CN109679707B

CN109679707B - Gas engine lubricating oil composition and preparation method thereof

Info

Publication number: CN109679707B
Application number: CN201710969220.9A
Authority: CN
Inventors: 苏朔; 孙文斌; 段庆华; 龙军; 武志强; 张倩; 张辉; 成欣
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: CN109679707A

Abstract

The invention provides a gas engine lubricating oil composition and a preparation method thereof. The gas engine lubricating oil composition comprises benzotriazole derivatives, polyisobutylene succinate ester dispersants, boronized succinimide ashless dispersants, calcium sulfonate detergents, naphthylamine type antioxidants, ashless friction modifiers, HSD type viscosity index improvers and lubricating oil base oil. The lubricating oil composition disclosed by the invention is low in ash content, has excellent wear resistance, high-temperature oxidation resistance, dispersibility and corrosion resistance, and can meet the requirements of high-performance gas engine lubricating oil.

Description

Gas engine lubricating oil composition and preparation method thereof

Technical Field

The invention relates to a lubricating oil composition, in particular to a lubricating oil composition for a gas engine.

Background

At present, the pollution of automobile exhaust emission to the environment is increasingly serious, and the development and application of clean energy are trending. Compared with the traditional gasoline and diesel oil, the natural gas used as the automobile fuel is safer to burn, can reduce the CO emission by 97 percent and discharge HCReduction of emission by 72%, reduction of NOx emission by 39%, reduction of SO ₂The emission was reduced by 90%, and a very small amount of emission particulate was generated. Therefore, the gas automobile is considered to be an effective way for solving the problem of automobile emission pollution at present, and the development prospect is bright.

However, natural gas as a fuel for automobile engines also poses many problems: firstly, after natural gas is used as fuel, the temperature of a combustion chamber of an engine is higher than that of fuel oil, and the generation of nitrogen oxides is increased, so that engine oil is required to have higher thermal oxidation stability and dispersion performance; secondly, under the action of high temperature, an oil film of the engine oil becomes thin and unstable, so that a more efficient antiwear agent is needed to prevent the piston and the cylinder from being worn; thirdly, the high-ash engine oil can generate a plurality of extremely hard sediments in a combustion chamber at high temperature, and the sediments are accumulated on a valve to cause the engine to ignite in advance and influence the engine power, so the ash content of the engine oil needs to be strictly controlled; fourthly, the natural gas contains a certain amount of sulfide besides the main component of methane, and the sulfur-containing compounds can form acidic compounds when meeting water in the working process to cause the corrosion and abrasion of the cylinder and the cylinder wall, so that the lubricating oil is required to have good corrosion resistance. In combination with the four problems, the common internal combustion engine oil can not meet the requirements of the gas engine on the lubricating oil, and special gas engine lubricating oil must be developed to provide more excellent high-temperature oxidation resistance, dispersibility, wear resistance and corrosion resistance.

Zinc dialkyldithiophosphate (ZDDP) is an antiwear, antioxidant, and anti-corrosion multifunctional additive and is commonly used in internal combustion engine oils, but phosphorus elements in ZDDP poison the catalyst of three-way catalytic converters and ZDDP readily decomposes to form deposits at the pistons at higher temperatures of gas engines, which makes ZDDP severely limited in gas engine lubricating oils, and it has therefore been a goal of efforts by those skilled in the art to seek more efficient ashless antiwear agents for use in gas engine lubricating oils.

CN 102690709B introduces a gas engine lubricating oil composition, which selects an antioxidant compounded by alkylated diphenylamine, thiophenol ester and thioether phenol, and has better high-temperature oxidation resistance and piston cleaning performance.

Disclosure of Invention

The invention provides a gas engine lubricating oil composition and a preparation method thereof.

Specifically, the present invention relates to the following aspects.

