CN106318556A - Vehicle gear lubricating oil composition and preparation method thereof - Google Patents

Abstract

The invention discloses a vehicle gear lubricating oil composition. Based on the weight of the lubricating oil composition, the lubricating oil composition contains the following components: 85-98 wt% of lubricating oil base oil, 0.01-10 wt% of an antioxidant multi-effect additive, 0.01-5 wt% of a thiophenolic ester antioxidant, 0-5 wt% of phosphate ester, and 0-5 wt% of an organic sulfur extreme pressure antiwear agent, wherein the antioxidant multi-effect additive is the compound with a structure shown as formula (I). The invention also provides a preparation method of the vehicle gear lubricating oil composition. The vehicle gear lubricating oil composition provided by the invention has excellent antiwear performance and oxidation resistance, can inhibit the formation of high-temperature deposits, and can be widely applied to the vehicle gear lubricating oil field. (formula (I)).

Description

A kind of vehicle gear lubricating oil composition and preparation method thereof

Technical field

The present invention relates to lubricating oil field, in particular it relates to a kind of gear of vehicle containing special additive Lubricant oil composite and preparation method thereof.

Background technology

Gear of vehicle lubricating oil is for mechanical transmission, drive axle and the gear of steering gear, bearing etc. zero The lubrication of part, plays lubrication, cooling, the antirust and effect of buffering.Owing to automobile gear working condition is multiple Miscellaneous, contact pressure is big, and peripheral speed is fast, and sliding speed is high, and oil temperature is high, therefore wants gear lubricant Ask higher.Wherein the working condition of hyperbolic wheel dirve is harsher, to Automobile gear lubricant usability Can require higher, without the gear of vehicle lubricating oil that serviceability is good, gear cannot be ensured Normal lubrication, is easily caused premature wear and the scratch of gear, even can cause big vehicle and person thing Therefore.Gear of vehicle lubricating oil to ensure having excellent bearing capacity, in low speed and large torque and high speed impact The flank of tooth can be protected under load working condition.

Along with the development of auto industry, gear-box volume diminishes, load increases, service condition is more disliked Bad, cause gear lubricant temperature rise, it is desirable to gear lubrication oil oxidation stability is higher, and to tooth The sediment monitoring of wheel lubricating oil requires the strictest so that pinion rotation is more smooth and easy, effectively reduces gear Abrasion, extends gearbox life, reduces unnecessary expensive maintenance cost.In order to meet automobile gear machine The industrial requirement constantly promoted of tool and day by day harsh working condition, develop that novel to have excellent antioxygen anti- The gear of vehicle lubricating oil of mill performance becomes new study hotspot.

It is currently known and can effectively play the lube oil additive of antioxidation and mainly include phenols and amine Compounds.Phenolic compound contains one or more hindered phenol functional group, and aminated compounds then contains one Individual or multiple nitrogen-atoms, these special functional groups can catch the free radical chemical combination that oxidizing process generates Thing, thus stop the continuation of oxidizing process to occur.Owing to the working condition of Current mechanical equipment tends to strong, Often accelerated oxidation speed, shortens the service life of lubricating oil, therefore efficiency and the economy to antioxidant Property is had higher requirement.

United States Patent (USP) US4824601A reports diphenylamine and the diisobutylene alkaline-earth metal in acid activation The lower alkylated amines mixture formed of catalyst (earth catalyst) effect, it lubricating oil and other Oxidation resistance performance excellence in functional fluid.

United States Patent (USP) US2005230664A1 reports the antioxidant 9 of a kind of below general formula, 10-dihydro The synthetic method of acridine, it is to use alkylated diphenylamine and aldehydes or ketones to contract under acidic catalyst effect Close preparation.

Patent CN1191340C uses the tert-butyl group phenols that is obstructed, aldehyde, Carbon bisulfide and dialkylamine to occur Compound is prepared in condensation, and this compound has stronger seizure free radical and the ability of peroxynitrite decomposition compound, More effectively protection can be provided to oil oxidation stability, may also function as wear-resistant effect.

Patent US4225450 reports a kind of by tert-butyl group phenols and the alkyl aminodithioformic acid of being obstructed Polysulfide phenolic antioxidant prepared by reactant salt, has preferable antioxidation and wear-resistant effect.

Summary of the invention

The invention aims to meet the antioxidation to gear of vehicle lubricating oil, the height of abrasion-resistance is wanted Ask, it is provided that a kind of vehicle gear lubricating oil composition and preparation method thereof.

