CN106318553A - Automatic transmission fluid lubricating oil composition and preparation method thereof - Google Patents
Automatic transmission fluid lubricating oil composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an automatic transmission fluid lubricating oil composition. Based on weight, the lubricating oil composition contains the following components: 85-98wt% of lubricating oil base oil, 0.01-10wt% of an anti-oxygen and antiwear multi-effect additive, 0.01-5wt% of a thiophenolic ester antioxidant, 0-5wt% of phosphate ester and 0-5wt% of dialkyl dithiocarbamate, wherein the anti-oxygen and antiwear multi-effect additive is a compound with a structure shown as formula (I). The invention also provides a preparation method of the automatic transmission fluid lubricating oil composition. The automatic transmission fluid lubricating oil composition provided by the invention has excellent antiwear properties and oxidation resistance, and can be widely applied to automobile engines and gearboxes. (formula (I)).
Description
Technical field
The present invention relates to lubricating oil field, in particular it relates to a kind of automatic transmission containing special additive
Liquid lubricant oil composite and preparation method thereof.
Background technology
Equipped with fluid torque-converter, gear mechanism, hydraulic mechanism, wet type clutch in the automatic transmission of automobile
Device, these parts all use automatic transmission fluid to lubricate.Automatic transmission fluid achieves lubrication, cooling, energy
A series of effects such as transmission and smooth auto-articulated speed change.
During automobile engine and change speed gear box use, the temperature of automatic transmission fluid is with automobile running condition not
With and change, especially long-term high-speed cruising, automatic transmission fluid can generate due to Oxidation greasy filth,
The materials such as paint film, make greasy property deteriorate, and also make metal parts be corroded.Along with automatic transmission day by day
Miniaturization, causes oil temperature to raise and the increasing of continuous high temperature motion conditions under high-load condition, automatically passes
The probability increase that hydrodynamic lubricating oil is oxidized, and the drain period extending hydraulic transmission oil requires the most urgent
Cut, so the requirement to the oxidation stability of automatic transmission fluid improves the most day by day.Automatic transmission fluid simultaneously
Development trend is to become the encapsulation oil of automobile life-cycle, it is no longer necessary to change.Therefore research and development have excellent oxygen
Change stability, the oil product of excellent abrasion resistance can significantly extend the working life of part, and vapour is greatly reduced
The maintenance cost of car change speed gear box.In order to meet the industrial requirement constantly promoted and day by day of automobile gear machinery
Harsh working condition, developing the novel vehicle automatic transmission fluid with excellent antioxidant and antiwear property energy becomes new
Study hotspot.
It is currently known and can effectively play the lube oil additive of antioxidation and mainly include phenols and amine
Compounds.Phenolic compound contains one or more hindered phenol functional group, and aminated compounds then contains one
Individual or multiple nitrogen-atoms, these special functional groups can catch the free radical chemical combination that oxidizing process generates
Thing, thus stop the continuation of oxidizing process to occur.Owing to the working condition of Current mechanical equipment tends to strong,
Often accelerated oxidation speed, shortens the service life of lubricating oil, therefore efficiency and the economy to antioxidant
Property is had higher requirement.
United States Patent (USP) US4824601A reports diphenylamine and the diisobutylene alkaline-earth metal in acid activation
The lower alkylated amines mixture formed of catalyst (earth catalyst) effect, it lubricating oil and other
Oxidation resistance performance excellence in functional fluid.
United States Patent (USP) US2005230664A1 reports the antioxidant 9 of a kind of below general formula, 10-dihydro
The synthetic method of acridine, it is to use alkylated diphenylamine and aldehydes or ketones to contract under acidic catalyst effect
Close preparation.
Patent CN1191340C uses the tert-butyl group phenols that is obstructed, aldehyde, Carbon bisulfide and dialkylamine to occur
Compound is prepared in condensation, and this compound has stronger seizure free radical and the ability of peroxynitrite decomposition compound,
More effectively protection can be provided to oil oxidation stability, may also function as wear-resistant effect.
Patent US4225450 reports a kind of by tert-butyl group phenols and the alkyl aminodithioformic acid of being obstructed
Polysulfide phenolic antioxidant prepared by reactant salt, has preferable antioxidation and wear-resistant effect.
