CN106318518B - A kind of automatic transmission fluid lubricant oil composite and preparation method thereof - Google Patents
A kind of automatic transmission fluid lubricant oil composite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of automatic transmission fluid lubricant oil composites, on the basis of the weight of lubricant oil composite, 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 %, the phosphate of 0-5 weight % and 0-5 weight % dialkyl dithiocarbamate, the antioxygen multipurpose additive be formula (I) shown in structure compound.The present invention also provides the preparation methods of automatic transmission fluid lubricant oil composite.Automatic transmission fluid lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can be widely applied to automobile engine and gearbox.
Description
Technical field
The present invention relates to lubricating oil fields, and in particular, to a kind of automatic transmission fluid lubricating oil containing special additive
Composition and preparation method thereof.
Background technique
Fluid torque-converter, gear mechanism, hydraulic mechanism, wet clutch, these are housed in the automatic transmission of automobile
Part is all lubricated using automatic transmission fluid.Automatic transmission fluid realizes lubrication, cooling, energy transmission and smooth auto-articulated speed change etc.
A series of effects.
In automobile engine and gearbox use process, the temperature of automatic transmission fluid is different with automobile running condition and becomes
Change, especially long-term high-speed cruising, automatic transmission fluid can be generated the substances such as greasy filth, paint film due to oxidation, make lubricity
It can deteriorate, also metal parts be made to be corroded.As automatic transmission increasingly minimizes, oil temperature is caused to increase and in high-load condition
A possibility that lower continuous high temperature motion conditions increase, and automatic transmission fluid lubricating oil is oxidized increase, and extend hydraulic transmission oil
Drain period require be increasingly urgent to, so the requirement to the oxidation stability of automatic transmission fluid also increasingly improves.It is automatic simultaneously
The development trend of transmission fluid is the encapsulation oil as the automobile life-cycle, it is no longer necessary to be replaced.Therefore research and development have excellent oxidation peace
The oil product of qualitative, excellent abrasion resistance can significantly extend the working life of part, and the maintenance expense of automobile gearbox is greatly reduced
With.In order to meet the industrial requirement constantly promoted and increasingly harsh working condition of automobile gear machinery, exploitation is novel to be had
The vehicle automatic transmission fluid of excellent antioxidant and antiwear property energy becomes new research hotspot.
It mainly includes phenols and aminated compounds that the lube oil additive of antioxidation can be effectively played by, which being currently known,.
Phenolic compound contains one or more and is obstructed phenol functional group, and aminated compounds then contains one or more nitrogen-atoms, these are special
Different functional group can capture the free radical compounds of oxidation process generation, so that oxidation process be prevented to continue to occur.Due to
The operating condition of Current mechanical equipment tends to strongly, often accelerated oxidation rate, shortens the service life of lubricating oil, therefore right
More stringent requirements are proposed for the efficiency and economy of antioxidant.
United States Patent (USP) US4824601A reports diphenylamine and diisobutylene in the alkaline-earth metal catalyst of acid activation
The lower alkylated amines mixture formed of (earth catalyst) effect, its anti-oxidant energy in lubricating oil and other functional fluids
Power is excellent in.
United States Patent (USP) US2005230664A1 reports a kind of antioxidant 9 of following general formula, the synthesis of 10- acridan
Method, it is to be condensed preparation under acidic catalyst effect using alkylated diphenylamine and aldehydes or ketones.
Using the tert-butyl phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine condensation preparationization occurs for patent CN1191340C
Object is closed, which has the stronger ability for capturing free radical and peroxynitrite decomposition compound, can provide to oil oxidation stability
More effectively protection, may also function as wear-resistant effect.
Patent US4225450A report it is a kind of by the tert-butyl phenols that is obstructed with Diethyldithiocarbamate the system of reacting
Standby polysulfide phenolic antioxidant has preferable antioxidation and wear-resistant effect.
Summary of the invention
The purpose of the invention is to meet wear-resistant and antioxygen property the high request to automatic transmission fluid lubricating oil, provide
A kind of automatic transmission fluid lubricant oil composite and preparation method thereof.
