CN106318546B

CN106318546B - A kind of diesel engine lubricating oil composite and preparation method thereof

Info

Publication number: CN106318546B
Application number: CN201510332922.7A
Authority: CN
Inventors: 谢欣; 陈政; 张建荣; 武志强; 孙洪伟; 段庆华; 贾秋莲
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: 2015-06-16
Filing date: 2015-06-16
Publication date: 2019-05-21
Anticipated expiration: 2035-06-16
Also published as: CN106318546A

Abstract

The invention discloses a diesel engine lubricating oil composition, which, based on the weight of the lubricating oil composition, contains the following components: 75-95 wt % of lubricating oil base oil, 0.01-10 wt % of anti-oxidative and anti-wearing oil performance additives, 0.02-8 wt% of a thiophenol ester antioxidant, 0.5-10 wt% of a mixture of polyisobutylene succinimide ashless dispersant and boronated polyisobutylene succinimide dispersant, 0.2 -10% by weight of a mixture of high base number magnesium salicylate and low base number calcium sulfonate, ≤ 0.15% by weight of zinc dialkyldithiophosphate and 0.01-5% by weight of ashless friction modifier based on phosphorus , the antioxidant and antiwear multi-effect additive is a compound of the structure shown in formula (I). Also provided are methods of making the diesel engine lubricating oil compositions. The diesel engine lubricating oil composition of the present invention has excellent antiwear and antioxidation properties, and can inhibit the formation of high temperature deposits.

Description

A kind of diesel engine lubricating oil composite and preparation method thereof

Technical field

The present invention relates to lubricating oil fields, and in particular, to a kind of diesel engine lubricant containing special additive Composition and preparation method thereof.

Background technique

In recent years, the specification grade of diesel engine lubricant subtracts with diesel engine structure, operating condition and energy conservation Row requires and sustainable development, diesel engine oil frequently upgrade.Diesel engine oil product specification is gradually upgraded to CH- from CF-4 4, CI-4 and newest CJ-4, the application of the diesel engine EGR exhaust circulatory system, NO_xDischarge reduce, bring cigarette in machine oil The problem of soot amount increases, mass ratio containing soot can in the lubricating oil that many diesel engine testboard bays such as Mack T11 are used Reach 6%.It is secondary that there are many frictions in engine, such as piston and cylinder sleeve, crankshaft journal and bearing, cam and follower, gear. Soot particulates are very rigid, and caused abrasive wear will cause seriously the service life of engine between engine friction pair It influences, to lubricating oil, more stringent requirements are proposed for this.

In addition, engine fuel oil and the unsaturated olefin in base oil, aromatic hydrocarbons and sulfur-containing compound are under oxygen effect Colloid is formed, and ultimately forms carbon distribution deposit, especially in the key positions such as piston, combustion chamber meeting acceleration motor deposit Generate, seriously affect the working performance of engine, cause engine start difficulty, unstable idle speed, driving is poor, acceleration is poor, The problems such as power loss is serious.It is this field that engine oil, which has excellent ability that is anti-oxidant and inhibiting high temperature deposition object to generate, The research that novel more efficient antioxidant additive is those skilled in the art is developed in the direction that researcher is continually striving to all the time Target.Additionally due to diesel oil sulfur content is higher, the acidic materials generated after burning are more, the high temperature that diesel engine work generates Soot is also more, can effectively reduce coking and top land carbon deposit using the formula of protosulfate ash content, reduces the abrasion of valve system, In addition low ash point can reduce corrosion resistance oxidation product, reduce engine component corrosion abrasion, extend the safe operation of engine Period and spare part service life.Therefore low ash divides I. C. engine oil to be the developing direction of I. C. engine oil.

It mainly includes phenols and aminated compounds that the lube oil additive of antioxidation can be effectively played by, which being currently known,. Phenolic compound contains one or more and is obstructed phenol functional group, and aminated compounds then contains one or more nitrogen-atoms, these are special Different functional group can capture the free radical compounds of oxidation process generation, so that oxidation process be prevented to continue to occur.Due to The operating condition of Current mechanical equipment tends to strongly, often accelerated oxidation rate, shortens the service life of lubricating oil, therefore right More stringent requirements are proposed for the efficiency and economy of antioxidant.

United States Patent (USP) US4824601A reports diphenylamine and diisobutylene in the alkaline-earth metal catalyst of acid activation The lower alkylated amines mixture formed of (earth catalyst) effect, its anti-oxidant energy in lubricating oil and other functional fluids Power is excellent in.

United States Patent (USP) US2005230664A1 reports a kind of synthesis of the antioxidant acridan of following general formula Method, it is to be condensed preparation under acidic catalyst effect using alkylated diphenylamine and aldehydes or ketones.

Using the tert-butyl phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine condensation preparationization occurs for patent CN1191340C Object is closed, which has the stronger ability for capturing free radical and peroxynitrite decomposition compound, can provide to oil oxidation stability More effectively protection, may also function as wear-resistant effect.

Patent US4225450 reports one kind and reacts preparation with Diethyldithiocarbamate by the tert-butyl phenols that is obstructed Polysulfide phenolic antioxidant, have preferable antioxidation and wear-resistant effect.

Summary of the invention

The purpose of the invention is to meet to the anti-oxidant, wear-resistant of diesel engine lubricating oil composite and inhibit high temperature The high request for the ability that deposit generates provides a kind of diesel engine lubricating oil composite and preparation method thereof.

The present inventor has found that lubricant oil composite contains the compound of structure shown in formula (I) under study for action:

And the compound and thiophenols ester type antioxidant are combined, and diesel engine lubricating oil composite can be made to have excellent The good performances such as anti-oxidant and wear-resistant, can effectively inhibit the generation of high temperature deposition object.

Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of diesel engine lubricating oil composite, On the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: the lubrication oil base of 75-95 weight % Thiophenols ester type antioxidant, the 0.5-10 of plinth oil, the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, 0.02-8 weight % The mixture of the polyisobutene succinimide ashless dispersant of weight % and boronation polyisobutene succinimide dispersing agent, The high base number magnesium salicylate of 0.2-10 weight % and the mixture of low alkali value sulfoacid calcium, in terms of phosphorus≤dialkyl group of 0.15 weight % The Ashless friction modifiers of zinc dithiophosphate and 0.01-5 weight %, the wear-resistant multipurpose additive of antioxygen are shown in formula (I) The compound of structure:

Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 75-85 The thiophenols ester type of the lube base oil of weight %, the wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, 0.1-3 weight % Antioxidant, the polyisobutene succinimide ashless dispersant of 3-7 weight % and boronation polyisobutene succinimide dispersing agent Mixture, 0.8-6 weight % high base number magnesium salicylate and low alkali value sulfoacid calcium mixture, the 0.01-0.1 in terms of phosphorus weight Measure the zinc dialkyl dithiophosphate of % and the Ashless friction modifiers of 0.05-1.2 weight %.

On the other hand, the present invention provides a kind of preparation method of diesel engine lubricating oil composite, the method packets It includes: lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, polyisobutene succinimide will be contained The mixture of ashless dispersant and boronation polyisobutene succinimide dispersing agent, high base number magnesium salicylate and low alkali value sulfoacid calcium Mixture, zinc dialkyl dithiophosphate and Ashless friction modifiers raw material be uniformly mixed and obtain lubricant oil composite, In, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 75-95 weight %, the wear-resistant multiple-effect of antioxygen adds The dosage for adding agent is 0.01-10 weight %, the dosage of thiophenols ester type antioxidant is 0.02-8 weight %, polyisobutene succinyl The dosage of the mixture of imines ashless dispersant and boronation polyisobutene succinimide dispersing agent is 0.5-10 weight %, high-alkali The dosage for being worth the mixture of magnesium salicylate and low alkali value sulfoacid calcium is 0.2-10 weight %, the dosage of zinc dialkyl dithiophosphate For in terms of phosphorus≤0.15 weight %, the dosages of Ashless friction modifiers is 0.01-5 weight %, the wear-resistant multiple-effect addition of antioxygen Agent is the compound of structure shown in formula (I):

Preferably, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 75-85 weight %, resists The dosage of the wear-resistant multipurpose additive of oxygen is 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is 0.1-3 weight %, it is different to gather The dosage of the mixture of butylene Ashless butyl diimide dispersant and boronation polyisobutene succinimide dispersing agent is 3-7 weight The dosage of the mixture of amount %, high base number magnesium salicylate and low alkali value sulfoacid calcium is 0.8-6 weight %, dialkyl dithiophosphoric acid The dosage of zinc is the weight % of the 0.01-0.1 in terms of phosphorus, and the dosage of Ashless friction modifiers is 0.05-1.2 weight %.

Diesel engine lubricating oil composite of the invention has excellent abrasion resistance and antioxygenic property, can inhibit height The generation of warm deposit, and there is the sulfur content no more than 0.5%, the phosphorus content no more than 0.1%, meet CJ-4 and with higher level The requirement of other diesel engine lubricant.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

Fig. 1 is the reaction equation of (a) the step of preparing antioxygen wear-resistant multipurpose additive.

Fig. 2 is the reaction equation of (b) the step of preparing antioxygen wear-resistant multipurpose additive.

Fig. 3 is the hydrogen spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.

Fig. 4 is the carbon spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.

Fig. 5 is the mass spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

On the one hand, the present invention provides a kind of diesel engine lubricating oil composites, are with the weight of lubricant oil composite Benchmark, lubricant oil composite contain following components: lube base oil, the antioxygen of 0.01-10 weight % of 75-95 weight % is anti- Grind the polyisobutene succinimide of multipurpose additive, the thiophenols ester type antioxidant of 0.02-8 weight %, 0.5-10 weight % The high base number magnesium salicylate of the mixture of ashless dispersant and boronation polyisobutene succinimide dispersing agent, 0.2-10 weight % With the mixture of low alkali value sulfoacid calcium, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.15 weight % and 0.01-5 weight % Ashless friction modifiers, the wear-resistant multipurpose additive of antioxygen are the compound of structure shown in formula (I):

In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably 75-85 weight Measure %；The content of the wear-resistant multipurpose additive of antioxygen is preferably 0.02-5 weight %, more preferably 0.1-4 weight %；Sulfophenates The content of type antioxidant is preferably 0.05-4 weight %, more preferably 0.1-3 weight %；Polyisobutene succinimide ashless point The content of the mixture of powder and boronation polyisobutene succinimide dispersing agent is preferably 1.5-8 weight %, more preferably 3-7 Weight %；The content of high base number magnesium salicylate and the mixture of low alkali value sulfoacid calcium is preferably 0.5-8 weight %, more preferably 0.8-6 weight %；The content of zinc dialkyl dithiophosphate is preferably 0.01-0.1 weight % in terms of phosphorus；Ashless friction modifiers Content be preferably 0.02-2 weight %, more preferably 0.05-1.2 weight %.

The present invention is directed to tie by the compound containing structure shown in formula (I) in lubricant oil composite, and shown in formula (I) The compound of structure and thiophenols ester type antioxidant are combined and realize goal of the invention, though lubricant oil composite have it is excellent wear-resistant With the performances such as anti-oxidant.Therefore, it for the selection of conventional constituents each in lubricant oil composite, does not limit specifically.

In the present invention, lube base oil can be lube base oil commonly used in the art, such as can be mine Object lubricating oil and/or synthetic lubricant fluid.

