CN107304379A - A kind of combustion gas turbine oil composition and preparation method thereof - Google Patents
A kind of combustion gas turbine oil composition and preparation method thereof Download PDFInfo
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- CN107304379A CN107304379A CN201610238057.4A CN201610238057A CN107304379A CN 107304379 A CN107304379 A CN 107304379A CN 201610238057 A CN201610238057 A CN 201610238057A CN 107304379 A CN107304379 A CN 107304379A
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- IERZEVFTXXSUFS-UHFFFAOYSA-N CC(C)(C)c1cc(Cc(cc2)ccc2Nc2ccc(C[n]3nnc4c3cccc4)cc2)cc(C(C)(C)C)c1O Chemical compound CC(C)(C)c1cc(Cc(cc2)ccc2Nc2ccc(C[n]3nnc4c3cccc4)cc2)cc(C(C)(C)C)c1O IERZEVFTXXSUFS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/05—Metals; Alloys
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
- C10M2215/224—Imidazoles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of combustion gas turbine oil composition, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components：85 99 weight % lube base oil, 0.01 10 weight % antioxygen multipurpose additive, the %2 of 0.01 5 weight, 2 ' thiobis [3 (3, the hydroxy phenyl of 5 di-t-butyl 4) ethyl propionate, 0.05 5 weight % Zinc oxide nanoparticle, 0.01 5 weight % matal deactivator, the steam turbine oil that said composition is mixed into, with excellent oxidation stability, high-temperature stability and liquid phase rust-preventing characteristic, point aqueous energy.The antioxygen multipurpose additive is the compound of structure shown in formula (I).Present invention also offers the preparation method of combustion gas turbine oil composition.The combustion gas turbine oil composition of the present invention has excellent abrasion resistance and antioxygenic property, can be widely applied to combustion gas steam-turbine lubrication field.
Description
Technical field
The present invention relates to lubricating oil field, in particular it relates to a kind of combustion gas steamer containing special additive
Engine oil base oil and preparation method thereof.
Background technology
Steam turbine oil is that the bearing lubrication and cooling of the turbine and generator such as electric power supply plant are used.Fire vapour steamer
The high-end temperature of unit is up to 200 DEG C, and the mean temperature of oil export is 70 DEG C or so.In such temperature
Under, the easy oxidation deterioration of steam turbine oil.And steam turbine oil consumption is big, change inconvenient, use time
Up to 10-15, the service life of increase steam turbine oil is the direction of this area research staff effort always.
The oil mass that steam turbine oil supplements consumption every year is the 5%-10% of internal circulating load.Within the so long time, by
The influence of air and moisture, steam turbine oil can aoxidize generation acidic materials or other oxides and be dissolved in oil
Or with Precipitation.When acidic materials accumulation it is excessive when, metal parts can be corroded, can accelerate lubricating oil after
Continuous oxidation, the generation of oxide precipitate can pollute lubricating system and the efficiency of lubrication device is greatly reduced.
Therefore steam turbine oil requirement has excellent anti-oxidative stability.While the bearing and decelerator tooth of gas turbine
Wheel is main motion parts.It is often possible to be in boundary lubrication condition in startup and parking.In this feelings
Under condition, if the lubricity of steam turbine oil is bad, wear resistence is poor, can occur adhesive wear, abrasive wear
And fatigue wear, cause the reduction of the component capabilities such as gear, the lost of life, system fault in production.Therefore,
Combustion gas steam turbine oil oil is needed with good abrasion-resistance and anti-extreme pressure energy.With the rapid hair of technology
Exhibition, new requirement is constantly proposed to combustion gas steam turbine oil, and load is increasingly weighed, and the wear resistence to oil product is carried
Higher requirement is gone out；Exploitation has the new of more preferable antioxygen abrasion-resistance relative to current existing product
The direction that combustion gas steam turbine oil oil is made great efforts as this area scientific research personnel.
The lube oil additive that can effectively play antioxidation is currently known mainly including phenols and amine
Class compound.Phenolic compound contains one or more phenol functional groups that are obstructed, and aminated compounds then contains one
Individual or multiple nitrogen-atoms, these special functional groups can catch the free radical compounds of oxidizing process generation,
So as to prevent the continuation of oxidizing process from occurring.It is past because the condition of work of Current mechanical equipment tends to be strong
Toward meeting accelerated oxidation speed, shorten the service life of lubricating oil, therefore to the efficiency and economy of antioxidant
Propose higher requirement.