The present inventor has found that lubricant oil composite contains the compound of structure shown in formula (I) under study for action:
And the compound and thiophenols ester type antioxidant are combined, and automatic transmission fluid lubricant oil composite can be made to have excellent
The good performances such as wear-resistant and anti-oxidant.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of automatic transmission fluid lubricant oil composite,
On the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: the lubrication oil base of 85-98 weight %
Plinth oil, the thiophenols ester type antioxidant of the antioxygen multipurpose additive of 0.01-10 weight %, 0.01-5 weight %, 0-5 weight %
The dialkyl dithiocarbamate of phosphate and 0-5 weight %, the antioxygen multipurpose additive are structure shown in formula (I)
Compound:
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 90-98
The lube base oil of weight %, the antioxygen multipurpose additive of 0.1-4 weight %, 0.1-3 weight % thiophenols ester type antioxygen
Agent, the phosphate of 0.5-3 weight % and 0.5-2 weight % dialkyl dithiocarbamate.
On the other hand, the present invention provides a kind of preparation method of automatic transmission fluid lubricant oil composite, the method packets
It includes: lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, phosphate and dialkyl dithio ammonia will be contained
The raw material of base formates is uniformly mixed and obtains lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, lubricating oil
The dosage of base oil is 85-98 weight %, the dosage of antioxygen multipurpose additive is 0.01-10 weight %, thiophenols ester type antioxygen
The dosage of agent is 0.01-5 weight %, the dosage of phosphate is 0-5 weight %, and the dosage of dialkyl dithiocarbamate is
0-5 weight %, the antioxygen multipurpose additive are the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 90-98 weight %, resists
The dosage of oxygen multipurpose additive is 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is 0.1-3 weight %, phosphate
Dosage is 0.5-3 weight %, and the dosage of dialkyl dithiocarbamate is 0.5-2 weight %.
Automatic transmission fluid lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can be extensive
Applied to automobile engine and gearbox.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the reaction equation of (a) the step of preparing antioxygen 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 the antioxygen multipurpose additive of preparation example preparation.
Fig. 5 is the carbon spectrum spectrogram of the antioxygen multipurpose additive of preparation example preparation.
Fig. 6 is the mass spectrogram of the antioxygen multipurpose additive of preparation example preparation.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
On the one hand, the present invention provides a kind of automatic transmission fluid lubricant oil composites, are with the weight of lubricant oil composite
Benchmark, the lubricant oil composite contain following components: the lube base oil of 85-98 weight %, 0.01-10 weight % it is anti-
Oxygen multipurpose additive, the thiophenols ester type antioxidant of 0.01-5 weight %, the phosphate of 0-5 weight % and 0-5 weight % two
Diethyldithiocarbamate, the antioxygen multipurpose additive are the compound of structure shown in formula (I):
In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably 90-98 weight
Measure %；The content of antioxygen multipurpose additive is preferably 0.02-5 weight %, more preferably 0.1-4 weight %；Thiophenols ester type is anti-
The content of oxygen agent is preferably 0.1-3 weight %；The content of phosphate is preferably 0.3-4 weight %, more preferably 0.5-3 weight
Measure %；The content of dialkyl dithiocarbamate is preferably 0.1-4 weight %, more preferably 0.5-2 weight %.
The present invention is directed to tie by the compound containing structure shown in formula (I) in lubricant oil composite, and shown in formula (I)
The compound of structure and thiophenols ester type antioxidant are combined and realize goal of the invention, though lubricant oil composite have it is excellent wear-resistant
With the performances such as anti-oxidant.Therefore, it for the selection of conventional constituents each in lubricant oil composite, does not limit specifically.
In the present invention, lube base oil can be lube base oil commonly used in the art, such as can be mine
Object lubricating oil and/or synthetic lubricant fluid.
Mineral lubricating oil in viscosity can from light fraction mineral oil to heavy distillat mineral oil, including saxol and plus
That hydrogen refines, the processed alkane of solvent, cycloalkanes and mixing par-affinic-naphthenic types mineral lubricating oil, are generally divided into I, II, Group III
Base oil, common trade names include I class 150SN, 600SN, II class 100N, 150N etc..
Synthetic lubricant fluid may include polymerization hydrocarbon ils, alkyl benzene and its derivative, polymerization hydrocarbon ils specific example include but
It is not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly- (1- hexene), poly- (1- octene), gathers
(1- decene), common trade names include PAO4, PAO6, PAO8, PAO10 etc., alkyl benzene and its derivative specific example
Including but not limited to detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethylhexyl) benzene, alkyl benzene derivate packet
Include alkylated diphenyl ether and alkylated diphenyl sulfide and its derivative, analog and homologue etc..
