CN109679723B

CN109679723B - Turbine lubricating oil composition and preparation method thereof

Info

Publication number: CN109679723B
Application number: CN201710969500.XA
Authority: CN
Inventors: 苏朔; 段庆华; 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: 2022-05-03
Anticipated expiration: 2037-10-18
Also published as: CN109679723A

Abstract

The invention provides a turbine lubricating oil composition and a preparation method thereof. The turbine lubricating oil composition comprises benzotriazole derivatives, antioxidants, rust inhibitors, anti-emulsifiers and lubricating base oil. The turbine lubricating oil composition disclosed by the invention not only has excellent wear resistance and high-temperature oxidation resistance, but also has excellent extreme pressure performance, corrosion resistance, antirust performance and emulsification resistance.

Description

Turbine lubricating oil composition and preparation method thereof

Technical Field

The invention relates to a lubricating oil composition, in particular to a turbine lubricating oil composition.

Background

The steam turbine is one of main devices in the power generation industry, and the power of the steam turbine is driven by steam, gas, water power and the like. The used turbine lubricating oil is also called turbine oil, generally comprises steam turbine lubricating oil, gas turbine lubricating oil, hydraulic turbine lubricating oil and the like, and is mainly used for lubricating sliding bearings, reduction gears, speed regulators, hydraulic systems and the like of a steam turbine and a phase-linked unit.

Steam turbines, gas turbines and hydro turbines which are widely used at present all require turbine lubricating oil to have high bearing capacity and long service life. The lubricating parts of the steam turbine are mainly a gearbox and a rotor bearing, and because the rotor shaft seal of the steam turbine has steam leakage, the lubricating system has high possibility of water inflow, and the equipment has high rotating speed, large load and long running period, so the requirements on the rust resistance, the emulsification resistance and the oxidation resistance of lubricating oil are high. The gas turbine directly applies work by using gas generated by combustion, and the temperature of the bearing can reach 260 ℃ at most. The gas turbine lubricating oil is acted by the hot surface of the bearing and used under the high pressure of a speed regulating system, and has excellent oxidation stability, thermal stability, good antirust performance and emulsification resistance. For a gear-driven steam turbine, the turbine also has good extreme pressure antiwear bearing capacity so as to meet the lubricating requirements of gear equipment in a system. The turbine lubricating oil used by the steam-gas combined cycle system not only meets the lubricating requirements of a steam turbine, but also meets the lubricating use requirements of a gas turbine, and has excellent high-temperature oxidation resistance and corrosion resistance.

In recent years, as the ratio of the output power to the oil consumption of a steam turbine has been significantly increased, that is, the circulation coefficient has been significantly increased, which causes the working condition of the steam turbine to be more severe and the working temperature to be greatly increased, the steam turbine lubricating oil is required to have excellent performance of stable operation under high temperature conditions, and not only is excellent bearing capacity and wear resistance, outstanding oxidation resistance required, but also good corrosion resistance, rust resistance and emulsification resistance required.

Although the existing antiwear agent has good antiwear property, the extreme pressure property, the thermal oxidation stability, the corrosion resistance and the antiwear durability of the existing antiwear agent are not ideal enough, and the development of turbine lubricating oil is influenced. The search for more effective antiwear additives and the development of new high performance turbine lubricating oils has been a continuing goal of efforts by those skilled in the art.

Chinese patent CN1161970 discloses a method for preparing boronized thiophosphate amine salt by reacting sulfide, phosphite ester, fatty amine, boride and formaldehyde, and the product synthesized by the method can be used as extreme pressure antiwear agent of gear oil. Chinese patent CN102766506 discloses a lubricating oil composition for a full transmission system, which contains a mixture of a di-n-butyl thiophosphoric acid fatty amine formaldehyde condensate, a di-n-butyl thiophosphoric acid benzotriazole formaldehyde condensate and a di-n-butyl thiophosphoric acid fatty amine salt.

