CN106318555A - Metal processing lubricating oil composition and preparation method thereof - Google Patents

Abstract

The invention discloses a metal processing 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 and antiwear multi-effect additive, 0.01-5 wt% of a thiophenolic ester antioxidant, 0.01-5 wt% of dinonylnaphthalene sulfonate and 0.01-5 wt% of organic anti-friction agent. The antioxidant and antiwear multi-effect additive is a compound with a structure shown as formula (I). The invention also provides a preparation method of the metal processing lubricating oil composition. The metal processing lubricating oil composition provided by the invention has excellent antiwear properties and oxidation resistance, and can be widely applied in the metal processing field as a metal working fluid. (formula (I)).

Description

A kind of Metalworking lubricating oil compositions and preparation method thereof

Technical field

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

Background technology

Intermetallic composite coating includes rolling, forging, stamping, drawing, molding, cutting and grinding.Intermetallic composite coating All kinds metal working fluid will be used, metal cutting process liquid, metal plastic forming can be divided into process The big class of liquid two.In this two classes course of processing, all produce among cutter, mould and processed metal works Raw bigger friction and high temperature, thus metal working fluid has the highest wanting to lubrication and high-temperature oxidation resistance Ask.Metal working fluid is generally lubricant oil composite.

Metal cutting process is generally divided into two stages: i.e. chip generation and the timely removing of chip, these are two years old The individual stage also exists cutter and workpiece (chip produces the stage), cutter and chip (chip elimination stage) Between the biggest friction, this frictional force consumption and can be changed into heat in a large number, thus affect working (machining) efficiency and Workpiece quality, even damages cutter and equipment.In grinding, grinding speed is up to 1000 ms/min Above, temperature is up to 1000 DEG C, in order to cool down and lubricate cutter and workpiece, it is necessary to use metal working fluid, Take away produced heat during cutting in time, reduce cutter and the temperature of workpiece and play lubrication and wear-resistant work With, reduce the roughness of surface of the work, tool life.Along with the requirement of energy-conserving and environment-protective is continuous Improve, and improving constantly the requirement of intermetallic composite coating quality, the stage of replacement that metal working fluid uses is more The longest, it is holding of this area research worker that exploitation has the most wear-resistant and antioxygen property metal working fluid Continuous R&D target.

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 height to the wear-resistant of Metalworking lubricating oil and antioxygen property want Ask, it is provided that a kind of Metalworking lubricating oil compositions 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 Metalworking lubricating oil compositions There is the performances such as excellent wear-resistant and antioxidation.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of Metalworking 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 wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, 0.01-5 The thiophenols ester type antioxidant of weight %, the dinonylnaphthalene sulfonic acid salt of 0.01-5 weight % and 0.01-5 weight % Organic anti-friction agent, the wear-resistant multipurpose additive of described antioxygen 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 wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, 0.1-3 The thiophenols ester type antioxidant of weight %, the dinonylnaphthalene sulfonic acid salt of 0.2-3 weight % and 0.2-3 weight % Organic anti-friction agent.

On the other hand, the invention provides the preparation method of a kind of Metalworking lubricating oil compositions, described Method includes: will containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, The raw material mix homogeneously of dinonylnaphthalene sulfonic acid salt and organic anti-friction agent obtains lubricant oil composite, wherein, with On the basis of the weight of lubricant oil composite, the consumption of lube base oil be 85-98 weight %, antioxygen resist The consumption of mill multipurpose additive be 0.01-10 weight %, the consumption of thiophenols ester type antioxidant be 0.01-5 Weight %, the consumption of dinonylnaphthalene sulfonic acid salt are 0.01-5 weight %, and the consumption of organic anti-friction agent is 0.01-5 Weight %, the wear-resistant multipurpose additive of described antioxygen 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 The consumption of the wear-resistant multipurpose additive of weight %, antioxygen is 0.1-4 weight %, the use of thiophenols ester type antioxidant Amount is 0.2-3 weight % for 0.1-3 weight %, the consumption of dinonylnaphthalene sulfonic acid salt, the use of organic anti-friction agent Amount is 0.2-3 weight %.

The Metalworking lubricating oil compositions of the present invention has abrasion resistance and the antioxygenic property of excellence, can To be widely used in metal processing sectors as metal working fluid.

