derivative, which has a structure shown in a general formula (I).

According to the invention, in the general formula (I), the radical R' is chosen from C_1-25Hydrocarbyl radical, C_3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000.

According to a particular embodiment of the invention, in formula (I), the radical R' is chosen from C_1-20Hydrocarbyl and C_3-20Straight or branched heteroalkyl.

According to a particular embodiment of the invention, in formula (I), the radical R' is chosen from C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl, C_10-25Straight-chain or branched alkynyl, C_10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000.

According to one embodiment of the invention, in formula (I), the radical R' represents C_10-25Straight or branched chain alkyl. Here, as the C_10-25Straight or branched alkyl, such as C_10-25Examples of the straight-chain alkyl group include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tetracosyl group, neododecyl group, neotridecyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, and neotetracosyl group.

According to one embodiment of the invention, in formula (I), the radical R' represents C_10-25Straight-chain or branched alkenyl. Here, as the C_10-25Straight-chain or branched alkenyl, for example, C_10-25Examples of the straight chain alkenyl group include a n-6-dodecenyl group, a n-6-tridecenyl group, a n-7-tetradecenyl group, a n-7-pentadecenyl group, a n-8-hexadecenyl group, a n-8-heptadecenyl group, a n-9-octadecenyl group and a n-6-octadecenyl group9-eicosenyl, n-10-heneicosenyl, n-12-tetracosenyl, new 6-dodecenyl, new 6-tridecenyl, new 7-tetradecenyl, new 7-pentadecenyl, new 8-hexadecenyl, new 8-heptadecenyl, new 9-octadecenyl, new 9-eicosenyl, new 10-heneicosenyl, new 12-tetracosenyl, and the like.

According to a particular embodiment of the invention, in formula (I), the radical R' represents a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. Here, as the hydrocarbon group having a number average molecular weight Mn of 300-3000, for example, a hydrocarbon group (referred to as a polyolefin residue) obtained by removing one hydrogen atom from a polyolefin having a number average molecular weight Mn of 300-3000 (particularly, the terminal of the polyolefin molecular chain) can be mentioned. Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500-2000, more preferably 500-1500. Examples of the polyolefin include ethylene, propylene and C ₄-C₁₀A homo-polymerization of α -olefins such as n-butene, isobutene, n-pentene, n-hexene, n-octene or n-decene or a polyolefin obtained by copolymerization of two or more of these olefins, with Polyisobutylene (PIB) being more preferred.

According to the invention, in the general formula (I), n is selected from integers from 0 to 10.

According to a particular embodiment of the invention, in formula (I), n is chosen from integers from 0 to 5.

According to a particular embodiment of the invention, in formula (I), n is 0, 1, 2 or 3, such as 0.

According to the invention, in the general formula (I), n radicals R₀Are the same or different from each other and are each independently selected from C_1-10Straight or branched chain alkylene.

According to a particular embodiment of the invention, in the general formula (I), n radicals R₀Are the same or different from each other and are each independently selected from C_2-5Straight or branched chain alkylene. Here, as the C_2-5Examples of the straight-chain or branched alkylene group include an ethylene group and a propylene group.

According to the invention, in the general formula (I), n +2 radicals A are identical to or different from one anotherEach independently selected from hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2), and C_1-25A hydrocarbon group and a hydrocarbon group having a number average molecular weight Mn of 300-3000.

According to a particular embodiment of the invention, in the general formula (I), n +2 radicals A, equal to or different from each other, are each independently selected from hydrogen, the radical represented by formula (I-1), the radical represented by formula (I-2), C_1-6Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25Linear or branched alkenyl groups and polyisobutenyl groups having a number average molecular weight Mn of 300-3000.

According to a particular embodiment of the invention, in the general formula (I), n +2 groups A, equal to or different from each other, are each independently selected from hydrogen, the group represented by formula (I-1), the group represented by formula (I-2) and C_1-4Straight or branched chain alkyl.

According to a particular embodiment of the invention, in the general formula (I), n +2 groups A, equal to or different from each other, are each independently selected from hydrogen, the group represented by formula (I-1) and the group represented by formula (I-2).

According to one embodiment of the invention, in the general formula (I), the group a represents hydrogen.

According to one embodiment of the invention, in the general formula (I), the group A represents C_1-4Straight or branched chain alkyl.

According to one embodiment of the invention, in the general formula (I), the group A represents C_10-25Straight or branched chain alkyl. Here, as the C_10-25Straight or branched alkyl, such as C _10-25Examples of the straight-chain alkyl group include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tetracosyl group, neododecyl group, neotridecyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, and neotetracosyl group.

According to one embodiment of the invention, in the general formula (I), the group A represents C_10-25Straight or branched alkenyl. Here, as the C_10-25Straight-chain or branched alkenyl, for example, C_10-25Examples of the linear alkenyl group include n-6-dodecenyl, n-6-tridecenyl, n-7-tetradecenyl, n-7-pentadecenyl, n-8-hexadecenyl, n-8-heptadecenyl, n-9-octadecenyl, n-9-eicosenyl, n-10-heneicosenyl, n-12-tetracosenyl, new 6-dodecenyl, new 6-tridecenyl, new 7-tetradecenyl, new 7-pentadecenyl, new 8-hexadecenyl, new 8-heptadecenyl, new 9-octadecenyl, new 9-eicosenyl, new 10-heneicosenyl, new 12-tetracosenyl and the like.

According to a particular embodiment of the invention, in formula (I), the group A represents a hydrocarbon radical having an average molecular weight Mn of 300-3000. Here, as the hydrocarbon group having an average molecular weight Mn of 300-3000, for example, a hydrocarbon group (referred to as a polyolefin residue) obtained by removing one hydrogen atom from a polyolefin having a number average molecular weight Mn of 300-3000 (particularly, the terminal of the polyolefin molecular chain) can be mentioned. Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500-2000, more preferably 500-1500. Examples of the polyolefin include ethylene, propylene and C₄-C₁₀A homo-polymerization of α -olefins such as n-butene, isobutene, n-pentene, n-hexene, n-octene or n-decene or a polyolefin obtained by copolymerization of two or more of these olefins, with Polyisobutylene (PIB) being more preferred.

According to the invention, in the general formula (I), at least one of the n +2 groups A is a group represented by the formula (I-1), and at least one of the n +2 groups A is a group represented by the formula (I-2). Specifically, for example, when n is 0, in the general formula (I), one of 2 groups A is a group represented by the formula (I-1), and the other is a group represented by the formula (I-2). Or, specifically for example, when n is 1, in the general formula (I), one of 3 said groups A is a group represented by the formula (I-1) and the other two are groups represented by the formula (I-2), or two of 3 said groups A are groups represented by the formula (I-1) and the other is a group represented by the formula (I-2). Or, specifically For example, when n is 1, in the general formula (I), one of 3 said groups A is a group represented by the formula (I-1), one is a group represented by the formula (I-2), one is hydrogen, C_1-4Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25A linear or branched alkenyl group or a hydrocarbyl group having a number average molecular weight Mn of 300-3000.