The present inventor finds under study for action, and lubricant oil composite contains structure shown in formula (I) Compound:

And this compound is combined with thiophenols ester type antioxidant, it is possible to make vehicle gear lubricating oil composition There is excellent antioxidation and the performance such as wear-resistant, it is possible to effectively suppress the generation of high temperature deposition thing.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of gear of vehicle lubricating oil Compositions, on the basis of the weight of lubricant oil composite, described lubricant oil composite contains following components: The lube base oil of 85-98 weight %, the antioxygen multipurpose additive of 0.01-10 weight %, 0.01-5 weight The amount thiophenols ester type antioxidant of %, the phosphate ester of 0-5 weight %, the organic sulfur extreme pressure of 0-5 weight % resist Grinding agent, described antioxygen multipurpose additive is the compound of structure shown in formula (I):

Preferably, on the basis of the weight of lubricant oil composite, described lubricant oil composite contains following group Point: the lube base oil of 90-98 weight %, the antioxygen multipurpose additive of 0.1-4 weight %, 0.1-3 weight Amount the thiophenols ester type antioxidant of %, the phosphate ester of 0.5-3 weight %, the organic sulfur extreme pressure of 0.5-2 weight % Antiwear additive.

On the other hand, the invention provides the preparation method of a kind of vehicle gear lubricating oil composition, described Method includes: will containing lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, appoint The phosphate ester of choosing, the raw material mix homogeneously of optional organic sulfur extreme pressure anti-wear additives obtain lubricant oil composite, Wherein, on the basis of the weight of lubricant oil composite, the consumption of lube base oil be 85-98 weight %, The consumption of antioxygen multipurpose additive be 0.01-10 weight %, the consumption of thiophenols ester type antioxidant be 0.01-5 Weight %, the consumption of phosphate ester are 0-5 weight %, and the consumption of organic sulfur extreme pressure anti-wear additives is 0-5 weight %, Described antioxygen multipurpose additive is the compound of structure shown in formula (I):

Preferably, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is 90-98 Weight %, the consumption of antioxygen multipurpose additive are that 0.1-4 weight %, the consumption of thiophenols ester type antioxidant are 0.1-3 weight %, the consumption of phosphate ester are 0.5-3 weight %, and the consumption of organic sulfur extreme pressure anti-wear additives is 0.5-2 Weight %.

The vehicle gear lubricating oil composition of the present invention has abrasion resistance and the antioxygenic property of excellence, can The generation of suppression high temperature deposition thing, can be widely applied to gear of vehicle lubricating area.

Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.

Accompanying drawing explanation

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

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

Fig. 3 is the reaction equation of the step (c) preparing antioxygen multipurpose additive.

Fig. 4 is the hydrogen spectrum spectrogram of antioxygen multipurpose additive prepared by preparation example.

Fig. 5 is the carbon spectrum spectrogram of antioxygen multipurpose additive prepared by preparation example.

Fig. 6 is the mass spectrogram of antioxygen multipurpose additive prepared by preparation example.

Detailed description of the invention

Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.

On the one hand, the invention provides a kind of vehicle gear lubricating oil composition, with lubricant oil composite On the basis of weight, lubricant oil composite contains following components: the lube base oil of 85-98 weight %, The antioxygen multipurpose additive of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %, 0-5 The phosphate ester of weight %, the organic sulfur extreme pressure anti-wear additives of 0-5 weight %, antioxygen multipurpose additive is formula (I) The compound of shown structure:

In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably 90-98 weight %；The content of antioxygen multipurpose additive is preferably 0.02-5 weight %, more preferably 0.1-4 Weight %；The content of thiophenols ester type antioxidant is preferably 0.1-3 weight %；The content of phosphate ester is preferably 0.3-4 weight %, more preferably 0.5-3 weight %；The content of organic sulfur extreme pressure anti-wear additives is preferably 0.1-4 Weight %, more preferably 0.5-2 weight %.

It is contemplated that by lubricant oil composite contains the compound of structure shown in formula (I), and The compound of structure shown in formula (I) is combined with thiophenols ester type antioxidant and realizes goal of the invention, even if Lubricant oil composite has the performances such as excellent wear-resistant and antioxidation.Therefore, in lubricant oil composite The selection of each conventional constituents, the most specifically limits.

