CN109679710A

CN109679710A - Hydraulic fluid compositions and preparation method thereof

Info

Publication number: CN109679710A
Application number: CN201710969241.0A
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: 2019-04-26
Anticipated expiration: 2037-10-18
Also published as: CN109679710B

Abstract

The invention proposes a kind of hydraulic fluid compositions and preparation method thereof.Hydraulic fluid compositions of the invention include benzotriazole derivatives, antioxidant, extreme pressure anti-wear additives, Ashless friction modifiers, ashless dispersant and lubricating base oil.Hydraulic fluid compositions of the invention not only have splendid abrasion resistance, antioxygenic property and detergent-dispersant performance energy, also have excellent corrosion resistance and antifriction performance, sufficiently meet the requirement of the hydraulic oil product of various specifications.

Description

Hydraulic fluid compositions and preparation method thereof

Technical field

The present invention relates to a kind of lubricant oil composite more particularly to a kind of hydraulic fluid compositions.

Background technique

Hydraulic machinery is widely used in the industries such as steel, electric power, coal and machinery.Hydraulic oil is the biography for hydraulic system Dynamic medium, main transmitting, conversion and the control for realizing energy, also plays a part of lubrication, antirust, anti-corrosion and the cooling of system. With the development of modern hydraulic technology, the operating condition of hydraulic system is increasingly harsh, pressure is increasing, operation temperature increasingly It is high.Under the high temperature conditions, hydraulic oil is easier oxidative degradation, generates the products such as acidic materials, greasy filth or paint film, and then lead to oil Product lubricity is deteriorated, and the friction in valve increases, and increases energy consumption, also results in viscous valve, especially precise hydraulic element such as department and takes valve With proportioning valve etc., the operating accuracy of hydraulic device is influenced.It is deteriorated in addition, paint film and greasy filth also result in heat-transfer effect, operates temperature Degree increases, and shortens the service life of the elements such as valve, filter, pump.This is just to the thermal oxidation stability of hydraulic oil, wear resistence and detergency Propose requirements at the higher level.

In order to extend the service life of hydraulic device, delays the oxidation deterioration of oil product, reduce friction, reduce energy consumption, generally It needs largely to add antioxidant and antiwear additive.ZDDP is to be most commonly used for the wear-resistant multipurpose additive of one of hydraulic oil antioxygen, Can not only peroxynitrite decomposition compound, slow down or prevent oil oxidation, also can metal surface generate protective film play the role of it is wear-resistant with Anti- rotten effect.But its shortcomings that is that have corrosion to the system of argentiferous and copper part, and contain zinc, ash content easily generated, tangible lacquering The tendency of the deposits such as film.

Though existing ash-free antiwear agent has good wear resistence, its thermal oxidation stability, corrosion resistance and wear-resistant durable Property is not ideal enough, affects the development of hydraulic oil.Seek more efficiently antiwear additive and develops the hydraulic of novel high-performance Oil is always the target that those skilled in the art make great efforts.

Chinese patent CN1237158 (2006) proposes a kind of by dialkyl dithiophosphoric acid, propylene oxide, acid phosphorous The condensation product that acid dialkyl ester and fatty amine react may be used as lubricating grease multiple function additive.Chinese patent CN1161970 discloses a kind of reacted by sulfide, phosphite ester, fatty amine, boride and formaldehyde and prepares boronation thiophosphoric acid The method of ester amine salt, the product that the method synthesizes may be used as gear oil extreme pressure antiwear additive.Chinese patent CN102766506 It discloses one kind and contains di-n-butyl thiophosphoric acid fat amine formaldehyde condensation product, di-n-butyl thiophosphoric acid benzotriazole formaldehyde condensation The full transmission system lubricant oil composite of object and di-n-butyl thiophosphoric acid fat amine salt mixture.

Document " Mannich reaction prepares benzotriazole aliphatic amine derivative and its performance " elaborate with benzotriazole, formaldehyde and Fatty amine is that raw material carries out Mannich reaction, prepares benzotriazole-formaldehyde-fatty amine condensate method.The condensation product is on basis Preferable corrosion resistance, extreme pressure and antiwear behavior and antifriction performance are shown in oil, but its preparation process is complicated, and use Highly basic and strong acid generate a large amount of waste water, are affected to environment.

Summary of the invention

The invention proposes a kind of hydraulic fluid compositions and preparation method thereof.

Specifically, the present invention relates to the contents of following aspect.

1. a kind of hydraulic fluid compositions, including benzotriazole derivatives, antioxidant, extreme pressure anti-wear additives, Ashless friction improve Agent, ashless dispersant and lubricating base oil, the structure of the benzotriazole derivatives is as shown in logical formula (I):

In logical formula (I), group R' is selected from C_1-25Alkyl, C_3-25Linear chain or branched chain miscellaneous alkyl and number-average molecular weight Mn are The alkyl of 300-3000 (preferably 500-2000, more preferable 500-1500), or it is selected from C_1-20Alkyl and C_3-20Linear chain or branched chain is miscellaneous Alkyl is preferably selected from C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl, C_10-25Linear chain or branched chain alkynyl, C_10-25Directly Chain or branched heteroalkyl groups and number-average molecular weight Mn are the polyisobutene of 300-3000 (preferably 500-2000, more preferable 500-1500) Base, more preferable C_10-25Linear or branched alkyl group；N is selected from the integer of 0-10, is preferably selected from the integer of 0-5, and more preferable 0；N group R₀It is same or different to each other, is separately selected from C_1-10Linear chain or branched chain alkylidene is preferably separately selected from C_2-5Straight chain Or branched alkylidene；N+2 group A is same or different to each other, and is separately selected from group, formula representated by hydrogen, formula (I-1) (I-2) group, C representated by_1-25Alkyl and number-average molecular weight Mn are 300-3000 (preferably 500-2000, more preferable 500- 1500) alkyl is preferably separately selected from group representated by hydrogen, formula (I-1), group, C representated by formula (I-2)_1-6 Linear or branched alkyl group, C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl and number-average molecular weight Mn are 300-3000 The polyisobutenyl of (preferably 500-2000, more preferable 500-1500), it is preferably separately representative selected from hydrogen, formula (I-1) Group, group and C representated by formula (I-2)_1-4Linear or branched alkyl group is preferably separately selected from hydrogen, formula (I-1) institute Group representated by the group and formula (I-2) of representative, on condition that at least one of described n+2 group A is formula (I-1) institute's generation The group of table, and at least one of described n+2 group A is group representated by formula (I-2)；When at least one base Group A is C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl or number-average molecular weight Mn are 300-3000 (preferably 500- 2000, more preferable 500-1500) alkyl when, the group R' can also be hydrogen,

In general formula (I-1) and general formula (I-2), group R₅And R₆It is same or different to each other, is separately selected from C_1-20Hydrocarbon Base (especially C_1-20Linear or branched alkyl group), preferably separately it is selected from C_1-15Linear or branched alkyl group, it is more preferably only respectively On the spot it is selected from C_3-12Linear or branched alkyl group；Group X and Y are same or different to each other, separately former selected from oxygen atom and sulphur Son, preferably two group X are sulphur atom, and two group Y are oxygen atom；Two group R " are same or different to each other, respectively Independently selected from hydrogen and C_1-20Alkyl is preferably separately selected from hydrogen and C_1-20Linear or branched alkyl group, more preferably independently Ground is selected from hydrogen and C_1-6Linear or branched alkyl group is more preferably hydrogen；Group R₁、R₂、R₃、R₄It is same or different to each other, it is only respectively On the spot it is selected from hydrogen and C_1-20Alkyl is preferably separately selected from hydrogen and C_1-10Linear or branched alkyl group, more preferable R₁And R₄It is Hydrogen, R₂And R₃In one be C_1-10Linear or branched alkyl group (preferably C_1-6Linear or branched alkyl group), another is hydrogen, described straight Chain or branched heteroalkyl groups refer to the carbon-chain structure of linear or branched alkyl group by one or more (such as 1 to 5,1 to 4,1 To 3,1 to 2 or 1) selected from-O- ,-S- and-NR-, (wherein, group R is selected from H and C_1-4Linear or branched alkyl group, preferably Selected from H and methyl) miscellaneous group interrupt and obtain group.

2. according to hydraulic fluid compositions described in any preceding aspect, which is characterized in that the benzotriazole derivatives choosing From particular compound below or its any two or more of mixture:

3. a kind of hydraulic fluid compositions, including benzotriazole derivatives, antioxidant, extreme pressure anti-wear additives, Ashless friction improve Agent, ashless dispersant and lubricating base oil, the manufacturing method of the benzotriazole derivatives include phosphorus representated by formula (I-A) Benzotriazole cpd representated by amine compounds representated by compound, formula (I-B) and formula (I-C) is representative in formula (I-D) Aldehyde in the presence of the step of reacting,

