CN106318547B - A kind of methanol-fueled engine lubricant oil composite and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of methanol-fueled engine lubricant oil composites, on the basis of the weight of lubricant oil composite, contain following components: the lube base oil of 75-95 weight %, the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.02-5 weight %, the polyisobutene succinimide ashless dispersant of 0.5-10 weight % and the mixture of polyisobutylene succinic acid ester dispersing agent, the sodium sulfonate of 0.2-10 weight % and the mixture of calcium naphthenate, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.08 weight % and the compound friction improving agent of 0.01-5 weight %, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I).Additionally provide the preparation method of lubricant oil composite.Lubricant oil composite of the invention has excellent wear-resistant and antioxygenic property, can inhibit the generation of high temperature deposition object, can be widely applied to methanol-fueled engine.

Description

A kind of methanol-fueled engine lubricant oil composite and preparation method thereof

Technical field

The present invention relates to lubricating oil fields, and in particular, to a kind of methanol-fueled engine profit containing special additive Sliding oil composition and preparation method thereof.

Background technique

The methanol fuel alternative energy source novel as one is with a wide range of applications, and the by-product that methanol burning generates Object is acid by force, it is rotten to easily lead to engine oil.Methanol gasoline in use, unavoidably has methanol to enter in lubricating oil. Gas blowby in engine working process, the cooling procedure of engine working process are likely to make methanol condensed and enter lubricating oil. Methanol can aoxidize generation formaldehyde in combustion, and formaldehyde is the intermediate product in methanol combustion process, and then aoxidize and generate first Acid.Oxidation product formic acid will make each component of engine generate stronger corrosive wear.Therefore, it is fired using the methanol of 100% content Material, or mixing different proportion carbinol gasoline fuel engine the high-temperature oxidation resistance of lubricating oil is proposed it is very high Requirement.Methanol-fueled engine oil is easier to be diluted relative to normal engine oil, therefore it is required that having preferably wear-resistant The requirement such as performance.Engine oil for methanol fuel has better deposit resistant to high temperatures and abrasion-resistance is in a research and development Difficult point.

The high-temperature oxidation resistance of engine lubricating oil is always an important indicator in oil specification.Engine technology Continuous development, the especially application of the gentle in-cylinder direct-jet technology of turbocharging technology, the temperature ratio at the positions such as engine piston Pervious engine significantly improves, and the speed of engine oil aged deterioration is dramatically speeded up, and the consumption of engine oil increases, and especially exists The generation of the key positions engine high-temperature deposit such as piston, combustion chamber, seriously affects the working performance of engine, causes to start The problems such as machine difficulty in starting, unstable idle speed, driving are poor, acceleration is poor, power loss is serious.In new SN/GF-5 in 2010 Harsher requirement is proposed to the piston deposit of IIIG engine test test engine oil in specification, piston deposit is commented Divide and promoted by 3.5 to 4 by index, severity greatly improves.This proposes new demand to the high temperature antioxygen property of antioxidant, Develop direction of the novel high-temperature antioxidant as the research effort of those skilled in the art.

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 methanol-fueled engine lubricating oil and inhibit high temperature heavy The high request for the ability that product object generates, provides a kind of methanol-fueled engine lubricant 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 methanol-fueled engine lubricant oil composite can be made to have There are the excellent 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 methanol-fueled engine lubricating oil compositions Object, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: the lubrication of 75-95 weight % Oil base oil, the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, 0.02-5 weight % thiophenols ester type antioxidant, The mixture of the polyisobutene succinimide ashless dispersant of 0.5-10 weight % and polyisobutylene succinic acid ester dispersing agent, The mixture of the sodium sulfonate of 0.2-10 weight % and calcium naphthenate, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.08 weight % With the compound friction improving agent of 0.01-5 weight %, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I):

Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 78-90 The sulfophenates of the lube base oil of weight %, the wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, 0.2-1.5 weight % Type antioxidant, the polyisobutene succinimide ashless dispersant of 3-6 weight % and polyisobutylene succinic acid ester dispersing agent it is mixed Close the dialkyl disulfides of object, the mixture of the sodium sulfonate of 1.2-6 weight % and calcium naphthenate, the weight of the 0.01-0.08 in terms of phosphorus % For the compound friction improving agent of trbasic zinc phosphate and 0.05-1.2 weight %.