1. A gas engine lubricating oil composition comprises a benzotriazole derivative, a polyisobutylene succinate ester dispersant, a boronized succinimide ashless dispersant, a calcium sulfonate detergent, a naphthylamine antioxidant, an ashless friction modifier, an HSD viscosity index improver and lubricating oil base oil, wherein the structure of the benzotriazole derivative is shown as the 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_3-20Straight or branched heteroalkyl, 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 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 or 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. The gas engine lubricating oil composition according to any one of the preceding aspects, wherein the benzotriazole derivative is selected from the following specific compounds or a mixture of any two or more thereof:

3. a gas engine lubricating oil composition comprising a benzotriazole derivative, a polyisobutylene succinate ester dispersant, a boronated succinimide ashless dispersant, a calcium sulfonate detergent, a naphthylamine type antioxidant, an ashless friction modifier, an HSD type viscosity index improver, and a lubricating oil base oil, said benzotriazole derivative being produced by a process 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 chain 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_10-25When the alkyl is a linear or branched alkenyl or a hydrocarbyl with the number average molecular weight Mn of 300-3000 (preferably 500-2000, more preferably 500-1500), the group R' can also be hydrogen; 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 of each otherSelected 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 gas engine lubricating oil composition according to any preceding aspect, wherein the benzotriazole derivative constitutes from 0.1% to 10% (preferably from 0.5% to 2%) of the total mass of the lubricating oil composition; the succinate dispersant accounts for 1-15% (preferably 1-6%) of the total mass of the lubricating oil composition; the ashless boronized succinimide dispersant accounts for 1-15% (preferably 1-6%) of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 0.2-10% (preferably 1-4%) of the total mass of the lubricating oil composition; the naphthylamine antioxidant accounts for 0.5-10% (preferably 1-4%) of the total mass of the lubricating oil composition; the ashless friction modifier accounts for 0.01-5% (preferably 0.05-2%) of the total mass of the lubricating oil composition; the HSD type viscosity index improver accounts for 3-15% (preferably 5-10%) of the total mass of the lubricating oil composition; the lubricant base oil constitutes the main component of the lubricating oil composition.

7. The gas engine lubricating oil composition according to any one of the preceding aspects, wherein the number average molecular weight of the polyisobutylene moiety in the polyisobutylene succinate dispersant is 500 to 1500; the number average molecular weight of a polyisobutene part in the boronized succinimide ashless dispersant is 1600-2500, and the nitrogen content is 1% -2%; the calcium sulfonate detergent is selected from one or more of low-base-number calcium sulfonate, medium-base-number calcium sulfonate and high-base-number calcium sulfonate; the ashless friction modifier is selected from fatty acid esters and/or fatty amines; the lubricating oil base oil is selected from one or more of API I, II, III, IV and V base oils.

The succinate dispersant may be selected from LZL156 manufactured by Lubrizol additives, Inc., LZ6401 manufactured by Lubrizol Corporation, etc.

The ashless boronated succinimide dispersant may be C-200 manufactured by Mobil Chemical Company, MX 3316 manufactured by Agip Petroli, Hitec 648 manufactured by Ethyl petroleum additives, and the like.

The calcium sulfonate detergent can be low-base-number calcium sulfonate, medium-base-number calcium sulfonate and high-base-number calcium sulfonate. In order to better control the sulfated ash of the oil product, the medium-base-number calcium sulfonate with the base number of (130-200) mgKOH/g is preferably selected. The calcium sulfonate detergent may be T105, T106, T104 from additive factories of Kanzhou petrochemical company, T102, T103, T107B from offshore additive factories, LZ6478, LZ58B, LZ75, LZ6446 from Lubrizol Corporation, C9353, C9330 from Infineum company, etc.

The naphthylamine antioxidant can be Irganox L106 produced by Ciba-Geigy Ltd, T531 produced by Tianjin Pengyi chemical plant, and the like.

The ashless friction modifier may be selected from fatty acid esters and/or fatty amines, such as butyl stearate, butyl oleate, ethylene glycol oleate, hexadecylamine, octadecylammonium benzotriazole, and the like. The ashless friction modifier may be selected from T403A, T403B and T403C manufactured by Trifolium Corp.L. of the refining Co., Ltd, T406A manufactured by Nanjing Ningjiang chemical plant, Base MT and Base ML manufactured by Ferro Corporation, etc.