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

Mineral lubricating oil can be from light fraction mineral oil to heavy distillat mineral oil in viscosity, including liquid stone Alkane, cycloalkanes and the mixing par-affinic-naphthenic types mineral lubricant that wax oil and hydrorefined, solvent processed Oil, is generally divided into I, II, Group III base oil, and common trade names include I class 150SN, 600SN, II class 100N, 150N, 350N etc..

Synthetic lubricant fluid can include being polymerized hydrocarbon ils, alkyl benzene and its derivative, the example that polymerization hydrocarbon ils is concrete Son includes but not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly-(1- Hexene), poly-(1-octene), poly-(1-decene), common trade names include PAO4, PAO6, PAO8, PAO10 etc., alkyl benzene and its derivative specific example includes but not limited to detergent alkylate, the tetradecane Base benzene, dinonyl benzene, two (2-ethylhexyl) benzene, alkyl benzene derivate includes alkylating diphenyl ether With alkylating diphenyl sulfide and derivant, analog and homologue etc..

Another applicable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (as phthalic acid, Succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, Azelaic Acid, suberic acid, decanedioic acid, anti- Butene dioic acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic) with Various alcohol (such as butanol, hexanol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, propylene glycol) are sent out The ester of raw condensation reaction generation or complex ester.The object lesson of these esters includes but not limited to adipic acid two fourth Ester, decanedioic acid two (2-ethylhexyl) ester, the most own ester of fumaric acid acid two, di-n-octyl sebacate, nonyl Diacid di-isooctyl, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, Decanedioic acid two (larane base) ester, the 2-ethylhexyl diester etc. of linoleic acid dimer.

Another applicable type of synthetic lubricant fluid can be fischer tropsch process synthetic hydrocarbon oil and to this synthesis hydrocarbon Oil by hydroisomerizing, be hydrocracked, lube base oil that the PROCESS FOR TREATMENT such as dewaxing obtains.

In the present invention, lube base oil preferred viscosities index more than 80, saturated hydrocarbon content is more than 90 weights Amount %, sulfur content are 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, Can be such as the double lauryl alcohol ester (DLTDP) of thio-2 acid, the double octadecyl ester of thio-2 acid (DSTDP), 2,5-dimercapto-1,3,4-thiadiazoles (DMTD) and 2,2'-thiobis [3-(the tertiary fourth of 3,5-bis- Base-4-hydroxy phenyl) ethyl propionate] at least one, preferably 2,2'-thiobis [3-(3,5-di-t-butyls -4-hydroxy phenyl) ethyl propionate], the antioxidant 1035 that such as Yong Ye Chemical Co., Ltd. in Sichuan produces, moral The IRGANOX L115 that BASF AG of state produces.

In the present invention, phosphate ester can be phosphate ester commonly used in the art, such as, can select Shandong Zibo The di-n-butyl phosphite T304 that Hui Hua Chemical Co., Ltd. produces, the phosphorus that Peng Pu chemical plant, Shanghai produces Acid front three phenolic ester T306, the dialkyl dithiophosphate Irgalube 353 that BASF Corp. of Germany produces Deng.

In the present invention, organic sulfur extreme pressure anti-wear additives can be organic sulfur extreme pressure anti-wear additives commonly used in the art, Such as can be in sulfuration Oleum Gossypii semen, sulfurized olefin cotton oil, sulfide isobutene and benzyl disulfide At least one, preferably sulfide isobutene, such as sulfide isobutene T321.

The lubricant oil composite of the present invention can also contain at least in antirust agent, pour-point depressant and anti-foaming agent Kind.Antirust agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5-glyoxalidine, alkene At least one in base imidazoline succinate and alkenyl succinic acid ester, such as, can select the safe profit in Jinzhou T746, T703, T747 that oil additive company limited produces.Pour-point depressant can be selected from poly alpha olefin, Vinyl acetate copolymer and dialkyl fumarate that alkyl is C8-C18, poly-alkyl methacrylate At least one in ester, alkylnaphthalene, such as can select south, Wuxi petroleum additive company T803, The V385 etc. of Run Yinglian company.Anti-foaming agent can select polysiloxane type anti-foaming agent, such as, can be silicon Oil and/or polydimethylsiloxane.For the content of viscosity index improver, antirust agent, pour-point depressant and anti-foaming agent without spy Different requirement, can be the content of this area routine, and this is known to those skilled in the art, at this no longer Repeat.