Summary of the invention
The invention aims to meet the wear-resistant of automatic transmission fluid lubricating oil and the height of antioxygen property
Requirement, it is provided that a kind of automatic transmission fluid lubricant oil composite and preparation method thereof.
The present inventor finds under study for action, and lubricant oil composite contains structure shown in formula (I)
Compound:
And this compound is combined with thiophenols ester type antioxidant, it is possible to make automatic transmission fluid lubricating oil composition
Thing has the performances such as excellent wear-resistant and antioxidation.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of automatic transmission fluid lubrication
Fluid composition, on the basis of the weight of lubricant oil composite, described lubricant oil composite contains following components:
The lube base oil of 85-98 weight %, the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, 0.01-5
Thiophenols ester type antioxidant, the phosphate ester of 0-5 weight % and the dialkyl disulfides of 0-5 weight % of weight %
For carbaminate, the wear-resistant multipurpose additive of described antioxygen is the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, described lubricant oil composite contains following group
Point: the lube base oil of 90-98 weight %, the wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, 0.1-3
Thiophenols ester type antioxidant, the phosphate ester of 0.5-3 weight % and the dialkyl group of 0.5-2 weight % of weight %
Dithiocar-bamate.
On the other hand, the invention provides the preparation method of a kind of automatic transmission fluid lubricant oil composite, institute
The method of stating includes: will be containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxygen
The raw material mix homogeneously of agent, phosphate ester and dialkyl dithiocarbamate obtains lubricant oil composite,
Wherein, on the basis of the weight of lubricant oil composite, the consumption of lube base oil be 85-98 weight %,
The consumption of the wear-resistant multipurpose additive of antioxygen is that 0.01-10 weight %, the consumption of thiophenols ester type antioxidant are
0.01-5 weight %, the consumption of phosphate ester are 0-5 weight %, the use of dialkyl dithiocarbamate
Amount is 0-5 weight %, and the wear-resistant multipurpose additive of described antioxygen is the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is 90-98
The consumption of the wear-resistant multipurpose additive of weight %, antioxygen is 0.1-4 weight %, the use of thiophenols ester type antioxidant
Amount is 0.5-3 weight % for 0.1-3 weight %, the consumption of phosphate ester, dialkyl dithiocarbamate
Consumption be 0.5-2 weight %.
The automatic transmission fluid lubricant oil composite of the present invention has abrasion resistance and the antioxygenic property of excellence,
Can be widely applied to automobile engine and change speed gear box.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is the reaction equation of the step (a) preparing the wear-resistant multipurpose additive of antioxygen.
Fig. 2 is the reaction equation of the step (b) preparing the wear-resistant multipurpose additive of antioxygen.
Fig. 3 is the hydrogen spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen prepared by preparation example.
Fig. 4 is the carbon spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen prepared by preparation example.
Fig. 5 is the mass spectrogram of the wear-resistant multipurpose additive of antioxygen prepared by preparation example.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of automatic transmission fluid lubricant oil composite, with lubricant oil composite
Weight on the basis of, described lubricant oil composite contains following components: the lubrication oil base of 85-98 weight %
Plinth oil, the thiophenols ester type of the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, 0.01-5 weight % resist
Oxygen agent, the phosphate ester of 0-5 weight % and the dialkyl dithiocarbamate of 0-5 weight %, described anti-
The wear-resistant multipurpose additive of oxygen is the compound of structure shown in formula (I):
In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably
90-98 weight %；The content of the wear-resistant multipurpose additive of antioxygen is preferably 0.02-5 weight %, more preferably
0.1-4 weight %；The content of thiophenols ester type antioxidant is preferably 0.1-3 weight %；The content of phosphate ester
It is preferably 0.3-4 weight %, more preferably 0.5-3 weight %；Containing of dialkyl dithiocarbamate
Amount is preferably 0.1-4 weight %, more preferably 0.5-2 weight %.
It is contemplated that by lubricant oil composite contains the compound of structure shown in formula (I), and
The compound of structure shown in formula (I) is combined with thiophenols ester type antioxidant and realizes goal of the invention, even if
Lubricant oil composite has the performances such as excellent wear-resistant and antioxidation.Therefore, in lubricant oil composite
The selection of each conventional constituents, the most specifically limits.