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 the wear-resistant multipurpose additive of antioxygen.

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

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

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

Fig. 5 is the mass spectrogram of the wear-resistant multipurpose additive of antioxygen 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 Metalworking lubricating oil compositions, with lubricant oil composite On the basis of weight, lubricant oil composite contains following components: the lube base oil of 85-98 weight %, The wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %, The dinonylnaphthalene sulfonic acid salt of 0.01-5 weight % and organic anti-friction agent of 0.01-5 weight %, antioxygen is wear-resistant many Effect additive 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 90-98 weight %；The content of the wear-resistant multipurpose additive of antioxygen 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 %；Dinonylnaphthalene sulfonic acid The content of salt is preferably 0.1-4 weight %, more preferably 0.2-3 weight %；The content of organic anti-friction agent is excellent Elect 0.1-4 weight %, more preferably 0.2-3 weight % as.

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 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, dinonylnaphthalene sulfonic acid salt can be dinonyl naphthalene sulfonate barium, dinonylnaphthalene sulfonic acid zinc, At least one in dinonylnaphthalene sulfonic acid calcium and dinonylnaphthalene sulfonic acid ammonium, preferably dinonyl naphthalene sulfonate barium, Such as T705, T705A of Suzhou specialty oil factory.

In the present invention, organic anti-friction agent can be polyol esters of fatty acids, aliphatic amine and aliphatic amide In at least one.Wherein, aliphatic alkyl be preferably saturated between 6-60 of carbon number or Unsaturated alkyl, more preferably the carbon number saturated or unsaturated alkyl between 10-50.Fatty acid Polyol ester such as can include fatty glyceride, fatty acid pentaerythritol ester, ethylene glycol fatty acid, Fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, fatty acid triethanolamine ester Deng monoesters, dibasic acid esters or the polyester of compound, such as monoolein, oleic acid diglyceride, stearic acid list Pentaerythritol ester, lauric acid/dodecanoic acid diethylene glycol dilaurate, oleic acid diethanolamine monoesters, triethanolamine oleate monoesters etc.； Aliphatic amine such as can include that alkyl replaces monoamine or polyamine, the alkyl replacement unitary of alkoxylate Amine or polyamine and alkyl ether amine etc., such as tallow amine and the Adeps Bovis seu Bubali fat of ethoxylation of ethoxylation Ether amines；Aliphatic amide such as can include oleamide, coconut oleoyl amine, oleic acid diethyl amide etc.. Organic anti-friction agent can select F10, F20 etc. of BASF Aktiengesellschaft.

The lubricant oil composite of the present invention can also contain antirust agent and/or anti-foaming agent.Antirust agent can select From imidazoles and/or alkenyl succinic acid esters, such as, can be 4,5-glyoxalidine, alkenyl imidazoline fourth two At least one in hydrochlorate and alkenyl succinic acid ester, such as, can select the safe lube oil additive in Jinzhou to have T746, T703, T747 that limit company produces.Anti-foaming agent can select polysiloxane type anti-foaming agent, example As being silicone oil and/or polydimethylsiloxane.Content for antirust agent and anti-foaming agent is wanted without special Asking, can be the content of this area routine, this be known to those skilled in the art, does not repeats them here.

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

A aniline, Disulfur dichloride and 4-chloroaniline are reacted by (), generate the intermediate shown in formula (II) M,

B intermediate M that step (a) is obtained by () is with dimercapto-1,3,4-thiadiazoles in the basic conditions Carry out nucleophilic substitution, generate the multipurpose additive shown in formula (I),

In step (a) of the present invention, aniline, Disulfur dichloride and 4-chloroaniline are carried out the concrete mode reacted Preferably include:

(i) under an inert atmosphere, in the first solvent, by aniline and Disulfur dichloride at-20-0 DEG C fully React；

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

In step (i) of the present invention, the first solvent be preferably selected from dichloromethane, oxolane, toluene, At least one in dimethylbenzene and dioxane, more preferably dichloromethane and/or oxolane, more enter one Step is preferably dichloromethane.