The HSD type viscosity index improver may be JINEX 9900 manufactured by Jinzhou lubricating oil additives, LZ7441 manufactured by Lubrizol Corporation, SV251, SV260, SV261 manufactured by Infineum, or the like.

The lubricating oil base oil is preferably one or more of hydrogenated base oil, polyolefin synthetic base oil, alkylbenzene base oil and ester synthetic base oil.

8. A method for producing a lubricating oil composition for a gas engine, characterized by mixing each additive in the lubricating oil composition according to any one of the above aspects with a lubricating base oil. The mixing temperature is preferably 40 ℃ to 90 ℃ and the mixing time is preferably 1 hour to 6 hours.

The lubricating oil composition has excellent wear resistance, high-temperature oxidation resistance, dispersibility and corrosion resistance, and can meet the requirements of high-performance gas engine lubricating oil.

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 show significantly improved antiwear properties and extreme pressure properties as compared with prior art lubricating oil additives, 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, exhibits excellent abrasion resistance and, at the same time, further exhibits excellent thermal oxidation stability (thermal stability). This is not the case with the prior art lubricating oil additives.

The benzotriazole derivative according to the present invention, in a preferred embodiment, exhibits excellent anti-wear properties while further exhibiting excellent anti-corrosion properties. This is not the case with the prior art lubricating oil additives.

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. This is not the case with the prior art lubricating oil additives.

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. This is not the case with the prior art lubricating oil additives.

The method for preparing the benzotriazole derivative has the characteristics of simple process, no waste gas discharge, 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 description, anything or things not mentioned apply directly to what is known in the art without any changes, except where explicitly stated. 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_1-4Examples of the straight-chain or branched alkyl 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 alkyl group prior to the interruption is still used to refer to the number of carbon atoms in the linear or branched alkyl group after the interruption The number of carbon atoms of the branched heteroalkyl group.

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 expressly indicated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless otherwise generally recognized by those skilled in the art.

According to the invention, firstly, the benzotriazole derivative is shown as 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_3-20Linear 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 chain orBranched alkyl groups 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 or branched alkenyl. Here, the C is defined as_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), 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 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), 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 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 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 groups A, equal to or different from each other, are each independently selected from hydrogen, a group represented by formula (I-1), a group represented by formula (I-2), 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 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), 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-chain or branched alkenyl. Here, the C is defined as_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 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), 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, for example, when n is 1, in the general formula (I), one of 3 said groups A is a group represented by formula (I-1), one is a group represented by 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 toAccording to the invention, in the general formula (I-1), the group 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, 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), 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, 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 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 the general formula (I-1), the radicalsThe group R' is selected from hydrogen and C_1-6Straight or branched chain alkyl. Here, as the C_1-6Straight-chain or branched alkyl, such as C _1-6More specific examples 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 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 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 bookAccording to the invention, in the general formula (I-2), the radical 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 groups.

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 selected 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 formula (I-B), the radical R' 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 the 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 present 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 present invention, in the general formula (I-B), n is 0, 1, 2 or 3, and a specific example thereof is 0.

According to the invention, in the general formula (I-B), n radicals R₀Are the same or different from each other and are each independentlyIs 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 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-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_10-25Linear 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-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 the formula (I-B), the radical 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) 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.

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), at least two of said n +2 groups A' represent hydrogen. For example, when n is 0, 2 of the groups A' in formula (I-B) 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 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), 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 or branched chain alkyl, such as C_1-6Straight or branched alkyl, more specific examples being C_1-6More specific examples of the straight-chain alkyl group include methyl, n-butyl, isobutyl, and n-hexyl groups.