In the present invention, lube base oil can be lube base oil commonly used in the art, such as
Can be mineral lubricating oil and/or synthetic lubricant fluid.
Mineral lubricating oil can be from light fraction mineral oil to heavy distillat mineral oil in viscosity, including liquid stone
Alkane, cycloalkanes and the mixing par-affinic-naphthenic types mineral lubricant that wax oil and hydrorefined, solvent processed
Oil, is generally divided into I, II, Group III base oil, and common trade names include I class 150SN, 600SN,
II class 100N, 150N etc..
Synthetic lubricant fluid can include being polymerized hydrocarbon ils, alkyl benzene and its derivative, the example that polymerization hydrocarbon ils is concrete
Son includes but not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly-(1-
Hexene), poly-(1-octene), poly-(1-decene), common trade names include PAO4, PAO6, PAO8,
PAO10 etc., alkyl benzene and its derivative specific example includes but not limited to detergent alkylate, the tetradecane
Base benzene, dinonyl benzene, two (2-ethylhexyl) benzene, alkyl benzene derivate includes alkylating diphenyl ether
With alkylating diphenyl sulfide and derivant, analog and homologue etc..
Another applicable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (as phthalic acid,
Succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, Azelaic Acid, suberic acid, decanedioic acid, anti-
Butene dioic acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic) with
Various alcohol (such as butanol, hexanol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, propylene glycol) are sent out
The ester of raw condensation reaction generation or complex ester.The object lesson of these esters includes but not limited to adipic acid two fourth
Ester, decanedioic acid two (2-ethylhexyl) ester, the most own ester of fumaric acid acid two, di-n-octyl sebacate, nonyl
Diacid di-isooctyl, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate,
Decanedioic acid two (larane base) ester, the 2-ethylhexyl diester etc. of linoleic acid dimer.
Another applicable type of synthetic lubricant fluid can be fischer tropsch process synthetic hydrocarbon oil and to this synthesis hydrocarbon
Oil by hydroisomerizing, be hydrocracked, lube base oil that the PROCESS FOR TREATMENT such as dewaxing obtains.
In the present invention, lube base oil preferred viscosities index more than 80, saturated hydrocarbon content is more than 90 weights
Amount %, sulfur content are less than the lube base oil of 0.03 weight %.
In the present invention, thiophenols ester type antioxidant can be thiophenols ester type antioxidant commonly used in the art,
Can be such as the double lauryl alcohol ester (DLTDP) of thio-2 acid, the double octadecyl ester of thio-2 acid
(DSTDP), 2,5-dimercapto-1,3,4-thiadiazoles (DMTD) and 2,2'-thiobis [3-(the tertiary fourth of 3,5-bis-
Base-4-hydroxy phenyl) ethyl propionate] at least one, preferably 2,2'-thiobis [3-(3,5-di-t-butyls
-4-hydroxy phenyl) ethyl propionate], the antioxidant 1035 that such as Yong Ye Chemical Co., Ltd. in Sichuan produces, moral
The IRGANOX L115 that BASF AG of state produces.
In the present invention, phosphate ester can be various phosphate esters commonly used in the art, such as, can select Shandong
The di-n-butyl phosphite T304 that Zibo Hui Hua Chemical Co., Ltd. produces, Peng Pu chemical plant, Shanghai produces
Tricresyl phosphate T306, BASF Corp. of Germany produce dialkyl dithiophosphate Irgalube
353 etc..
In the present invention, the metal in dialkyl dithiocarbamate is preferably zinc, lead or antimony, dioxane
Alkyl in base dithiocar-bamate is preferably the alkane of the alkyl of C2-C12, more preferably C2-C8
Base, more preferably ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl,
Isopentyl, n-hexyl, isohesyl, n-octyl, 2-ethylhexyl, cyclohexyl or methylcyclopentyl.Example
As, dialkyl dithiocarbamate can select the T353 that Wangcheng, Changsha petrochemical plant produces,
Vanlube 71, Vanlube73 and Vanlube622 etc. that Vanderbilt company of the U.S. produces.