According to a particular embodiment of the invention, in formula (I), when at least one of said n +2 groups A represents said C_10-25Straight or branched alkyl, said C_10-25The radical R' may also be hydrogen or hydrogen in the case of a linear or branched alkenyl radical or in the case of a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. In other words, according to this particular embodiment of the invention, in formula (I), at least one of the group A and the group R' must represent said C_10-25Straight or branched alkyl, said C_10-25A linear or branched alkenyl group or a hydrocarbyl group having a number average molecular weight Mn of 300-3000.

According to the invention, in the general formula (I-1), the radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C_1-20A hydrocarbyl group.

According to a particular embodiment of the invention, in formula (I-1), the radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C _1-10Straight or branched chain alkyl. Here, the C is defined as_1-10Straight-chain or branched alkyl, such as C_1-6Straight or branched alkyl, more specific examples being C_1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.

According to a particular embodiment of the present invention, in the general formula (I-1), R₁And R₄Are each hydrogen, R₂And R₃One of them is C_1-10Straight or branched chain alkyl, the other being hydrogen. Here, as the C_1-10Straight-chain or branched alkyl, such as C_1-6Straight or branched alkyl, more specific examples being C_1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.

According to a particular embodiment of the present invention, in the general formula (I-1), R₁、R₃And R₄Are each hydrogen, R₂Is C_1-10Straight or branched chain alkyl. Here, the C is defined as_1-10Straight-chain or branched alkyl, such as C_1-6Straight or branched alkyl, more specific examples being C_1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.

According to the invention, in the general formula (I-1), the radical R' is chosen from hydrogen and C_1-20A hydrocarbyl group.

According to a particular embodiment of the invention, in formula (I-1), the radical R' is chosen from hydrogen and C _1-20Straight or branched chain alkyl.

According to a particular embodiment of the invention, in formula (I-1), the radical R' is chosen from hydrogen and C_1-6Straight or branched chain alkyl. Here, the C is defined as_1-6Straight-chain or branched alkyl, such as C_1-6Examples of the straight-chain alkyl group include methyl, ethyl and n-propyl.

According to a particular embodiment of the invention, in formula (I-1), the radical R' represents hydrogen.

According to the invention, in the general formula (I-2), the radical R₅And R₆Are the same or different from each other and are each independently selected from C_1-20A hydrocarbyl group.

According to a particular embodiment of the invention, in formula (I-2), the radical R₅And R₆Are identical to or different from each other, are divided intoAre each independently selected from C_1-20Straight or branched chain alkyl.

According to a particular embodiment of the invention, in formula (I-2), the radical R₅And R₆Are the same or different from each other and are each independently selected from C_1-15Straight or branched chain alkyl.

According to a particular embodiment of the invention, in formula (I-2), the radical R₅And R₆Are the same or different from each other and are each independently selected from C_3-12Straight or branched chain alkyl. Here, as the C_3-12Specific examples of the linear or branched alkyl group include n-propyl, n-butyl, n-hexyl, n-decyl, n-dodecyl, isobutyl, isopentyl, isooctyl, isodecyl, isododecyl, 2-ethyl-n-hexyl, 2-ethyl-n-heptyl, 2-ethyl-n-octyl, and 2-ethyl-n-decyl.

According to the invention, in the general formula (I-2), the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom.

According to a particular embodiment of the invention, in formula (I-2), both groups X are sulfur atoms and both groups Y are oxygen atoms.

According to the invention, in formula (I-2), the group R' is selected from hydrogen and C_1-20A hydrocarbyl group.

According to a particular embodiment of the invention, in formula (I-2), the radical R' is chosen from hydrogen and C_1-20Straight or branched chain alkyl.

According to a particular embodiment of the invention, in formula (I-2), the radical R' is chosen from hydrogen and C_1-6Straight or branched chain alkyl. Here, as the C_1-6Straight-chain or branched alkyl, such as C_1-6Examples of the straight-chain alkyl group include methyl, ethyl and n-propyl.

According to a particular embodiment of the invention, in formula (I-2), the radical R' represents hydrogen.

According to the present invention, the benzotriazole derivative may be present, produced or used in the form of a single (pure) compound, or in the form of a mixture (in any ratio) of two or more thereof, without affecting the achievement of the effects of the present invention.

According to the present invention, the benzotriazole derivative can be produced, for example, by the following production method.

According to the present invention, the production method comprises a step of reacting the phosphorus compound represented by the formula (I-A), the amine compound represented by the formula (I-B), and the benzotriazole compound represented by the formula (I-C) in the presence of the aldehyde represented by the formula (I-D). This step will be referred to simply as the reaction step hereinafter.

According to the invention, in the general formula (I-A), the radical R₅And R₆Are the same or different from each other and are each independently selected from C_1-20A hydrocarbyl group.

According to a particular embodiment of the invention, in the formula (I-A), the radical R₅And R₆Are the same or different from each other and are each independently selected from C_1-20Straight or branched chain alkyl.

According to a particular embodiment of the invention, in the formula (I-A), the radical R₅And R₆Are the same or different from each other and are each independently selected from C_1-15Straight or branched chain alkyl.

According to a particular embodiment of the invention, in the formula (I-A), the radical R₅And R₆Are the same or different from each other and are each independently selected from C_3-12Straight or branched chain alkyl. Here, as the C_3-12Specific examples of the linear or branched alkyl group include n-propyl, n-butyl, n-hexyl, n-decyl, n-dodecyl, isobutyl, isopentyl, isooctyl, isodecyl, isododecyl, 2-ethyl-n-hexyl, 2-ethyl-n-heptyl, 2-ethyl-n-octyl, and 2-ethyl-n-decyl.

According to the invention, in the general formula (I-A), the groups X and Y, equal to or different from each other, are each independently chosen from an oxygen atom and a sulphur atom.

According to a particular embodiment of the invention, in formula (I-A), both groups X are sulfur atoms and both groups Y are oxygen atoms.

According to the present invention, the phosphorus compound represented by the formula (I-A) may be produced by a commercially available method as it is or by a method conventionally known in the art, and is not particularly limited. Further, the phosphorus compound represented by the formula (I-A) may be used alone or in combination of two or more.

According to the invention, in the general formula (I-B), the radical R' is chosen from C_1-25Hydrocarbyl radical, C_3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000.

According to a particular embodiment of the invention, in formula (I-B), the radical R' is chosen from C_1-20Hydrocarbyl and C_3-20Linear or branched heteroalkyl.

According to a particular embodiment of the invention, in formula (I-B), the radical R' is chosen from C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl, C_10-25Straight-chain or branched alkynyl, C_10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000.

According to one embodiment of the invention, in the general formula (I-B), the radical R' represents C_10-25Straight or branched chain alkyl. Here, as the C_10-25Straight or branched alkyl, such as C_10-25Examples of the straight-chain alkyl group include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tetracosyl group, neododecyl group, neotridecyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, and neotetracosyl group.

According to one embodiment of the invention, in the general formula (I-B), the radical R' represents C_10-25Straight or branched alkenyl. Here, as the C_10-25Straight-chain or branched alkenyl groups, for example, may include C_10-25Examples of the linear alkenyl group include n-6-dodecenyl, n-6-tridecenyl, n-7-tetradecenyl, n-7-pentadecenyl, n-8-hexadecenyl, n-8-heptadecenyl, n-9-octadecenyl, n-9-eicosenyl, n-10-heneicosenyl, n-12-tetracosenyl, new 6-dodecenyl, new 6-tridecenyl, new 7-tetradecenyl, new 7-pentadecenyl, new 8-hexadecenyl, new 8-heptadecenyl, new 9-octadecenyl, new 9-eicosenyl, new 10-heneicosenyl, new 12-tetracosenyl and the like.