In the present invention in step (i), fully carry out reacting i.e. referring to reaction completely, i.e. reaction raw materials is complete Entirely react.Can use method commonly used in the art that reaction is monitored, to confirm reaction completely, The methods such as thin layer chromatography (TLC) or gas chromatogram such as can be used to be monitored.

In step of the present invention (ii), at 15-30 DEG C, react 1-3h, preferably the most anti-in step (i) Ying Hou, is gradually increased to 15-30 DEG C by the temperature of reaction system, adds 4-chloroaniline and carries out reacting 1-3h. Under this preferable case, reaction yield can be improved further.

In step of the present invention (ii), the feed postition of 4-chloroaniline is preferably and adds by several times, the most permissible Divide 3-4 time to add.Under this preferable case, reaction yield can be improved further.For adding by several times Time, each addition can be identical, it is also possible to different, in order to easy to operate, and the most each addition Measure identical.

In step of the present invention (ii), reacting 1-3h, the mode of stopped reaction can be people in the art The thinkable various modes of member, for example, it is possible to add quencher to carry out cancellation, quencher can be this The quencher that field is conventional, such as, can be saturated aqueous common salt.

In the present invention, the consumption of aniline, Disulfur dichloride and 4-chloroaniline is substantially equimolar amounts, but aniline Can be suitably excessive with Disulfur dichloride.The mol ratio of aniline, Disulfur dichloride 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 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 washing Wash, be dried, removal of solvent under reduced pressure, such as, by the reaction system after cancellation respectively with distilled water and saturated Brine It, then adds the desiccant such as anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C, Keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C, remove solvent, To obtain intermediate M.

In step (a) of the present invention, aniline, Disulfur dichloride and 4-chloroaniline carry out the reaction equation reacted As it is shown in figure 1, in Fig. 1, the first solvent uses dichloromethane, 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 nucleophilic substitution preferably includes: under an inert atmosphere, In the second solvent, dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed at 15-30 DEG C 10-30min, is subsequently adding intermediate M, fully reacts.I.e. alkalescence condition is provided by alkaline reagent.

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

In the present invention, intermediate M is preferably slowly added to, such as, can add by several times, typically can divide Add for 3-4 time.Under this preferable case, reaction yield can be improved further.It is fashionable for adding by several times, Each addition can be identical, it is also possible to different, in order to easy to operate, and the most each addition phase With.

In the present invention, the second solvent is preferably selected from dichloromethane, oxolane, toluene, dimethylbenzene, N, N- At least one in dimethylformamide, more preferably dichloromethane and/or DMF, Further it is preferably N,N-dimethylformamide.

In the present invention, alkaline reagent is preferably selected from the inorganic bases such as potassium carbonate, sodium carbonate, Feldalat NM extremely Few one.

In the present invention, catalyst is preferably potassium sulfate.

In step (b) of the present invention, dimercapto-1,3,4-thiadiazole, alkaline reagent and the use of intermediate M Amount substantially equimolar amounts, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Two The mol ratio of sulfydryl-1,3,4-thiadiazoles, alkaline reagent and intermediate M is preferably 0.9-3.0:0.9-5.0: 0.8-1.5。

In step (b) of the present invention, the consumption of catalyst can be catalytic amount, with dimercapto-1, and 3,4-thiophenes two On the basis of the molal quantity of azoles, the consumption of catalyst is preferably 5-100 mole of %, more preferably 10-50 and rubs You are %.

In step (b) of the present invention, dimercapto-1,3,4-thiadiazole and intermediate M carry out the reaction reacted Equation as in figure 2 it is shown, in Fig. 2, alkaline reagent uses potassium carbonate, mesh 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, the i.e. present invention Multipurpose additive, the present invention prepares the method for multipurpose additive and the most also includes entering reacted system Row post processing, the mode of post processing can include washing, dry, removal of solvent under reduced pressure, such as, will fill Reacted system is divided to pour in the ethyl acetate (or dichloromethane) of 1-10 times of volume, respectively with steaming Distilled water and saturated aqueous common salt washing, then add anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C In desiccant, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C Lower removing solvent, to obtain end product.