The lubricant oil composite of the present invention can also contain at least in antirust agent, pour-point depressant and anti-foaming agent
Kind.Antirust agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5-glyoxalidine, alkene
At least one in base imidazoline succinate and alkenyl succinic acid ester, such as, can select the safe profit in Jinzhou
T746, T703, T747 that oil additive company limited produces.Pour-point depressant can be selected from poly alpha olefin,
Vinyl acetate copolymer and dialkyl fumarate that alkyl is C8-C18, poly-alkyl methacrylate
At least one in ester, alkylnaphthalene, such as can select south, Wuxi petroleum additive company T803,
V385, Luo Mankesi VISCOPLEX1-248 etc. of Run Yinglian company.Anti-foaming agent can select poly-silicon
Oxygen alkane type anti-foaming agent, such as, can be silicone oil and/or polydimethylsiloxane.The lubricating oil composition of the present invention
Can also contain metal deactivator in thing, metal deactivator can be various metal deactivatings commonly used in the art
Agent, such as, can be BTA, thiadiazoles derivative etc..For antirust agent, pour-point depressant, anti-bubble
The content of agent and metal deactivator, without particular/special requirement, can be the content of this area routine, and this is this area
Well known to technical staff, do not repeat them here.
In the present invention, shown in formula (I), the preparation method of the compound of structure preferably includes:
A aniline, Disulfur dichloride and 4-chloroaniline are reacted by (), generate the intermediate shown in formula (II)
M,
B intermediate M that step (a) is obtained by () is with dimercapto-1,3,4-thiadiazoles in the basic conditions
Carry out nucleophilic substitution, generate the multipurpose additive shown in formula (I),
In step (a) of the present invention, aniline, Disulfur dichloride and 4-chloroaniline are carried out the concrete mode reacted
Preferably include:
(i) under an inert atmosphere, in the first solvent, by aniline and Disulfur dichloride at-20-0 DEG C fully
React；
(ii) 4-chloroaniline is added in the reaction system of step (i), at 15-30 DEG C, react 1-3h.
In the present invention, inert atmosphere can be the inert atmosphere that this area is conventional, such as can by nitrogen,
The gases such as argon provide.
In step (i) of the present invention, the first solvent be preferably selected from dichloromethane, oxolane, toluene,
At least one in dimethylbenzene and dioxane, more preferably dichloromethane and/or oxolane, more enter one
Step is preferably dichloromethane.
In the present invention in step (i), fully carry out reacting i.e. referring to reaction completely, i.e. reaction raw materials is complete
Entirely react.Can use method commonly used in the art that reaction is monitored, to confirm reaction completely,
The methods such as thin layer chromatography (TLC) or gas chromatogram such as can be used to be monitored.
In step of the present invention (ii), at 15-30 DEG C, react 1-3h, preferably the most anti-in step (i)
Ying Hou, is gradually increased to 15-30 DEG C by the temperature of reaction system, adds 4-chloroaniline and carries out reacting 1-3h.
Under this preferable case, reaction yield can be improved further.
In step of the present invention (ii), the feed postition of 4-chloroaniline is preferably and adds by several times, the most permissible
Divide 3-4 time to add.Under this preferable case, reaction yield can be improved further.For adding by several times
Time, each addition can be identical, it is also possible to different, in order to easy to operate, and the most each addition
Measure identical.
In step of the present invention (ii), reacting 1-3h, the mode of stopped reaction can be people in the art
The thinkable various modes of member, for example, it is possible to add quencher to carry out cancellation, quencher can be this
The quencher that field is conventional, such as, can be saturated aqueous common salt.
In the present invention, the consumption of aniline, Disulfur dichloride and 4-chloroaniline is substantially equimolar amounts, but aniline
Can be suitably excessive with Disulfur dichloride.The mol ratio of aniline, Disulfur dichloride and 4-chloroaniline is preferably 0.9-1.5:
0.9-1.5:0.8-1.2.
It will be understood by those skilled in the art that in step (a) of the present invention, purer in order to obtain
Intermediate M, in addition it is also necessary to reacted system is carried out post processing, and the mode of post processing can include washing
Wash, be dried, removal of solvent under reduced pressure, such as, by the reaction system after cancellation respectively with distilled water and saturated
Brine It, then adds the desiccant such as anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C,
Keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C, remove solvent,
To obtain intermediate M.
In step (a) of the present invention, aniline, Disulfur dichloride and 4-chloroaniline carry out the reaction equation reacted
As it is shown in figure 1, in Fig. 1, the first solvent uses dichloromethane, purpose by way of example only,
The scope of the present invention is not construed as limiting.