According to a particular embodiment of the invention, in formula (I-C), R₁、R₃And R₄Are all 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' 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 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 lubricating base oils, more specifically, those having a viscosity of 20 to 120 centistokes (cSt) at 40 ℃ and a viscosity index of at least 50 or moreMore specifically, the mineral lubricant base oil has 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 C₄-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 produced 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, there may be mentioned C_2-10Aliphatic nitriles (e.g. acetonitrile, etc.), C_6-20Aromatic hydrocarbons (e.g. benzene, toluene, xylene and cumene), C_6-10Alkanes (e.g. n-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 dichloromethane, 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 benzotriazole derivatives, 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 with the aforementioned diluent (if used) can be produced. These reaction products are all contemplated by the present invention, and the difference in the form of existence thereof does not affect the achievement of the effects of the present invention. Accordingly, 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 invention are particularly suitable for use in 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 comprise a certain amount of the diluent after being manufactured as described above, then the amount of the diluent added can be correspondingly reduced, and even used directly 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 properties in examples and comparative examples were evaluated as follows.

(1) Evaluation of abrasion resistance

The lubricating oil compositions produced in examples or comparative examples were evaluated for anti-wear properties as test samples according to SH/T0189 standard method. The test conditions of the abrasion resistance test are 392N (40kg) force action, 75 ℃ of oil groove temperature, 1200r/min of top ball rotating speed and 60min of time. The abrasion resistance of the sample was evaluated by the average value of the wear-scar diameters of the following three balls.

(2) Evaluation of copper sheet corrosion inhibition performance

The lubricating oil compositions produced in the examples or comparative examples were subjected to a copper sheet corrosion test as test samples with reference to the ASTM D130 standard method. And immersing the polished copper sheet in the sample, heating to the test temperature of 121 ℃, keeping for 3 hours, taking out the copper sheet after the test is finished, and comparing the copper sheet with a corrosion standard color plate after washing to determine the corrosion grade.

(3) Thermal oxidation stability

The lubricating oil compositions produced in examples or comparative examples were used as test samples, and the thermo-oxidative stability of the test samples was evaluated by a Pressurized Differential Scanning Calorimetry (PDSC) test, and expressed as the oxidation induction period (in min) of the test samples. The PDSC test was carried out at a temperature of 210 ℃ and a pressure of 0.5MPa with an oxygen flow rate of 100 mL/min.

(4) Dispersing Properties

Adding 10g of carbon black into 90g of oil product, stirring and grinding for 2h to prepare carbon black ointment; the lubricating oil compositions prepared in examples or comparative examples were used as test samples, 20g of the test samples were mixed with 1g of carbon black paste, the mixture was stirred at a high speed for 20min, the temperature was raised to 100 ℃, a clean glass rod was taken, the oil sample was dropped onto the center of filter paper, the filter paper was left to stand for 24h, the diameter D of the diffuser and the diameter D of the oil ring were measured, and the dispersion coefficient r (r: D/D) of the test samples was calculated.

Example 1

In a 250ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, 23.01 g (86mmol) of octadecylamine, 20.27 g (250mmol) of a formaldehyde solution, 12.51 g (105mmol) of benzotriazole and 32.79 g (110mmol) of n-butyl 2-ethylhexyl dithiophosphoric acid were charged, rapidly stirred, and heated to 90 ℃ for reaction for 5 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-1.

Product characterization data are as follows:

¹H NMR(300MHz，CDCl₃)：δ0.88(9H)，1.03-1.72(40H)，2.12-3.93(10H)，4.20-4.54(2H)，5.18-6.17(4H)，7.18-8.08(4H)；

C₃₈H₆₉N₄O₂PS₂calcd for C64.37, H9.81, N7.90, O4.51, P4.37, S9.04; measurement value: c64.57, H10.05, N7.54, O4.37, P4.42, S9.05.

Example 2

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-2.

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.

Example 3

Under the protection of nitrogen, 45 g of polyisobutene amine (with the number average molecular weight of about 600), 9 g (300mmol) of paraformaldehyde, 10.16 g (85mmol) of benzotriazole and 150mL 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 100 ℃, added with 24.4 g (100mmol) of di-n-butyl dithiophosphoric acid dropwise and reacted for 5 hours at constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, 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)：δ0.86(9H)，0.97-1.91(86H)，3.46-4.87(6H)，5.23-6.35(2H)，7.19-8.08(4H)；

the element content measured value is: c69.91, H11.23, N5.68, O3.35, P3.22, S6.61.