According to a particular embodiment of the invention, in formula (I-B) the radical R' represents a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. Here, as the hydrocarbon group having a number average molecular weight Mn of 300-3000, for example, a hydrocarbon group (referred to as a polyolefin residue) obtained by removing one hydrogen atom from a polyolefin having a number average molecular weight Mn of 300-3000 (particularly, the terminal of the polyolefin molecular chain) can be mentioned. Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500-2000, more preferably 500-1500.

In the context of the present specification, the polyolefin residues may be saturated (present as long-chain alkyl groups) or may contain an amount of olefinic double bonds in the polymer chain (such as those remaining during the polyolefin production process), depending on the starting polyolefin species or the production process, but this does not affect the achievement of the effect of the present invention, and the present invention is not intended to make explicit this amount.

According to a particular embodiment of the invention, the polyolefin is, for example, ethylene, propylene or C₄-C₁₀Homo-polymerization of alpha-olefins such as n-butene, isobutene, n-pentene, n-hexene, n-octene or n-decene or polyolefins obtained by copolymerization of two or more of these olefins.

According to a particular embodiment of the present invention, as the polyolefin, polybutene is more preferred. As used herein, unless otherwise indicated, the term "polybutene" broadly includes polymers obtained by the homopolymerization of 1-butene or isobutylene, as well as polymers obtained by the copolymerization of two or three of 1-butene, 2-butene and isobutylene. Commercial products of such polymers may also contain negligible amounts of other olefinic components, but this does not affect the practice of the invention.

According to a particular embodiment of the invention, as the polyolefin, Polyisobutylene (PIB) or highly reactive polyisobutylene (HR-PIB) is further preferred. In such polyisobutenes, at least 20% by weight (preferably at least 50% by weight, more preferably at least 70% by weight) of the total terminal olefinic double bonds are provided by methylvinylidene groups.

According to the invention, in the general formula (I-B), n is selected from integers from 0 to 10.

According to a particular embodiment of the invention, in formula (I-B), n is chosen from integers from 0 to 5.

According to a particular embodiment of the invention, in the general formula (I-B), n is 0, 1, 2 or 3, and may be, for example, 0.

According to the invention, in the general formula (I-B), n radicals R ₀Are the same or different from each other and are each independently selected from C_1-10Straight chain or branched alkylene.

According to a particular embodiment of the invention, in the formula (I-B), n radicals R₀Are the same or different from each other and are each independently selected from C_2-5Straight chain or branched alkylene. Here, as the C_2-5Examples of the straight-chain or branched alkylene group include an ethylene group and a propylene group.

According to the invention, in the general formula (I-B), n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C_1-25A hydrocarbon group and a hydrocarbon group having a number average molecular weight Mn of 300-3000.

According to a particular embodiment of the invention, in the general formula (I-B), n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C_1-6Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl anda polyisobutenyl group having a number average molecular weight Mn of 300-3000.

According to a particular embodiment of the invention, in the general formula (I-B), n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen and C_1-4Straight or branched chain alkyl.

According to one embodiment of the invention, in the general formula (I-B), the group A' represents hydrogen.

According to one embodiment of the invention, in the formula (I-B), the group A' represents C _1-4Straight or branched chain alkyl.

According to one embodiment of the invention, in the formula (I-B), the group A' represents C_10-25Straight or branched chain alkyl. Here, as the C_10-25Straight or branched alkyl, such as C_10-25Examples of the straight-chain alkyl group include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tetracosyl group, neododecyl group, neotridecyl group, neotetradecyl group, neopentadecyl group, neohexadecyl group, neoheptadecyl group, neooctadecyl group, neoeicosyl group, neoheneicosyl group, and neotetracosyl group.

According to one embodiment of the invention, in the formula (I-B), the group A' represents C_10-25Straight or branched alkenyl. Here, as the C_10-25Straight-chain or branched alkenyl, for example, C_10-25Examples of the linear alkenyl group include n-6-dodecenyl, n-6-tridecenyl, n-7-tetradecenyl, n-7-pentadecenyl, n-8-hexadecenyl, n-8-heptadecenyl, n-9-octadecenyl, n-9-eicosenyl, n-10-heneicosenyl, n-12-tetracosenyl, new 6-dodecenyl, new 6-tridecenyl, new 7-tetradecenyl, new 7-pentadecenyl, new 8-hexadecenyl, new 8-heptadecenyl, new 9-octadecenyl, new 9-eicosenyl, new 10-heneicosenyl, new 12-tetracosenyl and the like.

According to a particular embodiment of the invention, in formula (I-B), the group A' represents a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. Here, as the hydrocarbon group having a number average molecular weight Mn of 300-3000, for example, a hydrocarbon group (referred to as a polyolefin residue) obtained by removing one hydrogen atom from a polyolefin having a number average molecular weight Mn of 300-3000 (particularly, the terminal of the polyolefin molecular chain) is mentioned. Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500-2000, more preferably 500-1500.

In the context of the present specification, depending on the starting polyolefin species or the manufacturing process, the polyolefin residues may be saturated (present as long chain alkyl groups) or may contain a certain amount of olefinic double bonds in the polymer chain (such as remaining during the polyolefin manufacturing process), but this does not affect the achievement of the effect of the present invention, nor does the present invention intend to make this amount explicit.

According to a particular embodiment of the invention, as the polyolefin, polybutene is more preferred. As used herein, unless otherwise indicated, the term "polybutene" broadly includes polymers obtained by the homopolymerization of 1-butene or isobutylene, as well as polymers obtained by the copolymerization of two or three of 1-butene, 2-butene and isobutylene. Commercial products of such polymers may also contain negligible amounts of other olefinic components, but this does not affect the practice of the invention.

According to the invention, in formula (I-B), at least two of the n +2 groups A' represent hydrogen. For example, when n is 0, in the general formula (I)-B) 2 of said groups A' each represent hydrogen. Or, by way of specific example, when n is 1, in formula (I-B), two of the 3 said groups A' represent hydrogen and the other represents hydrogen, C _1-4Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl or hydrocarbyl with a number average molecular weight Mn of 300-3000.

According to a particular embodiment of the invention, in formula (I-B), when at least one of said n +2 groups A' represents said C_10-25Straight or branched alkyl, said C_10-25The radical R' may also be hydrogen or hydrogen in the case of a linear or branched alkenyl radical or in the case of a hydrocarbon radical having a number-average molecular weight Mn of 300-3000. In other words, according to this particular embodiment of the invention, in formula (I-B), at least one of the groups A 'and R' must represent said C_10-25Straight or branched alkyl, said C_10-25A linear or branched alkenyl group or a hydrocarbyl group having a number average molecular weight Mn of 300-3000.

According to the present invention, the amine compound represented by the formula (I-B) may be produced by a method conventionally known in the art without any particular limitation, as it is, or by a commercially available product. In addition, the amine compound represented by the formula (I-B) may be used alone or in combination of two or more.