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

A (), by 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene carry out condensation reaction, generate shown in formula (II) Intermediate M,

B intermediate M that step (a) is obtained by () contacts with bromide reagent and carries out bromo-reaction, raw Become the bromination product shown in formula (III),

C bromination product that () makes step (b) obtain contacts with the compound shown in formula (IV) and carries out idol Connection reaction, generates the antioxidant shown in formula (I),

In step (a) of the present invention, the condition of condensation reaction preferably includes: under an inert atmosphere, In one solvent, in the presence of the first catalyst, by 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene are at-20-0 DEG C Rise to 15-30 DEG C after lower reaction 0.5-1.5h, be then heated to 70-80 DEG C of reaction 1-3h.

In the present invention, inert atmosphere can be the inert atmosphere that this area is conventional, such as can by nitrogen, The gases such as argon provide.

It will be understood by those skilled in the art that to make stable reaction carry out, react at-20-0 DEG C 15-30 DEG C is risen to, it should be to slowly warm up to 15-30 DEG C after 0.5-1.5h, for example, it is possible to will be at-20-0 DEG C System after lower reaction 0.5-1.5h is placed under the ambient temperature of 15-30 DEG C, makes reaction system self slow It is warming up to 15-30 DEG C.

In the present invention, the first solvent is preferably selected from methanol, ethanol, DMF and acetonitrile At least one, more preferably methanol and/or acetonitrile, the most preferably methanol.

In the present invention, the first catalyst can be mineral acid or organic acid, is preferably selected from acetic acid, to methyl At least one in benzoic acid and benzenesulfonic acid, more preferably acetic acid.

In the present invention, the consumption of 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene is substantially equimolar amounts, but Formaldehyde and benzene can be suitably excessive.The mol ratio of 2,6 di t butyl phenol, formaldehyde and benzene is preferably 0.9-1.5:0.9-10:0.9-10。

In step (a) of the present invention, the consumption of the first catalyst can be catalytic amount, with 2, and the tertiary fourth of 6-bis- On the basis of the molal quantity of base phenol, the consumption of the first catalyst is preferably 5-100 mole of %, more preferably 10-30 mole of %.

It will be understood by those skilled in the art that in step (a) of the present invention, purer in order to obtain Intermediate M, in addition it is also necessary to reacted system is carried out post processing, and the mode of post processing can include subtracting Pressure removes solvent, then through solvent dilution, wash, be dried, reduce pressure removes solvent again, such as, general is instead System after should removes solvent at 0.01-0.05MPa, 40-60 DEG C, is subsequently poured into 1-10 times of volume In ethyl acetate (or dichloromethane), respectively with distilled water and saturated aqueous common salt washing, then at 15-30 DEG C The desiccant such as lower addition anhydrous calcium chloride or anhydrous sodium sulfate, keep 10-60min.It is filtered to remove dry After agent, at 0.01-0.05MPa, 40-60 DEG C, remove solvent, to obtain intermediate M.

In step (a) of the present invention, 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction of condensation reaction Equation is as it is shown in figure 1, in Fig. 1, the first solvent uses methanol, and the first catalyst uses Acetic acid, purpose by way of example only, the scope of the present invention is not construed as limiting.

In step (b) of the present invention, the condition of bromo-reaction preferably includes: under an inert atmosphere, In two solvents, in the presence of the second catalyst, under the conditions of lucifuge, during step (a) is obtained Mesosome M and bromide reagent react 1-2h at 15-30 DEG C, then use quencher cancellation.

" inert atmosphere " be not as it was previously stated, repeat them here.

It will be understood by those skilled in the art that and more stably carry out, preferably to intermediate to react M is slowly added to brominated reagent.

In the present invention, the second solvent is preferably selected from oxolane, dichloromethane, chloroform and ether extremely Few one, more preferably oxolane.

In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azo At least one in bis-isobutyronitrile (AIBN).

In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br₂, more excellent Elect NBS as.

In step (b) of the present invention, carrying out cancellation with quencher, quencher can be commonly used in the art Quencher, such as, can be saturated aqueous common salt.

In step (b) of the present invention, intermediate M is substantially equimolar amounts with the consumption of bromide reagent, But bromide reagent typically can be suitably excessive, reaches 1.1-3 times of equivalent of reaction substrate.Intermediate M with Bromide reagent mol ratio is preferably 0.9-1.2:0.9-3.0.

In step (b) of the present invention, the consumption of the second catalyst can be catalytic amount, with intermediate M's On the basis of molal quantity, the consumption of the second catalyst is preferably 10-100 mole of %, more preferably 40-60 and rubs You are %.