Wherein, group R' is selected from C_1-25Alkyl, C_3-25Linear chain or branched chain miscellaneous alkyl and number-average molecular weight Mn are 300-3000 The alkyl of (preferably 500-2000, more preferable 500-1500), or it is selected from C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl, it is excellent Choosing is selected from C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl, C_10-25Linear chain or branched chain alkynyl, C_10-25Straight chain or branch Chain miscellaneous alkyl and number-average molecular weight Mn are the polyisobutenyl of 300-3000 (preferably 500-2000, more preferable 500-1500), more It is preferred that C_10-25Linear or branched alkyl group；N is selected from the integer of 0-10, is preferably selected from the integer of 0-5, and more preferable 0；N group R₀That This is identical or different, is separately selected from C_1-10Linear chain or branched chain alkylidene is preferably separately selected from C_2-5Straight chain or branch Chain alkylidene；N+2 group A' is same or different to each other, and is separately selected from hydrogen, C_1-25Alkyl and number-average molecular weight Mn are The alkyl of 300-3000 (preferably 500-2000, more preferable 500-1500) is preferably separately selected from hydrogen, C_1-6Straight chain or branch Alkyl group, C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl and number-average molecular weight Mn be 300-3000 (preferably 500-2000, more preferable 500-1500) polyisobutenyl, preferably separately be selected from hydrogen and C_1-4Linear or branched alkyl group, On condition that at least two in the n+2 group A' represent hydrogen；When at least one described group A' is C_10-25Linear chain or branched chain Alkyl, C_10-25Linear chain or branched chain alkenyl or number-average molecular weight Mn are 300-3000 (preferably 500-2000, more preferable 500-1500) Alkyl when, the group R' can also be hydrogen；Group R₅And R₆It is same or different to each other, is separately selected from C_1-20Alkyl (especially C_1-20Linear or branched alkyl group), preferably separately it is selected from C_1-15Linear or branched alkyl group, more preferably independently Ground is selected from C_3-12Linear or branched alkyl group；Group X and Y are same or different to each other, and are separately selected from oxygen atom and sulphur atom, It is preferred that two group X are sulphur atom, two group Y are oxygen atom；Group R " is selected from hydrogen and C_1-20Alkyl is preferably selected from hydrogen And C_1-20Linear or branched alkyl group is more preferably selected from hydrogen and C_1-6Linear or branched alkyl group, more preferable hydrogen；Group R₁、R₂、R₃、R₄That This is identical or different, is separately selected from hydrogen and C_1-20Alkyl is preferably separately selected from hydrogen and C_1-10Linear chain or branched chain alkane Base, more preferable R₁And R₄It is hydrogen, R₂And R₃In one be C_1-10Linear or branched alkyl group (preferably C_1-6Linear chain or branched chain alkane Base), another is hydrogen, and the linear chain or branched chain miscellaneous alkyl refers to that the carbon-chain structure of linear or branched alkyl group is one or more (such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1) be selected from-O- ,-S- and-NR- (wherein, group R be selected from H and C_1-4Linear or branched alkyl group is preferably selected from H and methyl) miscellaneous group interrupt and obtain group.

4. according to manufacturing method described in any preceding aspect, wherein the reaction time of the reaction is 0.1-24h, preferably 0.5-6h, the reaction temperature of the reaction are 0-250 DEG C, preferably 60-120 DEG C.

5. according to manufacturing method described in any preceding aspect, wherein phosphorus compound representated by the formula (I-A) and institute The molar ratio for stating amine compounds representated by formula (I-B) is 1:0.1-10, preferably 1:0.6-1.5；Representated by the formula (I-A) The molar ratio of phosphorus compound and benzotriazole cpd representated by the formula (I-C) is 1:0.1-10, preferably 1:0.6-1.5； The molar ratio of phosphorus compound representated by the formula (I-A) and aldehyde representated by the formula (I-D) is 1:1-10, preferably 1:2-4.

6. the benzotriazole derivatives account for lubricant oil composite according to hydraulic fluid compositions described in any preceding aspect The 0.001%-30% (preferably 0.05%-20%) of gross mass；The antioxidant accounts for the 0.01%- of lubricant oil composite gross mass 10% (preferably 0.05%-5%)；The extreme pressure anti-wear additives account for the 0.01%-10% of lubricant oil composite gross mass (preferably 0.05%-8%)；The Ashless friction modifiers account for 0.01%-5% (the preferably 0.02%- of lubricant oil composite gross mass 4%)；The ashless dispersant accounts for the 0.01%-10% (preferably 0.1%-5%) of lubricant oil composite gross mass；The lubrication The main component of base oil composition lubricant oil composite.

7. the antioxidant is selected from shielding phenol and/or second level virtue according to hydraulic fluid compositions described in any preceding aspect Amine；The extreme pressure anti-wear additives are selected from phosphate derivative；The Ashless friction modifiers be selected from aliphatic acid, fatty acid amide, One of polyol esters of fatty acids and aliphatic amine are a variety of；The ashless dispersant is selected from polyisobutene succinimide； The lubricating base oil is selected from one of API I, II, III, IV and V class lubricating base oil or a variety of.

The shielding phenol can be double selected from shielding single phenol, shielding bis-phenol, shielding polyphenol, vulcanization shielding single phenol and vulcanization shielding One of phenol is a variety of, for example can select 2,6- di-tert-butyl-4-methy phenol (antioxidant T501), the tertiary fourth of 2,6- bis- Base -4- ethyl -phenol (antioxidant DBEP), 2,6- di-t-butyl -4- normal-butyl phenol (antioxidant 678), 2,6- di-t-butyl - α-methoxyl group-paracresol (antioxidant BHT-MO), 6- di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (antioxidant 703), 2,2'- are sub- Methyl-bis- (4- methyl-6-tert-butylphenol) (antioxidant 2246s), 4,4'- methylene-bis- (2- methyl-6-tert-butylphenol (antioxidant methene 736), 2,2'- methylene-bis- (4- ethyl -6- tert-butyl phenol) (antioxidant 425), 4,4'- methylene-bis- (2,6 di t butyl phenol) (antioxidant T511), 4,4'- methylene-bis- (2-TBP) (antioxidant 702), four (3, 5- di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester (antioxidant 1010), 4,4'- thiobis (3- methyl-6-tert butyl Phenol) (antioxidant 300), 2,2'- thiobis (4- methyl-6-tert-butylphenol) (antioxidant 2246-S), 4,4'- thiobis (2- methyl-6-tert-butylphenol) (antioxidant 736), 2,2'- thiobis (4- octyl phenol), bis- (3,5- di-t-butyl -4- hydroxyls Base benzyl) thioether (antioxidant methene 4426-S), the bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) of 2,2'- sulfurous ethyl glycol Propionic ester] (antioxidant 1035, T535) etc..

The secondary aromatic amine can be selected from alkylated diphenylamine, nonox derivative and p-phenylene diamine derivative, such as Octyl/butyl diphenylamines (antioxidant L57, T534), 4,4'- dioctyl diphenylamine, 4,4' diisooctyl diphenylamine can be selected (antioxidant Vanlube 81), styrenated diphenylamine (antioxidant D FL), 4,4'- diheptyl diphenylamines, 4,4'- dinonyl two Aniline (antioxidant T536), N- phenyl-α-naphthylamine (antioxidant T531, antioxidant A), N- phenyl-β-naphthylamine (antioxidant d), N- p-methoxyphenyl-alpha-naphthylamine (anti-aging agent 102), p-hydroxyphenyl-beta-naphthylamine (antioxidant D-OH), iso-octyl-phenyl-α- Naphthylamines (antioxidant L06), N- phenyl-N'- cyclohexyl-p-phenylenediamine (antioxidant 4010), N- (1,3- dimethylbutyl)-N'- Phenyl-pphenylenediamine's (antioxidant 4020), N, N'- is bis--(1,4- dimethyl amyl group-p-phenylenediamine) (anti-aging agent 4030), N- pairs Tolyl-N'- (1,3- dimethylbutyl)-p-phenylenediamine (anti-aging agent 4040), N- isopropyl-N'- p-methylphenyl-are to benzene two Amine (anti-aging agent methyl 4010NA) etc..

The antioxidant is preferably selected from the combination of shielding phenol and secondary aromatic amine, and the mass ratio in the combination between the two is 0.01:1-100:1, is preferably in a proportion of 0.05:1-20:1, and more preferable ratio is 0.1:1-10:1.

The phosphate derivative can selected from di-n-butyl phosphite, phosphorous acid di-n-octyl, phosphorous acid diisobutyl ester, One of phosphorous acid di-isooctyl, tricresyl phosphate and phosphate amine salt are a variety of, such as can select Shandong Zibo favour Di-n-butyl phosphite T304, the tricresyl phosphate T306 etc. of magnificent Chemical Co., Ltd.'s production.

The Ashless friction modifiers can be selected from aliphatic acid, fatty acid amide, polyol esters of fatty acids and aliphatic One of amine is a variety of, wherein aliphatic alkyl is saturation or unsaturated alkyl of the carbon atom number between 6-60, preferably Saturation or unsaturated alkyl of the carbon atom number between 10-50.The aliphatic acid includes linolenic acid, linoleic acid, oleic acid, Pork and beans Cool acid, ricinoleic acid, palmitinic acid, cocinic acid, lauric acid and stearic acid etc..The example of the aliphatic amide includes oleic acid acyl Amine, coconut oleoyl amine, palmitamide, oleic acid diethyl amide etc..The polyol esters of fatty acids includes fatty glyceride, rouge Fat acid pentaerythritol ester, ethylene glycol fatty acid, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, Monoesters, dibasic acid esters or the polyester of the compounds such as fatty acid triethanolamine ester, such as glyceryl monooleate, oleic acid diglyceride, single tristearin Sour pentaerythritol ester, lauric acid/dodecanoic acid diethylene glycol dilaurate, glyceryl monooleate, Masine 35-1, glycerin monostearate, Dan Yue Cinnamic acid glyceride, monopalmitin, oleic acid diethanol amine, triethanolamine oleate etc.；The aliphatic amine includes that alkyl takes Replace monoamine or polyamine and alkyl ether amine etc. for monoamine or polyamine, alkoxylated alkyl, such as lauryl amine, 18 The butter fat ether amines of amine, the tallow amine of ethoxylation and ethoxylation.

The ashless dispersant can be selected from polyisobutene succinimide.The polyisobutene succinimide can select From monosubstituted polyisobutene succinimide, disubstituted polyisobutene succinimide, polysubstituted polyisobutene succinimide With one of boronation polyisobutene succinimide or a variety of, wherein the number-average molecular weight of the part polyisobutene (PIB) is 800-4000, preferably 900-3000, preferably 1000-2400, for example, can select Suzhou specialty oil factory produce T151, T161, T161A, T161B of the production of Jinzhou Petrochemical Company additive factory, the production of Lu Borun Lan Lian additive Co., Ltd LZLl57, LZ6418, LZ6420 of Lubrizol Corp.'s production, the Hitec646 etc. of Afton Chemical Corp.'s production.