Another suitable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (such as phthalic acid, succinic acid, alkane
Base succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimerization
Object, malonic acid, alkyl malonic acid, alkenyl malonic) with various alcohol (such as butanol, hexanol, dodecyl alcohol, 2- ethylhexyl alcohol,
Ethylene glycol, propylene glycol) ester or complex ester that condensation reaction generates occurs.The specific example of these esters includes but is not limited to adipic acid
Dibutyl ester, decanedioic acid two (2- ethylhexyl) ester, the just own ester of fumaric acid acid two, dioctyl sebacate, azelaic acid two are different pungent
Ester, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, decanedioic acid two (larane base) ester, linoleic acid
2- ethylhexyl diester of dimer etc..
Another suitable type of synthetic lubricant fluid can be for fischer tropsch process synthetic hydrocarbon oil and to this synthetic hydrocarbon oil by adding
Hydrogen isomery such as is hydrocracked, dewaxes at the lube base oil that process obtain.
In the present invention, lube base oil preferred viscosities index is greater than 80, saturated hydrocarbon content and is greater than 90 weight %, sulfur content
Less than the lube base oil of 0.03 weight %.
In the present invention, thiophenols ester type antioxidant can be thiophenols ester type antioxidant commonly used in the art, such as can be with
For thiodipropionic acid bis-dodecanol ester (DLTDP), thio-2 acid double octadecyl esters (DSTDP), 2,5- dimercapto -1,3,4- thiophene two
Azoles (DMTD) and 2, at least one of 2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], preferably
2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], such as the production of Sichuan Yong Ye Chemical Co., Ltd.
Antioxidant 1035, BASF Aktiengesellschaft production IRGANOX L115.
In the present invention, phosphate can be various phosphates commonly used in the art, such as Shandong Zibo favour can be selected magnificent
The di-n-butyl phosphite T304 of Chemical Co., Ltd.'s production, the tricresyl phosphate T306 of the Shanghai chemical plant Peng Pu production, moral
The dialkyl dithiophosphate Irgalube 353 etc. of BASF AG, state production.
In the present invention, the metal in dialkyl dithiocarbamate is preferably zinc, lead or antimony, dialkyl dithio ammonia
Alkyl in base formates is preferably the alkyl of C2-C12, more preferably the alkyl of C2-C8, more preferably ethyl, n-propyl, different
Propyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, 2- ethylhexyl, hexamethylene
Base or methylcyclopentyl.For example, dialkyl dithiocarbamate can select Changsha Wangcheng petrochemical plant to produce
T353, Vanlube 71, Vanlube73 and the Vanlube622 etc. of the production of Vanderbilt company, the U.S..
Lubricant oil composite of the invention can also contain at least one of antirust agent, pour-point depressant and anti-foaming agent.Antirust
Agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline succinate and alkene
At least one of base succinate, for example, can select Jinzhou Kangtai Lube Additive Co., Ltd. produce T746,
T703,T747.The dialkyl group fumaric acid that pour-point depressant can be C8-C18 selected from poly alpha olefin, vinyl acetate copolymer and alkyl
At least one of ester, poly- alkylmethacrylate, alkylnaphthalene, such as Wuxi south petroleum additive company can be selected
V385, Luo Mankesi VISCOPLEX1-248 of T803, Run Yinglian company etc..Anti-foaming agent can select the anti-bubble of polysiloxane type
Agent, such as can be silicone oil and/or dimethyl silicone polymer.Metal deactivating can also be contained in lubricant oil composite of the invention
Agent, metal deactivator can be various metal deactivators commonly used in the art, such as can be benzotriazole, thiadiazole derivs
Object etc..For antirust agent, pour-point depressant, anti-foaming agent and metal deactivator content without particular/special requirement, can be conventional for this field
Content, this is known to those skilled in the art, and details are not described herein.