Mineral lubricating oil in viscosity can from light fraction mineral oil to heavy distillat mineral oil, including saxol and plus That hydrogen refines, the processed alkane of solvent, cycloalkanes and mixing par-affinic-naphthenic types mineral lubricating oil, are generally divided into I, II, Group III Base oil, common trade names include I class 150SN, 600SN, II class 100N, 150N, 350N etc..

Synthetic lubricant fluid may include polymerization hydrocarbon ils, alkyl benzene and its derivative, polymerization hydrocarbon ils specific example include but It is not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly- (1- hexene), poly- (1- octene), gathers (1- decene), common trade names include PAO4, PAO6, PAO8, PAO10 etc., alkyl benzene and its derivative specific example Including but not limited to detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethylhexyl) benzene, alkyl benzene derivate packet Include alkylated diphenyl ether and alkylated diphenyl sulfide and its derivative, analog and homologue etc..

Another suitable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (such as phthalic acid, succinic acid, alkane Base succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimerization Object, malonic acid, alkyl malonic acid, alkenyl malonic) with various alcohol (such as butanol, hexanol, dodecyl alcohol, 2- ethylhexyl alcohol, Ethylene glycol, propylene glycol) ester or complex ester that condensation reaction generates occurs.The specific example of these esters includes but is not limited to adipic acid Dibutyl ester, decanedioic acid two (2- ethylhexyl) ester, the just own ester of fumaric acid acid two, dioctyl sebacate, azelaic acid two are different pungent Ester, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, decanedioic acid two (larane base) ester, linoleic acid 2- ethylhexyl diester of dimer etc..

Another suitable type of synthetic lubricant fluid can be for fischer tropsch process synthetic hydrocarbon oil and to this synthetic hydrocarbon oil by adding Hydrogen isomery such as is hydrocracked, dewaxes at the lube base oil that process obtain.

In the present invention, lube base oil preferred viscosities index is greater than 80, saturated hydrocarbon content and is greater than 90 weight %, sulfur content Less than the lube base oil of 0.03 weight %.

In the present invention, thiophenols ester type antioxidant can be thiophenols ester type antioxidant commonly used in the art, such as can be with For thiodipropionic acid bis-dodecanol ester (DLTDP), thio-2 acid double octadecyl esters (DSTDP), 2,5- dimercapto -1,3,4- thiophene two Azoles (DMTD) and 2, at least one of 2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], preferably 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], such as the production of Sichuan Yong Ye Chemical Co., Ltd. Antioxidant 1035, the IRGANOX L115 etc. of BASF Aktiengesellschaft's production.

In the present invention, the number-average molecular weight of polyisobutene part is preferably in polyisobutene succinimide ashless dispersant 800-4000, more preferably 900-3000, further preferably 1000-2400.Polyisobutene succinimide ashless dispersant Such as the T161 that Suzhou specialty oil factory can be selected to produce, T161A, T161B of the production of Jinzhou Petrochemical Company additive factory, The LZLl57 of Lu Borun Lan Lian additive Co., Ltd production, LZ6418, LZ6420 of Lubrizol Corp.'s production, Afton Chemical Corp. The Hitec646 etc. of production.

In the present invention, the number-average molecular weight of polyisobutene part is preferably in boronation polyisobutene succinimide dispersing agent 500-4000, more preferable 700-2500, further preferably 1000-2300.Boronation polyisobutene succinimide dispersing agent example Can such as select Agip Petroli company produce MX3316, Afton Chemical Corp. production Hitec648, Hitec7714 and The LZ935 etc. of Lubrizol Corp.'s production.

In the present invention, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersing agent The weight ratio of polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersing agent is excellent in mixture It is selected as 1-3:1.

In the present invention, the base number of high base number magnesium salicylate is preferably 100-450mgKOH/g, more preferably 300- 450mgKOH/g, the base number of low alkali value sulfoacid calcium preferably≤100mgKOH/g, more preferably≤50mgKOH/g, high base number salicylic acid The weight ratio of magnesium and low alkali value sulfoacid calcium is preferably 0.1-10:1, more preferably 0.6-3:1.High base number magnesium salicylate and low alkali value T101, T102, T103, T104 that the mixture of sulfoacid calcium can for example select Wuxi south additive company to produce, Run Yinglian C9006, C9012 etc. of company's production.

In the present invention, the alkyl in zinc dialkyl dithiophosphate is preferably the alkyl of C2-C12, more preferably C2-C8's Alkyl, further preferably ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, just oneself Base, isohesyl, n-octyl, iso-octyl, 2- ethylhexyl, cyclohexyl or methylcyclopentyl.Zinc dialkyl dithiophosphate can be with T202, the T203 for selecting WUXI SOUTH PETROLEUM ADDITIVE Co., LTD. to produce, the primary of the production of Jinzhou Petrochemical Company additive factory Alkyl T202, primary alkyl T203, brothers alkyl T204, secondary alkyl T205, LZ1371, LZ1375 of Lubrizol Corp.'s production, profit C9417, C9425, C9426 of Ying Lian company production, Hitec7169, Hitec1656 etc. of Afton Chemical Corp.'s production.

In the present invention, Ashless friction modifiers are preferably selected from polyol esters of fatty acids, aliphatic amine and aliphatic amide One or more, the more preferably mixture of polyol esters of fatty acids and aliphatic amide, polyol esters of fatty acids and fat The weight ratio of race's amide is preferably 0.5-3:1, wherein aliphatic alkyl be preferably saturation of the carbon atom number between 6-60 or The saturation or unsaturated alkyl of unsaturated alkyl, more preferably carbon atom number between 10-50.