The lubricating base oil can select one of API I, II, III, IV and V class lubricating base oil or a variety of, than It can such as enumerate selected from one of mineral lubricating oil and synthetic lubricant fluid or a variety of；The viscosity index (VI) one of the mineral lubricating oil As be greater than that 80, saturated hydrocarbons mass fraction is greater than 90%, sulfur content mass fraction is less than 0.03%.The lubricating base oil preferably adds One of hydrogen base oil, polyolefin synthetic base oil, alkylbenzene base oil and esters synthetic base oil are a variety of.

8. a kind of preparation method of hydraulic fluid compositions, which is characterized in that by lubricating oil group described in any preceding aspect Close each additive and lubricating base oil mixing in object.Mixing temperature is preferably 40 DEG C -90 DEG C, and incorporation time is preferably 1 hour -6 Hour.

Hydraulic fluid compositions of the invention not only have splendid abrasion resistance, antioxygenic property and detergent-dispersant performance energy, Also there is excellent corrosion resistance and antifriction performance, sufficiently meet the requirement of the hydraulic oil product of various specifications.

Technical effect

Benzotriazole derivatives according to the present invention are free of metallic element, are not likely to produce ash content and deposit, belong to environment Friendly lube oil additive.

Benzotriazole derivatives according to the present invention show and significantly change compared with the lube oil additive of the prior art Kind wear resistance and extreme pressure property can effectively improve the wear resistance and bearing capacity of lubricating oil.

Benzotriazole derivatives according to the present invention are showing excellent abrasion resistance in a preferred embodiment While energy, excellent thermal oxidation stability energy (thermal stability) is also exhibited further.This is that the lubricating oil of the prior art adds Agent is added not to be provided simultaneously with.

Benzotriazole derivatives according to the present invention are showing excellent abrasion resistance in a preferred embodiment While energy, excellent corrosion resistance is also exhibited further.This is that the lube oil additive of the prior art does not have simultaneously Standby.

Benzotriazole derivatives according to the present invention are showing excellent abrasion resistance in a preferred embodiment While energy, excellent rustless property is also exhibited further.This is that the lube oil additive of the prior art is not provided simultaneously with 's.

Benzotriazole derivatives according to the present invention are showing excellent abrasion resistance in a preferred embodiment While energy, excellent antifriction performance is also exhibited further.This is that the lube oil additive of the prior art is not provided simultaneously with 's.

The manufacturing method of benzotriazole derivatives according to the present invention, have simple process, non-exhaust emission, waste water few and The features such as safety and environmental protection.

Specific embodiment

Detailed description of the preferred embodiments below, it should be noted however that protection of the invention Range is not limited to these specific embodiments, and but is determined by the appended claims.

All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference. Unless otherwise defined, all technical and scientific terms used herein all has what those skilled in the art routinely understood to contain Justice.In case of conflict, it is subject to the definition of this specification.

When this specification with prefix " well known to those skilled in the art ", " prior art " or its synonym come derived materials, Whens substance, method, step, device or component etc., object derived from the prefix is covered commonly used in the art when the application proposes Those of, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.

In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in Hold, unless those skilled in the art think that the combination is obvious unreasonable.

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

In the context of the present invention, term " alkyl " has conventionally known in the art meaning, including linear chain or branched chain Alkyl, linear chain or branched chain alkenyl, linear chain or branched chain alkynyl, naphthenic base, cycloalkenyl, aryl or combinations thereof group.As the hydrocarbon Base, preferably linear or branched alkyl group, linear chain or branched chain alkenyl, aryl or combinations thereof group.As the alkyl, specifically such as may be used To enumerate C_1-30Alkyl more specifically can such as enumerate C_1-30Linear or branched alkyl group, C_2-30Linear chain or branched chain alkenyl, C_3-20Ring Alkyl, C_3-20Cycloalkenyl, C_6-20Aryl or combinations thereof group.

In the context of the present specification, as C_1-4Linear or branched alkyl group, for example, can enumerate methyl, ethyl or Propyl etc., and as C_2-4Linear chain or branched chain alkenyl, for example vinyl, allyl or acrylic can be enumerated etc..

In the context of the present invention, term " linear chain or branched chain miscellaneous alkyl " refers to the carbochain knot of linear or branched alkyl group (wherein, structure is selected from-O- ,-S- and-NR- by one or more (such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1) Group R is selected from H and C_1-4Linear or branched alkyl group is preferably selected from H and methyl) miscellaneous group interrupt and obtain group.From structure Stability angle is set out preferably, when there are multiple, not Direct Bonding between miscellaneous group described in any two.Obvious It is that the miscellaneous group is not at the carbochain end of the linear or branched alkyl group or the linear chain or branched chain miscellaneous alkyl.It needs herein Although it should be particularly noted that, it is described interruption sometimes (such as by miscellaneous group-NR- interrupt and R represent C_1-4Linear or branched alkyl group When) it may result in the linear chain or branched chain miscellaneous alkyl from the linear or branched alkyl group with different total carbon atom numbers, but For the sake of in order to express easily, institute after still referring to the interruption with the carbon atom number of the interruption foregoing description linear or branched alkyl group State the carbon atom number of linear chain or branched chain miscellaneous alkyl.

In the context of the present specification, in case of no particular description, number-average molecular weight Mn is by gel infiltration Chromatography (GPC) measurement.

In the context of the present specification, in case of no particular description, any gel permeation chromatography being related to (GPC) or the determination condition of GPC spectrogram is equal are as follows: instrument uses 2695 type gel permeation chromatography of Waters, US waters Analyzer, mobile phase use tetrahydrofuran, flow velocity 1mL/min, and chromatogram column temperature is 35 DEG C, delivery time 40min, sample matter Amount score is 0.16-0.20%.

Finally, in the case where not clearly indicating, all percentages, number, ratio for being previously mentioned in this specification etc. It is all on the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.

According to the present invention, a kind of benzotriazole derivatives are first related to, structure is as shown in logical formula (I).

According to the present invention, in logical formula (I), group R' is selected from C_1-25Alkyl, C_3-25Linear chain or branched chain miscellaneous alkyl sum number is divided equally The alkyl that son amount Mn is 300-3000.

A special embodiment according to the present invention, in logical formula (I), group R' is selected from C_1-20Alkyl and C_3-20Straight chain Or branched heteroalkyl groups.

A special embodiment according to the present invention, in logical formula (I), group R' is selected from C_10-25Linear chain or branched chain alkane Base, C_10-25Linear chain or branched chain alkenyl, C_10-25Linear chain or branched chain alkynyl, C_10-25Linear chain or branched chain miscellaneous alkyl and number-average molecular weight Mn For the polyisobutenyl of 300-3000.

According to embodiment of the present invention, in logical formula (I), group R' represents C_10-25Linear or branched alkyl group.? This, as the C_10-25Linear or branched alkyl group, for example C can be enumerated_10-25Straight chained alkyl, or can such as enumerate positive ten Dialkyl group, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, positive two Ten alkyl, Heneicosane base, n-tetracosane base, new dodecyl, new tridecyl, new myristyl, new pentadecyl, New cetyl, new heptadecyl, new octadecyl, new eicosyl, new heneicosyl, new tetracosyl etc..

According to embodiment of the present invention, in logical formula (I), group R' represents C_10-25Linear chain or branched chain alkenyl.? This, as the C_10-25Linear chain or branched chain alkenyl, for example C can be enumerated_10-25Straight-chain alkenyl, or can such as enumerate positive 6- Laurylene base, positive 6- tridecylene base, positive 7- tetradecene base, 15 alkenyl of positive 7-, positive 8- hexadecylene base, 17 alkenyl of positive 8-, just 9- octadecylene base, positive 9- icosa alkene base, bis- hendecene base of positive 10-, bis- tetradecene base of positive 12-, new 6- laurylene base, new 6- 13 Alkenyl, new 7- tetradecene base, 15 alkenyl of new 7-, new 8- hexadecylene base, 17 alkenyl of new 8-, new 9- octadecylene base, new 9- bis- Ten alkenyls, bis- hendecene base of new 10-, bis- tetradecene base of new 12- etc..

A special embodiment according to the present invention, in logical formula (I), group R' represents number-average molecular weight Mn as 300- 3000 alkyl.Here, the alkyl for being 300-3000 as the number-average molecular weight Mn, for example can enumerate from number-average molecular weight Mn is that the polyolefin (the especially end of the molecular polyolefin chain) of 300-3000 removes the alkyl (title obtained after a hydrogen atom For polyene hydrocarbon residue).Here, as the polyolefin or the number-average molecular weight Mn of the polyene hydrocarbon residue, preferably 500-2000, More preferable 500-1500.As the polyolefin, for example can enumerate through ethylene, propylene or C₄-C₁₀Alpha-olefin (such as positive fourth Alkene, isobutene, n-pentene, n-hexylene, positive octene or positive decene) homopolymerization or pass through two or more in these alkene Copolymerization obtained from polyolefin, wherein more preferable polyisobutene (PIB).

According to the present invention, in logical formula (I), n is selected from the integer of 0-10.

A special embodiment according to the present invention, in logical formula (I), n is selected from the integer of 0-5.

A special embodiment according to the present invention, in logical formula (I), n is 0,1,2 or 3, specifically can such as be enumerated 0。

According to the present invention, in logical formula (I), n group R₀It is same or different to each other, is separately selected from C_1-10Straight chain Or branched alkylidene.

A special embodiment according to the present invention, in logical formula (I), n group R₀It is same or different to each other, respectively Independently selected from C_2-5Linear chain or branched chain alkylidene.Here, as the C_2-5Linear chain or branched chain alkylidene specifically can such as be lifted Ethylidene or propylidene out.