In the present invention, the preparation method of the compound of structure shown in formula (I) is preferably included:
(a) 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate intermediate M shown in formula (II),
(b) the intermediate M that step (a) obtains is contacted with bromide reagent and carries out bromo-reaction, generated shown in formula (III)
Bromination product,
(c) bromination product for obtaining step (b) is contacted with formula (IV) compound represented carries out coupling reaction, production
(I) antioxidant shown in,
In step (a) of the present invention, the condition of condensation reaction is preferably included: under an inert atmosphere, in the first solvent,
In the presence of one catalyst, 15- is risen to after 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are reacted 0.5-1.5h at -20-0 DEG C
30 DEG C, it is then heated to 70-80 DEG C of reaction 1-3h.
In the present invention, inert atmosphere can be the inert atmosphere of this field routine, such as can be by gases such as nitrogen, argon gas
It provides.
It will be understood by those skilled in the art that reacting 0.5-1.5h at -20-0 DEG C to carry out stable reaction
After rise to 15-30 DEG C, it should be to slowly warm up to 15-30 DEG C, for example, can by -20-0 DEG C react 0.5-1.5h after body
System is placed under 15-30 DEG C of environment temperature, and reaction system itself is made to be to slowly warm up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from least one in methanol, ethyl alcohol, n,N-Dimethylformamide and acetonitrile
Kind, 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, p-methylbenzoic acid and benzene
At least one of sulfonic acid, more preferably acetic acid.
In the present invention, the dosage of 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene is substantially equimolar amounts, but formaldehyde and benzene can
With appropriate excessive.The molar 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 dosage of the first catalyst can be catalytic amount, with mole of 2,6- DI-tert-butylphenol compounds
On the basis of number, the dosage 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 purer intermediate M, goes back in order to obtain in step (a) of the present invention
It needing to post-process the system after reaction, the mode of post-processing may include that solvent is removed under reduced pressure, then diluted through solvent,
Washing, dry, decompression remove solvent again, for example, the system after reaction is removed into solvent at 0.01-0.05MPa, 40-60 DEG C,
It is subsequently poured into the ethyl acetate (or methylene chloride) of 1-10 times of volume, uses distilled water and saturated common salt water washing respectively, then
The desiccant such as anhydrous calcium chloride or anhydrous sodium sulfate are added at 15-30 DEG C, keep 10-60min.It is filtered to remove desiccant
Afterwards, 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 equation of condensation reaction as schemed
Shown in 1, in Fig. 1, the first solvent is using methanol, and the first catalyst is using acetic acid, purpose by way of example only, no
The scope of the present invention is construed as limiting.
In step (b) of the present invention, the condition of bromo-reaction is preferably included: under an inert atmosphere, in the second solvent,
In the presence of two catalyst, under the conditions of being protected from light, the intermediate M that step (a) obtains is reacted at 15-30 DEG C with bromide reagent
Then 1-2h is quenched with quencher.
" inert atmosphere " is as previously mentioned, details are not described herein.
It will be understood by those skilled in the art that more stably being carried out to react, slowly add preferably into intermediate M
Enter brominated reagent.
In the present invention, the second solvent is preferably selected from least one of tetrahydrofuran, methylene chloride, chloroform and ether, more
Preferably tetrahydrofuran.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azodiisobutyronitrile
At least one of (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, more preferably NBS.
In step (b) of the present invention, it is quenched with quencher, quencher can be quencher commonly used in the art, such as
It can be saturated salt solution.
In step (b) of the present invention, the dosage of intermediate M and bromide reagent is substantially equimolar amounts, but bromide reagent one
As can be suitably excessive, reach 1.1-3 times of equivalent of reaction substrate.Intermediate M and bromide reagent molar ratio are preferably 0.9-
1.2:0.9-3.0。
In step (b) of the present invention, the dosage of the second catalyst can be catalytic amount, on the basis of the molal quantity of intermediate M,
The dosage of second catalyst is preferably 10-100 moles of %, more preferably 40-60 moles of %.
In the method for the present invention step (b), intermediate M contacts the reaction equation for carrying out bromo-reaction with bromide reagent as schemed
Shown in 2, in Fig. 2, bromide reagent is using NBS, and purpose by way of example only is not construed as limiting the scope of the present invention.
In step (b) of the present invention, other than generating bromination product shown in formula (III), there are also the bromos at micro ortho position to produce
Object generates, and the bromination product of meta position does not generate, but the amount of the bromination product at ortho position very pettiness, to subsequent reactions without substantive shadow
It rings, can be ignored.