The polyol esters of fatty acids is preferably selected from fatty glyceride, fatty acid pentaerythritol ester, fatty acid ethylene glycol The compounds such as ester, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, fatty acid triethanolamine ester At least one of monoesters, dibasic acid esters and polyester are more preferably selected from glyceryl monooleate, double oleins, stearic acid single cropping penta At least one of four alcohol esters, lauric acid/dodecanoic acid diethylene glycol dilaurate, oleic acid diethanol amine monoesters and triethanolamine oleate monoesters；The rouge Fat race amine is preferably selected from alkyl and monoamine or polyamine, alkoxylated alkyl is replaced to replace monoamine or polyamine and alkyl ether The butter fat ether amines of at least one of amine etc., the more preferably tallow amine of ethoxylation and/or ethoxylation；It is described Aliphatic amide is preferably selected from least one of oleamide, coconut oleoyl amine and oleic acid diethyl amide etc..Ashless friction changes F10, F20 etc. of BASF Aktiengesellschaft can be for example selected into agent.

Lubricant oil composite of the invention can also contain at least one in antirust agent, pour-point depressant, anti-foaming agent and tackifier Kind.Antirust agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline fourth two At least one of hydrochlorate and alkenyl succinic acid ester, such as Jinzhou Kangtai Lube Additive Co., Ltd. can be selected to produce T746,T703,T747.The dialkyl group that pour-point depressant can be C8-C18 selected from poly alpha olefin, vinyl acetate copolymer and alkyl At least one of fumarate, poly- alkylmethacrylate, alkylnaphthalene, such as Wuxi south petroleum additive can be selected V385, Luo Mankesi VISCOPLEX1-248 of T803, Run Yinglian company of company etc..Anti-foaming agent can select polysiloxane type Anti-foaming agent, such as can be silicone oil and/or dimethyl silicone polymer.Tackifier can be selected from ethylene propylene copolymer, poly- methyl At least one of methyl acrylate and hydrogenated styrene isoprene copolymer, for example, can select T601, SV260, Lz7065 etc..For antirust agent, pour-point depressant, tackifier and anti-foaming agent content without particular/special requirement, can be conventional for this field Content, this is known to those skilled in the art, and details are not described herein.

In the present invention, the preparation method of the compound of structure shown in formula (I) is preferably included:

(a) aniline, sulfur chloride and 4- chloroaniline are reacted, generate intermediate M shown in formula (II),

(b) the intermediate M and dimercapto -1,3,4- thiadiazoles that step (a) obtains nucleophilic is carried out under alkaline condition to take Generation reaction, generates multipurpose additive shown in formula (I),

In step (a) of the present invention, the concrete mode that aniline, sulfur chloride and 4- chloroaniline react is preferably included:

(i) under an inert atmosphere, in the first solvent, aniline is sufficiently reacted at -20-0 DEG C with sulfur chloride；

(ii) 4- chloroaniline is added in the reaction system of step (i), reacts 1-3h at 15-30 DEG C.

In the present invention, inert atmosphere can be the inert atmosphere of this field routine, such as can be by gases such as nitrogen, argon gas It provides.

In step (i) of the present invention, the first solvent is preferably selected from methylene chloride, tetrahydrofuran, toluene, dimethylbenzene and dioxy six At least one of ring, more preferably methylene chloride and/or tetrahydrofuran are still more preferably methylene chloride.

It in the present invention in step (i), is sufficiently reacted and refers to fully reacting, is i.e. reaction raw materials are reacted completely. Reaction can be monitored using method commonly used in the art, to confirm fully reacting, such as thin layer chromatography can be used (TLC) or the methods of gas-chromatography is monitored.

In step (ii) of the present invention, 1-3h is reacted at 15-30 DEG C, preferably after step (i) sufficiently reaction, by reactant The temperature of system is gradually increased to 15-30 DEG C, adds 4- chloroaniline and carries out reaction 1-3h.It, can be further under the preferable case Improve reaction yield.

In step (ii) of the present invention, the adding manner of 4- chloroaniline is preferably to be added by several times, such as can divide 3-4 times and add Enter.Under the preferable case, reaction yield can be further improved.When gradation is added, each additional amount can be identical, It can also be different, in order to easy to operate, preferably each additional amount is identical.

In step (ii) of the present invention, react 1-3h, stop reaction mode can for those skilled in the art it is contemplated that Various modes, be quenched for example, quencher can be added, quencher can be quencher commonly used in the art, such as can Think saturated salt solution.

In the present invention, the dosage of aniline, sulfur chloride and 4- chloroaniline is substantially equimolar amounts, but aniline and sulfur chloride can With appropriate excessive.The molar ratio of aniline, sulfur chloride and 4- chloroaniline is preferably 0.9-1.5:0.9-1.5:0.8-1.2.

It will be understood by those skilled in the art that purer intermediate M, goes back in order to obtain in step (a) of the present invention It needing to post-process the system after reaction, the mode of post-processing may include washing, drying, solvent be removed under reduced pressure, for example, Reaction system after being quenched is used into distilled water and saturated common salt water washing respectively, anhydrous calcium chloride then is added at 15-30 DEG C Or the desiccant such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C Solvent is removed, to obtain intermediate M.

In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4- chloroaniline are reacted is as shown in Figure 1, figure In 1, the first solvent is using methylene chloride, and purpose by way of example only is not construed as limiting the scope of the present invention.

In step (b) of the present invention, the condition of nucleophilic substitution is preferably included: under an inert atmosphere, in the second solvent, Dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed into 10-30min at 15-30 DEG C, intermediate is then added M is sufficiently reacted.I.e. alkaline condition is provided by alkaline reagent.

" inert atmosphere ", " sufficiently being reacted " are as previously mentioned, details are not described herein.

In the present invention, intermediate M is preferably slowly added to, such as can be added by several times, and 3-4 addition can be generally divided.? Under the preferable case, reaction yield can be further improved.When gradation is added, each additional amount can be identical, can also With difference, in order to easy to operate, preferably each additional amount is identical.

In the present invention, the second solvent is preferably selected from methylene chloride, tetrahydrofuran, toluene, dimethylbenzene, N, N- dimethyl formyl At least one of amine, more preferably methylene chloride and/or n,N-Dimethylformamide are still more preferably N, N- dimethyl Formamide.