On the other hand, the present invention provides a kind of preparation method of methanol-fueled engine lubricant oil composite, the sides Method includes: that will contain lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, polyisobutene succinyl Mixture, the dioxane of the mixture of imines ashless dispersant and polyisobutylene succinic acid ester dispersing agent, sodium sulfonate and calcium naphthenate The raw material of base zinc dithiophosphate and compound friction improving agent is uniformly mixed and obtains lubricant oil composite, wherein with lubricating oil group On the basis of the weight for closing object, the dosage of lube base oil is 75-95 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-10 weight %, thiophenols ester type antioxidant dosage be 0.02-5 weight %, polyisobutene succinimide ashless disperse The dosage of the mixture of agent and polyisobutylene succinic acid ester dispersing agent is 0.5-10 weight %, the mixing of sodium sulfonate and calcium naphthenate The dosage of object is 0.2-10 weight %, the dosage of zinc dialkyl dithiophosphate be in terms of phosphorus≤0.08 weight %, compound friction The dosage of modifier is 0.01-5 weight %, and the wear-resistant multipurpose additive of antioxygen 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 78-90 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 0.2-1.5 weight %, poly- The dosage of the mixture of isobutene Ashless butyl diimide dispersant and polyisobutylene succinic acid ester dispersing agent is 3-6 weight %, The dosage of the mixture of sodium sulfonate and calcium naphthenate is 1.2-6 weight %, and the dosage of zinc dialkyl dithiophosphate is in terms of phosphorus 0.01-0.08 weight %, the dosage of compound friction improving agent are 0.05-1.2 weight %.

Methanol-fueled engine lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can press down The generation of preparing high-temp deposit, can be widely applied to methanol-fueled engine.

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 methanol-fueled engine lubricant oil composites, with the weight of lubricant oil composite On the basis of amount, the lubricant oil composite contains following components: lube base oil, the 0.01-10 weight % of 75-95 weight % The wear-resistant multipurpose additive of antioxygen, the thiophenols ester type antioxidant of 0.02-5 weight %, 0.5-10 weight % polyisobutene fourth The sodium sulfonate and cycloalkanes of the mixture of imidodicarbonic diamide ashless dispersant and polyisobutylene succinic acid ester dispersing agent, 0.2-10 weight % The mixture of sour calcium, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.08 weight % and the compound friction of 0.01-5 weight % change Into agent, the wear-resistant multipurpose additive of antioxygen is 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 78-90 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 0.1-2 weight %, more preferably 0.2-1.5 weight %；Polyisobutene succinimide ashless The content of the mixture of dispersing agent and polyisobutylene succinic acid ester dispersing agent is preferably 1.5-8 weight %, more preferably 3-6 weight Measure %；The content of the mixture of sodium sulfonate and calcium naphthenate is preferably 0.8-8 weight %, more preferably 1.2-6 weight %；Dioxane The content of base zinc dithiophosphate is preferably 0.01-0.08 weight % in terms of phosphorus；The content of compound friction improving agent is 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 and thiophenols ester type antioxidant of structure are combined and realize goal of the invention, even if methanol-fueled engine lubricant oil composite With the excellent performances such as wear-resistant and anti-oxidant.Therefore, for the selection of conventional constituents each in lubricant oil composite, without spy Fixed limitation.

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 800- in polyisobutylene succinic acid ester dispersing agent 4000, more preferably 900-3000, further preferably 1000-2400.Polyisobutylene succinic acid ester dispersing agent can for example select The LZ936 etc. produced with Lubrizol Corp..

In the present invention, the weight ratio of polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent Preferably 1-3:1.

In the present invention, the base number of sodium sulfonate is preferably 100-450mgKOH/g, more preferably 200-450mgKOH/g, cycloalkanes The base number of sour calcium is preferably 100-200mgKOH/g, and the weight ratio of sodium sulfonate and calcium naphthenate is preferably 0.2-4:1, more preferably 0.5-2:1.The mixture of sodium sulfonate and calcium naphthenate can for example select Dushanzi petro-chemical corporation produce T112, T113, T114, the KT5448 etc. of Jinzhou Kangtai Lube Additive Co., Ltd.'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, compound friction improving agent preferably comprises oil-soluble organic molybdenum friction improver and Ashless friction improves Agent.