The document "Mannich reaction for preparing benzotriazole aliphatic amine derivatives and properties thereof" describes a method for preparing a benzotriazole-formaldehyde-aliphatic amine condensate by using benzotriazole, formaldehyde and aliphatic amine as raw materials to carry out Mannich reaction. The condensation compound shows better corrosion resistance, extreme pressure abrasion resistance and friction reduction performance in base oil, but the preparation process is complex, and strong alkali and strong acid are used, so that a large amount of waste water is generated, and the influence on the environment is larger.

Disclosure of Invention

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

Specifically, the present invention relates to the following aspects.

1. A turbine lubricating oil composition comprises a benzotriazole derivative, an antioxidant, an antirust agent, an anti-emulsifier and lubricating 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 radical having a number average molecular weight Mn of from 300 to 3000 (preferably from 500 to 2000, more preferably from 500 to 1500), or from the group 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 from 300 to 3000 (preferably from 500 to 2000, more preferably from 500 to 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_1-25A hydrocarbon group and a hydrocarbon group having a number average molecular weight Mn of 300 to 3000 (preferably 500 to 2000, more preferably 500 to 1500), and are preferably 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 to 3000 (preferably 500 to 2000, more preferably 500 to 1500)Preferably, each is independently selected from 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, 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_10-25Straight-chain or branched alkenyl or hydrocarbon radicals having a number-average molecular weight Mn of from 300 to 3000, preferably from 500 to 2000, more preferably from 500 to 1500, the radicals 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 referring to the carbon chain structure of the linear or branched alkylIs selected by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) from-O-, -S-and-NR- (wherein the group R is selected from H and C_1-4Straight-chain or branched alkyl, preferably selected from H and methyl).

2. Lubricating oil composition according to any preceding aspect, characterised in that the benzotriazole derivative is selected from the following specific compounds or mixtures of any two or more thereof:

3. a lubricating oil composition for a steam turbine comprising a benzotriazole derivative, an antioxidant, a rust inhibitor, an anti-emulsifier and a lubricating 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 radical having a number average molecular weight Mn of from 300 to 3000 (preferably from 500 to 2000, more preferably from 500 to 1500), or from the group 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_10-25Straight or branched heteroalkyl radicals andpolyisobutenyl having an average molecular weight Mn of from 300 to 3000 (preferably from 500 to 2000, more preferably from 500 to 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_1-25A hydrocarbon group and a hydrocarbon group having a number average molecular weight Mn of 300 to 3000 (preferably 500 to 2000, more preferably 500 to 1500), and preferably each independently selected from hydrogen and C_1-6Straight or branched alkyl, C_10-25Straight or branched alkyl, C_10-25Linear or branched alkenyl radicals and polyisobutenyl radicals having a number average molecular weight Mn of from 300 to 3000 (preferably from 500 to 2000, more preferably from 500 to 1500), each independently of the others, are preferably 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 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 from 300 to 3000 (preferably from 500 to 2000, more preferably from 500 to 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. The turbine lubricating oil composition according to any preceding aspect, wherein the benzotriazole derivative constitutes from 0.001% to 30% (preferably from 0.05% to 20%) of the total mass of the lubricating oil composition; the antioxidant accounts for 0.01-10% (preferably 0.05-5%) of the total mass of the lubricating oil composition; the antirust agent accounts for 0.001-10% (preferably 0.005-5%) of the total mass of the lubricating oil composition; the anti-emulsifier accounts for 0.001-1% (preferably 0.005-0.5%) of the total mass of the lubricating oil composition; the lubricating base oil constitutes the main component of the lubricating oil composition.

7. The turbine lubricating oil composition according to any preceding aspect, wherein the antioxidant is selected from a group consisting of a masked phenol and/or a secondary aromatic amine; the rust inhibitor may be selected from one or more of a sulfonate, an alkyl imidazoline derivative, and an alkenyl succinic acid derivative; the demulsifier may be selected from one or more of a propylene oxide diamine polycondensate, a polyethylene oxide/propylene oxide block polymer, a polyoxyalkylene ether and a polyoxyalkylene fatty acid ester; the lubricating base oil is selected from one or more of API group I, II, III, IV and V lubricating base oils.