According to the present invention, in logical formula (I), n+2 group A is same or different to each other, and is separately selected from hydrogen, formula (I-1) group, C representated by the group, formula (I-2) representated by_1-25The alkyl that alkyl and number-average molecular weight Mn are 300-3000.

A special embodiment according to the present invention, in logical formula (I), n+2 group A is same or different to each other, point Not independently selected from group, C representated by group representated by hydrogen, formula (I-1), formula (I-2)_1-6Linear or branched alkyl group, C_10-25 Linear or branched alkyl group, C_10-25The polyisobutenyl that linear chain or branched chain alkenyl and number-average molecular weight Mn are 300-3000.

A special embodiment according to the present invention, in logical formula (I), n+2 group A is same or different to each other, point Not independently selected from group and C representated by group representated by hydrogen, formula (I-1), formula (I-2)_1-4Linear or branched alkyl group.

A special embodiment according to the present invention, in logical formula (I), n+2 group A is same or different to each other, point Not independently selected from group representated by group representated by hydrogen, formula (I-1) and formula (I-2).

According to embodiment of the present invention, in logical formula (I), group A represents hydrogen.

According to embodiment of the present invention, in logical formula (I), group A represents C_1-4Linear or branched alkyl group.

According to embodiment of the present invention, in logical formula (I), group A represents C_10-25Linear or branched alkyl group.? This, as the C_10-25Linear or branched alkyl group, for example C can be enumerated_10-25Straight chained alkyl, or can such as enumerate positive ten Dialkyl group, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, positive two Ten alkyl, Heneicosane base, n-tetracosane base, new dodecyl, new tridecyl, new myristyl, new pentadecyl, New cetyl, new heptadecyl, new octadecyl, new eicosyl, new heneicosyl, new tetracosyl etc..

According to embodiment of the present invention, in logical formula (I), group A represents C_10-25Linear chain or branched chain alkenyl.? This, as the C_10-25Linear chain or branched chain alkenyl, for example C can be enumerated_10-25Straight-chain alkenyl, or can such as enumerate positive 6- Laurylene base, positive 6- tridecylene base, positive 7- tetradecene base, 15 alkenyl of positive 7-, positive 8- hexadecylene base, 17 alkenyl of positive 8-, just 9- octadecylene base, positive 9- icosa alkene base, bis- hendecene base of positive 10-, bis- tetradecene base of positive 12-, new 6- laurylene base, new 6- 13 Alkenyl, new 7- tetradecene base, 15 alkenyl of new 7-, new 8- hexadecylene base, 17 alkenyl of new 8-, new 9- octadecylene base, new 9- bis- Ten alkenyls, bis- hendecene base of new 10-, bis- tetradecene base of new 12- etc..

A special embodiment according to the present invention, in logical formula (I), group A represents average molecular weight Mn as 300- 3000 alkyl.Here, the alkyl for being 300-3000 as the average molecular weight Mn, for example can enumerate from number-average molecular weight Mn Remove the alkyl obtained after a hydrogen atom (referred to as the polyolefin (the especially end of the molecular polyolefin chain) of 300-3000 Polyene hydrocarbon residue).Here, as the polyolefin or the number-average molecular weight Mn of the polyene hydrocarbon residue, preferably 500-2000, more It is preferred that 500-1500.As the polyolefin, for example can enumerate through ethylene, propylene or C₄-C₁₀Alpha-olefin (such as positive fourth Alkene, isobutene, n-pentene, n-hexylene, positive octene or positive decene) homopolymerization or pass through two or more in these alkene Copolymerization obtained from polyolefin, wherein more preferable polyisobutene (PIB).

According to the present invention, in logical formula (I), at least one of described n+2 group A is base representated by formula (I-1) Group, and at least one of described n+2 group A is group representated by formula (I-2).For concrete example, when n is 0, In logical formula (I), one in 2 group A is group representated by formula (I-1), the other is representated by formula (I-2) Group.Alternatively, when n is 1, in logical formula (I), one in 3 group A is formula (I-1) institute's generation for concrete example The group of table is formula (I-1) institute's generation the other two are two in group representated by formula (I-2) or 3 group A The group of table, the other is group representated by formula (I-2).Alternatively, for concrete example, when n is 1, in logical formula (I), 3 One in a group A is group representated by formula (I-1), and one is group representated by formula (I-2), one be hydrogen, C_1-4Linear or branched alkyl group, C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl or number-average molecular weight Mn are The alkyl of 300-3000.

A special embodiment according to the present invention, in logical formula (I), as at least one of described n+2 group A Represent the C_10-25Linear or branched alkyl group, the C_10-25Linear chain or branched chain alkenyl or the number-average molecular weight Mn are 300- When 3000 alkyl, the group R' can also be hydrogen either hydrogen.In other words, special embodiment party according to the present invention Formula, in logical formula (I), at least one of group A and group R' must represent the C_10-25It is linear or branched alkyl group, described C_10-25The alkyl that linear chain or branched chain alkenyl or the number-average molecular weight Mn are 300-3000.

According to the present invention, in general formula (I-1), group R₁、R₂、R₃、R₄It is same or different to each other, is separately selected from Hydrogen and C_1-20Alkyl.

A special embodiment according to the present invention, in general formula (I-1), group R₁、R₂、R₃、R₄It is mutually the same or not Together, hydrogen and C are separately selected from_1-10Linear or branched alkyl group.Here, as the C_1-10Linear or branched alkyl group is specific to compare C can such as be enumerated_1-6Linear or branched alkyl group more specifically can such as enumerate C_1-6Straight chained alkyl more specifically can such as be enumerated Methyl, normal-butyl, isobutyl group and n-hexyl etc..

A special embodiment according to the present invention, in general formula (I-1), R₁And R₄It is hydrogen, R₂And R₃In one For C_1-10Linear or branched alkyl group, another is hydrogen.Here, as the C_1-10Linear or branched alkyl group specifically can such as lift C out_1-6Linear or branched alkyl group more specifically can such as enumerate C_1-6Straight chained alkyl more specifically can such as enumerate methyl, positive fourth Base, isobutyl group and n-hexyl etc..

A special embodiment according to the present invention, in general formula (I-1), R₁、R₃And R₄It is hydrogen, R₂For C_1-10Straight chain Or branched alkyl.Here, as the C_1-10Linear or branched alkyl group specifically can such as enumerate C_1-6Linear or branched alkyl group, It more specifically can such as enumerate C_1-6Straight chained alkyl more specifically can such as enumerate methyl, normal-butyl, isobutyl group and n-hexyl etc..

According to the present invention, in general formula (I-1), group R " is selected from hydrogen and C_1-20Alkyl.

A special embodiment according to the present invention, in general formula (I-1), group R " is selected from hydrogen and C_1-20Straight chain or branch Alkyl group.

A special embodiment according to the present invention, in general formula (I-1), group R " is selected from hydrogen and C_1-6Straight chain or branch Alkyl group.Here, as the C_1-6Linear or branched alkyl group specifically can such as enumerate C_1-6Straight chained alkyl, more specifically such as Methyl, ethyl and n-propyl etc. can be enumerated.

A special embodiment according to the present invention, in general formula (I-1), group R " represents hydrogen.

According to the present invention, in general formula (I-2), group R₅And R₆It is same or different to each other, is separately selected from C_1-20Hydrocarbon Base.

A special embodiment according to the present invention, in general formula (I-2), group R₅And R₆It is same or different to each other, point Not independently selected from C_1-20Linear or branched alkyl group.

A special embodiment according to the present invention, in general formula (I-2), group R₅And R₆It is same or different to each other, point Not independently selected from C_1-15Linear or branched alkyl group.

A special embodiment according to the present invention, in general formula (I-2), group R₅And R₆It is same or different to each other, point Not independently selected from C_3-12Linear or branched alkyl group.Here, as the C_3-12Linear or branched alkyl group specifically can such as lift N-propyl, normal-butyl, n-hexyl, positive decyl, dodecyl, isobutyl group, isopentyl, iso-octyl, isodecyl, Permethyl 99A out Base, 2- ethyl n-hexyl, 2- ethyl n-heptyl, 2- ethyl n-octyl and 2- ethyl positive decyl etc..

According to the present invention, in general formula (I-2), group X and Y are same or different to each other, and are separately selected from oxygen atom And sulphur atom.

A special embodiment according to the present invention, in general formula (I-2), two group X are sulphur atom, two bases Group Y is oxygen atom.

According to the present invention, in general formula (I-2), group R " is selected from hydrogen and C_1-20Alkyl.

A special embodiment according to the present invention, in general formula (I-2), group R " is selected from hydrogen and C_1-20Straight chain or branch Alkyl group.

A special embodiment according to the present invention, in general formula (I-2), group R " is selected from hydrogen and C_1-6Straight chain or branch Alkyl group.Here, as the C_1-6Linear or branched alkyl group specifically can such as enumerate C_1-6Straight chained alkyl, more specifically such as Methyl, ethyl and n-propyl etc. can be enumerated.

A special embodiment according to the present invention, in general formula (I-2), group R " represents hydrogen.

According to the present invention, the benzotriazole derivatives can exist in the form of single one kind (pure) compound, manufacture Or use, can also exist in the form of the mixture (in any proportion) of two or more of them, make or use, this is not Influence the realization of effect of the present invention.

According to the present invention, the benzotriazole derivatives can such as be manufactured by following manufacturing method.

According to the present invention, the manufacturing method includes phosphorus compound representated by formula (I-A), representated by formula (I-B) It reacts in the presence of benzotriazole cpd aldehyde representated by formula (I-D) representated by amine compounds and formula (I-C) Step.The step is referred to as reaction step below.

According to the present invention, in general formula (I-A), group R₅And R₆It is same or different to each other, is separately selected from C_1-20Hydrocarbon Base.