In step (b) of the present invention, the condition of nucleophilic substitution preferably includes: under an inert atmosphere,
In the second solvent, dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed at 15-30 DEG C
10-30min, is subsequently adding intermediate M, fully reacts.I.e. alkalescence condition is provided by alkaline reagent.
" inert atmosphere ", " fully reacting " be not as it was previously stated, repeat them here.
In the present invention, intermediate M is preferably slowly added to, such as, can add by several times, typically can divide
Add for 3-4 time.Under this preferable case, reaction yield can be improved further.It is fashionable for adding by several times,
Each addition can be identical, it is also possible to different, in order to easy to operate, and the most each addition phase
With.
In the present invention, the second solvent is preferably selected from dichloromethane, oxolane, toluene, dimethylbenzene, N, N-
At least one in dimethylformamide, more preferably dichloromethane and/or DMF,
Further it is preferably N,N-dimethylformamide.
In the present invention, alkaline reagent is preferably selected from the inorganic bases such as potassium carbonate, sodium carbonate, Feldalat NM extremely
Few one.
In the present invention, catalyst is preferably potassium sulfate.
In step (b) of the present invention, dimercapto-1,3,4-thiadiazole, alkaline reagent and the use of intermediate M
Amount substantially equimolar amounts, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Two
The mol ratio of sulfydryl-1,3,4-thiadiazoles, alkaline reagent and intermediate M is preferably 0.9-3.0:0.9-5.0:
0.8-1.5。
In step (b) of the present invention, the consumption of catalyst can be catalytic amount, with dimercapto-1, and 3,4-thiophenes two
On the basis of the molal quantity of azoles, the consumption of catalyst is preferably 5-100 mole of %, more preferably 10-50 and rubs
You are %.
In step (b) of the present invention, dimercapto-1,3,4-thiadiazole and intermediate M carry out the reaction reacted
Equation as in figure 2 it is shown, in Fig. 2, alkaline reagent uses potassium carbonate, mesh by way of example only
, the scope of the present invention is not construed as limiting.
It will be understood by those skilled in the art that to obtain purer end product, the i.e. present invention
Multipurpose additive, the present invention prepares the method for multipurpose additive and the most also includes entering reacted system
Row post processing, the mode of post processing can include washing, dry, removal of solvent under reduced pressure, such as, will fill
Reacted system is divided to pour in the ethyl acetate (or dichloromethane) of 1-10 times of volume, respectively with steaming
Distilled water and saturated aqueous common salt washing, then add anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C
In desiccant, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C
Lower removing solvent, to obtain end product.
The present invention is prepared each step of the method for the compound of structure shown in formula (I) the most under agitation
Carry out, for mixing speed without particular/special requirement, can be the mixing speed of this area routine, such as, stir
Mixing speed can be 100-800rpm.
In the present invention, for the amount of the first solvent and the second solvent without particular/special requirement, can be that this area is normal
The solvent load of rule, this is known to those skilled in the art, does not repeats them here.
As it has been described above, it is contemplated that by lubricant oil composite contains the change of structure shown in formula (I)
Compound, and the combination of the compound of structure shown in formula (I) and thiophenols ester type antioxidant and realize invention
Purpose, even if lubricant oil composite has the performances such as excellent wear-resistant and antioxidation.Therefore, for lubrication
The preparation method of fluid composition, without particular/special requirement, can use method commonly used in the art, such as,
Second aspect, present invention also offers the preparation method of a kind of automatic transmission fluid lubricant oil composite, the party
Method includes: will containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant,
The raw material mix homogeneously of phosphate ester and dialkyl dithiocarbamate obtains lubricant oil composite, its
In, on the basis of the weight of lubricant oil composite, the consumption of lube base oil be 85-98 weight %,
The consumption of the wear-resistant multipurpose additive of antioxygen is that 0.01-10 weight %, the consumption of thiophenols ester type antioxidant are
0.01-5 weight %, the consumption of phosphate ester are 0-5 weight %, the use of dialkyl dithiocarbamate
Amount is 0-5 weight %, and the wear-resistant multipurpose additive of described antioxygen is the compound of structure shown in formula (I):
In the inventive method, it is preferable that on the basis of the weight of lubricant oil composite, lube base oil
Consumption be 90-98 weight %；The consumption of the wear-resistant multipurpose additive of antioxygen is 0.02-5 weight %, more excellent
Elect 0.1-4 weight % as；The consumption of thiophenols ester type antioxidant is 0.1-3 weight %；The consumption of phosphate ester
For 0.3-4 weight %, more preferably 0.5-3 weight %；The consumption of dialkyl dithiocarbamate is
0.1-4 weight %, more preferably 0.5-2 weight %.