Oil-soluble organic molybdenum friction improver is preferably selected from molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen Molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex and molybdenum One of esters of gallic acid oil-soluble organic molybdenum friction improver is a variety of, has in above-mentioned organic molybdenum former comprising enough carbon The organic group of subnumber is so that organic molybdenum is dissolved in or is scattered in base oil, and the general carbon atom number is in 6- Between 60, between preferably 10-50.Oil-soluble organic molybdenum friction improver can for example select Vanderbilt company, the U.S. to produce MolyVan L, 822,855, the Japanese rising sun electrification company production 515,525,710 etc..Oil-soluble organic molybdenum friction improver It is preferred that accounting for the 5-50% of compound friction improving agent gross mass, more preferably 10-40%.

Ashless friction modifiers are preferably selected from one kind or more of polyol esters of fatty acids, aliphatic amine and aliphatic amide Kind, wherein aliphatic alkyl is preferably saturation or unsaturated alkyl of the carbon atom number between 6-60, more preferably carbon atom Saturation or unsaturated alkyl of the number between 10-50.The polyol esters of fatty acids is preferably selected from fatty glyceride, fatty acid Pentaerythritol ester, ethylene glycol fatty acid, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, fat At least one of monoesters, dibasic acid esters and polyester of the compounds such as triethylenetetraminehexaacetic acid alkanolamine ester are more preferably selected from glyceryl monooleate, double oil Acid glyceride, stearic acid monopentaerythritol ester, lauric acid/dodecanoic acid diethylene glycol dilaurate, oleic acid diethanol amine monoesters and triethanolamine oleate list At least one of ester；The aliphatic amine is preferably selected from alkyl and monoamine or polyamine, alkoxylated alkyl is replaced to replace At least one of monoamine or polyamine and alkyl ether amine etc., the more preferably tallow amine and/or ethoxy of ethoxylation The butter fat ether amines of base；The aliphatic amide is preferably selected from oleamide, coconut oleoyl amine and oleic acid diethyl amide etc. At least one of.Ashless friction modifiers can for example select the F10 of BASF Aktiengesellschaft, F20 etc..Ashless friction improves Agent preferably accounts for the 50-95% of compound friction improving agent gross mass, more preferably 60-90%.

Lubricant oil composite of the invention can also contain at least one in antirust agent, pour-point depressant, tackifier and anti-foaming agent 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..Tackifier can be total selected from ethylene, propylene At least one of polymers, polymethyl methacrylate and hydrogenated styrene isoprene copolymer, for example, can select T601, SV260, Lz7065 etc..Anti-foaming agent can select polysiloxane type anti-foaming agent, such as can be silicone oil and/or polydimethylsiloxanes Alkane.For antirust agent, pour-point depressant, tackifier and anti-foaming agent content without particular/special requirement, can be the content of this field routine, this Known to those skilled in the art, 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 methanol The preparation method of engine fuel lubricant oil composite, this method comprises: will add containing lube base oil, the wear-resistant multiple-effect of antioxygen Add agent, thiophenols ester type antioxidant, polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent The raw material mixing of mixture, the mixture of sodium sulfonate and calcium naphthenate, zinc dialkyl dithiophosphate and compound friction improving agent Uniformly obtain lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 75- 95 weight %, the wear-resistant multipurpose additive of antioxygen dosage be 0.01-10 weight %, the dosage of thiophenols ester type antioxidant is The use of the mixture of 0.02-5 weight %, polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent Measuring is 0.5-10 weight %, and the dosage of the mixture of sodium sulfonate and calcium naphthenate is 0.2-10 weight %, dialkyl dithio phosphorus The dosage of sour zinc be in terms of phosphorus≤0.08 weight %, the dosage of compound friction improving agent is 0.01-5 weight %, and the antioxygen is anti- Mill multipurpose additive 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 78-90 weight %, the wear-resistant multipurpose additive of antioxygen dosage be 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is The mixture of 0.2-1.5 weight %, polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent Dosage is 3-6 weight %, and the dosage of the mixture of sodium sulfonate and calcium naphthenate is 1.2-6 weight %, dialkyl dithiophosphoric acid The dosage of zinc is the weight % of the 0.01-0.08 in terms of phosphorus, and the dosage of compound friction improving agent is 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 Mixture, the dialkyl disulfides of the mixture of grey dispersing agent and polyisobutylene succinic acid ester dispersing agent, sodium sulfonate and calcium naphthenate For trbasic zinc phosphate, compound friction improving agent, antirust agent, pour-point depressant, tackifier and anti-foaming agent as previously mentioned, 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, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 1.5 parts by weight Acetoacetic ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 1.5 parts by weight 1000), the polyisobutylene succinic acid ester dispersing agent (number-average molecular weight of polyisobutene part is 1000) of 1.5 parts by weight, 1 weight Part sodium sulfonate (base number 200mgKOH/g), the calcium naphthenates (base number 100mgKOH/g) of 1 parts by weight, 0.2 parts by weight Two isohesyl zinc dithiophosphates, the dibutyl dithio molybdenum phosphate of 0.12 parts by weight, 1.08 parts by weight lauric acid/dodecanoic acid ethylene glycol Dibasic acid esters, the pour-point depressant T803 (be purchased from Wuxi south petroleum additive company) of 0.2 parts by weight and the tackifier of 4.8 parts by weight SV260, be added to 87 parts by weight 600SN lube base oil (viscosity index (VI) 87, saturated hydrocarbon content be 92 weight %, sulphur Content is 0.02 weight %) in, 3h is stirred at 60 DEG C, is uniformly mixed and obtains lubricant oil composite A1.