A special embodiment according to the present invention, in general formula (I-A), group R₅And R₆It is same or different to each other, point Not independently selected from C_1-20Linear or branched alkyl group.

A special embodiment according to the present invention, in general formula (I-A), group R₅And R₆It is same or different to each other, point Not independently selected from C_1-15Linear or branched alkyl group.

A special embodiment according to the present invention, in general formula (I-A), group R₅And R₆It is same or different to each other, point Not independently selected from C_3-12Linear or branched alkyl group.Here, as the C_3-12Linear or branched alkyl group specifically can such as lift N-propyl, normal-butyl, n-hexyl, positive decyl, dodecyl, isobutyl group, isopentyl, iso-octyl, isodecyl, Permethyl 99A out Base, 2- ethyl n-hexyl, 2- ethyl n-heptyl, 2- ethyl n-octyl and 2- ethyl positive decyl etc..

According to the present invention, in general formula (I-A), group X and Y are same or different to each other, and are separately selected from oxygen atom And sulphur atom.

A special embodiment according to the present invention, in general formula (I-A), two group X are sulphur atom, two bases Group Y is oxygen atom.

According to the present invention, phosphorus compound representated by the formula (I-A) can directly use commercially available product, can also lead to It crosses conventionally known in the art method to be manufactured, be not particularly limited.In addition, phosphatization representated by the formula (I-A) One kind can be used only by closing object, can also be used with combination of two or more.

According to the present invention, in general formula (I-B), group R' is selected from C_1-25Alkyl, C_3-25Linear chain or branched chain miscellaneous alkyl sum number is equal Molecular weight Mn is the alkyl of 300-3000.

A special embodiment according to the present invention, in general formula (I-B), group R' is selected from C_1-20Alkyl and C_3-20Directly Chain or branched heteroalkyl groups.

A special embodiment according to the present invention, in general formula (I-B), group R' is selected from C_10-25Linear chain or branched chain alkane Base, C_10-25Linear chain or branched chain alkenyl, C_10-25Linear chain or branched chain alkynyl, C_10-25Linear chain or branched chain miscellaneous alkyl and number-average molecular weight Mn For the polyisobutenyl of 300-3000.

According to embodiment of the present invention, in general formula (I-B), group R' represents C_10-25Linear or branched alkyl group. Here, as the C_10-25Linear or branched alkyl group, for example C can be enumerated_10-25Straight chained alkyl, or can such as enumerate just Dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, just Eicosyl, Heneicosane base, n-tetracosane base, new dodecyl, new tridecyl, new myristyl, new pentadecane Base, new cetyl, new heptadecyl, new octadecyl, new eicosyl, new heneicosyl, new tetracosyl etc..

According to embodiment of the present invention, in general formula (I-B), group R' represents C_10-25Linear chain or branched chain alkenyl. Here, as the C_10-25Linear chain or branched chain alkenyl, for example C can be enumerated_10-25Straight-chain alkenyl, or can such as enumerate just 6- laurylene base, positive 6- tridecylene base, positive 7- tetradecene base, 15 alkenyl of positive 7-, positive 8- hexadecylene base, 17 alkenyl of positive 8-, Positive 9- octadecylene base, positive 9- icosa alkene base, bis- hendecene base of positive 10-, bis- tetradecene base of positive 12-, new 6- laurylene base, new 6- ten Trialkenyl, new 7- tetradecene base, 15 alkenyl of new 7-, new 8- hexadecylene base, 17 alkenyl of new 8-, new 9- octadecylene base, new 9- Icosa alkene base, bis- hendecene base of new 10-, bis- tetradecene base of new 12- etc..

A special embodiment according to the present invention, in general formula (I-B), group R' represent number-average molecular weight Mn as The alkyl of 300-3000.Here, the alkyl for being 300-3000 as the number-average molecular weight Mn, for example can enumerate and divide equally from number The polyolefin (the especially end of the molecular polyolefin chain) that son amount Mn is 300-3000 removes the hydrocarbon obtained after a hydrogen atom Base (referred to as polyene hydrocarbon residue).Here, as the polyolefin or the number-average molecular weight Mn of the polyene hydrocarbon residue, preferably 500- 2000, more preferable 500-1500.

In the context of the present specification, depending on starting polyolefin type or the difference of manufacturing method, the polyolefin Residue may be (being rendered as chain alkyl) of saturation, it is also possible in polymer chain containing a certain amount of olefinic double bond (such as It is remaining in polyolefin manufacturing process), but this has no effect on the realization of effect of the present invention, the present invention also have no intention to the amount into Row is clear.

A special embodiment according to the present invention, as the polyolefin, for example can enumerate through ethylene, propylene Or C₄-C₁₀The homopolymerization of alpha-olefin (such as n-butene, isobutene, n-pentene, n-hexylene, positive octene or positive decene) passes through Polyolefin obtained from two or more of copolymerization in these alkene.

A special embodiment according to the present invention, as the polyolefin, more preferable polybutene.Unless otherwise saying Bright, term as used herein " polybutene " broadly includes the polymer as obtained from 1- butylene or isobutylene homopolymerisation, and Polymer prepared by copolymerization is passed through as two or three in 1- butylene, 2- butylene and isobutene.This quasi polymer it is commercially available Product may also be containing other olefinic components of negligible quantity, but this has no effect on implementation of the invention.

A special embodiment according to the present invention, as the polyolefin, further preferred polyisobutene (PIB) or Person's high-activity polyisobutylene (HR-PIB).In this kind of polyisobutene, and at least 20wt% (preferably at least 50wt%, it is more excellent Select at least 70wt%) total terminal ethylenic double bond be to be provided by methyl ethenylidene.

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

A special embodiment according to the present invention, in general formula (I-B), n is selected from the integer of 0-5.

A special embodiment according to the present invention, in general formula (I-B), n is 0,1,2 or 3, specifically can such as be lifted Out 0.

According to the present invention, in general formula (I-B), n group R₀It is same or different to each other, is separately selected from C_1-10Directly Chain or branched alkylidene.

A special embodiment according to the present invention, in general formula (I-B), n group R₀It is same or different to each other, point Not independently selected from C_2-5Linear chain or branched chain alkylidene.Here, as the C_2-5Linear chain or branched chain alkylidene, specifically such as can be with Enumerate ethylidene or propylidene.

According to the present invention, in general formula (I-B), n+2 group A' is same or different to each other, separately selected from hydrogen, C_1-25The alkyl that alkyl and number-average molecular weight Mn are 300-3000.

A special embodiment according to the present invention, in general formula (I-B), n+2 group A' is same or different to each other, Separately it is selected from hydrogen, C_1-6Linear or branched alkyl group, C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl sum number Average molecular weight Mn is the polyisobutenyl of 300-3000.

A special embodiment according to the present invention, in general formula (I-B), n+2 group A' is same or different to each other, Separately it is selected from hydrogen and C_1-4Linear or branched alkyl group.

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

According to embodiment of the present invention, in general formula (I-B), group A' represents C_1-4Linear or branched alkyl group.

According to embodiment of the present invention, in general formula (I-B), group A' represents C_10-25Linear or branched alkyl group. Here, as the C_10-25Linear or branched alkyl group, for example C can be enumerated_10-25Straight chained alkyl, or can such as enumerate just Dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, just Eicosyl, Heneicosane base, n-tetracosane base, new dodecyl, new tridecyl, new myristyl, new pentadecane Base, new cetyl, new heptadecyl, new octadecyl, new eicosyl, new heneicosyl, new tetracosyl etc..

According to embodiment of the present invention, in general formula (I-B), group A' represents C_10-25Linear chain or branched chain alkenyl. Here, as the C_10-25Linear chain or branched chain alkenyl, for example C can be enumerated_10-25Straight-chain alkenyl, or can such as enumerate just 6- laurylene base, positive 6- tridecylene base, positive 7- tetradecene base, 15 alkenyl of positive 7-, positive 8- hexadecylene base, 17 alkenyl of positive 8-, Positive 9- octadecylene base, positive 9- icosa alkene base, bis- hendecene base of positive 10-, bis- tetradecene base of positive 12-, new 6- laurylene base, new 6- ten Trialkenyl, new 7- tetradecene base, 15 alkenyl of new 7-, new 8- hexadecylene base, 17 alkenyl of new 8-, new 9- octadecylene base, new 9- Icosa alkene base, bis- hendecene base of new 10-, bis- tetradecene base of new 12- etc..

A special embodiment according to the present invention, in general formula (I-B), group A' represent number-average molecular weight Mn as The alkyl of 300-3000.Here, the alkyl for being 300-3000 as the number-average molecular weight Mn, for example can enumerate and divide equally from number The polyolefin (the especially end of the molecular polyolefin chain) that son amount Mn is 300-3000 removes the hydrocarbon obtained after a hydrogen atom Base (referred to as polyene hydrocarbon residue).Here, as the polyolefin or the number-average molecular weight Mn of the polyene hydrocarbon residue, preferably 500- 2000, more preferable 500-1500.

According to the present invention, in general formula (I-B), at least two in the n+2 group A' represent hydrogen.Concrete example and Speech, when n is 0, in general formula (I-B), 2 group A' represent hydrogen.Alternatively, for concrete example, when n is 1, In general formula (I-B), two in 3 group A' represent hydrogen, another represents hydrogen, C_1-4Linear or branched alkyl group, C_10-25Directly Chain or branched alkyl, C_10-25The alkyl that linear chain or branched chain alkenyl or number-average molecular weight Mn are 300-3000.

A special embodiment according to the present invention, in general formula (I-B), when in the n+2 group A' at least One represents the C_10-25Linear or branched alkyl group, the C_10-25Linear chain or branched chain alkenyl or the number-average molecular weight Mn are When the alkyl of 300-3000, the group R' can also be hydrogen either hydrogen.In other words, special implementation according to the present invention Mode, in general formula (I-B), at least one of group A' and group R' must represent the C_10-25Linear or branched alkyl group, The C_10-25The alkyl that linear chain or branched chain alkenyl or the number-average molecular weight Mn are 300-3000.