In the present invention, alkaline reagent is preferably selected from least one of inorganic bases such as potassium carbonate, sodium carbonate, sodium methoxide.

In the present invention, catalyst is preferably potassium sulfate.

In step (b) of the present invention, the dosage of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate M is substantially etc. Mole, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Dimercapto -1,3,4- thiadiazoles, alkalinity examination The molar ratio of agent and intermediate M are preferably 0.9-3.0:0.9-5.0:0.8-1.5.

In step (b) of the present invention, the dosage of catalyst can be catalytic amount, with mole of dimercapto-1,3,4-thiadiazole On the basis of number, the dosage of catalyst is preferably 5-100 moles of %, more preferably 10-50 moles of %.

In step (b) of the present invention, reaction equation such as Fig. 2 that dimercapto-1,3,4-thiadiazole and intermediate M are reacted Shown, in Fig. 2, alkaline reagent is using potassium carbonate, purpose by way of example only, does not constitute and limits to the scope of the present invention System.

It will be understood by those skilled in the art that purer final product, i.e., multiple-effect of the invention add in order to obtain Add agent, the present invention prepares the method for multipurpose additive it is also preferable to include post-processing to the system after reaction, the side of post-processing Formula may include washing, drying, solvent be removed under reduced pressure, for example, the system after abundant reaction to be poured into the acetic acid of 1-10 times of volume In ethyl ester (or methylene chloride), distilled water and saturated common salt water washing are used respectively, anhydrous calcium chloride then is added at 15-30 DEG C Or the desiccant such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C Solvent is removed, to obtain final product.

Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention preferably carries out under stiring, for Mixing speed can be the mixing speed of this field routine, for example, mixing speed can be 100-800rpm without particular/special requirement.

In the present invention, for the first solvent and the second solvent amount without particular/special requirement, can be the solvent of this field routine Dosage, this is known to those skilled in the art, and details are not described herein.

As described above, the present invention is directed to the compound by containing structure shown in formula (I) in lubricant oil composite, and formula (I) compound and thiophenols ester type antioxidant of structure shown in are combined and realize goal of the invention, even if lubricant oil composite has The excellent performances such as wear-resistant and anti-oxidant, inhibit the generation of high temperature deposition object.Therefore, for the preparation method of lubricant oil composite Without particular/special requirement, method commonly used in the art can be used, for example, second aspect, the present invention also provides a kind of diesel oil The preparation method of engine oil composition, this method comprises: by being added containing lube base oil, the wear-resistant multiple-effect of antioxygen Agent, thiophenols ester type antioxidant, polyisobutene succinimide ashless dispersant and the dispersion of boronation polyisobutene succinimide The mixture of agent, the mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium, zinc dialkyl dithiophosphate and Ashless friction The raw material of modifier is uniformly mixed and obtains lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, lubricates oil base The dosage of plinth oil is 75-95 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-10 weight %, thiophenols ester type is anti- The dosage of oxygen agent is 0.02-8 weight %, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide The dosage of the mixture of dispersing agent is 0.5-10 weight %, the dosage of the mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium For 0.2-10 weight %, the dosage of zinc dialkyl dithiophosphate be in terms of phosphorus≤0.15 weight %, Ashless friction modifiers Dosage is 0.01-5 weight %, and the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I):

In the method for the present invention, it is preferable that on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 75-85 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen are 0.02-5 weight %, more preferably 0.1-4 weight %, thiophenols The dosage of ester type antioxidant is 0.05-4 weight %, more preferably 0.1-3 weight %, polyisobutene succinimide ashless dispersion The dosage of the mixture of agent and boronation polyisobutene succinimide dispersing agent is 1.5-8 weight %, more preferably 3-7 weight The dosage of the mixture of amount %, high base number magnesium salicylate and low alkali value sulfoacid calcium is 0.5-8 weight %, more preferably 0.8-6 weight % is measured, the dosage of zinc dialkyl dithiophosphate is the weight % of the 0.01-0.1 in terms of phosphorus, and the dosage of Ashless friction modifiers is 0.02-2 weight %, more preferably 0.05-1.2 weight %.

As previously mentioned, raw material can also be containing in antirust agent, pour-point depressant, tackifier and anti-foaming agent in the method for the present invention It is at least one.

In the method for the present invention, for mixed mode without particular/special requirement, such as each original of lube base oil can will be removed Material component is added separately in lube base oil, can also will be mixed and made into concentrate again except each component of lube base oil It is added in lube base oil.

In the method for the present invention, mixed condition is preferably included: temperature is 40-90 DEG C, time 1-6h.

The wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, polyisobutene succinimide without The mixture of grey dispersing agent and boronation polyisobutene succinimide dispersing agent, high base number magnesium salicylate and low alkali value sulfoacid calcium For example preceding institute of mixture, zinc dialkyl dithiophosphate, Ashless friction modifiers, antirust agent, pour-point depressant, tackifier and anti-foaming agent It states, details are not described herein.

Embodiment

The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.

In the following Examples and Comparative Examples:

The method for monitoring fully reacting: thin-layer chromatography chromatography (TLC) fluorescence developing method.

Gross production rate=final product mole/aniline moles × 100%

The physico-chemical analysis method of product: constituent content is measured by inductively coupled plasma body ion emission spectroscopy method.

Structure characterization methods: nuclear magnetic resonance method (¹H hydrogen spectrum,¹³C carbon spectrum), high resolution mass spectrum.