In the inventive method step (b), intermediate M contacts with bromide reagent and carries out the anti-of bromo-reaction Answer equation as in figure 2 it is shown, in Fig. 2, bromide reagent uses NBS, mesh by way of example only , the scope of the present invention is not construed as limiting.

In step (b) of the present invention, in addition to generating the bromination product shown in formula (III), also trace The bromination product at ortho position generates, and does not has the bromination product of meta to generate, but the amount of the bromination product at ortho position is very Pettiness, does not has materially affect to subsequent reactions, is negligible.

It will be understood by those skilled in the art that in step (b) of the present invention, purer in order to obtain Bromination product, in addition it is also necessary to the system after cancellation is carried out post processing, and the mode of post processing can include water Wash, be dried, removal of solvent under reduced pressure, such as, by the system distilled water wash after cancellation, then exist Add the desiccant such as anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C, keep 10-60min.Filter After removing desiccant, at 0.01-0.05MPa, 40-60 DEG C, remove solvent, to obtain bromination product.

In step (c) of the present invention, the condition of coupling reaction preferably includes: under an inert atmosphere, In three solvents, in the presence of the 3rd catalyst, the bromination product that step (b) is obtained and formula (IV) Shown compound reacts 4-8h at 80-100 DEG C.

" inert atmosphere " be not as it was previously stated, repeat them here.

In the present invention, in order to make stable reaction carry out, preferably it is gradually heating to 80-100 DEG C, then exists 4-8h is reacted at 80-100 DEG C.

In the present invention, the 3rd solvent is preferably selected from dichloromethane, chloroform, toluene and oxolane extremely Few one, more preferably dichloromethane.

In the present invention, the 3rd catalyst preferably includes palladium salt, part and alkali.Palladium salt is preferably selected from palladium And/or palladium-dibenzalacetone complex [Pd₂(dba)₃]；Part is preferably selected from tri-tert phosphorus, dinaphthol (BINAP) at least one and in double (diphenylphosphino) ferrocene (dppf)；Alkali is preferably selected from uncle At least one in sodium butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate.

In step (c) of the present invention, the bromination product that step (b) obtains and the chemical combination shown in formula (IV) The consumption of thing is substantially equimolar amounts, but the compound shown in formula (IV) can be suitably excessive.Step B bromination product that () obtains is preferably 0.9-1.5:0.9-2.5 with the mol ratio of the compound shown in formula (IV).

In step (c) of the present invention, the consumption of catalyst can be catalytic amount, with bromination product mole On the basis of number, the consumption of palladium salt is preferably 5-50 mole of %, more preferably 5-20 mole %, more enters one Step is preferably 5-10 mole of %；The consumption of part is preferably 5-50 mole of %, more preferably 10-30 mole %； The consumption of alkali is preferably 5-50 mole of %, more preferably 10-30 mole %.

In step (c) of the present invention, the bromination product that step (b) obtains and the chemical combination shown in formula (IV) Thing contact carries out the reaction equation of coupling reaction as it is shown on figure 3, in Fig. 3, palladium salt uses acetic acid Palladium, purpose by way of example only, the scope of the present invention is not construed as limiting.

It will be understood by those skilled in the art that to obtain purer end product, i.e. formula (I) Shown antioxidant, the inventive method the most also includes reacted system is carried out post processing, post processing Mode can include filtration, solvent dilution, wash, be dried, removal of solvent under reduced pressure, such as, will be anti- The filtrate after system filtration after should is poured in the ethyl acetate (or dichloromethane) of 1-10 times of volume, Then with distilled water wash, at 15-30 DEG C, anhydrous calcium chloride or anhydrous sodium sulfate etc. are then added dry Drying prescription, keeps 10-60min.After being filtered to remove desiccant, remove at 0.01-0.05MPa, 40-60 DEG C Remove solvent, to obtain the antioxidant shown in formula (I).

The present invention is prepared each step of the method for the compound of structure shown in formula (I) the most under agitation Carry out, for mixing speed without particular/special requirement, can be the mixing speed of this area routine, such as, stir Mixing speed can be 100-800rpm.

In the method for the compound that the present invention prepares structure shown in formula (I), for the first solvent, second The amount of solvent and the 3rd solvent, without particular/special requirement, can be the solvent load of this area routine, and this is ability Well known to field technique personnel, do not repeat them here.