According to the present invention, amine compounds representated by the formula (I-B) can directly use commercially available product, can also lead to It crosses conventionally known in the art method to be manufactured, be not particularly limited.In addition, amination representated by the formula (I-B) One kind can be used only by closing object, can also be used with combination of two or more.

According to the present invention, in general formula (I-C), group R₁、R₂、R₃、R₄It is same or different to each other, is separately selected from Hydrogen and C_1-20Alkyl.

A special embodiment according to the present invention, in general formula (I-C), group R₁、R₂、R₃、R₄It is mutually the same or not Together, hydrogen and C are separately selected from_1-10Linear or branched alkyl group.Here, as the C_1-10Linear or branched alkyl group is specific to compare C can such as be enumerated_1-6Linear or branched alkyl group more specifically can such as enumerate C_1-6Straight chained alkyl more specifically can such as be enumerated Methyl, normal-butyl, isobutyl group and n-hexyl etc..

A special embodiment according to the present invention, in general formula (I-C), R₁And R₄It is hydrogen, R₂And R₃In one For C_1-10Linear or branched alkyl group, another is hydrogen.Here, as the C_1-10Linear or branched alkyl group specifically can such as lift C out_1-6Linear or branched alkyl group more specifically can such as enumerate C_1-6Straight chained alkyl more specifically can such as enumerate methyl, positive fourth Base, isobutyl group and n-hexyl etc..

A special embodiment according to the present invention, in general formula (I-C), R₁、R₃And R₄It is hydrogen, R₂For C_1-10Straight chain Or branched alkyl.Here, as the C_1-10Linear or branched alkyl group specifically can such as enumerate C_1-6Linear or branched alkyl group, It more specifically can such as enumerate C_1-6Straight chained alkyl more specifically can such as enumerate methyl, normal-butyl, isobutyl group and n-hexyl etc..

According to the present invention, benzotriazole cpd representated by the formula (I-C) can directly use commercially available product, It can be manufactured, be not particularly limited by conventionally known in the art method.In addition, the formula (I-C) is representative Benzotriazole cpd can be used only one kind, can also be used with combination of two or more.

According to the present invention, in general formula (I-D), group R " is selected from hydrogen and C_1-20Alkyl.

A special embodiment according to the present invention, in general formula (I-D), group R " is selected from hydrogen and C_1-20Straight chain or branch Alkyl group.

A special embodiment according to the present invention, in general formula (I-D), group R " is selected from hydrogen and C_1-6Straight chain or branch Alkyl group.Here, as the C_1-6Linear or branched alkyl group specifically can such as enumerate C_1-6Straight chained alkyl, more specifically such as Methyl, ethyl and n-propyl etc. can be enumerated.

A special embodiment according to the present invention, in general formula (I-D), group R " represents hydrogen.

According to the present invention, aldehyde representated by the formula (I-D) can directly use commercially available product, can also pass through Conventionally known in the art method is manufactured, and is not particularly limited.In addition, aldehyde representated by the formula (I-D) One kind can be used only, can also be used with combination of two or more.

A special embodiment according to the present invention, aldehyde representated by the formula (I-D) is formaldehyde.As the first Aldehyde, for example the form of formalin, paraformaldehyde or paraformaldehyde can be used, it is not particularly limited.

According to the present invention, in the reaction step, for example, the reaction time of the reaction is generally 0.1-24h, It is preferred that 0.2-12h, most preferably 0.5-6h, but is not limited thereto.

According to the present invention, in the reaction step, for example, the reaction temperature of the reaction is generally 0-250 DEG C, It is preferred that 20-180 DEG C, most preferably 60-120 DEG C, but is not limited thereto.

According to the present invention, in the reaction step, for example, phosphorus compound and institute representated by the formula (I-A) The molar ratio for stating amine compounds representated by formula (I-B) is generally 1:0.1-10, preferably 1:0.5-5.0, more preferable 1:0.6- 1.5, but is not limited thereto.

According to the present invention, in the reaction step, for example, phosphorus compound and institute representated by the formula (I-A) The molar ratio for stating benzotriazole cpd representated by formula (I-C) is generally 1:0.1-10, preferably 1:0.5-5.0, and more preferable 1: 0.6-1.5, but is not limited thereto.

According to the present invention, in the reaction step, for example, phosphorus compound and institute representated by the formula (I-A) The molar ratio for stating aldehyde representated by formula (I-D) is generally 1:1-10, preferably 1:1.5-6.0, more preferable 1:2-4, but sometimes not It is limited to this.

According to the present invention, in the reaction step, to the feed way of each reaction raw materials, there is no particular limitation, such as It can be added at one time, be added portionwise or be added dropwise.

According to the present invention, in the reaction step, the charging sequence of each reaction raw materials is not particularly limited, specifically For example it can enumerate according to amine compounds representated by phosphorus compound representated by the formula (I-A), the formula (I-B), described The charging sequence of aldehyde representated by benzotriazole cpd representated by formula (I-C) and the formula (I-D), can also be with any suitable Sequence charging.

According to the present invention, the reaction step can carry out in the presence of diluent and/or solvent, can also not use Diluent and/or solvent.

According to the present invention, in the reaction step, for example, as the diluent, for example it can enumerate and be selected from One of polyolefin, mineral base oil and polyethers are a variety of.As the mineral base oil, for example, can enumerate API I, II, Group III mineral lubricant base oil, more specifically can such as enumerate 40 DEG C of viscosity be 20-120 centistoke (cSt), viscosity index (VI) extremely Few mineral lubricant base oil 50 or more more specifically can such as enumerate 40 DEG C of viscosity and refer to for 28-110 centistoke (cSt), viscosity Number at least 80 or more mineral lubricant base oil.As the polyolefin, for example can enumerate through ethylene, propylene or C₄- C₁₀One of the homopolymerization of alpha-olefin or the polyolefin as obtained from two or more copolymerization in these alkene are a variety of, It is preferred that 100 DEG C of viscosity are in the poly alpha olefin (PAO) of 2-25 centistoke (cSt) (preferably 100 DEG C of viscosity are 6-10 centistoke (cSt)) It is one or more.Wherein, as the C₄-C₁₀Alpha-olefin, for example, can enumerate n-butene, isobutene, n-pentene, n-hexylene, Positive octene and positive decene.In addition, the number-average molecular weight Mn of the polyolefin is generally 500-3000, preferably 500-2500, it is optimal Select 500-1500.As the polyethers, for example can enumerate by alcohol and epoxide reaction polymer generated.As described Alcohol, for example ethylene glycol and/or 1,3-PD can be enumerated.As the epoxides, for example, can enumerate ethylene oxide and/ Or propylene oxide.In addition, the number-average molecular weight Mn of the polyethers is generally 500-3000, preferably 700-3000, most preferably 1000- 2500.One kind can be used only in these diluents, can also be used with combination of two or more.

According to the present invention, in the reaction step, for example, as the solvent, for example C can be enumerated_2-10Rouge Fat race nitrile (such as acetonitrile etc.), C_6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C_6-10Alkane (such as n-hexane, Hexamethylene and petroleum ether), C_1-6Aliphatic alcohol (such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C_2-20 Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C_3-10Ketone (such as acetone, butanone and methyl tert-butyl Base ketone) or C_3-10Amide (such as dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone) etc..These solvents can One kind is used only, can also be used with combination of two or more.

A special embodiment according to the present invention, the diluent and/or solvent can be in the reaction steps Any stage is added according to the conventional amount used of this field, is not particularly limited.

According to the present invention, it should be apparent that the reaction step generally carries out under the protection of inert gas atmosphere.As institute State inert gas, for example nitrogen and argon gas can be enumerated etc., it is not particularly limited.

According to the present invention, after the manufacturing method of the benzotriazole derivatives, pass through conventionally known any side Formula obtains benzotriazole derivatives after removing moisture and solvent that may be present in the reaction mixture finally obtained.Cause This, the invention further relates to the benzotriazole derivatives of the manufacturing method of benzotriazole derivatives above-mentioned according to the present invention manufacture.

According to the present invention, by the manufacturing method of benzotriazole derivatives above-mentioned, as reaction product, it is possible to produce A kind of single benzotriazole derivatives, can also produce the mixture being made of a variety of benzotriazole derivatives, or by one The mixture that kind or a variety of benzotriazole derivatives and aforementioned diluent (if you are using) are constituted.These reaction products It is all desired by the present invention, the difference of existence form has no effect on the realization of effect of the present invention.Therefore, above and below this specification These reaction products are collectively termed as benzotriazole derivatives without distinction in text.In consideration of it, according to the present invention, and be not present The reaction product is further purified, or is further separated out the benzotriazole derivative of a certain specific structure from the reaction product The absolute necessity of object.Certainly, the purifying or separation are preferred for the further promotion of desired effect of the present invention, but Not necessarily in the present invention.Even so, as the purifying or separation method, for example, can enumerate through column chromatography method or The methods of preparation chromatography is purified or separated the reaction product.

Benzotriazole derivatives of the invention are used particularly suitable for manufacture antiwear agents or as antiwear agents, special It is not lubrication oil antiwear damage agent.Antiwear agents of the invention not only have excellent extreme pressure and antiwear performance, but also have both heat One of Oxidation Stability, corrosion resistance, rustless property and antifriction performance or a variety of excellent properties.According to the present invention one A particularly preferred embodiment, the antiwear agents not only have excellent extreme pressure and antiwear performance, but also have both excellent Thermal oxidation stability energy, corrosion resistance, rustless property and antifriction performance.

According to the present invention, the antiwear agents include that (or it any compares the present invention any benzotriazole derivatives above-mentioned Example mixture) or according to the present invention benzotriazole derivatives above-mentioned manufacturing method manufacture benzotriazole derivatives.