As it was previously stated, in the inventive method, raw material can also contain in antirust agent, pour-point depressant and anti-foaming agent
At least one, it is also possible to containing metal deactivator.
In the inventive method, for the mode of mixing without particular/special requirement, such as can be except lube base
Each raw material components of oil is added separately in lube base oil, it is also possible to each by except lube base oil
Component is mixed and made into concentrate and is then added in lube base oil.
In the inventive method, the condition of mixing preferably includes: temperature is 40-90 DEG C, and the time is 1-6h.
The wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, phosphate ester, two
Diethyldithiocarbamate, antirust agent, pour-point depressant, anti-foaming agent, metal deactivator as it was previously stated,
Do not repeat them here.
Embodiment
The present invention is further illustrated for below example, but and is not so limited the present invention.
In the following Examples and Comparative Examples:
Monitor and react method completely: thin layer chromatography chromatograph (TLC) fluorescence developing method.
Gross production rate=end product mole/aniline moles × 100%
The physico-chemical analysis method of product: measure element by inductively coupled plasma ion emission spectroscopy method
Content.
Structure characterization methods: nuclear magnetic resonance method (1H hydrogen is composed,13C carbon is composed), high resolution mass spectrum.
Preparation example
In the 500ml flask with electromagnetic agitation (mixing speed is 300rpm), it is filled with nitrogen protect
Protect, add the dichloromethane of 150ml, be subsequently adding the Disulfur dichloride of 0.2mol, in ice-water bath fully
After cooling, add the aniline of 0.2mol.Monitoring removes ice-water bath to reaction completely, is placed in 25 DEG C of rooms
Under temperature, after question response system is gradually increased to 25 DEG C, point 3 addition 4-chloroanilines react, every time
Addition is identical, adds 4-chloroaniline 0.15mol altogether.Sustained response adds the saturated food of 30ml after 2 hours
Saline cancellation is reacted, and then proceeds in separatory funnel by reaction system, respectively with 50ml distilled water and 50ml
Saturated aqueous common salt washs, and adds 10g anhydrous sodium sulfate dry 20min at 25 DEG C.Filter after filtration
Liquid, at 40 DEG C, is evaporated off solvent under 0.05MPa, obtains intermediate M1.
In the 500ml flask with electromagnetic agitation (mixing speed is 400rpm), it is filled with nitrogen protect
Protect, add the DMF (DMF) of 150ml, be subsequently adding 0.2mol dimercapto-1,3,4-
Thiadiazoles and the potassium carbonate of 0.2mol, the potassium sulfate of 0.05mol, stir 20 minutes at 25 DEG C, divides 3
Secondary addition above-mentioned intermediate M1, each addition is identical, adds intermediate M1 0.12mol altogether.Monitoring
To reaction completely, then reaction system is added 250ml ethyl acetate, and proceeds in separatory funnel, point
Not Yong 100ml distilled water (twice) and the washing of 50ml saturated aqueous common salt, and add 15g anhydrous slufuric acid
Sodium is dried 20min at 25 DEG C.Filtrate after filtration 40 DEG C, solvent is evaporated off under 0.03MPa, obtain
End product S1.Calculating gross production rate is 76%.
The physico-chemical analysis data of product are as follows: sulfur content, and 41.3%；Nitrogen content, 13.9%.
S1 is carried out structural characterization, respectively obtains hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectively
See Fig. 3, Fig. 4 and Fig. 5.
From the physico-chemical analysis data of above-mentioned preparation example, Fig. 3, Fig. 4 and Fig. 5 it can be seen that S1 has formula
(I) structure shown in.
Embodiment 1
The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.