It will be understood by those skilled in the art that in step (b) of the present invention, purer bromination product in order to obtain,
It also needs to post-process the system after being quenched, the mode of post-processing may include washing, drying, solvent, example be removed under reduced pressure
Such as, the system after being quenched is washed with distilled water, it is dry that anhydrous calcium chloride or anhydrous sodium sulfate etc. is then added at 15-30 DEG C
Drying prescription keeps 10-60min.After being filtered to remove desiccant, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain bromine
For product.
In step (c) of the present invention, the condition of coupling reaction is preferably included: under an inert atmosphere, in third solvent,
In the presence of three catalyst, the bromination product that step (b) obtains is reacted at 80-100 DEG C with formula (IV) compound represented
4-8h。
" inert atmosphere " is as previously mentioned, details are not described herein.
In the present invention, in order to carry out stable reaction, it is preferably gradually heated to 80-100 DEG C, it is then anti-at 80-100 DEG C
Answer 4-8h.
In the present invention, third solvent is preferably selected from least one of methylene chloride, chloroform, toluene and tetrahydrofuran, more
Preferably methylene chloride.
In the present invention, third catalyst preferably includes palladium salt, ligand and alkali.Palladium salt is preferably selected from palladium acetate and/or palladium-two
BENZYLIDENE ACETONE complex compound [Pd2(dba)3]；Ligand is preferably selected from tri-tert-butylphosphine, dinaphthol (BINAP) and bis- (diphenylphosphines
At least one of base) ferrocene (dppf)；Alkali is preferably selected from sodium tert-butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate extremely
Few one kind.
In step (c) of the present invention, the dosage of bromination product and formula (IV) compound represented that step (b) obtains is substantially
For equimolar amounts, but formula (IV) compound represented can be suitably excessive.Shown in the bromination product and formula (IV) that step (b) obtains
The molar ratio of compound be preferably 0.9-1.5:0.9-2.5.
In step (c) of the present invention, the dosage of catalyst can be catalytic amount, on the basis of the molal quantity of bromination product, palladium
The dosage of salt is preferably 5-50 moles of %, more preferably 5-20 moles of %, is still more preferably 5-10 moles of %；The use of ligand
Amount is preferably 5-50 moles of %, more preferably 10-30 moles of %；The dosage of alkali is preferably 5-50 moles of %, more preferably 10-30
Mole %.
In step (c) of the present invention, the bromination product that step (b) obtains is contacted with formula (IV) compound represented to be coupled
The reaction equation of reaction is as shown in figure 3, in Fig. 3, and palladium salt is using palladium acetate, purpose by way of example only, not to this
The range of invention is construed as limiting.
It will be understood by those skilled in the art that purer final product, i.e. antioxygen shown in formula (I) in order to obtain
Agent, for the method for the present invention it is also preferable to include post-processing to the system after reaction, the mode of post-processing may include filtering, solvent
Washing, drying, solvent is removed under reduced pressure in dilution, for example, the filtered filtrate of system after reaction to be poured into the second of 1-10 times of volume
It in acetoacetic ester (or methylene chloride), is then washed with distilled water, anhydrous calcium chloride or anhydrous sulphur is then added at 15-30 DEG C
The desiccant such as sour sodium keep 10-60min.After being filtered to remove desiccant, solvent is removed at 0.01-0.05MPa, 40-60 DEG C,
To obtain antioxidant shown in formula (I).
Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention preferably carries out under stiring, for
Mixing speed can be the mixing speed of this field routine, for example, mixing speed can be 100-800rpm without particular/special requirement.
The present invention is prepared in the method for the compound of structure shown in formula (I), molten for the first solvent, the second solvent and third
The amount of agent can be the solvent usage of this field routine, this is known to those skilled in the art, herein no longer without particular/special requirement
It repeats.