As it has been described above, it is contemplated that by lubricant oil composite contains the change of structure shown in formula (I) Compound, and the combination of the compound of structure shown in formula (I) and thiophenols ester type antioxidant and realize invention Purpose, even if lubricant oil composite has the performances such as excellent wear-resistant and antioxidation, suppresses high temperature deposition thing Generation.Therefore, for the preparation method of lubricant oil composite without particular/special requirement, this area can be used Conventional use of method, such as, second aspect, present invention also offers a kind of gear of vehicle lubrication line of oils The preparation method of compound, the method includes: will be containing lube base oil, antioxygen multipurpose additive, sulfur For phenolic ester type antioxidant, optional phosphate ester, the raw material mix homogeneously of optional organic sulfur extreme pressure anti-wear additives Obtain lubricant oil composite, wherein, on the basis of the weight of lubricant oil composite, lube base oil Consumption be 85-98 weight %, the consumption of antioxygen multipurpose additive be 0.01-10 weight %, thiophenols ester type The consumption of antioxidant be 0.01-5 weight %, the consumption of phosphate ester be 0-5 weight %, organic sulfur extreme pressure resists The consumption of grinding agent is 0-5 weight %, and described antioxygen multipurpose additive is the compound of structure shown in formula (I):

In the inventive method, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is excellent Elect 90-98 weight % as, the consumption of antioxygen multipurpose additive is preferably 0.02-5 weight %, more preferably 0.1-4 weight %, the consumption of thiophenols ester type antioxidant are preferably the consumption of 0.1-3 weight %, phosphate ester Being preferably 0.3-4 weight %, more preferably 0.5-3 weight %, the consumption of organic sulfur extreme pressure anti-wear additives is preferred For 0.1-4 weight %, more preferably 0.5-2 weight %.

As it was previously stated, in the inventive method, raw material can also contain in antirust agent, pour-point depressant and anti-foaming agent At least one.

In the inventive method, for the mode of mixing without particular/special requirement, such as can be except lube base Each raw material components of oil is added separately in lube base oil, it is also possible to each by except lube base oil Component is mixed and made into concentrate and is then added in lube base oil.

In the inventive method, the condition of mixing preferably includes: temperature is 40-90 DEG C, and the time is 1-6h.

Lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, phosphate ester, organic sulfur Extreme pressure anti-wear additives, antirust agent, pour-point depressant and anti-foaming agent be not as it was previously stated, repeat them here.

Embodiment

The present invention is further illustrated for below example, but and is not so limited the present invention.

In the following Examples and Comparative Examples:

The physico-chemical analysis method of product: measure element by inductively coupled plasma ion emission spectroscopy method Content.

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

Preparation example

In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), it is filled with nitrogen protect Protect, add the methanol of 150ml and the acetic acid of 0.01mol, sufficiently cool in ice-water bath after, then divide Do not add the 2 of 0.1mol, 6-DI-tert-butylphenol compounds, the formaldehyde of 0.2mol and the benzene of 0.3mol.Reaction 1 Remove ice-water bath after hour, rise to stopped reaction after 25 DEG C of post-heating persistently reflux 2 hours to 75 DEG C, By reacted system at 0.03MPa, steam solvent at 50 DEG C, be subsequently adding 250ml ethyl acetate, And proceed in separatory funnel, respectively with 100ml distilled water (twice) and the washing of 50ml saturated aqueous common salt, And adding 10g anhydrous calcium chloride dry 20min at 25 DEG C, the filtrate after filtration is at 40 DEG C, 0.03MPa Under solvent is evaporated off, obtain midbody product M1.

In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), it is filled with nitrogen protect Protect, add the dry tetrahydrofuran of 150ml, then dissolve in midbody product M1, and add 0.05mol Ammonium nitrate, under the conditions of lucifuge, be slowly added into 0.1mol brominated reagent NBS.At 25 DEG C, stirring is anti- Answer 1.5h, then use saturated aqueous common salt cancellation, then wash with 100ml distilled water (twice), and add Enter 10g anhydrous sodium sulfate at 25 DEG C, be dried 20min.Filtrate after filtration is at 40 DEG C, 0.03MPa Under solvent is evaporated off, obtain bromination product.