Example 4

50 g of polyisobutylene amide (number average molecular weight: about 600), 10.8 g (360mmol) of paraformaldehyde, 10.16 g (85mmol) of benzotriazole and 150mL of toluene were added to a 500mL four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, rapidly stirred, heated to 100 ℃ and 53.24 g (220mmol) of di-n-butyl dithiophosphoric acid was added dropwise and reacted for 5 hours at a constant temperature. And after the reaction is finished, distilling under reduced pressure to remove the solvent and residual water, filtering to remove impurities, and separating by column chromatography to obtain a final product, wherein the label is M-4.

Product characterization data were as follows:

¹H NMR(300MHz，CDCl₃)：δ0.86(9H)，0.97-1.75(101H)，2.54-4.03(16H)，4.26-5.93(6H)，7.19-8.08(4H)；

the measured value of the element content is as follows: c63.62, H10.55, N6.32, O4.95, P4.68, S9.88.

Comparative example 1

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.

Comparative example 2

In a 250mL four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, 12.51 g (105mmol) of benzotriazole, 7.5 g (250mmol) of paraformaldehyde, 42.54 g (120mmol) of di-n-octyldithiophosphoric acid and 80mL of toluene were added, rapidly stirred, heated to 95 ℃ and reacted for 4 hours at a constant temperature. 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 D-2.

Product characterization data were as follows:

¹H NMR(300MHz，CDCl₃)：δ0.88(6H)，1.12-1.75(24H)，5.66(2H)，3.59-3.95(4H)，7.18-8.08(4H)；

C₂₃H₄₀N₃O₂PS₂calcd for C56.88, H8.30, N8.65, O6.59, P6.38, S13.20; measurement value: c56.94, H8.35, N8.39, O6.64, P6.43, S13.25.

The sources of additives used in the present invention are as follows: hitec 648 ashless boronated succinimide dispersant, ETHYL Inc

LZL 156, polyisobutylene succinate dispersant, LZL 156, T105, Lubrian additives Limited, Medium-alkali calcium sulfonate, Calif. petrochemical

Irganox L106, naphthylamine antioxidant, Ciba-Geigy Ltd

SV261, HSD viscosity index improver, Infineum Corp

T202, zinc butyl/isooctyl dithiophosphate, tin-free south additive plant

Examples I-1 to I-4 and comparative examples ID-1 to ID-5

Examples I-1 to I-4 and comparative examples ID-1 to ID-4, which were gas engine lubricating oil compositions, were prepared according to the formulation compositions of Table 1. Comparative example ID-5 is a commercial gas engine oil of the same viscosity grade.

TABLE 1

The lubricating oil compositions of the above examples and the lubricating oil composition of the comparative example were evaluated for anti-wear properties, copper sheet corrosion inhibition properties, dispersibility, and thermal oxidation stability, respectively, and the results are shown in Table 2.

TABLE 2

As can be seen from Table 2, the lubricating oil composition of the present invention has excellent antiwear properties, corrosion inhibition properties, dispersancy properties and antioxidant properties.

Claims

1. A gas engine lubricating oil composition comprises a benzotriazole derivative, a polyisobutylene succinate ester dispersant, an ashless boronized succinimide dispersant, a calcium sulfonate detergent, a naphthylamine antioxidant, an ashless friction modifier, an HSD viscosity index improver and lubricating oil base oil, wherein the benzotriazole derivative has 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_1-25A hydrocarbon group and a hydrocarbon group having a number average molecular weight Mn of 300-3000, provided that 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); when at least one of said groups A is C_10-25Straight or branched alkyl, C_10-25Straight-chain or branched alkenyl or hydrocarbon radicals having a number average molecular weight Mn of 300-3000, the radicals R' may also be hydrogen,

in the general formula (I-1) and the general formula (I-2), the group R₅And R₆Are identical to each other orDifferent, 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. The lubricating oil composition 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_10-25A linear or 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 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-.

