CN106318553B - 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 wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %, the phosphate of 0-5 weight % and the dialkyl dithiocarbamate of 0-5 weight %, and the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I).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 US4225450 reports one kind and reacts preparation with Diethyldithiocarbamate by the tert-butyl phenols that is obstructed
Polysulfide phenolic antioxidant, have 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 wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %, 0-5 weight
The phosphate of % and the dialkyl dithiocarbamate of 0-5 weight % are measured, the wear-resistant multipurpose additive of antioxygen is formula (I)
The compound of shown structure:
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 90-98
The thiophenols ester type of the lube base oil of weight %, the wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, 0.1-3 weight %
The dialkyl dithiocarbamate of antioxidant, the phosphate of 0.5-3 weight % and 0.5-2 weight %.
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, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, phosphate and dialkyl disulfides will be contained
For carbaminate raw material be uniformly mixed obtain lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, profit
The dosage of lubricant base oil is 85-98 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-10 weight %, thiophenols
The dosage of ester type antioxidant is 0.01-5 weight %, the dosage of phosphate is 0-5 weight %, dialkyl dithiocarbamate
Dosage be 0-5 weight %, the wear-resistant multipurpose additive of antioxygen be formula (I) shown in structure compound:
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 the wear-resistant multipurpose additive of oxygen is 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is 0.1-3 weight %, phosphoric acid
The dosage of ester 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 wear-resistant multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing antioxygen wear-resistant multipurpose additive.
Fig. 3 is the hydrogen spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.
Fig. 4 is the carbon spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.
Fig. 5 is the mass spectrogram of the wear-resistant multipurpose additive of antioxygen 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-
The wear-resistant multipurpose additive of oxygen, the thiophenols ester type antioxidant of 0.01-5 weight %, 0-5 weight % phosphate and 0-5 weight %
Dialkyl dithiocarbamate, the wear-resistant multipurpose additive of antioxygen be formula (I) shown in structure compound:
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 the wear-resistant multipurpose additive of antioxygen is preferably 0.02-5 weight %, more preferably 0.1-4 weight %；Sulfophenates
The content of type antioxidant 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 Irgalube353 etc. of BASF AG of 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 of 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) aniline, sulfur chloride and 4- chloroaniline are reacted, generate intermediate M shown in formula (II),
(b) the intermediate M and dimercapto -1,3,4- thiadiazoles that step (a) obtains nucleophilic is carried out under alkaline condition to take
Generation reaction, generates multipurpose additive shown in formula (I),
In step (a) of the present invention, the concrete mode that aniline, sulfur chloride and 4- chloroaniline react is preferably included:
(i) under an inert atmosphere, in the first solvent, aniline is sufficiently reacted at -20-0 DEG C with sulfur chloride；
(ii) 4- chloroaniline is added in the reaction system of step (i), reacts 1-3h at 15-30 DEG C.
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.
In step (i) of the present invention, the first solvent is preferably selected from methylene chloride, tetrahydrofuran, toluene, dimethylbenzene and dioxy six
At least one of ring, more preferably methylene chloride and/or tetrahydrofuran are still more preferably methylene chloride.
It in the present invention in step (i), is sufficiently reacted and refers to fully reacting, is i.e. reaction raw materials are reacted completely.
Reaction can be monitored using method commonly used in the art, to confirm fully reacting, such as thin layer chromatography can be used
(TLC) or the methods of gas-chromatography is monitored.
In step (ii) of the present invention, 1-3h is reacted at 15-30 DEG C, preferably after step (i) sufficiently reaction, by reactant
The temperature of system is gradually increased to 15-30 DEG C, adds 4- chloroaniline and carries out reaction 1-3h.It, can be further under the preferable case
Improve reaction yield.
In step (ii) of the present invention, the adding manner of 4- chloroaniline is preferably to be added by several times, such as can divide 3-4 times and add
Enter.Under the preferable case, reaction yield can be further improved.When gradation is added, each additional amount can be identical,
It can also be different, in order to easy to operate, preferably each additional amount is identical.
In step (ii) of the present invention, react 1-3h, stop reaction mode can for those skilled in the art it is contemplated that
Various modes, be quenched for example, quencher can be added, quencher can be quencher commonly used in the art, such as can
Think saturated salt solution.
In the present invention, the dosage of aniline, sulfur chloride and 4- chloroaniline is substantially equimolar amounts, but aniline and sulfur chloride can
With appropriate excessive.The molar ratio of aniline, sulfur chloride 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 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 washing, drying, solvent be removed under reduced pressure, for example,
Reaction system after being quenched is used into distilled water and saturated common salt water washing respectively, anhydrous calcium chloride then is added at 15-30 DEG C
Or the desiccant such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain intermediate M.
In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4- chloroaniline are reacted is as shown in Figure 1, figure
In 1, the first solvent is using methylene chloride, 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, the condition of nucleophilic substitution is preferably included: under an inert atmosphere, in the second solvent,
Dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed into 10-30min at 15-30 DEG C, intermediate is then added
M is sufficiently reacted.I.e. alkaline condition is provided by alkaline reagent.
" inert atmosphere ", " sufficiently being reacted " are as previously mentioned, details are not described herein.
In the present invention, intermediate M is preferably slowly added to, such as can be added by several times, and 3-4 addition can be generally divided.?
Under the preferable case, reaction yield can be further improved.When gradation is added, each additional amount can be identical, can also
With difference, in order to easy to operate, preferably each additional amount is identical.
In the present invention, the second solvent is preferably selected from methylene chloride, tetrahydrofuran, toluene, dimethylbenzene, N, N- dimethyl formyl
At least one of amine, more preferably methylene chloride and/or n,N-Dimethylformamide are still more preferably N, N- dimethyl
Formamide.