Preparation example

It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 300rpm), 150ml is added Methylene chloride, then be added 0.2mol sulfur chloride, after being fully cooled in ice-water bath, the aniline of 0.2mol is added.Monitoring Ice-water bath is moved back to fully reacting, is placed in 25 DEG C at room temperature, after reaction system is gradually increased to 25 DEG C, is added three times 4- chlorine Aniline is reacted, and each additional amount is identical, and 4- chloroaniline 0.15mol is added altogether.30ml saturation is added after sustained response 2 hours Reaction system, is then transferred in separatory funnel by saline solution quenching reaction, uses 50ml distilled water and 50ml saturated salt solution respectively Washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is evaporated off molten under 40 DEG C, 0.05MPa Agent obtains intermediate M1.

It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 400rpm), 150ml is added DMF (n,N-Dimethylformamide), be then added 0.2mol dimercapto-1,3,4-thiadiazole and 0.2mol potassium carbonate, The potassium sulfate of 0.05mol stirs 20 minutes at 25 DEG C, is added three times above-mentioned intermediate M1, and each additional amount is identical, is added altogether Intermediate M10.12mol.Then to fully reacting 250ml ethyl acetate is added in reaction system by monitoring, and be transferred to separatory funnel In, 100ml distilled water (twice) and 50ml saturated common salt water washing are used respectively, and 15g anhydrous sodium sulfate is added and does at 25 DEG C Dry 20min.Solvent is evaporated off at 40 DEG C, 0.03MPa in filtered filtrate, obtains final product S1.Calculating gross production rate is 76%.

The physico-chemical analysis data of product are as follows: sulfur content, and 41.3%；Nitrogen content, 13.9%.

S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 3, Fig. 4 and Fig. 5.

It can be seen that S1 with knot shown in formula (I) from the physico-chemical analysis data of above-mentioned preparation example, Fig. 3, Fig. 4 and Fig. 5 Structure.

Embodiment 1

The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.

By the S1 of 0.1 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 3 parts by weight Ethyl ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 1.5 parts by weight 1600), 1.5 parts by weight boronation polyisobutene succinimide dispersing agent (number-average molecular weight of polyisobutene part be 1000, Boron content be 0.5 weight %), the high base number magnesium salicylate (base number 300mgKOH/g) of 4.5 parts by weight, 1.5 parts by weight it is low Base number calcium sulfonate (base number 50mgKOH/g), two isohesyl zinc dithiophosphates of 0.11 parts by weight, the list of 0.03 parts by weight are oily Acid glyceride, the oleamide of 0.02 parts by weight, 0.1 parts by weight pour-point depressant VISCOPLEX1-248 (be purchased from U.S. Luo Manke This Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S.) and 6.8 parts by weight tackifier Lz7065, be added to the 600SN lube base oil of 80.84 parts by weight In (viscosity index (VI) 87, saturated hydrocarbon content are 92 weight %, and sulfur content is 0.02 weight %), 3h is stirred at 60 DEG C, is mixed Uniformly obtain the diesel engine lubricating oil composite A1 that viscosity rank is 15W-40.

Embodiment 2

By the S1 of 0.3 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 0.3 parts by weight Acetoacetic ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 5.25 parts by weight 1000), (number-average molecular weight of polyisobutene part is the boronation polyisobutene succinimide dispersing agent of 1.75 parts by weight 1300, boron content is 0.5 weight %), the high base number magnesium salicylate (base number 350mgKOH/g) of 1.4 parts by weight, 0.6 parts by weight Low alkali value sulfoacid calcium (base number 30mgKOH/g), the isobutyl group iso-octyl zinc dithiophosphate of 1.1 parts by weight, 0.2 parts by weight Double oleins, the coconut oleoyl amines of 0.4 parts by weight, 0.1 parts by weight pour-point depressant VISCOPLEX1-248 (be purchased from U.S. sieve Man Kesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S.) and 6.8 parts by weight tackifier Lz7065, be added to the II class 150N base oil of 73 parts by weight The mixed lubrication oil base oil of the II class 600N base oil (viscosity index (VI) 103) of (viscosity index (VI) 101) and 8.8 parts by weight In, 6h is stirred at 40 DEG C, is uniformly mixed and obtains the diesel engine lubricating oil composite A2 that viscosity rank is 15W-40.

Embodiment 3

By the S1 of 4 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 0.1 parts by weight Ethyl ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 3.34 parts by weight 2400), (number-average molecular weight of polyisobutene part is the boronation polyisobutene succinimide dispersing agent of 1.67 parts by weight 2300, boron content is 0.5 weight %), the high base number magnesium salicylate (base number 450mgKOH/g) of 0.3 parts by weight, 0.5 parts by weight Low alkali value sulfoacid calcium (base number 40mgKOH/g), the n-hexyl n-octyl zinc dithiophosphate of 0.53 parts by weight, 0.9 weight Part stearic acid monopentaerythritol ester, the oleic acid diethyl amides of 0.3 parts by weight, 0.1 parts by weight pour-point depressant VISCOPLEX1- The tackifier Lz7065 of 248 (being purchased from U.S. Luo Mankesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S.) and 6.8 parts by weight, is added to 81.46 parts by weight 300SN lube base oil (viscosity index (VI) 91, saturated hydrocarbon content be 92 weight %, sulfur content be 0.01 weight %) in, 1h is stirred at 90 DEG C, is uniformly mixed and obtains the diesel engine lubricating oil composite A3 that viscosity rank is 15W-40.

Comparative example 1

Lubricant oil composite is prepared according to the method for embodiment 2, unlike, S1 is replaced with etc. the 2,2'- of parts by weight Thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] obtains the diesel engine that viscosity rank is 15W-40 Lubricant oil composite D1.

Comparative example 2

Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by 2,2'- thiobis [3- (3,5- bis- uncles Butyl -4- hydroxy phenyl) ethyl propionate] S1 that the parts by weight such as replaces with, obtain the diesel engine that viscosity rank is 15W-40 Lubricant oil composite D2.

Comparative example 3

Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5- Di-tert-butyl-hydroxy phenyl) ethyl propionate] zinc dibutyl dithiocarbamate that the parts by weight such as replaces with, obtain viscosity Rank is the diesel engine lubricating oil composite D3 of 15W-40.