United States Patent (USP) US4824601A reports the alkaline-earth metal of diphenylamine and diisobutylene in acid activation
The lower alkylated amines mixture formed of catalyst (earth catalyst) effect, it is in lubricating oil and other
Oxidation resistance performance is excellent in functional fluid.
United States Patent (USP) US2005230664A1 reports a kind of antioxidant 9 of below general formula, 10- dihydros
The synthetic method of acridine, it is to be contracted using alkylated diphenylamine and aldehydes or ketones under acidic catalyst effect
Close and prepare.
Patent CN1191340C is occurred using the tert-butyl group phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine
Prepare compound is condensed, the compound has the stronger ability for catching free radical and peroxynitrite decomposition compound,
More effective protection can be provided to oil oxidation stability, wear-resistant effect is may also function as.
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, with preferable antioxidation and wear-resistant effect.
The content of the invention
The invention aims to meet anti-oxidant, abrasion-resistance the high request to combustion gas steam turbine oil,
A kind of combustion gas turbine oil composition and preparation method thereof is provided.
The present inventor has found that lubricant oil composite contains structure shown in formula (I) under study for action
Compound：
And [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate type resists the compound with 2,2 '-thiobis
Oxygen agent is combined, and combustion gas turbine oil composition can be made to have the excellent performance such as anti-oxidant and wear-resistant.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of combustion gas steam turbine oil group
Compound, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components：
85-99 weight % lube base oil, 0.01-10 weight % antioxygen multipurpose additive, 0.01-5
Quality %2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate, 0.05-5 weight % oxygen
Change zinc nanoparticles, 0.01-5 mass % matal deactivator, the antioxygen multipurpose additive is formula (I)
The compound of shown structure：
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains with the following group
Point：90-98 weight % lube base oil, 0.1-4 weight % antioxygen multipurpose additive, 0.01-5
Quality %2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate, 0.1-3 weight %
The matal deactivator class compound of Zinc oxide nanoparticle, 0.05-2 mass %.
On the other hand, the invention provides a kind of preparation method of combustion gas turbine oil composition, the side
Method includes：Lube base oil, antioxygen multipurpose additive, 2,2 '-thiobis [3- (tertiary fourths of 3,5- bis- will be contained
Base -4- hydroxy phenyls) ethyl propionate type antioxidant, Zinc oxide nanoparticle, organic carboxyl acid class compound
Raw material is well mixed to obtain lubricant oil composite, wherein, on the basis of the weight of lubricant oil composite, profit
The consumption of lubricant base oil be 85-99 weight %, the consumption of antioxygen multipurpose additive be 0.01-10 weight %,
0.01-5 quality %2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate, 0.05-5 weights
Measure % Zinc oxide nanoparticle, 0.01-5 mass % matal deactivator, the antioxygen multipurpose additive
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 90-99
Weight %, the consumption of antioxygen multipurpose additive are 0.1-4 weight %, 2,2 '-thiobis [3- (3,5- di-t-butyls
- 4- hydroxy phenyls) ethyl propionate antioxidant consumption be 0.1-3 weight %, the consumption of Zinc oxide nanoparticle
For 0.1-3 weight %, the consumption of matal deactivator is 0.05-2 weight %.
The combustion gas turbine oil composition of the present invention has excellent abrasion resistance and antioxygenic property, can be with
It is widely used in combustion gas steam turbine oil lubricating area.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Fig. 1 is the reaction equation of (a) the step of preparing antioxygen multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing antioxygen multipurpose additive.
Fig. 3 is the reaction equation of (c) the step of 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.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of combustion gas turbine oil composition, with the weight of lubricant oil composite
On the basis of amount, lubricant oil composite contains following components：85-99 weight % lube base oil,
0.01-10 weight % antioxygen multipurpose additive, 0.01-5 quality %2,2 '-thiobis [3- (tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyls) ethyl propionate, 0.05-5 weight % Zinc oxide nanoparticle, 0.01-5 mass %
Matal deactivator, antioxygen multipurpose 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 antioxygen multipurpose additive is preferably 0.02-5 weight %, more preferably 0.1-4
Weight %；[content of 3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate antioxidant is excellent for 2,2 '-thiobis
Elect 0.1-3 weight % as；The content of Zinc oxide nanoparticle is preferably 0.05-4 weight %, more preferably
0.1-3 weight %；The content of matal deactivator is preferably 0.01-4 weight %, more preferably 0.05-2 weight %.