Embodiment 2

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

By the S1 of 0.6 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 0.6 parts by weight Acetoacetic ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 3 parts by weight 1300), the polyisobutylene succinic acid ester dispersing agent (number-average molecular weight of polyisobutene part is 1300) of 2 parts by weight, 0.5 weight Part sodium sulfonate (base number 300mgKOH/g), the calcium naphthenates (base number 170mgKOH/g) of 1 parts by weight, 0.9 parts by weight Two isohesyl zinc dithiophosphates, the dibutyl dithiocaarbamate molybdenum of 0.05 parts by weight, 0.2 parts by weight single oleic Ester, the pour-point depressant T803 (be purchased from Wuxi south petroleum additive company) of 0.2 parts by weight and the tackifier SV260 of 4.8 parts by weight, It is added to the Group III 150N base oil (viscosity index (VI) 124) of 45 parts by weight and the Group III 350N base oil of 41.15 parts by weight In the mixed lubrication oil base oil of (viscosity index (VI) 126), 6h is stirred at 40 DEG C, is uniformly mixed and obtains lubricant oil composite A2。

Embodiment 3

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

By the S1 of 4 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 0.2 parts by weight Ethyl ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 4.5 parts by weight 2400), the polyisobutylene succinic acid ester dispersing agent (number-average molecular weight of polyisobutene part is 2400) of 1.5 parts by weight, 4 weight Part sodium sulfonate (base number 450mgKOH/g), the calcium naphthenates (base number 200mgKOH/g) of 2 parts by weight, 0.5 parts by weight Two isohesyl zinc dithiophosphates, the dibutyl dithio phosphoric acid oxygen molybdenum of 0.02 parts by weight, 0.03 parts by weight stearic acid single cropping Doutrate, the pour-point depressant T803 (be purchased from Wuxi south petroleum additive company) of 0.2 parts by weight and the tackifier of 4.8 parts by weight SV260 is added to the 100N lube base oil of 78.25 parts by weight (viscosity index (VI) 112, saturated hydrocarbon content are 96 weight %) In, 1h is stirred at 90 DEG C, is uniformly mixed and obtains lubricant oil composite A3.

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 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 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, it is lubricated Fluid composition D3.

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 phosphite that the parts by weight such as replaces with, obtain lubricating oil composition Object D4.

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, obtain lubricant 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.

Wear scar diameter is measured using SH/T 0189.It the results are shown in Table 1.

Table 1

	A1	A2	A3	D1	D2	D3	D4	D5
									Initial oxidation temperature, DEG C	239	227	258	204	218	206	186	188
Oxidation induction period, min	57.9	50.2	75.7	32.4	41.6	28.5	17.9	15.1
									Deposit production quantity, mg	25.2	21.8	11.3	57.4	30.6	52.3	84.2	79.9
Wear scar diameter d60 40, μm	616	565	483	664	592	678	677	791

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.

Methanol-fueled engine lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can press down The generation of preparing high-temp deposit, can be widely applied to methanol-fueled engine.