As described above, the present invention is directed to the compound by containing structure shown in formula (I) in lubricant oil composite, and formula
(I) compound and thiophenols ester type antioxidant of structure shown in are combined and realize goal of the invention, even if lubricant oil composite has
The excellent performances such as wear-resistant and anti-oxidant.It therefore, can be using this for the preparation method of lubricant oil composite without particular/special requirement
The conventional use of method in field, for example, second aspect, the present invention also provides a kind of systems of automatic transmission fluid lubricant oil composite
Preparation Method, this method comprises: will containing lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, phosphate and
The raw material of dialkyl dithiocarbamate is uniformly mixed and obtains lubricant oil composite, wherein with the weight of lubricant oil composite
On the basis of amount, the dosage of lube base oil is 85-98 weight %, the dosage of antioxygen multipurpose additive be 0.01-10 weight %,
The dosage of thiophenols ester type antioxidant is 0.01-5 weight %, the dosage of phosphate is 0-5 weight %, dialkyl dithio amino
The dosage of formates is 0-5 weight %, and the antioxygen multipurpose additive is the compound of structure shown in formula (I):
In the method for the present invention, it is preferable that on the basis of the weight of lubricant oil composite, the dosage of lube base oil is
90-98 weight %；The dosage of antioxygen multipurpose additive is 0.02-5 weight %, more preferably 0.1-4 weight %；Thiophenols ester type
The dosage of antioxidant is 0.1-3 weight %；The dosage of phosphate is 0.3-4 weight %, more preferably 0.5-3 weight %；Dioxane
The dosage of base dithiocar-bamate is 0.1-4 weight %, more preferably 0.5-2 weight %.
As previously mentioned, raw material can also contain at least one in antirust agent, pour-point depressant and anti-foaming agent in the method for the present invention
Kind, metal deactivator can also be contained.
In the method for the present invention, for mixed mode without particular/special requirement, such as each original of lube base oil can will be removed
Material component is added separately in lube base oil, can also will be mixed and made into concentrate again except each component of lube base oil
It is added in lube base oil.
In the method for the present invention, mixed condition is preferably included: temperature is 40-90 DEG C, time 1-6h.
Lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, phosphate, dialkyl dithio amino
Formates, antirust agent, pour-point depressant, anti-foaming agent, metal deactivator are as previously mentioned, details are not described herein.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In the following Examples and Comparative Examples:
The physico-chemical analysis method of product: constituent content is measured by inductively coupled plasma body ion emission spectroscopy method.
Structure characterization methods: nuclear magnetic resonance method (1H hydrogen spectrum,13C carbon spectrum), high resolution mass spectrum.
Preparation example
It is filled with nitrogen protection in the 500mL flask with electromagnetic agitation sub (mixing speed 200rpm), 150mL is added
Methanol and 0.01mol acetic acid, after being fully cooled in ice-water bath, be then respectively adding 2, the 6- di-tert-butyl of 0.1mol
Phenol, the formaldehyde of 0.2mol and the benzene of 0.3mol.Reaction moves back ice-water bath in 1 hour, and 75 DEG C are heated to after rising to 25 DEG C and is persistently returned
Stream stops reaction after 2 hours, the system after reaction is steamed solvent at 0.03MPa, 50 DEG C, and 250mL acetic acid second is then added
Ester, and be transferred in separatory funnel, 100mL distilled water (twice) and 50mL saturated common salt water washing are used respectively, and it is anhydrous that 10g is added
Calcium chloride dry 20min, filtered filtrate at 25 DEG C are evaporated off solvent at 40 DEG C, 0.03MPa, obtain midbody product
M1。
It is filled with nitrogen protection in the 500mL flask with electromagnetic agitation sub (mixing speed 200rpm), 150mL is added
Dry tetrahydrofuran, then dissolve in midbody product M1, and the ammonium nitrate of 0.05mol is added, under the conditions of being protected from light slowly plus
Enter 0.1mol brominated reagent NBS.It is stirred to react 1.5h at 25 DEG C, is then quenched with saturated salt solution, is then distilled with 100mL
Water (twice) washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is in 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain bromination product.
It is filled with nitrogen protection in the 500mL flask with electromagnetic agitation sub (mixing speed 200rpm), 150mL is added
Methylene chloride as solvent, be separately added into above-mentioned bromination product and the benzotriazole compound of 0.12mol, then be added
The tri-tert-butylphosphine of 0.02mol, the sodium tert-butoxide of 0.02mol and the Pd (OAc) of 0.005mol2.90 DEG C are gradually heated to, is continued
Stir 6h.Then 250mL ethyl acetate is added in the filtered filtrate of system after reaction, and be transferred in separatory funnel, used
100mL distilled water (twice) washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is 40
DEG C, solvent is evaporated off under 0.03MPa, obtain final product S1.