According to the invention, in the general formula (I-C), the radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C _1-20A hydrocarbyl group.

According to a particular embodiment of the invention, in the formula (I-C), the radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C_1-10Straight or branched chain alkyl. Here, as the C_1-10Straight-chain or branched alkyl, such as C_1-6Straight chainOr a branched alkyl group, more specifically such as C_1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.

According to a particular embodiment of the invention, in the general formula (I-C), R₁And R₄Are each hydrogen, R₂And R₃Is one of C_1-10Straight or branched chain alkyl, the other being hydrogen. Here, as the C_1-10Straight-chain or branched alkyl, such as C_1-6Straight or branched alkyl, more specific examples being C_1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.

According to a particular embodiment of the invention, in the general formula (I-C), R₁、R₃And R₄Are each hydrogen, R₂Is C_1-10Straight or branched chain alkyl. Here, as the C_1-10Straight-chain or branched alkyl, such as C_1-6Straight or branched alkyl, more specific examples being C_1-6Examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl and n-hexyl.

According to the present invention, the benzotriazole compound represented by the formula (I-C) may be produced by a method conventionally known in the art without any particular limitation, as it is, using a commercially available product. Further, the benzotriazole compound represented by the formula (I-C) may be used alone or in combination of two or more.

According to the invention, in the general formula (I-D), the radical R' is chosen from hydrogen and C_1-20A hydrocarbyl group.

According to a particular embodiment of the invention, in the general formula (I-D), the radical R' is chosen from hydrogen and C_1-20Straight or branched chain alkyl.

According to a particular embodiment of the invention, in the general formula (I-D), the radical R ″, isSelected from hydrogen and C_1-6Straight or branched chain alkyl. Here, as the C_1-6Straight-chain or branched alkyl, such as C_1-6Examples of the straight-chain alkyl group include methyl, ethyl and n-propyl.

According to a particular embodiment of the invention, in the general formula (I-D), the radical R' represents hydrogen.

According to the present invention, the aldehyde represented by the formula (I-D) may be produced by a commercially available product as it is or by a method conventionally known in the art, and is not particularly limited. In addition, the aldehyde represented by the formula (I-D) may be used alone or in combination of two or more.

According to a particular embodiment of the invention, the aldehyde represented by formula (I-D) is formaldehyde. The formaldehyde may be, for example, an aqueous formaldehyde solution, paraformaldehyde or paraformaldehyde, and is not particularly limited.

According to the present invention, in the reaction step, the reaction time of the reaction is generally 0.1 to 24 hours, preferably 0.2 to 12 hours, and most preferably 0.5 to 6 hours, for example, but is not limited thereto in some cases.

According to the present invention, in the reaction step, for example, the reaction temperature of the reaction is generally 0 to 250 ℃, preferably 20 to 180 ℃, and most preferably 60 to 120 ℃, but is not limited thereto in some cases.

According to the present invention, in the reaction step, for example, the molar ratio of the phosphorus compound represented by the formula (I-A) to the amine compound represented by the formula (I-B) is generally 1: 0.1 to 10, preferably 1: 0.5 to 5.0, more preferably 1: 0.6 to 1.5, but is not limited thereto in some cases.

According to the present invention, in the reaction step, for example, the molar ratio of the phosphorus compound represented by the formula (I-A) to the benzotriazole compound represented by the formula (I-C) is generally 1: 0.1 to 10, preferably 1: 0.5 to 5.0, more preferably 1: 0.6 to 1.5, but is not limited thereto in some cases.

According to the present invention, in the reaction step, for example, the molar ratio of the phosphorus compound represented by the formula (I-A) to the aldehyde represented by the formula (I-D) is generally 1: 1 to 10, preferably 1: 1.5 to 6.0, more preferably 1: 2 to 4, but is not limited thereto in some cases.

According to the present invention, in the reaction step, the manner of feeding each reaction raw material is not particularly limited, and may be, for example, one-time feeding, batch feeding or dropwise feeding.

According to the present invention, the order of feeding the reaction raw materials in the reaction step is not particularly limited, and specific examples thereof include the order of feeding the phosphorus compound represented by the formula (I-A), the amine compound represented by the formula (I-B), the benzotriazole compound represented by the formula (I-C), and the aldehyde represented by the formula (I-D), and the feeding may be carried out in any order.

According to the present invention, the reaction step may be carried out in the presence of a diluent and/or a solvent, or may be carried out without using a diluent and/or a solvent.

According to the present invention, in the reaction step, for example, as the diluent, one or more selected from the group consisting of polyolefin, mineral base oil and polyether can be cited. The mineral base oil includes, for example, API group I, II, and III mineral lubricant base oils, more specifically, mineral lubricant base oils having a viscosity of 20 to 120 centistokes (cSt) at 40 ℃ and a viscosity index of at least 50, and still more specifically, mineral lubricant base oils having a viscosity of 28 to 110 centistokes (cSt) at 40 ℃ and a viscosity index of at least 80. Examples of the polyolefin include ethylene, propylene and C ₄-C₁₀One or more of polyolefins obtained by homopolymerization of alpha-olefins or copolymerization of two or more of these olefins, preferably one or more of Polyalphaolefins (PAO) having a viscosity of 2 to 25 centistokes (cSt) at 100 ℃ (preferably having a viscosity of 6 to 10 centistokes (cSt) at 100 ℃). Wherein, as said C₄-C₁₀Examples of the α -olefin include n-butene, isobutene, n-pentene, n-hexene, n-octene, and n-decene. In addition, the number average molecular weight Mn of the polyolefin is generally 500-3000, preferably 500-2500, and most preferably 500-1500. Examples of the polyether include polymers obtained by reacting an alcohol with an epoxide. Examples of the alcohol include ethylene glycol and/or 1, 3-propanediol. Examples of the epoxide include ethylene oxide and/or propylene oxide. In addition, the number average molecular weight Mn of the polyether is generally 500-3000, preferably 700-3000, and most preferably 1000-2500. These diluents may be used alone or in combination of two or more.

According to the present invention, in the reaction step, for example, as the solvent, C may be mentioned_2-10Aliphatic nitriles (e.g. acetonitrile, etc.), C_6-20Aromatic hydrocarbons (e.g. benzene, toluene, xylene and cumene), C _6-10Alkanes (e.g. hexane, cyclohexane and petroleum ether), C_1-6Aliphatic alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol and ethylene glycol), C_2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and 1, 2-dichlorobenzene), C_3-10Ketones (e.g. acetone, butanone and methyl isobutyl ketone) or C_3-10Amides (such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone) and the like. These solvents may be used alone or in combination of two or more.

According to a particular embodiment of the present invention, the diluent and/or solvent may be added at any stage of the reaction step in an amount conventional in the art, and is not particularly limited.

According to the invention, it is evident that said reaction step is generally carried out under protection of an inert gas atmosphere. Examples of the inert gas include nitrogen gas and argon gas, and are not particularly limited.

According to the present invention, after the end of the process for producing the benzotriazole derivative, the benzotriazole derivative is obtained by removing water and a solvent, if any, from the finally obtained reaction mixture by any conventionally known means. Accordingly, the present invention also relates to a benzotriazole derivative produced by the aforementioned method for producing a benzotriazole derivative of the present invention.