It is contemplated that the compound by containing structure shown in formula (I) in lubricant oil composite, and
The compound of structure shown in formula (I) and 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid second
Ester type antioxidant is combined and realizes goal of the invention, even if lubricant oil composite has excellent wear-resistant and antioxygen
The performances such as change.Therefore, for the selection of each conventional constituents in lubricant oil composite, do not limit specifically
System.
In the present invention, lube base oil can be lube base oil commonly used in the art, for example
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
Wax oil and hydrofinishing, the alkane that solvent is treated, cycloalkanes and mixing par-affinic-naphthenic types mineral lubricant
Oil, is generally divided into I, II, Group III base oil, and common trade names include I classes 150SN, 600SN,
II classes 100N, 150N, 350N etc..
Synthetic lubricant fluid can include polymerization hydrocarbon ils, alkyl benzene and its derivative, polymerize the specific example of hydrocarbon ils
Son includes but is not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly- (1-
Hexene), poly- (1- octenes), poly- (1- decene), common trade names include PAO4, PAO6, PAO8,
PAO10 etc., alkyl benzene and its derivative specific example includes but is not limited to detergent alkylate, the tetradecane
Base benzene, dinonyl benzene, two (2- ethylhexyls) benzene, alkyl benzene derivate include the diphenyl ether of alkylation
Diphenyl sulfide and its derivative, analog and homologue with alkylation etc..
Another suitable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (such as phthalic acid,
It is butanedioic 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 alcohols, ethylene glycol, propane diols) hairs
The ester or complex ester of raw condensation reaction generation.The specific example of these esters includes but is not limited to the fourth of adipic acid two
Ester, decanedioic acid two (2- ethylhexyls) ester, the just 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, 2- ethylhexyl diester of linoleic acid dimer etc..
Another suitable type of synthetic lubricant fluid can be for fischer tropsch process synthetic hydrocarbon oil and to this synthesis hydrocarbon
Oil by hydroisomerizing, be hydrocracked, the lube base oil that the PROCESS FOR TREATMENT such as dewax is obtained.
In the present invention, lube base oil preferred viscosities index is more than 80, saturated hydrocarbon content and is more than 90 weights
Measure the lube base oil that %, sulfur content are less than 0.03 weight %.
In the present invention, Zinc oxide nanoparticle is the single or composite Nano of the composition containing Zinc oxide nanoparticle
Particle.The high-temperature chain lubricating oil of addition Zinc oxide nanoparticle has preferable high temperature wear resistance, adds
Plus the abrasion resistance of rear oil product is improved.The particle diameter of nano-particle is 3-150nm.
In the present invention, metal deactivator can be 2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles,
At least one of four benzyl BTAs, 2-mercaptobenzothiazole, alkyl thiadiazoles.For example may be used
To select Yantai Heng Nuo Chemical Industry Science Co., Ltd 2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiophenes two
Azoles.Such as can be from the T561 of Yantai Heng Nuo Chemical Industry Science Co., Ltd.
The present invention lubricant oil composite can also containing in antirust agent, pour-point depressant and anti-foaming agent at least
It is a kind of.Antirust agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine,
At least one of alkenyl imidazoline succinate and alkenyl succinic acid ester, for example can be safe from Jinzhou
T746, T703, T747 of lube oil additive Co., Ltd production.Pour-point depressant can be selected from poly- α-alkene
Hydrocarbon, vinyl acetate copolymer and alkyl are C8-C18 dialkyl fumarate, poly- alkyl methyl third
At least one of olefin(e) acid ester, alkylnaphthalene, for example can be from the southern petroleum additive company in Wuxi
V385 of T803, Run Yinglian company etc..Anti-foaming agent can select polysiloxane type anti-foaming agent, for example may be used
Think silicone oil and/or dimethyl silicone polymer.For antirust agent, pour-point depressant and anti-foaming agent content without special
It is required that, can be the conventional content in this area, this is known to those skilled in the art, no longer goes to live in the household of one's in-laws on getting married herein
State.