By the S1 of 0.1 weight portion, the 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) of 3 weight portions
Ethyl propionate], the tricresyl phosphate T306 (being purchased from Peng Pu chemical plant, Shanghai) of 0.5 weight portion, 2 weights
The amount dibutyl dithiocaarbamate molybdenum of part, the BTA of 0.3 weight portion join 94.1 weight
(viscosity index (VI) is 87 to the 600SN lube base oil of part, and saturated hydrocarbon content is 92 weight %, and sulfur contains
Amount is 0.02 weight %) in, at 60 DEG C, stirring 3h, mix homogeneously obtains lubricant oil composite A1.
Embodiment 2
The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.
By the S1 of 1.1 weight portions, the 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) of 1 weight portion
Ethyl propionate], the di-n-butyl phosphite T304 of 3 weight portions (be purchased from Shandong Zibo favour China chemical industry limited
Company), the dibutyl dithiocaarbamate molybdenum of 1.1 weight portions, the BTA of 0.3 weight portion add
Enter to the Group III Yubase4 of 47 weight portions and the mixed lubrication of the Group III Yubase6 of 46.5 weight portions
In oil base oil, stirring 6h at 40 DEG C, mix homogeneously obtains lubricant oil composite A2.
Embodiment 3
The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.
By the S1 of 4 weight portions, the 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) of 0.1 weight portion
Ethyl propionate], the Irgalube 353 (being purchased from BASF Corp. of Germany) of 1.5 weight portions, 0.5 weight portion
Dibutyl dithiocaarbamate molybdenum, the BTA of 0.3 weight portion join 93.6 weight portions
In 100N lube base oil (viscosity index (VI) is 112, and saturated hydrocarbon content is 96 weight %), at 90 DEG C
Lower stirring 1h, mix homogeneously obtains lubricant oil composite A3.
Comparative example 1
Prepare lubricant oil composite according to the method for embodiment 2, except for the difference that, the weight such as S1 is replaced with
The 2 of amount part, 2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate], obtain lubricating oil composition
Thing D1.
Comparative example 2
Lubricant oil composite is prepared according to the method for embodiment 2, except for the difference that, by 2,2'-thiobis [3-(3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] S1 of weight portion such as replace with, obtain lubricant oil composite
D2。
Comparative example 3
Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2
Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] dibutyl dithio of weight portion such as replace with
Carbaminate, obtains lubricant oil composite D3.
Comparative example 4
Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2
Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] the trimethylphenyl phosphorous of weight portion such as replace with
Acid zinc, obtains lubricant oil composite D4.
Comparative example 5
Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2
Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] the fourth octyl diphenylamine of weight portion such as replace with,
Obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested the most as follows:
TA5000-DSC2910 differential thermal analyzer is used to carry out the mensuration of initial oxidation temperature；
High Pressure Difference heat scan mensuration (PDSC) is used to carry out the mensuration of oxidation induction period；
High-frequency reciprocating frictional testing machine (purchased from PCS company of Britain, HFRR) is used to carry out the height of oil product
The wear-resistant test of temperature, experimental condition is: load 1000g, and temperature is 80 DEG C, and test period is 120min,
The wear scar diameter formed on steel ball is measured after off-test.The results are shown in Table 1.
Table 1
| A1 | A2 | A3 | D1 | D2 | D3 | D4 | D5 | |
| Initial oxidation temperature, DEG C | 233 | 238 | 252 | 216 | 230 | 214 | 221 | 207 |
| Oxidation induction period, min | 41.8 | 37.1 | 53.5 | 27.1 | 31.8 | 25.3 | 24.5 | 23.2 |
| Wear scar diameter, μm | 271 | 262 | 253 | 297 | 282 | 314 | 316 | 367 |
It will be understood by those skilled in the art that initial oxidation temperature is the highest, the heat stability of lubricating oil
The best；Oxidation induction period is the longest, and the antioxygenic property of lubricating oil is the best；Wear scar diameter is the least, lubricating oil
Wear resistance the best.
A2 is compared with D1-D5 respectively it can be seen that the lubricant oil composite of the present invention has more
Good heat stability, non-oxidizability and abrasion resistance.