According to the present invention, by the aforementioned method for producing a benzotriazole derivative, a single benzotriazole derivative can be produced as a reaction product, or a mixture of a plurality of benzotriazole derivatives, or a mixture of one or more of the benzotriazole derivatives and the diluent (if used) can be produced. These reaction products are all intended for the present invention, and the difference in the form of their existence does not affect the achievement of the effects of the present invention. Therefore, these reaction products are collectively referred to as benzotriazole derivatives without distinction in the context of this specification. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product or to further isolate a benzotriazole derivative of a specific structure from the reaction product. Of course, such purification or isolation is preferable for further improvement of the intended effect of the present invention, but is not essential to the present invention. As the purification or separation method, for example, the reaction product may be purified or separated by a column chromatography method, a preparative chromatography method or the like.

The benzotriazole derivatives of the present invention are particularly useful for the manufacture of or as antiwear agents, especially lubricating oil antiwear agents. The antiwear agent of the present invention not only has excellent extreme pressure antiwear performance, but also has one or more excellent performances of thermal oxidation stability, corrosion resistance, antirust performance and antifriction performance. According to a particularly preferred embodiment of the present invention, the anti-wear agent has not only excellent extreme pressure anti-wear properties but also excellent thermal oxidation stability, anti-corrosion properties, anti-rust properties and anti-friction properties.

According to the present invention, the anti-wear agent comprises any of the benzotriazole derivatives of the present invention described previously (or mixtures thereof in any proportion) or a benzotriazole derivative produced according to the method of producing the benzotriazole derivatives described previously of the present invention.

According to the present invention, in order to manufacture the anti-wear agent, the aforementioned diluent or other components conventionally used in the art for manufacturing anti-wear agents may be further added to the benzotriazole derivative. In this case, the diluents may be used alone or in combination of two or more. Of course, if the benzotriazole derivatives of the present invention already contain a certain amount of the diluent after the preparation as described above, then the amount of the diluent added can be correspondingly reduced, and even used as an anti-wear agent without further addition of the diluent, as will be apparent to those skilled in the art.

Generally, in the anti-wear agent of the present invention, the benzotriazole derivative accounts for 5% to 100%, preferably 30% to 90%, by mass of the total mass of the anti-wear agent.

According to the present invention, in order to manufacture the anti-wear agent, for example, the benzotriazole derivative, the diluent, and the other components (if used) may be mixed at 20 ℃ to 60 ℃ for 1h to 6h, without particular limitation.

Since the diluent used in the foregoing description of the present invention is also often used as a lubricant base oil in the art in practice, it is directly classified as a lubricant base oil in the following description and is not described as a separate component.

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

The performance evaluation in examples and comparative examples was carried out as follows.

The dropping point is determined by a GB/T3498 method;

the cone penetration is measured by a GB/T269 method;

the oxidation stability is measured by SH/T0325 method;

the method for measuring the oil separation of the steel mesh adopts an SH/T0324 method;

the GB/T5018 method is adopted for measuring the corrosion resistance;

the SH/T0109 method is adopted for measuring the water leaching loss;

test for four-ball machine_B、P_DAdopting an SH/T0202 method;

the GB/T7326 method is adopted for measuring the corrosion performance of the copper sheet;

the SH/T0204 method is adopted for measuring the antiwear property.

TABLE 1 sources of raw materials

Name of raw materials	Manufacturer of the product
		500SN base oil	Yanshan petrochemical
150BS base oil	Shuanglong Co Ltd
		PAO6 synthetic hydrocarbon oil	Mobil Corp.
500SN base oil	Mobil Corp.
		12-Hydroxystearic acid	Zhengzhou Jinbang chemical Co., Ltd
Adipic acid	Henan sublimation chemical products Co., Ltd
		Terephthalic acid (TPA)	Dongying Wei Ain chemical Co Ltd
Stearic acid	Suzhou Yuan Tairun chemical Co., Ltd
		Sebacic acid	Henan sublimation chemical industryProducts Co Ltd
Azelaic acid	Henan sublimation chemical products Co., Ltd
		Lithium hydroxide	Zhengzhou bannuo chemical products Co Ltd
N-phenyl-alpha-naphthylamines	Jinjinle chemical Co, Zhejiang Ltd
		Diphenylamine	Henan Mingxuan chemical products Co Ltd
Diisooctyl diphenylamine	Zhejiang Jinjinle chemical Co Ltd
		Beta-naphthylamine	Zhejiang Jinjinle chemical Co Ltd

Example 1

Under the protection of nitrogen, 34.47 g (90mmol) of N-hydrogenated tallow dipropylene triamine, 13.5 g (450mmol) of paraformaldehyde, 10.16 g (85mmol) of benzotriazole and 100mL of toluene were added to a 500mL four-necked flask equipped with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 100 ℃, and 48.4 g (200mmol) of di-N-butyl dithiophosphoric acid was added dropwise and reacted for 6 hours at constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-1.

Product characterization data are as follows:

1H NMR(300MHz，CDCl3)：δ0.88(3H)，1.03(12H)，1.06-1.91(53H)，2.34-3.46(10H)，3.54-4.57(12H)，5.23-6.11(2H)，7.19-8.08(4H)；

C₄₉H₉₆N₆O₄P₂S₄calcd for C57.50, H9.45, N8.21, O6.25, P6.05, S12.53; measurement value: c57.42, H9.43, N8.16, O6.35, P6.10, S12.54.

Preparing the lithium complex grease:

the raw material components are as follows: 32kg of benzotriazole derivative (M-1); 1432kg of 500SN base oil (viscosity at 100 ℃ C. is 10 mm)²S); 32.78kg of lithium hydroxide monohydrate; 75.9kg of 12-hydroxystearic acid; 47.54kg of azelaic acid; 8kg of diphenylamine;

adding 720kg of base oil, 75.9kg of 12-hydroxystearic acid and 47.54kg of azelaic acid into a grease making kettle, heating and stirring, heating to 85 ℃, adding a lithium hydroxide aqueous solution (containing 32.78kg of lithium hydroxide and 262.24kg of water) to carry out saponification for 0.5h, heating to 190 ℃, and carrying out high-temperature refining for 5 min; adding 712kg of base oil, cooling to 100 ℃, adding 8kg of diphenylamine and 32kg of benzotriazole derivative (M-1), and uniformly stirring; the fat is formed by grinding 2 times by means of a three-roll mill, marked as Z-1.

According to the amount of the charged grease, the grease prepared in this example has the following composition based on the weight of the grease: 4.8 wt% lithium 12-hydroxystearate; lithium azelaic acid, 3.2 wt%; lubricating base oil, 89.5 wt%; diphenylamine, 0.5 wt%; benzotriazole derivative (M-1), 2% by weight.

Example 2

Under the protection of nitrogen, 34.47 g (90mmol) of N-hydrogenated tallow dipropylene triamine, 13.5 g (450mmol) of paraformaldehyde, 17.93 g (150mmol) of benzotriazole and 120mL of toluene were added to a 500mL four-necked flask equipped with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 100 ℃, and 24.2 g (100mmol) of di-N-butyl dithiophosphoric acid was added dropwise and reacted for 8 hours at a constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-2.