According to the present invention, in order to manufacture the antiwear agents, can also further add into the benzotriazole derivatives Enter diluent above-mentioned or this field in the manufacture conventional use of other components of antiwear agents.At this point, the diluent can be with It is used alone, can also be used with combination of two or more.Certainly, if benzotriazole derivatives of the invention are being made as previously described A certain amount of diluent is contained after making, then can accordingly reduce the additional amount of the diluent at this time, very To not needing the diluent is further added and can use directly as antiwear agents, this is to those skilled in the art It is obvious.

In general, in mass, the benzotriazole derivatives account for described wear-resistant in antiwear agents of the invention The 5%-100% of agent gross mass, preferably 30%-90%.

According to the present invention, in order to manufacture the antiwear agents, for example, by benzotriazole derivatives, described dilute Agent and the other components (if you are using) are released in 20 DEG C of -60 DEG C of mixing 1h-6h, are not particularly limited.

Since the aforementioned diluent used of the present invention frequently as lubricating base oil actually in the art also through using, because It is directly classified as lubricating base oil in the following description and separately described without being re-used as an individual component by this.

Embodiment

The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.

Performance in embodiment and comparative example is evaluated as follows.

(1) wear resistance is evaluated

According to 0189 standard method of SH/T, the lubricant oil composite that embodiment or comparative example are manufactured is as test specimen Carry out wear resistance evaluation.The experimental condition of wear-resistant test is the effect of 392N (40kg) power, 75 DEG C of oil sump temperature, and heading turns Fast 1200r/min, time 60min.The wear resistance of sample is evaluated by the average value of the wear scar diameter of following three balls.

(2) inhibit copper corrosion assessment of performance

Referring to ASTM D130 standard method, the lubricant oil composite that embodiment or comparative example are manufactured is as test specimen Carry out copper strip test.In the sample by the copper sheet polished submergence, 121 DEG C of test temperature are heated to, are kept for 3 hours, to Off-test takes out copper sheet, is compared after washed with Corrosion standards colour table, determines corrosion level.

(3) thermal oxidation stability energy

The lubricant oil composite that embodiment or comparative example are manufactured is as test specimen, using Pressurized Differential scanning amount heat examination The thermal oxidation stability energy that (PDSC) evaluates the test specimen is tested, is indicated with the oxidation induction period (unit is min) of test specimen. The temperature of PDSC test is 180 DEG C, pressure 0.5MPa, oxygen gas flow rate 100mL/min.

(4) high-frequency reciprocating friction test antifriction performance is evaluated

The lubricant oil composite that embodiment or comparative example manufacture is subjected to high-frequency reciprocating friction test as test specimen.It should The experimental condition of method is load 1000g, frequency 20Hz, 100 DEG C of temperature, test period 60min, records coefficient of friction.It rubs It is smaller to wipe coefficient, shows that the antifriction performance of test specimen is better.

(5) deposit generates rejection evaluation

The lubricant oil composite that embodiment or comparative example manufacture is subjected to coking plate simulation test as test specimen.The party Method is that coking plate analog meter is added in 300mL test specimen, is heated to 150 DEG C, uses continuation mode to temperature for 310 DEG C of aluminium Plate spilled oil is weighed the burnt amount generated on aluminium sheet after 6 hours, is indicated with sediment yield (unit is mg), and it is heavy on piston to simulate Product object.Coking amount is higher, and the cleansing performance for representing this test specimen is poorer.

Embodiment 1

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and water segregator, add Enter 31.26 grams of (116mmol) octadecylamines and 6.36 grams of (212mmol) paraformaldehydes, 9.05 grams of (76mmol) benzotriazole and 25.41 grams of (105mmol) di-n-butyl phosphordithiic acid stir rapidly, are warming up to 100 DEG C of reaction 3h.To end of reaction, decompression Remaining water is distilled off, is down to room temperature, settles 24 hours, is filtered to remove impurity, final product is obtained by column chromatography for separation, Labeled as M-1.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 0.88 (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)；

C₃₄H₆₃N₄O₂PS₂Calculated value C 62.35, H 9.70, N 8.55, O 4.89, P 4.73, S 9.79；Measured value: C 63.25, H 10.0, N 8.45, O 4.89, P 4.41, S 9.32.

Embodiment 2

Under nitrogen protection atmosphere, in the 500ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and water segregator, add Enter 60.10 grams of (223mmol) octadecylamines and 18.3 grams of (610mmol) paraformaldehydes and 30.60 grams of (230mmol) 5- methyl benzos Triazole stirs rapidly, is warming up to 85 DEG C, and 71.31 grams of (251mmol) isopropyl 2- ethylhexyl phosphordithiic acid, constant temperature is added dropwise React 6h.To end of reaction, vacuum distillation removes remaining water, is down to room temperature, settles 24 hours, is filtered to remove impurity, passes through Column chromatography for separation obtains final product, is labeled as M-2.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 0.88 (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)；

C₃₈H₇₁N₄O₂PS₂Calculated value C 64.18, H 10.06, N 7.88, O 4.50, P 4.36, S 9.02；Measured value: C 63.93, H 9.85, N 7.75, O 4.50, P 4.66, S 9.31.

Embodiment 3

Under nitrogen protection atmosphere, in the 500ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and water segregator, add Enter 25.9 grams of (130mmol) primene JM-Ts and 13.5 grams of (450mmol) paraformaldehydes, 21.89 grams of (125mmol) 6- butyl benzos Triazole and 100mL toluene stir rapidly, are warming up to 95 DEG C, and it is thio that 55.23 grams (150mmol) two (2- ethylhexyl) two is added dropwise Phosphoric acid, isothermal reaction 5h.To end of reaction, vacuum distillation removes solvent and remaining water, is down to room temperature, settles 24 hours, mistake Decontamination is filtered out, final product is obtained by column chromatography for separation, is labeled as M-3.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 0.89 (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)；

C₄₂H₇₉N₄O₂PS₂Calculated value C 65.75, H 10.38, N 7.30, O 4.17, P 4.04, S 8.36；Measured value: C 64.50, H 10.12, N 7.43, O 4.32, P 4.57, S 9.26.

Embodiment 4

Under nitrogen protection atmosphere, in the 500ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and water segregator, add Enter 34.47 grams of (90mmol) N- hydrogenated-tallow group dipropylenetriamines and 13.5 grams of (450mmol) paraformaldehydes, 17.93 grams (150mmol) benzotriazole and 120mL toluene stir rapidly, are warming up to 100 DEG C, and 24.2 grams of (100mmol) di-n-butyls two are added dropwise Thiophosphoric acid, isothermal reaction 8h.To end of reaction, vacuum distillation removes solvent and remaining water, is down to room temperature, and sedimentation 24 is small When, it is filtered to remove impurity, final product is obtained by column chromatography for separation, is labeled as M-4.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 0.88 (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)；

C₄₇H₈₂N₉O₂PS₂Calculated value C 62.70, H 9.18, N 14.00, O 3.55, P 3.44, S 7.12；Measured value: C 62.81, H 9.22, N 13.85, O 3.56, P 3.41, S 7.15.

Comparative example 1

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and water segregator, add Enter 35.04 grams of (130mmol) octadecylamines, 9 grams of (300mmol) paraformaldehydes, 29.78 grams of (250mmol) benzotriazole and 100mL Toluene stirs rapidly, is warming up to 90 DEG C, isothermal reaction 6h.To end of reaction, vacuum distillation removes solvent and remaining water, drop It to room temperature, settles 24 hours, is filtered to remove impurity up to product, is labeled as D-1.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 0.88 (3H), 1.25-1.51 (32H), 3.27 (2H), 5.55-6.24 (4H), 7.19-8.08(8H)；

C₃₂H₄₉N₇Calculated value C 72.27, H 9.29, N 18.44；Measured value: C 72.95, H 10.32, N 16.73.

Comparative example 2-4

The composition of antiwear additive comparative example 2~4 is shown in Table 1.

Table 1

	Compare antiwear additive
		Comparative example 2	Dialkyl dithiophosphoric acid-formaldehyde-fatty amine condensate
Comparative example 3	Benzotriazole fatty amine salt
		Comparative example 4	Dialkyl dithiophosphoric acid-formaldehyde-fatty amine condensate: benzotriazole fatty amine salt=1:1

The source of used antiwear additive is as follows:

Dialkyl dithiophosphoric acid-formaldehyde-fatty amine condensate uses Jiangsu Danyang Bo Er petroleum additive Co., Ltd The T307 of production；Benzotriazole fatty amine salt, the T406 produced using Shandong Zibo Hui Hua Chemical Co., Ltd..

Embodiment I-1 to embodiment I-4 and Comparative Examples I D-1 to Comparative Examples I D-4

The additive of embodiment is obtained respectively product, the product that comparative example obtains and comparative additive and other types According to the formula composition of table 2 in 40 DEG C of mixing 2h, lubricant oil composite of the embodiment I-1 to embodiment I-4, comparative example are obtained The lubricant oil composite of ID-1 to Comparative Examples I D-4.

Table 2

Wherein used primary raw material source is as follows: antioxidant: shielding phenol (trade names T501)；N- phenyl-α-naphthalene Amine (trade names T531).Extreme pressure anti-wear additives: phosphate nitrogen containing derivative (trade names T306).Ashless dispersant: monosubstituted Polyisobutene succinimide (trade names T151).Ashless friction modifiers: oleamide, it is limited that Jinan, Shandong Province beautiful jade contains chemical industry Company's production.