The shielding phenol can be one or more selected from shielding monophenol, shielding bisphenol, shielding polyphenol, vulcanized shielding monophenol and vulcanized shielding bisphenol, such as 2, 6-di-tert-butyl-4-methylphenol (antioxidant T501), 2, 6-di-tert-butyl-4-ethylphenol (antioxidant DBEP), 2, 6-di-tert-butyl-4-n-butylphenol (antioxidant 678), 2, 6-di-tert-butyl-alpha-methoxy-p-cresol (antioxidant BHT-MO), 6-di-tert-butyl-alpha-dimethylamino-p-cresol (antioxidant 703), 2 '-methylene-bis (4-methyl-6-tert-butylphenol) (antioxidant 2246), 4' -methylene-bis (2-methyl-6-tert-butylphenol (antioxidant methylene 736), 2,2 '-methylene-bis (4-ethyl-6-tert-butylphenol) (antioxidant 425), 4' -methylene-bis (2, 6-di-tert-butylphenol) (antioxidant T511), 4 '-methylene-bis (2-tert-butylphenol) (antioxidant 702), pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyphenylpropionate) (antioxidant 1010), 4' -thiobis (3-methyl-6-tert-butylphenol) (antioxidant 300), 2 '-thiobis (4-methyl-6-tert-butylphenol) (antioxidant 2246-S), 4' -thiobis (2-methyl-6-tert-butylphenol) (antioxidant 736), 2,2 '-thiobis (4-octylphenol), bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide (antioxidant methylene 4426-S), 2' -thiodiglycol bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1035, T535), and the like.

The secondary aromatic amine may be selected from alkylated diphenylamines, phenylnaphthylamine derivatives and p-phenylenediamine derivatives, for example octyl/butyldiphenylamine (antioxidant L57, T534), 4 '-dioctyldiphenylamine, 4' -diisooctyldiphenylamine (antioxidant Vanlube81), styrenated diphenylamine (antioxidant DFL), 4 '-diheptyldiphenylamine, 4' -dinonyldiphenylamine (antioxidant T536), N-phenyl-alpha-naphthylamine (antioxidant T531, antioxidant A), N-phenyl-beta-naphthylamine (antioxidant D), N-p-methoxyphenyl-alpha-naphthylamine (antioxidant 102), p-hydroxyphenyl-beta-naphthylamine (antioxidant D-OH), isooctylated-phenyl-alpha-naphthylamine (antioxidant L06) may be used, N-phenyl-N ' -cyclohexyl-p-phenylenediamine (antioxidant 4010), N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine (antioxidant 4020), N ' -bis- (1, 4-dimethylpentyl-p-phenylenediamine) (antioxidant 4030), N-p-tolyl-N ' - (1, 3-dimethylbutyl) -p-phenylenediamine (antioxidant 4040), N-isopropyl-N ' -p-methylphenyl-p-phenylenediamine (antioxidant methyl 4010NA), and the like.

The antioxidant is preferably selected from the combination of shielding phenol and secondary arylamine, and the mass ratio of the shielding phenol to the secondary arylamine is 0.01: 1-100: 1, preferably in a ratio of 0.05: 1-20: 1.

the rust inhibitor may be selected from one or more of a sulphonate, a hydrocarbyl imidazoline derivative, and an alkenyl succinic acid derivative. The sulfonate can be one or more selected from petroleum sodium sulfonate, barium petroleum sulfonate, barium alkyl sulfonate and synthetic magnesium sulfonate, for example, T701 of Jiangsu Wuxi Yu refined lubricating oil additive Co., Ltd, T702 of Guangzhou Sendzein chemical industry Co., Ltd, T705 of Shanghai Midcal chemical industry Co., Ltd, T707 of Shanghai Bohai great chemical industry Co., Ltd, and the like can be selected. The alkyl imidazoline derivative may be selected from alkyl imidazoline succinate and/or phosphate imidazoline, such as T703 available from Shanghai Middal chemical Limited. The alkenyl succinic acid derivative may be selected from dodecenyl succinic acid and/or dodecenyl succinic acid ester, for example, T746 and T747 manufactured by Shanghai Midagerde chemical Co., Ltd.