In the present invention, the preparation method of the compound of structure is preferably included shown in formula (I)：
(a) by 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene carry out condensation reaction, shown in generation formula (II)
Intermediate M,
(b) the intermediate M that step (a) is obtained is contacted into progress bromo-reaction with bromide reagent, it is raw
Into the bromination product shown in formula (III),
(c) bromination product that step (b) is obtained is made to contact progress with the compound shown in formula (IV) even
Connection reaction, the antioxidant shown in generation formula (I),
In step (a) of the present invention, the condition of condensation reaction is preferably included：Under an inert atmosphere,
In one solvent, in the presence of the first catalyst, by 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene at -20-0 DEG C
15-30 DEG C is risen to after lower reaction 0.5-1.5h, 70-80 DEG C of reaction 1-3h is then heated to.
In the present invention, inert atmosphere can be the conventional inert atmosphere in this area, for example can by nitrogen,
The gases such as argon gas are provided.
It will be understood by those skilled in the art that in order that stable reaction progress, reacts at -20-0 DEG C
15-30 DEG C is risen to after 0.5-1.5h, it should be to slowly warm up to 15-30 DEG C, for example, can be by -20-0 DEG C
System after lower reaction 0.5-1.5h is placed under 15-30 DEG C of environment temperature, makes reaction system itself 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 are still more preferably methanol.
In the present invention, the first catalyst can be inorganic acid or organic acid, be preferably selected from acetic acid, to methyl
At least one of benzoic acid and benzene sulfonic 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 the tertiary fourths of 2,6- bis-
On the basis of the molal quantity of base phenol, the consumption of the first catalyst is preferably 5-100 moles of %, more preferably
10-30 moles of %.
It will be understood by those skilled in the art that in step (a) of the present invention, it is purer in order to obtain
Intermediate M, in addition it is also necessary to reacted system is post-processed, the mode of post processing can include subtracting
Pressure removes solvent, then dilutes, washs through solvent, drying, depressurize and remove solvent again, for example, general is instead
Should after system remove solvent at 0.01-0.05MPa, 40-60 DEG C, be subsequently poured into 1-10 times of volume
In ethyl acetate (or dichloromethane), respectively with distilled water and saturated common salt water washing, then at 15-30 DEG C
The lower addition drier such as anhydrous calcium chloride or anhydrous sodium sulfate, keeps 10-60min.It is filtered to remove drying
After agent, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, 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 shown in figure 1, in Fig. 1, the first solvent uses methanol, and the first catalyst is used
Acetic acid, purpose by way of example only, is not construed as limiting to the scope of the present invention.
In step (b) of the present invention, the condition of bromo-reaction is preferably included：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 reacts 1-2h with bromide reagent at 15-30 DEG C, is then quenched with quencher.
" inert atmosphere " is as it was previously stated, will not be repeated here.
It will be understood by those skilled in the art that more stably being carried out to react, preferably to intermediate
Brominated reagent is slowly added in M.
In the present invention, the second solvent is preferably selected from tetrahydrofuran, dichloromethane, chloroform and ether extremely
Few one kind, more preferably tetrahydrofuran.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azo
At least one of bis-isobutyronitrile (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, it is more excellent
Elect NBS as.
In step (b) of the present invention, it is quenched with quencher, quencher can be commonly used in the art
Quencher, for example, can be saturated aqueous common salt.
In step (b) of the present invention, the consumption of intermediate M and bromide reagent is substantially equimolar amounts,
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 moles of %, and more preferably 40-60 rubs
You are %.
In the inventive method step (b), intermediate M is contacted with bromide reagent carries out the anti-of bromo-reaction
Equation is answered as shown in Fig. 2 in Fig. 2, bromide reagent uses NBS, mesh by way of example only
, the scope of the present invention is not construed as limiting.
It is also micro in addition to the bromination product shown in generation formula (III) in step (b) of the present invention
The amount of the bromination product generation at ortho position, the bromination product generation without meta, but the bromination product at ortho position is very
Subsequent reactions are not had materially affect by pettiness, can be ignored.
It will be understood by those skilled in the art that in step (b) of the present invention, it is purer in order to obtain
Bromination product, in addition it is also necessary to the system after to being quenched is post-processed, and the mode of post processing can include water
Wash, dry, removal of solvent under reduced pressure, for example, system after being quenched distillation water washing, then at 15-30 DEG C
The lower addition drier such as anhydrous calcium chloride or anhydrous sodium sulfate, keeps 10-60min.It is filtered to remove drying
After agent, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain bromination product.