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 (26)

1. a kind of methanol-fueled engine lubricant oil composite, which is characterized in that on the basis of the weight of lubricant oil composite, institute State lubricant oil composite and contain following components: lube base oil, the antioxygen of 0.01-10 weight % of 75-95 weight % is wear-resistant Multipurpose additive, the thiophenols ester type antioxidant of 0.02-5 weight %, 0.5-10 weight % polyisobutene succinimide without The mixture of grey dispersing agent and polyisobutylene succinic acid ester dispersing agent, 0.2-10 weight % sodium sulfonate and calcium naphthenate mixing Object, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.08 weight % and the compound friction improving agent of 0.01-5 weight %, it is described The wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I):

2. lubricant oil composite according to claim 1, wherein on the basis of the weight of lubricant oil composite, the profit Sliding oil composition contains following components: the lube base oil of 78-90 weight %, the wear-resistant multiple-effect of antioxygen of 0.1-4 weight % add Add agent, the thiophenols ester type antioxidant of 0.2-1.5 weight %, 3-6 weight % polyisobutene succinimide ashless dispersant With the mixture of polyisobutylene succinic acid ester dispersing agent, the mixture of the sodium sulfonate of 1.2-6 weight % and calcium naphthenate, in terms of phosphorus The zinc dialkyl dithiophosphate of 0.01-0.08 weight % and the compound friction improving agent of 0.05-1.2 weight %.

3. lubricant oil composite according to claim 1 or 2, wherein the lube base oil be mineral lubricating oil and/ Or synthetic lubricant fluid.

4. lubricant oil composite according to claim 1 or 2, wherein the thiophenols ester type antioxidant is that 2,2'- is thio Bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionates].

5. lubricant oil composite according to claim 1 or 2, wherein the polyisobutene succinimide ashless dispersion The number-average molecular weight of polyisobutene part is 800-4000 in agent；Polyisobutene portion in the polyisobutylene succinic acid ester dispersing agent The number-average molecular weight divided is 800-4000；The polyisobutene succinimide ashless dispersant and the polyisobutylene succinic acid The weight ratio of ester dispersing agent is 1-3:1.

6. lubricant oil composite according to claim 5, wherein in the polyisobutene succinimide ashless dispersant The number-average molecular weight of polyisobutene part is 900-3000；Polyisobutene part in the polyisobutylene succinic acid ester dispersing agent Number-average molecular weight is 900-3000.

7. lubricant oil composite according to claim 6, wherein in the polyisobutene succinimide ashless dispersant The number-average molecular weight of polyisobutene part is 1000-2400；Polyisobutene part in the polyisobutylene succinic acid ester dispersing agent Number-average molecular weight be 1000-2400.

8. lubricant oil composite according to claim 1 or 2, wherein the base number of the sodium sulfonate is 100-450mgKOH/ G, the base number of the calcium naphthenate are 100-200mgKOH/g, and the weight ratio of the sodium sulfonate and the calcium naphthenate is 0.2-4: 1。

9. lubricant oil composite according to claim 8, wherein the base number of the sodium sulfonate is 200-450mgKOH/g, The weight ratio of the sodium sulfonate and the calcium naphthenate is 0.5-2:1.

10. lubricant oil composite according to claim 1 or 2, wherein the alkyl in the zinc dialkyl dithiophosphate For the alkyl of C2-C12.

11. lubricant oil composite according to claim 10, wherein the alkyl in the zinc dialkyl dithiophosphate is The alkyl of C2-C8.

12. lubricant oil composite according to claim 11, wherein the alkyl in the zinc dialkyl dithiophosphate is Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl or 2- ethylhexyl.

13. lubricant oil composite according to claim 1 or 2, wherein the compound friction improving agent, which contains oil-soluble, to be had Machine molybdenum friction improver and Ashless friction modifiers, the oil-soluble organic molybdenum friction improver are selected from dialkyl dithiophosphoric acid Molybdenum, dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulphur One of complex compound, molybdenum amine complex and molybdic acid esters oil-soluble organic molybdenum friction improver or a variety of, carbon atom number 6- 60, the oil-soluble organic molybdenum friction improver accounts for the 5-50% of the compound friction improving agent gross mass；The Ashless friction Modifier is selected from one of polyol esters of fatty acids, aliphatic amine and aliphatic amide or a variety of, carbon atom number 6-60, institute State the 50-95% that Ashless friction modifiers account for the compound friction improving agent gross mass.