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 present invention, for the amount of the first solvent and the second solvent without particular/special requirement, can be that this area is normal The solvent load of rule, this is known to those skilled in the art, does not repeats 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.Therefore, for lubrication The preparation method of fluid composition, without particular/special requirement, can use method commonly used in the art, such as, Second aspect, present invention also offers the preparation method of a kind of Metalworking lubricating oil compositions, the method Including: will containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, two The raw material mix homogeneously of nonylnaphthalene sulfonates and organic anti-friction agent obtains lubricant oil composite, wherein, with profit On the basis of the weight of sliding oil composition, the consumption of lube base oil is that 85-98 weight %, antioxygen are wear-resistant 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 dinonylnaphthalene sulfonic acid salt are 0.01-5 weight %, and the consumption of organic anti-friction agent is 0.01-5 Weight %, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I):

In the inventive method, it is preferable that on the basis of the weight of lubricant oil composite, lube base oil Consumption be 90-98 weight %, the consumption of the wear-resistant multipurpose additive of antioxygen be 0.1-4 weight %, thiophenols The consumption of ester type antioxidant be 0.1-3 weight %, the consumption of dinonylnaphthalene sulfonic acid salt be 0.2-3 weight %, The consumption of organic anti-friction agent is 0.2-3 weight %.

As it was previously stated, in the inventive method, raw material can also contain antirust agent and/or anti-foaming agent.

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.

The wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, dinonyl naphthalene sulphur Hydrochlorate, organic anti-friction agent, antirust agent 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:

Monitor and react method completely: thin layer chromatography chromatograph (TLC) fluorescence developing method.

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

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 300rpm), it is filled with nitrogen protect Protect, add the dichloromethane of 150ml, be subsequently adding the Disulfur dichloride of 0.2mol, in ice-water bath fully After cooling, add the aniline of 0.2mol.Monitoring removes ice-water bath to reaction completely, is placed in 25 DEG C of rooms Under temperature, after question response system is gradually increased to 25 DEG C, point 3 addition 4-chloroanilines react, every time Addition is identical, adds 4-chloroaniline 0.15mol altogether.Sustained response adds the saturated food of 30ml after 2 hours Saline cancellation is reacted, and then proceeds in separatory funnel by reaction system, respectively with 50ml distilled water and 50ml Saturated aqueous common salt washs, and adds 10g anhydrous sodium sulfate dry 20min at 25 DEG C.Filter after filtration Liquid, at 40 DEG C, is evaporated off solvent under 0.05MPa, obtains intermediate M1.

In the 500ml flask with electromagnetic agitation (mixing speed is 400rpm), it is filled with nitrogen protect Protect, add the DMF (DMF) of 150ml, be subsequently adding 0.2mol dimercapto-1,3,4- Thiadiazoles and the potassium carbonate of 0.2mol, the potassium sulfate of 0.05mol, stir 20 minutes at 25 DEG C, divides 3 Secondary addition above-mentioned intermediate M1, each addition is identical, adds intermediate M10.12mol altogether.Monitoring To reaction completely, then reaction system is added 250ml ethyl acetate, and proceeds in separatory funnel, point Not Yong 100ml distilled water (twice) and the washing of 50ml saturated aqueous common salt, and add 15g anhydrous slufuric acid Sodium is dried 20min at 25 DEG C.Filtrate after filtration 40 DEG C, solvent is evaporated off under 0.03MPa, obtain End 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 carried out structural characterization, respectively obtains hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectively See Fig. 3, Fig. 4 and Fig. 5.