The physico-chemical analysis data of S1 are as follows: nitrogen content, and 11.2%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 4, Fig. 5 and
Fig. 6.
It can be seen that S1 with knot shown in formula (I) from the physico-chemical analysis data of above-mentioned preparation example, Fig. 4, Fig. 5 and Fig. 6
Structure.
Embodiment 1
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 0.1 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 3 parts by weight
Ethyl ester], the di-n-butyl phosphite T304 (being purchased from Shandong Zibo Hui Hua Chemical Co., Ltd.) of 0.5 parts by weight, 2 parts by weight two
Butyl molybdenum dithiocarbamate, 0.2 parts by weight benzotriazole be added to the 600SN lube base oil of 94.2 parts by weight
In (viscosity index (VI) 87, saturated hydrocarbon content are 92 weight %, and sulfur content is 0.02 weight %), 3h is stirred at 60 DEG C, is mixed
Uniformly obtain lubricant oil composite A1.
Embodiment 2
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 1.2 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 1.2 parts by weight
Acetoacetic ester], the tricresyl phosphate T306 (being purchased from the Shanghai chemical plant Peng Pu) of 2.7 parts by weight, 1.5 parts by weight two sulphur of dibutyl
The Group III Yubase4 and 40.2 parts by weight of 53 parts by weight are added to for the benzotriazole of carbamic acid molybdenum, 0.2 parts by weight
In the mixed lubrication oil base oil of Group III Yubase6,6h is stirred at 40 DEG C, is uniformly mixed and obtains lubricant oil composite A2.
Embodiment 3
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 4 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 0.1 parts by weight
Ethyl ester], the Irgalube 353 (being purchased from BASF Corp. of Germany) of 3 parts by weight, 0.5 parts by weight dibutyl dithiocaarbamate
Molybdenum, 0.2 parts by weight benzotriazole be added to the 100N lube base oil of 92.2 parts by weight (viscosity index (VI) 112, saturation
Hydrocarbon content is 96 weight %) in, 1h is stirred at 90 DEG C, is uniformly mixed and obtains lubricant oil composite A3.
Comparative example 1
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, S1 is replaced with etc. the 2,2'- of parts by weight
Thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], obtains lubricant oil composite D1.
Comparative example 2
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by 2,2'- thiobis [3- (3,5- bis- uncles
Butyl -4- hydroxy phenyl) ethyl propionate] S1 that the parts by weight such as replaces with, obtain lubricant oil composite D2.
Comparative example 3
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] zinc dibutyl dithiocarbamate that the parts by weight such as replaces with, it is lubricated
Fluid composition D3.
Comparative example 4
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the trimethylphenyl zinc phosphite that the parts by weight such as replaces with, obtain lubricating oil composition
Object D4.
Comparative example 5
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the fourth octyl diphenylamine that the parts by weight such as replaces with, obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively:
The measurement of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzer；
The measurement of oxidation induction period is carried out using high pressure differential scanning amount method (PDSC)；
The wear-resistant test of high temperature of oil product is carried out using high-frequency reciprocating frictional testing machine (being purchased from Britain PCS company, HFRR),
Experimental condition are as follows: load 400g, temperature are 80 DEG C, test period 60min, measure the mill spot formed on steel ball after the test
Diameter.It the results are shown in Table 1.
Table 1
| A1 | A2 | A3 | D1 | D2 | D3 | D4 | D5 | |
| Initial oxidation temperature, DEG C | 238 | 249 | 266 | 223 | 233 | 211 | 225 | 219 |
| Oxidation induction period, min | 47.1 | 44.9 | 62.6 | 28.3 | 35.2 | 27.5 | 18.4 | 29.2 |
| Wear scar diameter, μm | 223 | 212 | 194 | 268 | 239 | 270 | 261 | 338 |
It will be understood by those skilled in the art that initial oxidation temperature is higher, the thermal stability of lubricating oil is better；Oxidation
Induction period is longer, and the antioxygenic property of lubricating oil is better；Wear scar diameter is smaller, and the wear resistance of lubricating oil is better.