The demulsifier may be one or more selected from the group consisting of a propylene oxide diamine polycondensate, a polyethylene oxide/propylene oxide block polymer, a polyoxyalkylene ether and a polyoxyalkylene fatty acid ester, and for example, T1001 and DL32 manufactured by tokyo diun petrochemical co.

The lubricating base oil can be one or more of API I, II, III, IV and V lubricating base oils, such as one or more selected from mineral lubricating oil and synthetic lubricating oil; the mineral lubricating oil generally has a viscosity index of greater than 80, a saturated hydrocarbon mass fraction of greater than 90%, and a sulfur content mass fraction of less than 0.03%. The lubricating 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 preparing a turbine lubricating oil composition, characterized in that each additive in the lubricating oil composition according to any one of the preceding aspects is mixed 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 turbine lubricating oil composition disclosed by the invention not only has excellent extreme pressure performance and oxidation resistance, but also has excellent wear resistance, corrosion resistance, friction reduction performance and rust prevention performance, and fully meets the requirements of long-life industrial lubricating oil products under extreme pressure.

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 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, cycloalkeneA group, an aryl group, or a combination 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 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 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_3-25Straight-chain or branched heteroalkyl radicals and hydrocarbyl radicals having a number average molecular weight Mn of from 300 to 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_10-25Linear or branched heteroalkyl radicals and polyisobutenyl radicals having a number average molecular weight Mn of from 300 to 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, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, n-heneicosyl, n-tetracosyl, neododecyl, neotridecyl, neotetradecyl, neopentadecyl, neohexadecyl, and neoheptadecylNeooctadecyl, neoeicosyl, neoheneicosyl, neotetracosyl and the like.

According to one embodiment of the invention, in formula (I), 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 general formula (I), the radical R' represents a hydrocarbon radical having a number-average molecular weight Mn of from 300 to 3000. Examples of the hydrocarbon group having a number average molecular weight Mn of 300 to 3000 include 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 to 3000 (particularly, the terminal of the polyolefin molecular chain). Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500 to 2000, more preferably 500 to 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 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 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 hydrocarbyl group having a number average molecular weight Mn of 300 to 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 radicals and polyisobutenyl radicals having a number average molecular weight Mn of from 300 to 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_10-25Straight chain alkylExamples thereof 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 the general formula (I), the radical A represents a hydrocarbon radical having an average molecular weight Mn of from 300 to 3000. Examples of the hydrocarbon group having an average molecular weight Mn of 300 to 3000 include 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 to 3000 (particularly, the terminal of the polyolefin molecular chain). Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500 to 2000, more preferably 500 to 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), andat 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_10-25Straight-chain or branched alkenyl or hydrocarbyl having a number average molecular weight Mn of 300 to 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 when the linear or branched alkenyl radical or the hydrocarbon radical has a number-average molecular weight Mn of from 300 to 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 hydrocarbon group having a number average molecular weight Mn of 300 to 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 independentlySelected 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 formula (I-1), 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-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 invention, in the general formula (I-2), the radical R' is chosen 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 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_3-25Straight-chain or branched heteroalkyl radicals and hydrocarbyl radicals having a number average molecular weight Mn of from 300 to 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_10-25Linear or branched heteroalkyl radicals and polyisobutenyl radicals having a number average molecular weight Mn of from 300 to 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, 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 general formula (I-B), the radical R' represents a hydrocarbon radical having a number-average molecular weight Mn of from 300 to 3000. Examples of the hydrocarbon group having a number average molecular weight Mn of 300 to 3000 include 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 to 3000 (particularly, the terminal of the polyolefin molecular chain). Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500 to 2000, more preferably 500 to 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 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 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 hydrocarbyl group having a number average molecular weight Mn of 300 to 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 radicals and polyisobutenyl radicals having a number average molecular weight Mn of from 300 to 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_10-25Straight-chain alkenyl groups, or there may be mentioned, for example, n-6-dodecenyl, n-6-tridecenyl, n-7-tetradecenyl, n-7-pentadecenyl, n-8-hexadecenylN-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 general formula (I-B), the radical A' represents a hydrocarbon radical having a number-average molecular weight Mn of from 300 to 3000. Examples of the hydrocarbon group having a number average molecular weight Mn of 300 to 3000 include 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 to 3000 (particularly, the terminal of the polyolefin molecular chain). Here, the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500 to 2000, more preferably 500 to 1500.