Product characterization data are as follows:

1H NMR(300MHz，CDCl3)：δ0.88(3H)，1.03-1.95(51H)，2.45-3.30(9H)，3.54-4.32(7H)，5.58-6.20(4H)，7.19-8.08(8H)；

C₄₇H₈₂N₉O₂PS₂calcd for C62.70, H9.18, N14.00, O3.55, P3.44, S7.12; measurement value: c62.81, H9.22, N13.85, O3.56, P3.41, S7.15.

Preparing the lithium complex grease:

the raw material components are as follows: 1020kg of 150BS base oil (viscosity of 30mm at 100℃)²S); 28.52kg of lithium hydroxide monohydrate; 133.98kg of stearic acid; 15.64kg of terephthalic acid; 12kg of diisooctyl diphenylamine; 14.4kg of a benzotriazole derivative (M-2);

adding 774kg of base oil, 133.98kg of stearic acid and 15.64kg of terephthalic acid into a grease making kettle, heating and stirring, heating to 95 ℃, adding a lithium hydroxide aqueous solution (containing 28.52kg of lithium hydroxide and 171.12kg of water) to perform a saponification reaction for 0.8h, heating to 210 ℃, and performing high-temperature refining for 5 min; adding 246kg of base oil, cooling to 120 ℃, adding 12kg of diisooctyl diphenylamine and 14.4kg of benzotriazole derivative (M-2), and uniformly stirring; the fat is formed by grinding 2-3 times by a three-roll mill, and is marked as Z-2.

According to the amount of the charged grease, the grease prepared in this example has the following composition based on the weight of the grease: lithium stearate, 11.4 wt%; 1.4% by weight of lithium terephthalate; lubricating base oil, 85 wt%; 1% by weight of diisooctyldiphenylamine; benzotriazole derivative (M-2), 1.2% by weight.

Example 3

Under the protection of nitrogen, 34.47 g (90mmol) of N-hydrogenated tallow dipropylene triamine, 13.5 g (450mmol) of paraformaldehyde, 10.16 g (85mmol) of benzotriazole and 100mL of toluene were added into a 500mL four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 100 ℃, and 48.4 g (200mmol) of di-N-butyl dithiophosphoric acid was added dropwise and reacted for 6 hours at constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-3.

Product characterization data are as follows:

1H NMR(300MHz，CDCl3)：δ0.88(3H)，1.03(12H)，1.06-1.91(53H)，2.34-3.46(10H)，3.54-4.28(12H)，5.23-5.77(2H)，7.19-8.08(4H)；

C₄₉H₉₆N₆O₄P₂S₄calcd for C57.50, H9.45, N8.21, O6.25, P6.05, S12.53; measurement value: c57.62, H9.49, N8.13, O6.22, P6.09, S12.45.

Preparing the lithium complex grease:

the raw material components are as follows: 948kg (viscosity at 100 ℃ C. of 5.8 mm) of PAO6 synthetic hydrocarbon oil²S); 56.48kg of lithium hydroxide monohydrate; 148.58kg of stearic acid; 57.18kg of adipic acid; 12kg of beta-naphthylamine; 26.4kg of a benzotriazole derivative (M-3);

firstly, adding 660kg of base oil, 148.58kg of stearic acid and 57.18kg of adipic acid into a grease making kettle, heating and stirring, heating to 88 ℃, adding a lithium hydroxide aqueous solution (containing 56.48kg of lithium hydroxide and 45.19kg of water) to perform a saponification reaction for 0.6h, heating to 195 ℃, and performing high-temperature refining for 8 min; 288kg of base oil is added, the temperature is reduced to 110 ℃, 12kg of beta-naphthylamine and 26.4kg of benzotriazole derivatives (M-3) are added, and the mixture is stirred uniformly; the fat is formed by grinding 3 times by means of a three-roll mill, marked as Z-3.

According to the amount of the charged grease, the grease prepared in this example has the following composition based on the weight of the grease: lithium stearate, 12.64 wt%; lithium adipate, 5.16 wt%; lubricating base oil, 80 wt%; beta-naphthylamine, 1 wt%; benzotriazole derivative (M-3), 2.2% by weight.

Example 4

In a 500ml four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, 133.81 g (410mmol) of octadecylpropylenediamine and 25.8 g (860mmol) of paraformaldehyde, 55.89 g (380mmol) of 5-ethylbenzotriazole and 134.15 g (450mmol) of n-butyl 1-methylheptyl dithiophosphoric acid were added, stirred rapidly, and heated to 110 ℃ for reaction for 4 hours. And (3) after the reaction is finished, carrying out reduced pressure distillation to remove residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and carrying out column chromatography separation to obtain a final product, wherein the label is M-4.

Product characterization data were as follows:

¹H NMR(300MHz，CDCl₃)：δ0.88(6H)，1.03-1.93(57H)，2.43-2.74(8H)，3.46-4.10(4H)，4.24-4.63(2H)，5.31-6.20(2H)，7.19-7.82(3H)；

C₄₃H₈₂N₅O₂PS₂calcd for C64.86, H10.38, N8.80, O4.02, P3.89, S8.05; measurement value: c64.57, H10.05, N7.54, O4.37, P4.42, S9.05.

Preparing the lithium complex grease:

the raw material components are as follows: 1320kg of 500SN and 150BS mixed base oil (viscosity is 13mm at 100℃) ²S); 50.2kg of lithium hydroxide monohydrate; 175.6kg of 12-hydroxystearic acid; 58.68kg of sebacic acid; 32kg of N-phenyl-alpha-naphthylamine; 8kg of a benzotriazole derivative (M-4);

adding 1000kg of base oil, 175.6kg of 12-hydroxystearic acid and 58.68kg of sebacic acid into a grease making kettle, heating and stirring, heating to 92 ℃, adding a lithium hydroxide aqueous solution (wherein the lithium hydroxide aqueous solution contains 50.2kg of lithium hydroxide and 200.8kg of water) to carry out saponification reaction for 1h, heating to 205 ℃, and carrying out high-temperature refining for 8 min; adding 320kg of base oil, cooling to 105 ℃, adding 32kg of N-phenyl-alpha-naphthylamine and 8kg of benzotriazole derivative (M-4), and uniformly stirring; greasing was done by grinding 2 times with a three-roll mill, labeled Z-4.

According to the amount of the charged grease, the grease prepared in this example has the following composition based on the weight of the grease: lithium 12-hydroxystearate, 11.11 wt%; lithium sebacate, 3.89 wt%; lubricating base oil, 84.5 wt%; n-phenyl-alpha-naphthylamine, 2 wt%; benzotriazole derivative (M-4), 0.5% by weight.

Example 5

Under the protection of nitrogen, 25.9 g (130mmol) of tertiary primary amine carbonate, 13.5 g (450mmol) of paraformaldehyde, 21.89 g (125mmol) of 6-butylbenzotriazole and 100mL of toluene are added into a 500mL four-neck flask provided with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 95 ℃, and added with 55.23 g (150mmol) of bis (2-ethylhexyl) dithiophosphoric acid dropwise for 5 hours at constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-5.