In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), it is filled with nitrogen protect Protect, add the dichloromethane of 150ml as solvent, be separately added into above-mentioned bromination product and 0.12mol Benzotriazole compound, is subsequently added the tri-tert phosphorus of 0.02mol, the sodium tert-butoxide of 0.02mol and The Pd (OAc) of 0.005mol₂.It is gradually heating to 90 DEG C, continuously stirred 6h.Then by reacted body Filtrate after system filters adds 250ml ethyl acetate, and proceeds in separatory funnel, uses 100ml distilled water (twice) washing, and add 10g anhydrous sodium sulfate dry 20min at 25 DEG C.Filtrate after filtration 40 DEG C, solvent is evaporated off under 0.03MPa, obtain end product S1.

The physico-chemical analysis data of S1 are as follows: nitrogen content, and 11.2%.

S1 is carried out structural characterization, respectively obtains hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectively See Fig. 4, Fig. 5 and Fig. 6.

From the physico-chemical analysis data of above-mentioned preparation example, Fig. 4, Fig. 5 and Fig. 6 it can be seen that S1 has formula (I) structure shown in.

Embodiment 1

The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.

By the S1 of 0.1 weight portion, the 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) of 3 weight portions Ethyl propionate], the di-n-butyl phosphite of 2 weight portions (purchased from Shandong Zibo Hui Hua Chemical Co., Ltd., T304), the sulfide isobutene of 2 weight portions is (purchased from sky, Beijing one Yongchang Chemical Industry Science Co., Ltd, sulfur Change isobutene. T321), the 4,5-glyoxalidine of 0.2 weight portion join 92.7 weight portions 600SN profit In lubricant base oil, stirring 3h at 60 DEG C, mix homogeneously obtains lubricant oil composite A1.

Embodiment 2

The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.

By the S1 of 1.2 weight portions, the 2,2'-thiobis [3-(3,5-di-t-butyl-4-hydroxy benzenes of 1.2 weight portions Base) ethyl propionate], the tricresyl phosphate (purchased from Peng Pu chemical plant, Shanghai, T306) of 3 weight portions, 1.4 The sulfide isobutene of weight portion is (purchased from sky, Beijing one Yongchang Chemical Industry Science Co., Ltd, sulfide isobutene T321), the 4,5-glyoxalidine of 0.2 weight portion joins II class 150N base oil and II class 150BS In the mixed lubrication oil base oil (150N is 69 weight portions, and 150BS is 24 weight portions) of base oil, Stirring 6h at 40 DEG C, mix homogeneously obtains lubricant oil composite A2.

Embodiment 3

The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.

By the S1 of 4 weight portions, the 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) of 0.1 weight portion Ethyl propionate], the Irgalube 353 (purchased from BASF Corp. of Germany) of 0.5 weight portion, 0.5 weight portion Sulfide isobutene (purchased from sky, Beijing one Yongchang Chemical Industry Science Co., Ltd, sulfide isobutene T321), 0.2 The 4 of weight portion, 5-glyoxalidine joins in the dibutyl adipate of 94.7 weight portions, stirs at 90 DEG C Mixing 1h, mix homogeneously obtains lubricant oil composite A3.

Comparative example 1

Prepare lubricant oil composite according to the method for embodiment 2, except for the difference that, the weight such as S1 is replaced with The 2 of amount part, 2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate], obtain lubricating oil composition Thing D1.

Comparative example 2

Lubricant oil composite is prepared according to the method for embodiment 2, except for the difference that, by 2,2'-thiobis [3-(3,5- Di-tert-butyl-hydroxy phenyl) ethyl propionate] S1 of weight portion such as replace with, obtain lubricant oil composite D2。

Comparative example 3

Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2 Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] dibutyl dithio of weight portion such as replace with Carbaminate, obtains lubricant oil composite D3.

Comparative example 4

Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2 Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] the trimethylphenyl phosphorous of weight portion such as replace with Acid zinc, obtains lubricant oil composite D4.

Comparative example 5

Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2 Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] the fourth octyl diphenylamine of weight portion such as replace with, Obtain lubricant oil composite D5.

Test case

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

TA5000-DSC2910 differential thermal analyzer is used to carry out the mensuration of initial oxidation temperature；

High Pressure Difference heat scan mensuration (PDSC) is used to carry out the mensuration of oxidation induction period；

SH/T 0189 is used to measure wear scar diameter.The results are shown in Table 1.

Table 1

	A1	A2	A3	D1	D2	D3	D4	D5
									Initial oxidation temperature, DEG C	228	230	231	210	221	208	193	194
Oxidation induction period, min	51.3	49.5	44.9	30.8	39.2	28.4	21.6	28.0
									Wear scar diameter d60 40, mm	0.45	0.43	0.46	0.65	0.57	0.54	0.51	0.67

It will be understood by those skilled in the art that initial oxidation temperature is the highest, the heat stability of lubricating oil The best；Oxidation induction period is the longest, and the antioxygenic property of lubricating oil is the best；Wear scar diameter is the least, lubricating oil Wear resistance the best.