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 having a number average molecular weight Mn of 300 to 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 when the linear or branched alkenyl radical or the hydrocarbon radical has a number-average molecular weight Mn of from 300 to 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 hydrocarbon group having a number average molecular weight Mn of 300 to 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-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' 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, mineral lubricating 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 lubricating 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 C₄-C₁₀Homopolymerization of alpha-olefins or one or more of the polyolefins obtained by copolymerization of two or more of these olefins, preferably having a viscosity at 100 ℃ of2 to 25 centistokes (cSt), preferably 6 to 10 centistokes (cSt) at 100 ℃, of one or more Polyalphaolefins (PAO). 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 polyolefins is generally from 500 to 3000, preferably from 500 to 2500, most preferably from 500 to 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 polyethers generally have a number average molecular weight Mn of from 500 to 3000, preferably from 700 to 3000, most preferably from 1000 to 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. 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 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. 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 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 aforementioned benzotriazole derivatives of the present invention (or mixtures thereof in any proportion) or a benzotriazole derivative produced according to the aforementioned method for producing a benzotriazole derivative 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.

In general, 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 of the present invention is also often used in the art as a lubricating base oil in fact, it is directly classified as a lubricating base oil in the following description and is not described separately 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 the 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 rotation speed and 60min of time. The abrasion resistance of the sample was evaluated by the average value of the wear-mark diameters of the following three balls.

(2) Evaluation of extreme pressure Properties

The lubricating oil compositions produced in the examples or comparative examples were used as test samples for evaluation of extreme pressure properties according to the GB/T12583 standard method. The test conditions are that the main shaft rotating speed is 1760r/min and the sample temperature is 18-35 ℃. The load was applied in steps according to the standard specifications, a series of 10s tests were performed and the measured diameter of the wear scar was recorded until sintering occurred. Determination of the maximum No-seize load P of the samples_B。

(3) 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.

(4) Evaluation of Rust prevention Performance

The lubricating oil compositions produced in examples or comparative examples were subjected to corrosion resistance tests as test samples according to the GB/T11143 standard method. A300 mL sample was mixed with 30mL distilled water, and the test steel bar was immersed in the mixture and stirred at 60 ℃ for 24 hours, and after the test was completed, the test steel bar was observed for the trace of rust and the degree of rust.

(5) High temperature oxidation resistance

The lubricating oil compositions produced in examples or comparative examples were used as test samples, and the high-temperature oxidation resistance of the test samples was evaluated by a Pressurized Differential Scanning Calorimetry (PDSC) test, as the oxidation induction period (in min) of the test samples. The PDSC test was carried out at a temperature of 180 ℃ and a pressure of 0.5MPa with an oxygen flow rate of 100 mL/min.

(6) Evaluation of anti-emulsification Properties

The lubricating oil compositions of the examples or comparative examples were evaluated for anti-emulsifying properties as test samples according to the test method GB/T7305. The test temperature was 54 ℃ and 40mL of oil was mixed with 40mL of water with stirring and the time to reduce the emulsion layer to 3mL (noted as 40-37-3) was recorded, and the shorter the water separation time, in min, the better the demulsification effect.

Example 1

In a 250ml four-neck flask equipped with a stirrer, a thermometer, a condenser and a water separator under a nitrogen atmosphere, 31.26 g (116mmol) of octadecylamine, 6.36 g (212mmol) of paraformaldehyde, 9.05 g (76mmol) of benzotriazole and 25.41 g (105mmol) of di-n-butyl dithiophosphoric acid were added, stirred rapidly, and the temperature was raised to 100 ℃ for reaction for 3 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 were as follows:

¹H NMR(300MHz，CDCl₃)：δ0.88(3H)，1.03-1.71(46H)，2.61-3.93(6H)，4.22-4.54(2H)，5.20-6.15(2H)，7.18-8.08(4H)；

C₃₄H₆₃N₄O₂PS₂calcd for C62.35, H9.70, N8.55, O4.89, P4.73, S9.79; measurement value: c63.25, H10.0, N8.45, O4.89, P4.41, S9.32.