14. lubricant oil composite according to claim 13, wherein the oil-soluble organic molybdenum friction improver carbon atom Number is 10-50, and the oil-soluble organic molybdenum friction improver accounts for the 10-40% of the compound friction improving agent gross mass；It is described Ashless friction modifiers carbon atom number is 10-50, and the Ashless friction modifiers account for the compound friction improving agent gross mass 60-90%.

15. lubricant oil composite according to claim 14, wherein the polyol esters of fatty acids is selected from fatty acid glycerine At least one of ester, fatty acid pentaerythritol ester, the monoesters of ethylene glycol fatty acid, dibasic acid esters and polyester, the aliphatic amine In monoamine or polyamine and alkyl ether amine selected from monoamine or polyamine, the substitution of alkoxylated alkyl that alkyl replaces At least one, the aliphatic amide are selected from least one of oleamide, coconut oleoyl amine and oleic acid diethyl amide.

16. lubricant oil composite according to claim 15, wherein the polyol esters of fatty acids is selected from single oleic At least one of ester, double oleins, stearic acid monopentaerythritol ester and lauric acid/dodecanoic acid diethylene glycol dilaurate；The aliphatic amine For the tallow amine of ethoxylation and/or the butter fat ether amines of ethoxylation.

17. lubricant oil composite according to claim 1 or 2, wherein the lubricant oil composite also contain antirust agent, At least one of pour-point depressant, tackifier and anti-foaming agent.

18. lubricant oil composite according to claim 17, wherein the antirust agent is selected from imidazoles and/or allyl butyrate Two esters of gallic acid.

19. lubricant oil composite according to claim 18, wherein the antirust agent is 4,5- glyoxalidine and/or alkene Base succinate.

20. lubricant oil composite according to claim 17, wherein the pour-point depressant is selected from poly alpha olefin, alkyl C8- The poly- alkylmethacrylate and alkyl that dialkyl fumarate, the alkyl of C18 is C8-C18 are in the alkylnaphthalene of C8-C18 At least one.

21. lubricant oil composite according to claim 17, wherein the tackifier is ethylene propylene copolymer, poly- first At least one of base methyl acrylate and hydrogenated styrene isoprene copolymer.

22. lubricant oil composite according to claim 17, wherein the anti-foaming agent is polysiloxane type anti-foaming agent.

23. lubricant oil composite according to claim 22, wherein the anti-foaming agent is silicone oil, and the silicone oil includes poly- Dimethyl siloxane.

24. a kind of preparation method of methanol-fueled engine lubricant oil composite, which is characterized in that the described method includes: will contain There are the wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, polyisobutene succinimide ashless dispersion Mixture, the dialkyl dithiophosphoric acid of the mixture of agent and polyisobutylene succinic acid ester dispersing agent, sodium sulfonate and calcium naphthenate The raw material of zinc and compound friction improving agent is uniformly mixed and obtains lubricant oil composite, wherein is with the weight of lubricant oil composite Benchmark, the dosage of lube base oil is 75-95 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen be 0.01-10 weight %, The dosage of thiophenols ester type antioxidant is 0.02-5 weight %, polyisobutene succinimide ashless dispersant and polyisobutene fourth The dosage of the mixture of two acid esters dispersing agents is 0.5-10 weight %, and the dosage of the mixture of sodium sulfonate and calcium naphthenate is 0.2- 10 weight %, the dosage of zinc dialkyl dithiophosphate be in terms of phosphorus≤0.08 weight %, the dosage of compound friction improving agent is 0.01-5 weight %, the wear-resistant multipurpose additive of antioxygen are the compound of structure shown in formula (I):

25. according to the method for claim 24, wherein on the basis of the weight of lubricant oil composite, lube base oil Dosage be 78-90 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.1-4 weight %, thiophenols ester type antioxidant Dosage is the mixed of 0.2-1.5 weight %, polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent The dosage of object is closed as 3-6 weight %, the dosage of the mixture of sodium sulfonate and calcium naphthenate is 1.2-6 weight %, dialkyl disulfides Dosage for trbasic zinc phosphate is the weight % of the 0.01-0.08 in terms of phosphorus, and the dosage of compound friction improving agent is 0.05-1.2 weight %.

26. the method according to claim 24 or 25, wherein the mixed condition includes: that temperature is 40-90 DEG C, when Between be 1-6h.