Product characterization data are as follows:

¹H NMR(300MHz，CDCl₃)：δ0.89(18H)，1.05-1.93(48H)，2.34-2.50(2H)，3.43-3.72(4H)，4.24-4.72(2H)，5.31-6.20(2H)，7.19-7.82(3H)；

C₄₂H₇₉N₄O₂PS₂calcd for C65.75, H10.38, N7.30, O4.17, P4.04, S8.36; measurement value: c64.50, H10.12, N7.43, O4.32, P4.57, S9.26.

Preparing the lithium complex grease:

the raw material components are as follows: 48kg of benzotriazole derivative (M-5); 1408kg of 500SN base oil (viscosity of 10mm at 100℃)²S); 32.78kg of lithium hydroxide monohydrate; 75.9kg of 12-hydroxystearic acid; 47.54kg of azelaic acid; 16kg of diphenylamine;

firstly, adding 808kg of base oil, 75.9kg of 12-hydroxystearic acid and 47.54kg of azelaic acid into a grease making kettle, heating and stirring, heating to 85 ℃, adding a lithium hydroxide aqueous solution (containing 32.78kg of lithium hydroxide and 262.24kg of water) to carry out saponification reaction for 0.7h, heating to 190 ℃, and carrying out high-temperature refining for 5 min; adding 600kg of base oil, cooling to 100 ℃, adding 48kg of benzotriazole derivative (M-5) and 16kg of diphenylamine, and uniformly stirring; the fat is formed by grinding 2 times by means of a three-roll mill, marked as Z-5.

According to the amount of the charged grease, the grease prepared in this example has the following composition based on the weight of the grease: 4.8 wt% of lithium 12-hydroxystearate; lithium azelaic acid, 3.2 wt%; lubricating base oil, 88 wt%; diphenylamine, 1 wt.%; benzotriazole derivative (M-5), 3% by weight.

Comparative example 1

Preparation of comparative grease:

a lithium complex grease was prepared according to the method of example 4, except that no benzotriazole derivative was added during the preparation. The resulting comparative grease was labeled DZ-1.

Comparative example 2

Under the protection of nitrogen, 35.04 g (130mmol) of octadecylamine, 9 g (300mmol) of paraformaldehyde, 29.78 g (250mmol) of benzotriazole and 100mL of toluene were added into a 250mL four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator, rapidly stirred, heated to 90 ℃ and reacted at constant temperature for 6 hours. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, cooling to room temperature, settling for 24 hours, and filtering to remove impurities to obtain the product, wherein the label is D-1.

Product characterization data were as follows:

¹H NMR(300MHz，CDCl₃)：δ0.88(3H)，1.25-1.51(32H)，3.27(2H)，5.55-6.24(4H)，7.19-8.08(8H)；

C₃₂H₄₉N₇calcd for C72.27, H9.29, N18.44; measurement value: c72.95, H10.32, N16.73.

Preparation of comparative grease:

a comparative grease was prepared as in example 4 except that the benzotriazole derivative used was D-1 and the resulting comparative grease was designated DZ-2.

The composite lithium-based lubricating grease and the comparative lubricating grease prepared in the above way are subjected to performance evaluation of dropping point, penetration degree, oxidation stability, steel mesh oil separation, corrosion resistance, water spray loss, four-ball machine test, copper sheet corrosion performance and wear resistance respectively, and the results are shown in table 2.

From the results in table 2, it can be seen that the lithium complex grease of the present invention has a low friction coefficient, excellent wear resistance, extreme pressure performance, oxidation resistance, corrosion resistance, rust resistance, high temperature resistance, water resistance, adhesion, and colloid stability.

TABLE 2 grease Properties

Claims

1. A complex lithium grease comprises the following components by taking the total weight of the grease as a reference: benzotriazole derivatives, a complex lithium-based thickener, an antioxidant and a main amount of lubricating base oil, wherein the benzotriazole derivatives have a structure shown in a general formula (I):

in the general formula (I), the radical R' is selected from C_1-25Hydrocarbyl radical, C_3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000; n is an integer from 0 to 10; n radicals R₀Are the same or different from each other and are each independently selected from C_1-10A linear or branched alkylene group; n +2 groups A, which may be the same or different from each other, are each independently selected from the group consisting of hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2), C_1-25Hydrocarbyl group and hydrocarbyl group having number average molecular weight Mn of 300-3000With the proviso that at least one of the n +2 groups A is a group represented by formula (I-1) and at least one of the n +2 groups A is a group represented by formula (I-2); when at least one of said groups A is C _10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl or hydrocarbyl having a number average molecular weight Mn of 300-3000, the radical R' may also be hydrogen,

in the general formulae (I-1) and (I-2), the group R₅And R₆Are the same or different from each other and are each independently selected from C_1-20A hydrocarbyl group; the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom; the two radicals R' are identical or different from each other and are each independently selected from hydrogen and C_1-20A hydrocarbyl group; radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C_1-20A hydrocarbon radical, said linear or branched heteroalkyl referring to a radical obtained by interrupting the carbon chain structure of a linear or branched alkyl radical by one or more heteroatomic radicals selected from the group consisting of-O-, -S-and-NR-, wherein the radical R is selected from the group consisting of H and C_1-4Straight or branched chain alkyl.

2. Grease according to claim 1,

in the general formula (I), the radical R' is selected from C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl, C_10-25Straight-chain or branched alkynyl, C_10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000; n is an integer from 0 to 5; n radicals R₀Are the same or different from each other and are each independently selected from C_2-5A linear or branched alkylene group; n +2 groups A, which may be the same or different from each other, are each independently selected from the group consisting of hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2), C _1-6Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25Straight chain orA branched alkenyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000;

in the general formula (I-1) and the general formula (I-2), the group R₅And R₆Are the same or different from each other and are each independently selected from C_1-15A linear or branched alkyl group; both groups X are sulfur atoms and both groups Y are oxygen atoms; the two radicals R' are identical or different from each other and are each independently selected from hydrogen and C_1-20A linear or branched alkyl group; radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C_1-10A linear or branched alkyl group;

the straight or branched heteroalkyl means a group obtained by interrupting the carbon chain structure of a straight or branched alkyl group by 1 to 5 hetero atom groups selected from the group consisting of-O-, -S-, and-NR-.

3. Grease according to claim 1,

in the general formula (I), the radical R' is selected from C_10-25A linear or branched alkyl group; n is 0; n +2 groups A, which are the same or different from each other, are each independently selected from the group consisting of hydrogen, a group represented by the formula (I-1), a group represented by the formula (I-2) and C_1-4A linear or branched alkyl group;

in the general formula (I-1) and the general formula (I-2), the group R₅And R₆Are the same or different from each other and are each independently selected from C_3-12A linear or branched alkyl group; the two radicals R' are identical or different from each other and are each independently selected from hydrogen and C _1-6A linear or branched alkyl group; r is₁And R₄Are all hydrogen, R₂And R₃Is one of C_1-10Straight or branched chain alkyl, the other being hydrogen.

4. Grease according to claim 1, characterized in that in formula (I) the group R' is chosen from C_1-20Hydrocarbyl and C_3-20Straight or branched heteroalkyl.