A2 is compared with D1-D5 respectively it can be seen that the lubricant oil composite of the present invention has more Good non-oxidizability and abrasion resistance.

The vehicle gear lubricating oil composition of the present invention has abrasion resistance and the antioxygenic property of excellence, can The generation of suppression high temperature deposition thing, can be widely applied to gear of vehicle lubricating area.

The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, but, the present invention does not limit Detail in above-mentioned embodiment, in the technology concept of the present invention, can be to the present invention Technical scheme carry out multiple simple variant, these simple variant belong to protection scope of the present invention.

It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (8)

1. a vehicle gear lubricating oil composition, it is characterised in that with the weight of lubricant oil composite On the basis of, described lubricant oil composite contains following components: the lube base oil of 85-98 weight %, The antioxygen multipurpose additive of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %, 0-5 The phosphate ester of weight %, the organic sulfur extreme pressure anti-wear additives of 0-5 weight %, described antioxygen multipurpose additive is formula (I) compound of structure shown in:

Preferably, on the basis of the weight of lubricant oil composite, described lubricant oil composite contains following group Point: the lube base oil of 90-98 weight %, the antioxygen multipurpose additive of 0.1-4 weight %, 0.1-3 weight Amount the thiophenols ester type antioxidant of %, the phosphate ester of 0.5-3 weight %, the organic sulfur extreme pressure of 0.5-2 weight % Antiwear additive.

Lubricant oil composite the most according to claim 1, wherein, described lube base oil is Mineral lubricating oil and/or synthetic lubricant fluid.

Lubricant oil composite the most according to claim 1, wherein, described thiophenols ester type antioxygen Agent is the double lauryl alcohol ester of thio-2 acid, thio-2 acid double octadecyl ester, 2,5-dimercapto-1,3,4-thiadiazoles With at least one in 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate].

Lubricant oil composite the most according to claim 1, wherein, described phosphate ester is phosphorous acid At least one in di-n-butyl, tricresyl phosphate, dialkyl dithiophosphate.

Lubricant oil composite the most according to claim 1, wherein, described organic sulfur extreme-pressure anti-wear Agent is selected from least vulcanized in Oleum Gossypii semen, sulfurized olefin cotton oil, sulfide isobutene and benzyl disulfide Kind.

Lubricant oil composite the most according to claim 1, wherein, described lubricant oil composite is also Containing at least one in antirust agent, pour-point depressant and anti-foaming agent, described antirust agent is selected from imidazoles and/or alkene Base succinic acid esters, preferably 4,5-glyoxalidine, alkenyl imidazoline succinate and alkenyl succinic acid ester In at least one；Described pour-point depressant selected from poly alpha olefin, vinyl acetate copolymer and alkyl is At least one in the dialkyl fumarate of C8-C18, poly-alkylmethacrylate, alkylnaphthalene； Described anti-foaming agent is polysiloxane type anti-foaming agent, preferably silicone oil and/or polydimethylsiloxane.

7. the preparation method of a vehicle gear lubricating oil composition, it is characterised in that described method bag Include: by containing lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, optional phosphorus Acid esters, the raw material mix homogeneously of optional organic sulfur extreme pressure anti-wear additives obtain lubricant oil composite, wherein, On the basis of the weight of lubricant oil composite, the consumption of lube base oil is 85-98 weight %, antioxygen The consumption of multipurpose additive be 0.01-10 weight %, the consumption of thiophenols ester type antioxidant be 0.01-5 weight Amount %, the consumption of phosphate ester are 0-5 weight %, and the consumption of organic sulfur extreme pressure anti-wear additives is 0-5 weight %, Described antioxygen multipurpose additive is the compound of structure shown in formula (I):

Preferably, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is 90-98 Weight %, the consumption of antioxygen multipurpose additive are that 0.1-4 weight %, the consumption of thiophenols ester type antioxidant are 0.1-3 weight %, the consumption of phosphate ester are 0.5-3 weight %, and the consumption of organic sulfur extreme pressure anti-wear additives is 0.5-2 Weight %.

Method the most according to claim 7, wherein, the condition of described mixing includes: temperature is 40-90 DEG C, the time is 1-6h.