In step (c) of the present invention, the condition of coupling reaction is preferably included：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 " is as it was previously stated, will not be repeated here.
In the present invention, in order that stable reaction is carried out, 80-100 DEG C, Ran Hou are preferably gradually heating to
4-8h is reacted at 80-100 DEG C.
In the present invention, the 3rd solvent is preferably selected from dichloromethane, chloroform, toluene and tetrahydrofuran extremely
Few one kind, 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 compound [Pd2(dba)3]；Part is preferably selected from tri-tert phosphorus, dinaphthol
And at least one of double (diphenylphosphino) ferrocene (dppf) (BINAP)；Alkali is preferably selected from uncle
At least one of sodium butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate.
In step (c) of the present invention, the bromination product that step (b) is obtained 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) mol ratio of the compound shown in bromination product and formula (IV) obtained is preferably 0.9-1.5:0.9-2.5.
In step (c) of the present invention, the consumption of catalyst can be catalytic amount, with mole of bromination product
On the basis of number, the consumption of palladium salt is preferably 5-50 moles of %, more preferably 5-20 moles %, more enters one
Step is preferably 5-10 moles of %；The consumption of part is preferably 5-50 moles of %, more preferably 10-30 moles %；
The consumption of alkali is preferably 5-50 moles of %, more preferably 10-30 moles %.
In step (c) of the present invention, the bromination product that step (b) is obtained and the chemical combination shown in formula (IV)
Thing contact carries out the reaction equation of coupling reaction as shown in figure 3, in Fig. 3, palladium salt uses acetic acid
Palladium, purpose by way of example only, is not construed as limiting to the scope of the present invention.
It will be understood by those skilled in the art that in order to obtain purer final product, i.e. formula (I)
Shown antioxidant, the inventive method preferably also includes post-processing reacted system, post-processes
Mode can include filtering, solvent dilution, washing, dry, removal of solvent under reduced pressure, for example, will be anti-
The filtrate after system filtering after answering is poured into the ethyl acetate (or dichloromethane) of 1-10 times of volume,
Then with distillation water washing, anhydrous calcium chloride or anhydrous sodium sulfate etc. is then added at 15-30 DEG C and is done
Drying prescription, keeps 10-60min.It is filtered to remove after drier, is removed at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain the antioxidant shown in formula (I).
Each step of the method for the compound of structure shown in formula (I) is prepared in the present invention preferably under agitation
Carry out, can be the conventional mixing speed in this area, for example, stirring for mixing speed without particular/special requirement
It can be 100-800rpm to mix speed.
The present invention is prepared in the method for the compound of 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 conventional solvent load in this area, this is ability
Well known to field technique personnel, it will not be repeated here.
As described above, it is contemplated that passing through the change containing structure shown in formula (I) in lubricant oil composite
Compound, and the compound and 2 of structure shown in formula (I), 2 '-thiobis [3- (3,5- di-t-butyl -4- hydroxyls
Phenyl) ethyl propionate type antioxidant combination and realize goal of the invention, even if lubricant oil composite have it is excellent
The performance such as wear-resistant and anti-oxidant.Therefore, for lubricant oil composite preparation method without particular/special requirement,
Method commonly used in the art can be used, for example, second aspect, present invention also offers one kind combustion
The preparation method of gas turbine oil composition, this method includes：Will be many containing lube base oil, antioxygen
Imitate additive, 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate types antioxidant, oxygen
Change zinc nanoparticles, the raw material of organic carboxyl acid class compound is well mixed and obtains lubricant oil composite, wherein,
On the basis of the weight of lubricant oil composite, the consumption of lube base oil is 85-99 weight %, antioxygen
The consumption of multipurpose additive is 0.01-10 weight %, 2,2 '-thiobis [3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) consumption of ethyl propionate type antioxidant is that 0.01-5 weight %, the consumption of Zinc oxide nanoparticle are 0.1-5
Weight %, the consumption of metal deactivator is 0.01-5 weight %, and the antioxygen multipurpose additive is formula (I)
The compound of shown structure：
In the inventive method, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is excellent
It is preferably 0.02-5 weight % to elect 90-98 weight %, the consumption of antioxygen multipurpose additive as, more preferably
0.1-4 weight %, 2,2 '-thiobis be [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate type antioxidant
Consumption is preferably that 0.1-3 weight %, the consumption of Zinc oxide nanoparticle are preferably 0.05-4 weight %, more
Preferably 0.1-3 weight %, the consumption of metal deactivator is preferably 0.02-4 weight %, more preferably 0.05-2
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 mixing mode without particular/special requirement, can will for example remove lube base
Each raw material components of oil are added separately in lube base oil, can also will be each 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 is preferably included：Temperature is 40-90 DEG C, and the time is 1-6h.