A2 is compared with D1-D5 respectively as can be seen that lubricant oil composite of the invention has better thermostabilization
Property, inoxidizability and abrasion resistance.
Automatic transmission fluid lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can be extensive
Applied to automobile engine and gearbox.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (18)
1. a kind of automatic transmission fluid lubricant oil composite, which is characterized in that on the basis of the weight of lubricant oil composite, the profit
Sliding oil composition contains following components: the antioxygen multiple-effect addition of the lube base oil, 0.01-10 weight % of 85-98 weight %
Agent, the thiophenols ester type antioxidant of 0.01-5 weight %, the phosphate of 0-5 weight % and 0-5 weight % dialkyl dithio
Carbaminate, the antioxygen multipurpose additive are the compound of structure shown in formula (I):
2. lubricant oil composite according to claim 1, wherein on the basis of the weight of lubricant oil composite, the profit
Sliding oil composition contains following components: the lube base oil of 90-98 weight %, 0.1-4 weight % antioxygen multipurpose additive,
The dialkyl dithio of the thiophenols ester type antioxidant of 0.1-3 weight %, the phosphate of 0.5-3 weight % and 0.5-2 weight %
Carbaminate.
3. lubricant oil composite according to claim 1 or 2, wherein the lube base oil be mineral lubricating oil and/
Or synthetic lubricant fluid.
4. lubricant oil composite according to claim 1 or 2, wherein the thiophenols ester type antioxidant is that 2,2'- is thio
Bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionates].
5. lubricant oil composite according to claim 1 or 2, wherein the phosphate is tricresyl phosphate.
6. lubricant oil composite according to claim 1 or 2, wherein in the dialkyl dithiocarbamate
Metal is zinc, lead or antimony, the alkyl that the alkyl in the dialkyl dithiocarbamate is C2-C12.
7. lubricant oil composite according to claim 6, wherein the alkyl in the dialkyl dithiocarbamate
For the alkyl of C2-C8.
8. lubricant oil composite according to claim 7, wherein the alkyl in the dialkyl dithiocarbamate
For ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl
Or 2- ethylhexyl.
9. lubricant oil composite according to claim 1 or 2, wherein the lubricant oil composite also contains antirust agent, drop
Solidifying at least one of agent and anti-foaming agent.
10. lubricant oil composite according to claim 9, wherein the antirust agent is selected from imidazoles and/or allyl butyrate two
Esters of gallic acid.
11. lubricant oil composite according to claim 10, wherein the antirust agent is 4,5- glyoxalidine, alkenyl miaow
At least one of oxazoline succinate and alkenyl succinic acid ester.
12. lubricant oil composite according to claim 9, wherein the pour-point depressant is selected from poly alpha olefin, alkyl C8-
At least one of the dialkyl fumarate of C18, poly- alkylmethacrylate, alkylnaphthalene.
13. lubricant oil composite according to claim 9, wherein the anti-foaming agent is polysiloxane type anti-foaming agent.
14. lubricant oil composite according to claim 13, wherein the anti-foaming agent is silicone oil.
15. lubricant oil composite according to claim 13, wherein the anti-foaming agent is dimethyl silicone polymer.
16. a kind of preparation method of automatic transmission fluid lubricant oil composite, which is characterized in that the described method includes: profit will be contained
The original of lubricant base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, phosphate and dialkyl dithiocarbamate
Material is uniformly mixed and obtains lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, the dosage of lube base oil
Dosage for 85-98 weight %, antioxygen multipurpose additive is 0.01-10 weight %, the dosage of thiophenols ester type antioxidant is
0.01-5 weight %, phosphate dosage be 0-5 weight %, the dosage of dialkyl dithiocarbamate is 0-5 weight %,
The antioxygen multipurpose additive is the compound of structure shown in formula (I):
17. according to the method for claim 16, wherein on the basis of the weight of lubricant oil composite, lube base oil
Dosage be 90-98 weight %, the dosage that the dosage of antioxygen multipurpose additive is 0.1-4 weight %, thiophenols ester type antioxidant
Dosage for 0.1-3 weight %, phosphate is 0.5-3 weight %, and the dosage of dialkyl dithiocarbamate is 0.5-2 weight
Measure %.
18. method according to claim 16 or 17, wherein the mixed condition includes: that temperature is 40-90 DEG C, when
Between be 1-6h.
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