Comparative example 4

Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5- Di-tert-butyl-hydroxy phenyl) ethyl propionate] the trimethylphenyl zinc phosphites of parts by weight such as replace with, obtaining viscosity rank is The diesel engine lubricating oil composite D4 of 15W-40.

Comparative example 5

Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5- Di-tert-butyl-hydroxy phenyl) ethyl propionate] the fourth octyl diphenylamine that the parts by weight such as replaces with, obtaining viscosity rank is 15W- 40 diesel engine lubricating oil composite D5.

Test case

Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively:

The measurement of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzer；

The measurement of oxidation induction period is carried out using high pressure differential scanning amount method (PDSC)；

Deposit production quantity is measured using crankcase QZX experiment method: QZX experiment instrument is added in 300mL oil sample, Heating and keeping oil temperature is 130 DEG C, and aluminium sheet temperature is 290 DEG C, to the continuous spilled oil 6h of aluminium sheet, is generated on weighing aluminium sheet after test Jiao Liang, as deposit production quantity.

The wear-resistant test of high temperature of oil product is carried out using high-frequency reciprocating frictional testing machine (being purchased from Britain PCS company, HFRR), Experimental condition are as follows: load 1000g, temperature are 100 DEG C, test period 60min, measure the mill formed on steel ball after the test Spot diameter.It the results are shown in Table 1.

Table 1

	A1	A2	A3	D1	D2	D3	D4	D5
									Initial oxidation temperature, DEG C	224	218	241	199	207	195	186	182
Oxidation induction period, min	43.9	41.3	57.2	25.5	34.3	26.6	15.7	13.4
									Deposit production quantity, mg	30.6	29.8	20.4	53.5	42.7	56.9	61.6	63.7
Wear scar diameter, mm	0.48	0.47	0.44	0.73	0.58	0.74	0.69	0.76

It will be understood by those skilled in the art that initial oxidation temperature is higher, the thermal stability of lubricating oil is better；Oxidation Induction period is longer, and the antioxygenic property of lubricating oil is better；Deposit production quantity is higher, and lubricating oil inhibits high temperature deposition object to generate Ability is poorer；Wear scar diameter is smaller, and the wear resistance of lubricating oil is better.

A2 is compared with D1-D5 respectively as can be seen that lubricant oil composite of the invention has better thermostabilization Property, inoxidizability and abrasion resistance, there is the ability for preferably high temperature deposition object being inhibited to generate.

It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention Monotropic type, these simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims

1. A diesel engine lubricating oil composition, characterized in that, based on the weight of the lubricating oil composition, the lubricating oil composition contains the following components: 75-95 wt% lubricating oil base oil, 0.01-10 wt % % by weight of antioxidant and antiwear multi-effect additive, 0.02-8% by weight of thiophenol ester type antioxidant, 0.5-10% by weight of polyisobutylene succinimide ashless dispersant and boronated polyisobutylene succinyl Mixtures of imine dispersants, 0.2-10% by weight of magnesium salicylate with high base number and calcium sulfonate with low base number, ≤0.15% by weight of zinc dialkyldithiophosphates based on phosphorus, and 0.01-5 % by weight of an ashless friction modifier, the antioxidant and antiwear multi-effect additive is a compound of the structure represented by formula (I):

2. The lubricating oil composition according to claim 1, wherein, based on the weight of the lubricating oil composition, the lubricating oil composition contains the following components: 75-85 wt% lubricating oil base oil, 0.1-85 wt. 4% by weight of antioxidant and antiwear multi-effect additive, 0.1-3% by weight of thiophenol ester type antioxidant, 3-7% by weight of polyisobutylene succinimide ashless dispersant and boronated polyisobutylene butadiene A mixture of imide dispersants, a mixture of 0.8-6 wt% magnesium salicylate with a low base number and a low base number calcium sulfonate, 0.01-0.1 wt% zinc dialkyldithiophosphate and 0.05 wt% based on phosphorus - 1.2 wt% ashless friction modifier.

3. The lubricating oil composition according to claim 1 or 2, wherein the lubricating oil base oil is a mineral lubricating oil and/or a synthetic lubricating oil.

4. The lubricating oil composition according to claim 1 or 2, wherein the thiophenol ester type antioxidant is 2,2'-thiobis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl) ethyl propionate].

5. The lubricating oil composition according to claim 1 or 2, wherein the polyisobutylene moiety in the polyisobutylene succinimide ashless dispersant has a number average molecular weight of 800-4000; the boronized polyisobutylene butylene The number average molecular weight of the polyisobutylene part in the diimide dispersant is 500-4000; the weight ratio of the polyisobutylene succinimide ashless dispersant to the boronized polyisobutylene succinimide dispersant is 1 -3:1.

6. The lubricating oil composition according to claim 1 or 2, wherein the polyisobutylene moiety in the polyisobutylene succinimide ashless dispersant has a number average molecular weight of 900-3000.

7. The lubricating oil composition according to claim 1 or 2, wherein the polyisobutylene moiety in the polyisobutylene succinimide ashless dispersant has a number average molecular weight of 1000-2400.

8. The lubricating oil composition of claim 1 or 2, wherein the number average molecular weight of the polyisobutylene moiety in the boronated polyisobutylene succinimide dispersant is 700-2500.

9. The lubricating oil composition according to claim 1 or 2, wherein the number average molecular weight of the polyisobutylene moiety in the boronated polyisobutylene succinimide dispersant is 1000-2300.

10. The lubricating oil composition according to claim 1 or 2, wherein the base number of the high-base number magnesium salicylate is 100-450 mgKOH/g; the base number of the low-base number calcium sulfonate is less than or equal to 100 mgKOH /g; the weight ratio of the high base number magnesium salicylate and the low base number calcium sulfonate is 0.1-10:1.