Lube base oil, antioxygen multipurpose additive, 2,2 '-thiobis [3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) ethyl propionate type antioxidant, Zinc oxide nanoparticle, metal deactivator, antirust agent, pour-point depressant and
Anti-foaming agent is as it was previously stated, will not be repeated here.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the following Examples and Comparative Examples：
The physico-chemical analysis method of product：Element is determined 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
Nitrogen is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed is 200rpm) to protect
Shield, add 150ml methanol and 0.01mol acetic acid, it is sufficiently cool in ice-water bath after, Ran Houfen
Not Jia Ru 0.1mol 2,6- DI-tert-butylphenol compounds, 0.2mol formaldehyde and 0.3mol benzene.Reaction 1
Hour after remove ice-water bath, rise to after 25 DEG C be heated to 75 DEG C persistently flow back 2 hours after stop reaction,
Reacted system is steamed into solvent at 0.03MPa, 50 DEG C, 250ml ethyl acetate is then added,
And be transferred in separatory funnel, respectively with 100ml distilled water (twice) and 50ml saturated common salt water washings,
And 10g anhydrous calcium chlorides dry 20min at 25 DEG C is added, the filtrate after filtering is in 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain midbody product M1.
Nitrogen is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed is 200rpm) to protect
Shield, adds 150ml dry tetrahydrofuran, then dissolves in midbody product M1, and add 0.05mol
Ammonium nitrate, 0.1mol brominated reagents NBS is slowly added under the conditions of lucifuge.Stirred at 25 DEG C anti-
1.5h is answered, is then quenched with saturated aqueous common salt, is then washed with 100ml distilled water (twice), and is added
Enter 10g anhydrous sodium sulfates and 20min is dried at 25 DEG C.Filtrate after filtering is in 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain bromination product.
Nitrogen is filled with the 500ml flasks with electromagnetic agitation sub (mixing speed is 200rpm) to protect
Shield, adds 150ml dichloromethane as solvent, is separately added into above-mentioned bromination product and 0.12mol
Benzotriazole compound, is subsequently added 0.02mol tri-tert phosphorus, 0.02mol sodium tert-butoxide and
0.005mol Pd (OAc)2.90 DEG C are gradually heating to, 6h is persistently stirred.Then by reacted body
Filtrate after system's filtering adds 250ml ethyl acetate, and is transferred in separatory funnel, uses 100ml distilled water
(twice) wash, and add 10g anhydrous sodium sulfates and 20min is dried at 25 DEG C.Filtrate after filtering
Solvent is evaporated off under 40 DEG C, 0.03MPa, final product S1 is obtained.
S1 physico-chemical analysis data are as follows：Nitrogen content, 11.2%.
S1 is subjected to structural characterization, hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram is respectively obtained, respectively
See Fig. 4, Fig. 5 and Fig. 6.
Physico-chemical analysis data from above-mentioned preparation example, Fig. 4, Fig. 5 and Fig. 6 can be seen that S1 has formula
(I) structure shown in.
Embodiment 1
The present embodiment is used to illustrate lubricant oil composite of the present invention and preparation method thereof.
By the S1 of 0.1 parts by weight, 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) of 1 parts by weight
Ethyl propionate, 2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles of 0.5 parts by weight (are purchased from Yantai
Heng Nuo Chemical Industry Science Co., Ltd, T561), the single Zinc oxide nanoparticle (Shandong of 0.11 parts by weight
Turner rice Materials Co., Ltd), the poly dimethyl of the 4,5- glyoxalidine of 0.3 parts by weight and 0.02 parts by weight
Siloxanes (being purchased from Hubei xinsihai Chemical Co., Ltd.) is added to the 600SN of 97.88 parts by weight
(viscosity index (VI) is 87 to lube base oil, and saturated hydrocarbon content is 92 weight %, and sulfur content is 0.02 weight
Measure %) in, 3h is stirred at 60 DEG C, it is well mixed to obtain lubricant oil composite A1.