From the physico-chemical analysis data of above-mentioned preparation example, Fig. 3, Fig. 4 and Fig. 5 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 dinonyl naphthalene sulfonate barium of 3 weight portions, the stearic acid monopentaerythritol ester of 1.5 weight portions, The polydimethylsiloxane of 0.01 weight portion and the sorbitol monooleate of 0.3 weight portion join (PAO10 is 76 weight portions to the mixed lubrication oil base oil of PAO10 and PAO40, and PAO40 is 16.09 Weight portion) in, at 60 DEG C, stirring 3h, 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 1.4 weight portions, the 2,2'-thiobis [3-(3,5-di-t-butyl-4-hydroxy benzenes of 1.4 weight portions Base) ethyl propionate], the dinonyl naphthalene sulfonate barium of 0.2 weight portion, the triethanolamine oleate monoesters of 3 weight portions, The polydimethylsiloxane of 0.01 weight portion and the sorbitol monooleate of 0.3 weight portion join 93.69 The 600SN lube base oil of weight portion (viscosity index (VI) is 87, and saturated hydrocarbon content is 92 weight %, Sulfur content is 0.02 weight %) in, at 40 DEG C, stirring 6h, 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 dinonyl naphthalene sulfonate barium of 1.5 weight portions, the oleic acid diethyl amide of 0.2 weight portion, The polydimethylsiloxane of 0.01 weight portion and the sorbitol monooleate of 0.3 weight portion join 93.89 In the dibutyl adipate of weight portion, stirring 1h at 90 DEG C, 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: use TA5000-DSC2910 differential thermal analyzer carries out the mensuration of initial oxidation temperature；Use High Pressure Difference heat scan Mensuration (PDSC) carries out the mensuration of oxidation induction period；Use tetra-ball machine test method, measure by GB/T3142 PB, PD value, measures wear scar diameter by SH/T 0189.The results are shown in Table 1.

Table 1

	A1	A2	A3	D1	D2	D3	D4	D5
									Initial oxidation temperature, DEG C	204	225	251	203	213	205	191	192
Oxidation induction period, min	26.5	49.3	61.8	33.4	42.7	32.1	23.6	24.5
									PB, kgf	80	90	130	50	80	45	75	70
PD, kgf	245	285	320	210	250	205	245	240
									Wear scar diameter d60 40, mm	0.60	0.54	0.48	0.68	0.61	0.67	0.63	0.64

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；PB, PD value is the biggest, lubrication The wear resistance of oil is the best；Wear scar diameter is the least, and the wear resistance of lubricating oil is 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 Metalworking lubricating oil compositions of the present invention has abrasion resistance and the antioxygenic property of excellence, can To be widely used in metal processing sectors as metal working fluid.

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 Metalworking lubricating oil compositions, 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 wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %, The dinonylnaphthalene sulfonic acid salt of 0.01-5 weight % and organic anti-friction agent of 0.01-5 weight %, described antioxygen resists Mill 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 wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, 0.1-3 The thiophenols ester type antioxidant of weight %, the dinonylnaphthalene sulfonic acid salt of 0.2-3 weight % and 0.2-3 weight % Organic anti-friction agent.

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 dinonylnaphthalene sulfonic acid salt For in dinonyl naphthalene sulfonate barium, dinonylnaphthalene sulfonic acid zinc, dinonylnaphthalene sulfonic acid calcium and dinonylnaphthalene sulfonic acid ammonium At least one.

Lubricant oil composite the most according to claim 1, wherein, described organic anti-friction agent is fat At least one in fat acid polyol ester, aliphatic amine and aliphatic amide.

Lubricant oil composite the most according to claim 1, wherein, described lubricant oil composite is also Containing antirust agent and/or anti-foaming agent, described antirust agent is 4,5-glyoxalidine, alkenyl imidazoline succinate With at least one in alkenyl succinic acid ester；Described anti-foaming agent is silicone oil and/or polydimethylsiloxane.

7. the preparation method of a Metalworking lubricating oil compositions, it is characterised in that described method bag Include: will be containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, two nonyls The raw material mix homogeneously of base naphthalene sulfonate and organic anti-friction agent obtains lubricant oil composite, wherein, with lubrication On the basis of the weight of fluid composition, the consumption of lube base oil is that 85-98 weight %, antioxygen are wear-resistant many The consumption of effect additive be 0.01-10 weight %, the consumption of thiophenols ester type antioxidant be 0.01-5 weight Amount %, the consumption of dinonylnaphthalene sulfonic acid salt are 0.01-5 weight %, and the consumption of organic anti-friction agent is 0.01-5 Weight %, the wear-resistant multipurpose additive of described antioxygen 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 The consumption of the wear-resistant multipurpose additive of weight %, antioxygen is 0.1-4 weight %, the use of thiophenols ester type antioxidant Amount is 0.2-3 weight % for 0.1-3 weight %, the consumption of dinonylnaphthalene sulfonic acid salt, the use of organic anti-friction agent Amount is 0.2-3 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.