11. The lubricating oil composition according to claim 1 or 2, wherein the base value of the high base number magnesium salicylate is 300-450 mgKOH/g; the base number of the low base number calcium sulfonate is less than or equal to 50mgKOH /g; the weight ratio of the high base number magnesium salicylate and the low base number calcium sulfonate is 0.6-3:1.

12. The lubricating oil composition according to claim 1 or 2, wherein the alkyl group in the zinc dialkyldithiophosphate is a C2-C12 alkyl group.

13. The lubricating oil composition according to claim 1 or 2, wherein the alkyl group in the zinc dialkyldithiophosphate is a C2-C8 alkyl group.

14. The lubricating oil composition according to claim 1 or 2, wherein the alkyl group in the zinc dialkyldithiophosphate is ethyl, n-propyl, isopropyl, n-butyl, isobutyl , sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl or 2-ethylhexyl.

15. The lubricating oil composition according to claim 1 or 2, wherein the ashless friction modifier is selected from one or more of fatty acid polyol esters, aliphatic amines and aliphatic amides, fatty acid polyols Esters, aliphatic amines and aliphatic amides have 6-60 carbon atoms.

16. The lubricating oil composition according to claim 1 or 2, wherein the ashless friction modifier is a mixture of fatty acid polyol ester and aliphatic amide, and the weight ratio of fatty acid polyol ester and aliphatic amide is 0.5 -3:1.

17. The lubricating oil composition according to claim 15, wherein the fatty acid polyol ester, the aliphatic amine and the aliphatic amide have 10-50 carbon atoms.

18. The lubricating oil composition according to claim 15, wherein the fatty acid polyol ester is selected from at least one of fatty acid glycerides, fatty acid pentaerythritol esters, monoesters, diesters and polyesters of fatty acid ethylene glycol esters The aliphatic amine is selected from at least one of hydrocarbyl-substituted monoamine or polyamine, alkoxylated hydrocarbyl-substituted monoamine or polyamine and alkyl ether amine, and the aliphatic amide is selected from oil At least one of acid amide, cocamide and oleic acid diethanolamide.

19. The lubricating oil composition of claim 18, wherein the fatty acid polyol ester is selected from the group consisting of glycerol monooleate, glycerol dioleate, monopentaerythritol stearate, and ethylene glycol dilaurate At least one of esters; the aliphatic amine is ethoxylated tallow amine and/or ethoxylated tallow ether amine.

20. The lubricating oil composition according to claim 1 or 2, wherein the lubricating oil composition further contains at least one of a rust inhibitor, a pour point depressant, a tackifier and an antifoaming agent.

21. The lubricating oil composition according to claim 20, wherein the rust inhibitor is selected from the group consisting of imidazole type rust inhibitor, alkenyl succinate type rust inhibitor and alkenyl imidazoline succinate. at least one.

22. The lubricating oil composition according to claim 20, wherein the rust inhibitor is at least one of 4,5-dihydroimidazole and alkenyl succinate.

23. The lubricating oil composition according to claim 20, wherein the pour point depressant is selected from the group consisting of polyalpha-olefins and dialkyl fumarate with alkyl groups of C8-C18, polyalkyl methacrylates , at least one of alkylnaphthalenes.

24. The lubricating oil composition of claim 20, wherein the tackifier is at least one of ethylene propylene copolymer, polymethyl methacrylate, and hydrogenated styrene isoprene copolymer.

25. The lubricating oil composition according to claim 20, wherein the antifoaming agent is a silicone type antifoaming agent.

26. The lubricating oil composition of claim 20, wherein the antifoaming agent is a silicone oil.

27. The lubricating oil composition of claim 20, wherein the antifoaming agent is polydimethylsiloxane.

28. A method for preparing a diesel engine lubricating oil composition, characterized in that the method comprises: mixing a base oil containing lubricating oil, an antioxidant and antiwear multi-effect additive, a thiophenol ester type antioxidant, a polyisobutylene butylene Mixture of imide ashless dispersant and boronated polyisobutylene succinimide dispersant, mixture of overbase magnesium salicylate and low base number calcium sulfonate, zinc dialkyldithiophosphate and ashless The raw materials of the friction modifier are evenly mixed to obtain a lubricating oil composition, wherein, based on the weight of the lubricating oil composition, the amount of the lubricating oil base oil is 75-95% by weight, and the amount of the antioxidant and anti-wear multi-effect additive is 0.01-95% by weight. 10% by weight, the amount of thiophenol ester type antioxidant is 0.02-8% by weight, the amount of the mixture of polyisobutylene succinimide ashless dispersant and boronized polyisobutylene succinimide dispersant is 0.5- 10% by weight, the amount of the mixture of high base number magnesium salicylate and low base number calcium sulfonate is 0.2-10% by weight, the amount of zinc dialkyldithiophosphate is ≤0.15% by weight in terms of phosphorus, ashless The amount of friction modifier is 0.01-5% by weight, and the anti-oxidative and anti-wear multi-effect additive is a compound of the structure represented by formula (I):

29. The method according to claim 28, wherein, based on the weight of the lubricating oil composition, the amount of the lubricating oil base oil is 75-85% by weight, and the amount of the antioxidant and antiwear multi-effect additive is 0.1-4% by weight %, the amount of thiophenol ester type antioxidant is 0.1-3% by weight, the amount of the mixture of polyisobutylene succinimide ashless dispersant and boronized polyisobutylene succinimide dispersant is 3-7% by weight %, the amount of the mixture of high base number magnesium salicylate and low base number calcium sulfonate is 0.8-6% by weight, the amount of zinc dialkyldithiophosphate is 0.01-0.1% by weight based on phosphorus, ashless friction The modifier is used in an amount of 0.05-1.2% by weight.

30. The method according to claim 28 or 29, wherein the mixing conditions comprise: a temperature of 40-90° C. and a time of 1-6 h.