3. The lubricating oil composition 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; r₁And R₄Are each hydrogen, R₂And R₃One of them is C_1-10Straight or branched chain alkyl, the other being hydrogen.

4. Lubricating oil composition according to claim 1, characterized in that in formula (I), the group R' is selected from C_1-20Hydrocarbyl and C_3-20Linear or branched heteroalkyl.

5. Lubricating oil composition according to claim 1, characterized in that the number average molecular weight Mn is 500-2000.

6. Lubricating oil composition according to claim 1, characterised in that the number average molecular weight Mn is 500-1500.

7. Lubricating oil composition 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. a gas engine lubricating oil composition comprising a benzotriazole derivative, a polyisobutylene succinate ester dispersant, a boronated succinimide ashless dispersant, a calcium sulfonate detergent, a naphthylamine-type antioxidant, an ashless friction modifier, an HSD-type viscosity index improver, and a lubricating oil base oil, the process for producing the benzotriazole derivative 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 radical having a number average molecular weight Mn of 300-3000, with the proviso that at least two of the n +2 radicals A' represent hydrogen; when at least one of said groups 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 identical or different from each other and are each independently selected from hydrogen andC_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. The lubricating oil composition 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 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-.

10. The lubricating oil composition 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 identical or different from each otherAnd 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, R ₂And R₃Is one of C_1-10Straight or branched chain alkyl, the other being hydrogen.

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

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

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

14. The lubricating oil composition according to 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. Lubricating oil composition according to claim 8, wherein the reaction time of the reaction is from 0.5 to 6 hours and the reaction temperature of the reaction is from 60 to 120 ℃.

16. The lubricating oil composition according to 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 lubricating oil composition according to 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 1:0.6 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. Lubricating oil composition according to any one of claims 1 to 17, characterized in that the benzotriazole derivative constitutes from 0.1% to 10% of the total mass of the lubricating oil composition; the polyisobutylene succinate dispersant accounts for 1-15% of the total mass of the lubricating oil composition; the ashless boronized succinimide dispersant accounts for 1-15% of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 0.2-10% of the total mass of the lubricating oil composition; the naphthylamine antioxidant accounts for 0.5-10% of the total mass of the lubricating oil composition; the ashless friction modifier accounts for 0.01-5% of the total mass of the lubricating oil composition; the HSD type viscosity index improver accounts for 3-15% of the total mass of the lubricating oil composition; the lubricant base oil constitutes the main component of the lubricating oil composition.

19. Lubricating oil composition according to any of claims 1 to 17, characterised in that the benzotriazole derivative comprises from 0.5% to 2% by weight of the total lubricating oil composition; the polyisobutylene succinate ester dispersant accounts for 1-6% of the total mass of the lubricating oil composition; the ashless boronized succinimide dispersant accounts for 1-6% of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 1-4% of the total mass of the lubricating oil composition; the naphthylamine antioxidant accounts for 1-4% of the total mass of the lubricating oil composition; the ashless friction modifier accounts for 0.05-2% of the total mass of the lubricating oil composition; the HSD type viscosity index improver accounts for 5-10% of the total mass of the lubricating oil composition; the lubricant base oil constitutes the main component of the lubricating oil composition.

20. The lubricating oil composition as claimed in any one of claims 1 to 17, wherein the number average molecular weight of the polyisobutylene moiety in the polyisobutylene succinate dispersant is 500 to 1500; the number average molecular weight of a polyisobutene part in the ashless boronized succinimide dispersant is 1600-2500, and the nitrogen content is 1-2%; the calcium sulfonate detergent is selected from one or more of low-base-number calcium sulfonate, medium-base-number calcium sulfonate and high-base-number calcium sulfonate; the ashless friction modifier is selected from fatty acid esters and/or fatty amines; the lubricating oil base oil is selected from one or more of API I, II, III, IV and V base oils.

21. A method for preparing a lubricating oil composition as claimed in any one of claims 1 to 20, characterized in that the additives of the lubricating oil composition as claimed in any one of claims 1 to 20 are mixed with a lubricating base oil.