Example 2

60.10 g (223mmol) of octadecylamine, 18.3 g (610mmol) of paraformaldehyde and 30.60 g (230mmol) of 5-methylbenzotriazole are added into a 500ml four-neck flask provided with a stirrer, a thermometer, a condenser and a water knockout drum under the protection of nitrogen, the mixture is rapidly stirred, the temperature is increased to 85 ℃, 71.31 g (251mmol) of isopropyl 2-ethylhexyl dithiophosphoric acid is added dropwise, and the mixture is reacted for 6 hours at 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 M-2.

Product characterization data were as follows:

¹H NMR(300MHz，CDCl₃)：δ0.88(9H)，1.08-1.71(47H)，2.43-3.93(7H)，4.22-4.54(2H)，4.74(1H)，5.20-6.21(2H)，7.39-7.75(3H)；

C₃₈H₇₁N₄O₂PS₂calcd for C64.18, H10.06, N7.88, O4.50, P4.36, S9.02; measurement value: c63.93, H9.85, N7.75, O4.50, P4.66, S9.31.

Example 3

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-3.

Product characterization data were 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.

Example 4

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-4.

Product characterization data were 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.

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 examples 2 to 4

The compositions of the antiwear agents of comparative examples 2 to 4 are shown in Table 1.

TABLE 1

	Comparative antiwear agent
		Comparative example 2	Dialkyl dithiophosphate-formaldehyde-fatty amine condensates
Comparative example 3	Benzotriazole fatty amine salt
		Comparative example 4	Dialkyldithiophosphoric acid-formaldehyde-fatty amine condensates: benzotriazole fatty amine salt ═ 1:1

The sources of antiwear agents used are as follows:

a dialkyldithiophosphoric acid-formaldehyde-fatty amine condensate using T307 manufactured by jalapa petroleum additives ltd; the benzotriazole fatty amine salt is T406 produced by Shandong Zibo Huihua chemical Co., Ltd.

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

The products obtained in examples, the products obtained in comparative examples, and comparative additives and other kinds of additives were mixed at 40 ℃ for 2 hours according to the formulation composition of Table 2, respectively, to obtain lubricating oil compositions of examples I-1 to I-4 and lubricating oil compositions of comparative examples ID-1 to ID-4.

The sources of the raw materials used are as follows:

antioxidant: sulfurized shielding bisphenol (trade designation T535); diisooctyl diphenylamine (antioxidant Vanlube 81); antirust agent: dodecenylsuccinic acid (trade name T746); and (3) anti-emulsifier agent: a propylene oxide diamine polycondensate (commercial designation T1001); lubricating base oil: polyolefin synthetic base oil PAO-6, II base oil 100N.

TABLE 2

The lubricating oil compositions of the examples and the lubricating oil compositions of the comparative examples were used as test samples, and the wear resistance, extreme pressure properties, copper sheet corrosion inhibition properties, rust prevention properties, high temperature oxidation resistance, and demulsification performance were evaluated, and the results are shown in table 3.

TABLE 3

Claims

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_1-25Alkyl radical and number averageA hydrocarbon group having a molecular weight Mn of 300 to 3000, with the proviso 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_10-25Linear or branched alkenyl or hydrocarbyl having a number average molecular weight Mn of from 300 to 3000, said group R' is optionally also 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_1-20A 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 hetero radicals selected from-O-, -S-and-NR-, wherein the radical R is selected from H and C_1-4Straight or branched chain alkyl.

2. The turbine 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_10-25Linear or branched heteroalkyl groups and polyisobutenyl groups having a number average molecular weight Mn of from 300 to 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 chainOr branched alkyl, C_10-25Linear or branched alkenyl and polyisobutenyl having a number average molecular weight Mn of 300 to 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 groups selected from the group consisting of-O-, -S-, and-NR-.