The automatic transmission fluid lubricant oil composite of the present invention has abrasion resistance and the antioxygenic property of excellence,
Can be widely applied to automobile engine and change speed gear box.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, but, the present invention does not limit
Detail in above-mentioned embodiment, in the technology concept of the present invention, can be to the present invention
Technical scheme carry out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. an automatic transmission fluid lubricant oil composite, it is characterised in that with the weight of lubricant oil composite
On the basis of amount, described lubricant oil composite contains following components: the lube base oil of 85-98 weight %,
The wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %,
The phosphate ester of 0-5 weight % and the dialkyl dithiocarbamate of 0-5 weight %, described antioxygen is wear-resistant
Multipurpose additive is the compound of structure shown in formula (I):
Lubricant oil composite the most according to claim 1, wherein, with the weight of lubricant oil composite
On the basis of amount, described lubricant oil composite contains following components: the lube base oil of 90-98 weight %,
The wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, the thiophenols ester type antioxidant of 0.1-3 weight %, 0.5-3
The phosphate ester of weight % and the dialkyl dithiocarbamate of 0.5-2 weight %.
Lubricant oil composite the most according to claim 1 and 2, wherein, described lube base
Oil is mineral lubricating oil and/or synthetic lubricant fluid.
Lubricant oil composite the most according to claim 1 and 2, wherein, described thiophenols ester type
Antioxidant is the double lauryl alcohol ester of thio-2 acid, thio-2 acid double octadecyl ester, 2,5-dimercapto-1,3,4-
At least one in thiadiazoles and 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate].
Lubricant oil composite the most according to claim 1 and 2, wherein, described phosphate ester is sub-
At least one in di(2-ethylhexyl)phosphate N-butyl, tricresyl phosphate, dialkyl dithiophosphate.
Lubricant oil composite the most according to claim 1 and 2, wherein, described dialkyl disulfides
It is zinc, lead or antimony for the metal in carbaminate, the alkane in described dialkyl dithiocarbamate
Base is the alkyl of the alkyl of C2-C12, preferably C2-C8, more preferably ethyl, n-pro-pyl, isopropyl
Base, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl,
2-ethylhexyl, cyclohexyl or methylcyclopentyl.
Lubricant oil composite the most according to claim 1 and 2, wherein, described lubricating oil composition
Thing is possibly together with at least one in antirust agent, pour-point depressant and anti-foaming agent.
Lubricant oil composite the most according to claim 7, wherein, described antirust agent is selected from imidazoles
Class and/or alkenyl succinic acid esters, preferably 4,5-glyoxalidine, alkenyl imidazoline succinate and thiazolinyl
At least one in succinate.
Lubricant oil composite the most according to claim 7, wherein, described pour-point depressant selected from poly-α-
Alkene, vinyl acetate copolymer and alkyl are the dialkyl fumarate of C8-C18, poly-alkyl methyl
At least one in acrylate, alkylnaphthalene.
Lubricant oil composite the most according to claim 7, wherein, described anti-foaming agent is poly-silica
Alkane type anti-foaming agent, preferably silicone oil and/or polydimethylsiloxane.
The preparation method of 11. 1 kinds of automatic transmission fluid lubricant oil composites, it is characterised in that described method
Including: will be containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, phosphorus
The raw material mix homogeneously of acid esters and dialkyl dithiocarbamate obtains lubricant oil composite, wherein,
On the basis of the weight of lubricant oil composite, the consumption of lube base oil is 85-98 weight %, antioxygen
The consumption of wear-resistant multipurpose additive be 0.01-10 weight %, the consumption of thiophenols ester type antioxidant be 0.01-5
Weight %, the consumption of phosphate ester are 0-5 weight %, and the consumption of dialkyl dithiocarbamate is 0-5
Weight %, the wear-resistant multipurpose additive of described antioxygen is the compound of structure shown in formula (I):
12. methods according to claim 11, wherein, with the weight of lubricant oil composite as base
Standard, the consumption of lube base oil be 90-98 weight %, the consumption of the wear-resistant multipurpose additive of antioxygen be 0.1-4
Weight %, the consumption of thiophenols ester type antioxidant be 0.1-3 weight %, the consumption of phosphate ester be 0.5-3 weight
Amount %, the consumption of dialkyl dithiocarbamate is 0.5-2 weight %.
13. according to the method described in claim 11 or 12, and wherein, the condition of described mixing includes:
Temperature is 40-90 DEG C, and the time is 1-6h.
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| CN111088094A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Automatic transmission fluid and preparation method thereof |
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