Embodiment 2
The present embodiment is used to illustrate lubricant oil composite of the present invention and preparation method thereof.
By the S1 of 0.6 parts by weight, 2,2 '-thiobis [3- (3,5- di-t-butyl -4- hydroxy benzenes of 0.1 parts by weight
Base) ethyl propionate, (Turner rice limited material in Shandong is public for the single Zinc oxide nanoparticle of 0.15 parts by weight
Department), 2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles of 0.1 parts by weight is (purchased from the permanent promise in Yantai
Chemical Industry Science Co., Ltd, T561), poly- the two of 4, the 5- glyoxalidine of 0.3 parts by weight and 0.02 parts by weight
Methylsiloxane (being purchased from Hubei xinsihai Chemical Co., Ltd.) is added to PAO8 and PAO40
Mixed lubrication oil base oil (PAO8 be 68 parts by weight, PAO40 be 30.68 parts by weight) in,
6h is stirred at 40 DEG C, it is well mixed to obtain lubricant oil composite A2.
Embodiment 3
The present embodiment is used to illustrate lubricant oil composite of the present invention and preparation method thereof.
By the S1 of 1 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) of 0.1 parts by weight
Ethyl propionate], the single Zinc oxide nanoparticle (Shandong Turner rice Materials Co., Ltd) of 0.25 parts by weight,
2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles of 0.5 parts by weight (is purchased from Yantai Heng Nuo chemical industry section
Skill Co., Ltd, T561), the poly dimethyl silicon of 4, the 5- glyoxalidine of 0.3 parts by weight and 0.02 parts by weight
Oxygen alkane (being purchased from Hubei xinsihai Chemical Co., Ltd.) is added to the adipic acid two of 97.58 parts by weight
In butyl ester, 1h is stirred at 90 DEG C, it is well mixed to obtain lubricant oil composite A3.
Comparative example 1
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 replace with wait weigh
2, the 2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] of part is measured, lubricating oil composition is obtained
Thing D1.
Comparative example 2
Method according to embodiment 2 prepares lubricant oil composite, unlike, by 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] S1 of parts by weight such as replace with, obtain lubricant oil composite
D2。
Comparative example 3
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionates] dibutyl dithio of parts by weight such as replace with
Carbaminate, obtains lubricant oil composite D3.
Comparative example 4
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionates] the trimethylphenyl phosphorous of parts by weight such as replace with
Sour zinc, obtains lubricant oil composite D4.
Comparative example 5
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionates] the fourth octyl diphenylamine of parts by weight such as replace with,
Obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively：
The measure of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzers；
The measure of oxidation induction period is carried out using high pressure differential scanning amount method (PDSC)；
Using tetra-ball machine test method, PB, PD value are determined by GB/T3142；
Wear scar diameter is determined 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 | 215 | 219 | 225 | 203 | 207 | 208 | 197 | 191 |
| Oxidation induction period, min | 47.2 | 48.1 | 55.8 | 32.5 | 39.6 | 21.0 | 21.9 | 31.2 |
| PB, kgf | 95 | 100 | 100 | 40 | 60 | 50 | 65 | 45 |
| PD, kgf | 270 | 280 | 295 | 205 | 230 | 210 | 210 | 195 |
| Wear scar diameter d60 40, mm | 0.55 | 0.55 | 0.53 | 0.68 | 0.65 | 0.70 | 0.71 | 0.75 |
It will be understood by those skilled in the art that initial oxidation temperature is higher, the heat endurance of lubricating oil
Better；Oxidation induction period is longer, and the antioxygenic property of lubricating oil is better；PB, PD value are bigger, lubrication
The wear resistance of oil is better；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 the lubricant oil composite of the present invention has more
Good inoxidizability and abrasion resistance.