To the lubricant oil composite of the lubricant oil composite of above-described embodiment, comparative example as test specimen, carry out respectively Wear resistance, antifriction performance, inhibits copper corrosion performance and deposit to generate rejection evaluation at thermal oxidation stability, Measurement result is as shown in table 3.Table 3

Claims

1. a kind of hydraulic fluid compositions, including benzotriazole derivatives, antioxidant, extreme pressure anti-wear additives, Ashless friction modifiers, nothing Grey dispersing agent and lubricating base oil, the structure of the benzotriazole derivatives is as shown in logical formula (I):

In logical formula (I), group R' is selected from C_1-25Alkyl, C_3-25Linear chain or branched chain miscellaneous alkyl and number-average molecular weight Mn are 300- The alkyl of 3000 (preferably 500-2000, more preferable 500-1500), or it is selected from C_1-20Alkyl and C_3-20The miscellaneous alkane of linear chain or branched chain Base is preferably selected from C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl, C_10-25Linear chain or branched chain alkynyl, C_10-25Straight chain Or branched heteroalkyl groups and number-average molecular weight Mn are the polyisobutene of 300-3000 (preferably 500-2000, more preferable 500-1500) Base, more preferable C_10-25Linear or branched alkyl group；N is selected from the integer of 0-10, is preferably selected from the integer of 0-5, and more preferable 0；N group R₀It is same or different to each other, is separately selected from C_1-10Linear chain or branched chain alkylidene is preferably separately selected from C_2-5Straight chain Or branched alkylidene；N+2 group A is same or different to each other, and is separately selected from group, formula representated by hydrogen, formula (I-1) (I-2) group, C representated by_1-25Alkyl and number-average molecular weight Mn are 300-3000 (preferably 500-2000, more preferable 500- 1500) alkyl is preferably separately selected from group representated by hydrogen, formula (I-1), group, C representated by formula (I-2)_1-6 Linear or branched alkyl group, C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl and number-average molecular weight Mn are 300-3000 The polyisobutenyl of (preferably 500-2000, more preferable 500-1500), it is preferably separately representative selected from hydrogen, formula (I-1) Group, group and C representated by formula (I-2)_1-4Linear or branched alkyl group is preferably separately selected from hydrogen, formula (I-1) institute Group representated by the group and formula (I-2) of representative, on condition that at least one of described n+2 group A is formula (I-1) institute's generation The group of table, and at least one of described n+2 group A is group representated by formula (I-2)；When at least one base Group A is C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl or number-average molecular weight Mn are 300-3000 (preferably 500- 2000, more preferable 500-1500) alkyl when, the group R' can also be hydrogen,

In general formula (I-1) and general formula (I-2), group R₅And R₆It is same or different to each other, is separately selected from C_1-20Alkyl (especially C_1-20Linear or branched alkyl group), preferably separately it is selected from C_1-15Linear or branched alkyl group, more preferably independently Ground is selected from C_3-12Linear or branched alkyl group；Group X and Y are same or different to each other, and are separately selected from oxygen atom and sulphur atom, It is preferred that two group X are sulphur atom, two group Y are oxygen atom；Two group R " are same or different to each other, independently Ground is selected from hydrogen and C_1-20Alkyl is preferably separately selected from hydrogen and C_1-20Linear or branched alkyl group is more preferably separately selected From hydrogen and C_1-6Linear or branched alkyl group is more preferably hydrogen；Group R₁、R₂、R₃、R₄It is same or different to each other, separately Selected from hydrogen and C_1-20Alkyl is preferably separately selected from hydrogen and C_1-10Linear or branched alkyl group, more preferable R₁And R₄It is hydrogen, R₂ And R₃In one be C_1-10Linear or branched alkyl group (preferably C_1-6Linear or branched alkyl group), another is hydrogen, the straight chain or Branched heteroalkyl groups refer to the carbon-chain structure of linear or branched alkyl group by one or more (such as 1 to 5,1 to 4,1 to 3 It is a, 1 to 2 or 1) selected from-O- ,-S- and-NR-, (wherein, group R is selected from H and C_1-4Linear or branched alkyl group is preferably selected The group for interrupting and obtaining from the miscellaneous group of H and methyl).

2. lubricant oil composite described in accordance with the claim 1, which is characterized in that the benzotriazole derivatives are selected from the following Particular compound or its any two or more of mixture:

3. a kind of hydraulic fluid compositions, including benzotriazole derivatives, antioxidant, extreme pressure anti-wear additives, Ashless friction modifiers, nothing Grey dispersing agent and lubricating base oil, the manufacturing method of the benzotriazole derivatives include that phosphatization representated by formula (I-A) is closed Benzotriazole cpd aldehyde representated by formula (I-D) representated by amine compounds representated by object, formula (I-B) and formula (I-C) In the presence of the step of reacting,

Wherein, group R' is selected from C_1-25Alkyl, C_3-25Linear chain or branched chain miscellaneous alkyl and number-average molecular weight Mn be 300-3000 (preferably 500-2000, more preferable 500-1500) alkyl, or be selected from C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl, is preferably selected from C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl, C_10-25Linear chain or branched chain alkynyl, C_10-25The miscellaneous alkane of linear chain or branched chain Base and number-average molecular weight Mn are the polyisobutenyl of 300-3000 (preferably 500-2000, more preferable 500-1500), more preferably C_10-25Linear or branched alkyl group；N is selected from the integer of 0-10, is preferably selected from the integer of 0-5, and more preferable 0；N group R₀Phase each other It is same or different, separately it is selected from C_1-10Linear chain or branched chain alkylidene is preferably separately selected from C_2-5Linear chain or branched chain is sub- Alkyl；N+2 group A' is same or different to each other, and is separately selected from hydrogen, C_1-25Alkyl and number-average molecular weight Mn are 300- The alkyl of 3000 (preferably 500-2000, more preferable 500-1500) is preferably separately selected from hydrogen, C_1-6Linear chain or branched chain alkane Base, C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl and number-average molecular weight Mn are 300-3000 (preferably 500- 2000, more preferable 500-1500) polyisobutenyl, preferably separately be selected from hydrogen and C_1-4Linear or branched alkyl group, premise It is at least two to represent hydrogen in the n+2 group A'；When at least one described group A' is C_10-25Linear or branched alkyl group, C_10-25Linear chain or branched chain alkenyl or number-average molecular weight Mn are the alkyl of 300-3000 (preferably 500-2000, more preferable 500-1500) When, the group R' can also be hydrogen；Group R₅And R₆It is same or different to each other, is separately selected from C_1-20Alkyl is (especially C_1-20Linear or branched alkyl group), preferably separately it is selected from C_1-15Linear or branched alkyl group is more preferably separately selected from C_3-12Linear or branched alkyl group；Group X and Y are same or different to each other, separately be selected from oxygen atom and sulphur atom, preferably two A group X is sulphur atom, and two group Y are oxygen atom；Group R " is selected from hydrogen and C_1-20Alkyl is preferably selected from hydrogen and C_1-20 Linear or branched alkyl group is more preferably selected from hydrogen and C_1-6Linear or branched alkyl group, more preferable hydrogen；Group R₁、R₂、R₃、R₄Phase each other It is same or different, separately it is selected from hydrogen and C_1-20Alkyl is preferably separately selected from hydrogen and C_1-10Linear or branched alkyl group, More preferable R₁And R₄It is hydrogen, R₂And R₃In one be C_1-10Linear or branched alkyl group (preferably C_1-6Linear or branched alkyl group), separately One is hydrogen, and the linear chain or branched chain miscellaneous alkyl refers to the carbon-chain structure of linear or branched alkyl group by one or more (such as 1 To 5,1 to 4,1 to 3,1 to 2 or 1) selected from-O- ,-S- and-NR-, (wherein, group R is selected from H and C_1-4Straight chain Or branched alkyl, be preferably selected from H and methyl) miscellaneous group interrupt and obtain group.

4. lubricant oil composite described in accordance with the claim 3, which is characterized in that wherein the reaction time of the reaction is 0.1- For 24 hours, preferably 0.5-6h, the reaction temperature of the reaction are 0-250 DEG C, preferably 60-120 DEG C.

5. lubricant oil composite described in accordance with the claim 3, which is characterized in that wherein phosphatization representated by the formula (I-A) The molar ratio for closing amine compounds representated by object and the formula (I-B) is 1:0.1-10, preferably 1:0.6-1.5；The formula (I-A) The molar ratio of benzotriazole cpd representated by representative phosphorus compound and the formula (I-C) is 1:0.1-10, preferably 1: 0.6-1.5；The molar ratio of phosphorus compound representated by the formula (I-A) and aldehyde representated by the formula (I-D) is 1:1-10, excellent Select 1:2-4.

6. according to lubricant oil composite described in one of claim 1-5, which is characterized in that the benzotriazole derivatives account for The 0.001%-30% (preferably 0.05%-20%) of lubricant oil composite gross mass；It is total that the antioxidant accounts for lubricant oil composite The 0.01%-10% (preferably 0.05%-5%) of quality；The extreme pressure anti-wear additives account for the 0.01%- of lubricant oil composite gross mass 10% (preferably 0.05%-8%)；The Ashless friction modifiers account for the 0.01%-5% of lubricant oil composite gross mass (preferably 0.02%-4%)；The ashless dispersant accounts for the 0.01%-10% (preferably 0.1%-5%) of lubricant oil composite gross mass；Institute State the main component that lubricating base oil constitutes lubricant oil composite.

7. according to lubricant oil composite described in one of claim 1-5, which is characterized in that the antioxidant is selected from shielding phenol And/or secondary aromatic amine；The extreme pressure anti-wear additives are selected from phosphate derivative；The Ashless friction modifiers be selected from aliphatic acid, One of fatty acid amide, polyol esters of fatty acids and aliphatic amine are a variety of；The ashless dispersant is selected from polyisobutene Succimide；The lubricating base oil is selected from one of API I, II, III, IV and V class lubricating base oil or a variety of.

8. the preparation method of lubricant oil composite described in one of claim 1-7, which is characterized in that by claim 1-7 it Each additive and lubricating base oil mixing in lubricant oil composite described in one.