3. The turbine 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. The turbine lubricating oil composition according to claim 1, wherein in the general formula (I), the group R' is selected from C_1-20Hydrocarbyl and C_3-20Linear or branched heteroalkyl.

5. The turbine lubricating oil composition according to claim 1, wherein the number average molecular weight Mn is 500 to 2000.

6. The turbine lubricating oil composition according to claim 1, wherein the number average molecular weight Mn is 500 to 1500.

7. The turbine lubricating oil composition according to claim 1, wherein the benzotriazole derivative is selected from the following specific compounds or a mixture of any two or more thereof:

8. a lubricating oil composition for a steam turbine comprising a benzotriazole derivative, an antioxidant, a rust inhibitor, an anti-emulsifier and a lubricating 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; n is an integer from 0 to 10; n radicals R₀Are mutually connectedIs the same or different and is respectively and 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 from 300 to 3000, 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 radical R' is optionally also hydrogen when a linear or branched alkenyl radical or a hydrocarbon radical having a number-average molecular weight Mn of from 300 to 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 hetero radicals selected from-O-, -S-and-NR-, wherein the radical R is selected from H and C_1-4Straight or branched chain alkyl.

9. The turbine 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_10-25Linear or branched heteroalkyl groups and polyisobutenyl groups having a number average molecular weight Mn of from 300 to 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_10-25Linear or branched alkenyl and polyisobutenyl having a number average molecular weight Mn of 300 to 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 group R' is selected fromHydrogen 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;

10. The turbine 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 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. The turbine lubricating oil composition according to claim 8, wherein in the general formula (I), the group R' is selected from C_1-20Hydrocarbyl and C_3-20Linear or branched heteroalkyl.

12. The turbine lubricating oil composition according to claim 8, wherein the number average molecular weight Mn is 500 to 2000.

13. The turbine lubricating oil composition according to claim 8, wherein the number average molecular weight Mn is 500 to 1500.

14. The turbine 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. The turbine lubricating oil composition according to 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 steam turbine 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 steam turbine 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. The turbine lubricating oil composition as claimed in any one of claims 1 to 17, wherein the benzotriazole derivative accounts for 0.001% to 30% by mass of the total mass of the turbine lubricating oil composition; the antioxidant accounts for 0.01-10% of the total mass of the turbine lubricating oil composition; the antirust agent accounts for 0.001-10% of the total mass of the turbine lubricating oil composition; the anti-emulsifier accounts for 0.001-1% of the total mass of the turbine lubricating oil composition; the lubricating base oil constitutes the main component of the turbine lubricating oil composition.

19. The turbine lubricating oil composition according to any one of claims 1 to 17, wherein the benzotriazole derivative accounts for 0.05% to 20% by mass of the total mass of the turbine lubricating oil composition; the antioxidant accounts for 0.05 to 5 percent of the total mass of the turbine lubricating oil composition; the antirust agent accounts for 0.005-5% of the total mass of the turbine lubricating oil composition; the anti-emulsifier accounts for 0.005-0.5% of the total mass of the turbine lubricating oil composition; the lubricating base oil constitutes the main component of the turbine lubricating oil composition.

20. Turbine lubricating oil composition according to any one of claims 1 to 17, characterised in that the antioxidant is selected from the group consisting of masked phenols and/or secondary aromatic amines; the antirust agent is selected from one or more of sulfonate, alkyl imidazoline derivatives and alkenyl succinic acid derivatives; the demulsifier is selected from one or more of propylene oxide diamine polycondensates, polyethylene oxide/propylene oxide block polymers, polyoxyalkylene ethers and polyoxyalkylene fatty acid esters; the lubricating base oil is selected from one or more of API group I, II, III, IV and V lubricating base oils.

21. A method for producing a turbine lubricating oil composition as described in any one of claims 1 to 20, characterized by mixing each additive in the turbine lubricating oil composition as described in any one of claims 1 to 20 with a lubricating base oil.