The combustion gas turbine oil composition of the present invention has excellent abrasion resistance and antioxygenic property, can be with
It is widely used in combustion gas steam turbine oil lubricating area.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited
Detail in above-mentioned embodiment, can be to the present invention in the range of the technology design of the present invention
Technical scheme carry out a variety of simple variants, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment,
In the case of reconcilable, it can be combined by any suitable means, in order to avoid unnecessary
Repeat, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of combustion gas turbine oil composition, it is characterised in that using the weight of lubricant oil composite as
Benchmark, the lubricant oil composite contains following components：85-99 weight % lube base oil,
0.01-10 weight % antioxygen multipurpose additive, 0.01-5 weight %2,2 '-thiobis [3- (tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyls) ethyl propionate, 0.05-5 weight % Zinc oxide nanoparticle, 0.01-5 weight %
Matal deactivator, the antioxygen multipurpose additive is the compound of structure shown in formula (I)：
2. lubricant oil composite according to claim 1, wherein, with the weight of lubricant oil composite
On the basis of amount, the lubricant oil composite contains following components：90-99 weight % lube base oil,
0.1-4 weight % antioxygen multipurpose additive, 0.1-3 weight % 2,2 '-thiobis [3- (3,5- di-t-butyls
- 4- hydroxy phenyls) ethyl propionate antioxidant, 0.1-3 weight % Zinc oxide nanoparticle, 0.05-2 weight %
Metal deactivator.
3. lubricant oil composite according to claim 1 or 2, wherein, the lube base
Oil is mineral lubricating oil and/or synthetic lubricant fluid.
4. lubricant oil composite according to claim 1 or 2, wherein, described 2,2 '-thiobis
[3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate antioxidant is 2,2 '-thiobis [3- (3,5- with alkyl
At least one of di-tert-butyl-hydroxy phenyl) ethyl propionate.
5. lubricant oil composite according to claim 1 or 2, wherein, the zinc-oxide nano
Particle is the nano-particle of the composition containing Zinc oxide nanoparticle, and the particle diameter of nano-particle is 3-150nm.
6. lubricant oil composite according to claim 1 or 2, wherein, the matal deactivator
For 2,5- bis- (tert- molybdenum didodecyl dithiophosphate) -1,3,4- thiadiazoles, four benzyl BTAs, 2- sulfydryl benzene
At least one of and thiazole, alkyl thiadiazoles.
7. lubricant oil composite according to claim 1 or 2, wherein, the lubricating oil composition
Thing is also containing at least one of antirust agent, pour-point depressant and anti-foaming agent.
8. lubricant oil composite according to claim 7, wherein, the antirust agent is selected from imidazoles
Class and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline succinate and alkenyl
At least one of succinate.
9. lubricant oil composite according to claim 7, wherein, the pour-point depressant be selected from poly- α-
Alkene, vinyl acetate copolymer and alkyl are C8-C18 dialkyl fumarate, poly- alkyl methyl
At least one of acrylate, alkylnaphthalene.
10. lubricant oil composite according to claim 7, wherein, the anti-foaming agent is poly- silica
Alkane type anti-foaming agent, preferably silicone oil and/or dimethyl silicone polymer.
11. a kind of preparation method of combustion gas turbine oil composition, it is characterised in that methods described includes：
Lube base oil, antioxygen multipurpose additive, 2,2 '-thiobis [3- (3,5- di-t-butyl -4- hydroxyls will be contained
Phenyl) ethyl propionate, Zinc oxide nanoparticle, the raw material of metal deactivator well mixed obtain lubricating oil
Composition, wherein, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is 85-99
Weight %, the consumption of antioxygen multipurpose additive are 0.01-10 weight %, 2,2 '-thiobis [3- (tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyls) ethyl propionate consumption be 0.01-5 weight %, the consumption of Zinc oxide nanoparticle
It is 0.01-5 mass %, the antioxygen multipurpose additive for 0.05-5 weight %, matal deactivator consumption
The compound of structure shown in formula (I)：
12. method according to claim 11, wherein, using the weight of lubricant oil composite as base
Standard, the consumption of lube base oil is that 90-99 weight %, the consumption of antioxygen multipurpose additive are 0.1-4
[consumption of 3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate antioxidant is for weight %, 2,2 '-thiobis
0.1-3 weight %, the consumption of Zinc oxide nanoparticle are 0.1-3 weight %, and the consumption of matal deactivator is
0.05-2 weight %.
13. the method according to claim 11 or 12, wherein, the condition of the mixing includes：
Temperature is 40-90 DEG C, and the time is 1-6h.
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