5. Grease as claimed in claim 1, characterized in that the number average molecular weight Mn is 500-2000.

6. Grease according to claim 1, characterized in that the number average molecular weight Mn is 500-1500.

7. Grease according to claim 1, characterized in that the benzotriazole derivative is selected from the following specific compounds or mixtures of any two or more thereof:

8. the composite lithium-based lubricating grease comprises the following components by taking the total weight of the lubricating grease as a reference: a benzotriazole derivative, a complex lithium-based thickener, an antioxidant, and a major amount of a lubricating base oil, the benzotriazole derivative being produced by a method comprising the step of reacting a phosphorus compound represented by formula (I-A), an amine compound represented by formula (I-B), and a benzotriazole compound represented by formula (I-C) in the presence of an aldehyde represented by formula (I-D),

wherein the radical R' is selected from C_1-25Hydrocarbyl radical, C _3-25A linear or branched heteroalkyl group and a hydrocarbyl group having a number average molecular weight Mn of 300-3000; n is an integer from 0 to 10; n radicals R₀Are the same or different from each other and are each independently selected from C_1-10A linear or branched alkylene group; n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C_1-25A hydrocarbyl group having a number average molecular weight Mn of 300-3000, provided that at least two of said n +2 groups A' represent hydrogen; when at least one of saidThe radical A' is C_10-25Straight or branched alkyl, C_10-25The radical R' may also be hydrogen when it is a linear or branched alkenyl radical or a hydrocarbon radical having a number-average molecular weight Mn of 300-3000; radical R₅And R₆Are the same or different from each other and are each independently selected from C_1-20A hydrocarbyl group; the groups X and Y, equal to or different from each other, are each independently selected from an oxygen atom and a sulfur atom; the radical R' is selected from hydrogen and C_1-20A hydrocarbyl group; radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C_1-20A hydrocarbon radical, said linear or branched heteroalkyl referring to a radical obtained by interrupting the carbon chain structure of a linear or branched alkyl radical by one or more heteroatomic radicals selected from the group consisting of-O-, -S-and-NR-, wherein the radical R is selected from the group consisting of H and C_1-4Straight or branched chain alkyl.

9. Grease according to claim 8,

Wherein the radical R' is selected from C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl, C_10-25Straight-chain or branched alkynyl, C_10-25A linear or branched heteroalkyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000; n is an integer from 0 to 5; n radicals R₀Are the same or different from each other and are each independently selected from C_2-5A linear or branched alkylene group; n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen, C_1-6Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25A linear or branched alkenyl group and a polyisobutenyl group having a number average molecular weight Mn of 300-3000; radical R₅And R₆Are the same or different from each other and are each independently selected from C_1-15A linear or branched alkyl group; both groups X are sulfur atoms and both groups Y are oxygen atoms; the radical R' is selected from hydrogen and C_1-20A linear or branched alkyl group; radical R₁、R₂、R₃、R₄Are the same or different from each other and are each independently selected from hydrogen and C_1-10A linear or branched alkyl group;

the straight or branched heteroalkyl group means a group obtained by interrupting the carbon chain structure of the straight or branched alkyl group with 1 to 5 hetero atom groups selected from the group consisting of-O-, -S-, and-NR-.

10. Grease according to claim 8,

wherein the radical R' is selected from C_10-25A linear or branched alkyl group; n is 0; n +2 radicals A', equal to or different from each other, are each independently selected from hydrogen and C _1-4A linear or branched alkyl group; radical R₅And R₆Are the same or different from each other and are each independently selected from C_3-12A linear or branched alkyl group; the radical R' is selected from hydrogen and C_1-6A linear or branched alkyl group; r₁And R₄Are each hydrogen, R₂And R₃One of them is C_1-10Straight or branched chain alkyl, the other being hydrogen.

11. Grease according to claim 8, characterized in that in formula (I) the group R' is chosen from C_1-20Hydrocarbyl and C_3-20Linear or branched heteroalkyl.

12. Grease according to claim 8, characterized in that the number average molecular weight Mn is 500-2000.

13. Grease according to claim 8, characterized in that the number average molecular weight Mn is 500-1500.

14. The grease of claim 8, wherein the reaction time of the reaction is 0.1 to 24 hours and the reaction temperature of the reaction is 0 to 250 ℃.

15. The grease of claim 8, wherein the reaction time of the reaction is 0.5 to 6 hours and the reaction temperature of the reaction is 60 to 120 ℃.

16. The grease of claim 8, wherein the molar ratio of the phosphorus compound represented by the formula (I-a) to the amine compound represented by the formula (I-B) is 1:0.1 to 10; the molar ratio of the phosphorus compound represented by the formula (I-A) to the benzotriazole compound represented by the formula (I-C) is 1: 0.1-10; the molar ratio of the phosphorus compound represented by the formula (I-A) to the aldehyde represented by the formula (I-D) is 1: 1-10.

17. The grease of claim 8, wherein the molar ratio of the phosphorus compound represented by formula (I-a) to the amine compound represented by formula (I-B) is 1:0.6 to 1.5; the molar ratio of the phosphorus compound represented by the formula (I-A) to the benzotriazole compound represented by the formula (I-C) is 1:0.6 to 1.5; the molar ratio of the phosphorus compound represented by the formula (I-A) to the aldehyde represented by the formula (I-D) is 1: 2-4.

18. Grease according to any of claims 1-17, characterized in that the benzotriazole derivative constitutes from 0.01% to 10% of the total mass of the grease; the composite lithium-based thickening agent accounts for 5-35% of the total mass of the lubricating grease; the antioxidant accounts for 0.1-10% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.

19. Grease according to any of claims 1-17, characterized in that the benzotriazole derivative constitutes from 0.1 to 5% of the total mass of the grease; the composite lithium-based thickening agent accounts for 10-20% of the total mass of the lubricating grease; the antioxidant accounts for 0.5 to 2 percent of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.

20. The grease as claimed in any one of claims 1 to 17 wherein the complex lithium-based thickener is formed by reacting a mixed acid with lithium hydroxide; the antioxidant is selected from one or more of amine antioxidant, phenol antioxidant, ester antioxidant and sulfophenol ester antioxidant; the lubricating base oil is one or more of mineral oil, vegetable oil and synthetic oil.

21. The grease of claim 20, wherein the mixed acid is a mixture of a high molecular acid and a low molecular acid, and the high molecular acid is a C12-C25 fatty acid and/or a hydroxy fatty acid; the low molecular acid is C2-C11 organic acid.

22. A method of preparing a lithium complex grease as defined in any one of claims 1 to 21 comprising: the composite lithium-based thickener and the lubricating base oil as described in one of claims 1 to 21 are mixed uniformly, refined at a constant temperature of 230 ℃ at 180 ℃, cooled, added with the benzotriazole derivative and the antioxidant as described in one of claims 1 to 21, and ground into grease.

23. A method of preparing a grease as set forth in claim 21 comprising: mixing and heating part of base oil, high molecular acid and low molecular acid, heating to 85-95 ℃, adding an aqueous solution of lithium hydroxide for saponification, heating to 190-210 ℃ after the reaction is completed, performing high-temperature refining, adding the rest base oil, cooling to 100-120 ℃, adding the benzotriazole derivative and the antioxidant, and grinding into grease.