In the present invention, alkaline reagent is preferably selected from least one of inorganic bases such as potassium carbonate, sodium carbonate, sodium methoxide.
In the present invention, catalyst is preferably potassium sulfate.
In step (b) of the present invention, the dosage of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate M is substantially etc.
Mole, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Dimercapto -1,3,4- thiadiazoles, alkalinity examination
The molar ratio of agent and intermediate M are preferably 0.9-3.0:0.9-5.0:0.8-1.5.
In step (b) of the present invention, the dosage of catalyst can be catalytic amount, with mole of dimercapto-1,3,4-thiadiazole
On the basis of number, the dosage of catalyst is preferably 5-100 moles of %, more preferably 10-50 moles of %.
In step (b) of the present invention, reaction equation such as Fig. 2 that dimercapto-1,3,4-thiadiazole and intermediate M are reacted
Shown, in Fig. 2, alkaline reagent is using potassium carbonate, purpose by way of example only, does not constitute and limits to the scope of the present invention
System.
It will be understood by those skilled in the art that purer final product, i.e., multiple-effect of the invention add in order to obtain
Add agent, the present invention prepares the method for multipurpose additive it is also preferable to include post-processing to the system after reaction, the side of post-processing
Formula may include washing, drying, solvent be removed under reduced pressure, for example, the system after abundant reaction to be poured into the acetic acid of 1-10 times of volume
In ethyl ester (or methylene chloride), distilled water and saturated common salt water washing are used respectively, anhydrous calcium chloride then is added at 15-30 DEG C
Or the desiccant such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain final product.
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.
In the present invention, for the first solvent and the second solvent amount without particular/special requirement, can be the solvent of this field routine
Dosage, this is known to those skilled in the art, and details are not described herein.
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: lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, phosphoric acid will be contained
The raw material of ester and dialkyl dithiocarbamate is uniformly mixed and obtains lubricant oil composite, wherein with lubricant oil composite
Weight on the basis of, the dosage of lube base oil is 85-98 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-
10 weight %, thiophenols ester type antioxidant dosage be 0.01-5 weight %, the dosage of phosphate is 0-5 weight %, dialkyl group
The dosage of dithiocar-bamate is 0-5 weight %, and the wear-resistant multipurpose additive of antioxygen is the chemical combination of structure shown in formula (I)
Object:
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 the wear-resistant multipurpose additive of antioxygen is 0.02-5 weight %, more preferably 0.1-4 weight %；Thiophenols
The dosage of ester type antioxidant is 0.1-3 weight %；The dosage of phosphate is 0.3-4 weight %, more preferably 0.5-3 weight %；
The dosage of dialkyl dithiocarbamate 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.
The wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, phosphate, dialkyl dithio
Carbaminate, 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 method for monitoring fully reacting: thin-layer chromatography chromatography (TLC) fluorescence developing method.
Gross production rate=final product mole/aniline moles × 100%
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 300rpm), 150ml is added
Methylene chloride, then be added 0.2mol sulfur chloride, after being fully cooled in ice-water bath, the aniline of 0.2mol is added.Monitoring
Ice-water bath is moved back to fully reacting, is placed in 25 DEG C at room temperature, after reaction system is gradually increased to 25 DEG C, is added three times 4- chlorine
Aniline is reacted, and each additional amount is identical, and 4- chloroaniline 0.15mol is added altogether.30ml saturation is added after sustained response 2 hours
Reaction system, is then transferred in separatory funnel by saline solution quenching reaction, uses 50ml distilled water and 50ml saturated salt solution respectively
Washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is evaporated off molten under 40 DEG C, 0.05MPa
Agent obtains intermediate M1.
It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 400rpm), 150ml is added
DMF (n,N-Dimethylformamide), be then added 0.2mol dimercapto-1,3,4-thiadiazole and 0.2mol potassium carbonate,
The potassium sulfate of 0.05mol stirs 20 minutes at 25 DEG C, is added three times above-mentioned intermediate M1, and each additional amount is identical, is added altogether
Intermediate M1 0.12mol.Then to fully reacting 250ml ethyl acetate is added in reaction system by monitoring, and be transferred to liquid separation leakage
In bucket, 100ml distilled water (twice) and 50ml saturated common salt water washing are used respectively, and 15g anhydrous sodium sulfate is added at 25 DEG C
Dry 20min.Solvent is evaporated off at 40 DEG C, 0.03MPa in filtered filtrate, obtains final 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 subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 3, Fig. 4 and
Fig. 5.
It can be seen that S1 with knot shown in formula (I) from the physico-chemical analysis data of above-mentioned preparation example, Fig. 3, Fig. 4 and Fig. 5
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 tricresyl phosphate T306 (being purchased from the Shanghai chemical plant Peng Pu) of 0.5 parts by weight, 2 parts by weight dibutyl dithio ammonia
Base formic acid molybdenum, 0.3 parts by weight benzotriazole be added to the 600SN lube base oil of 94.1 parts by weight (viscosity index (VI) be
87, saturated hydrocarbon content is 92 weight %, and sulfur content is 0.02 weight %) in, 3h is stirred at 60 DEG C, is uniformly mixed and is lubricated
Fluid composition A1.
Embodiment 2
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 1.1 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 1 parts by weight
Ethyl ester], the di-n-butyl phosphite T304 (being purchased from Shandong Zibo Hui Hua Chemical Co., Ltd.) of 3 parts by weight, 1.1 parts by weight two
Butyl molybdenum dithiocarbamate, 0.3 parts by weight benzotriazole be added to the Group III Yubase4 and 46.5 of 47 parts by weight
In the mixed lubrication oil base oil of the Group III Yubase6 of parts by weight, 6h is stirred at 40 DEG C, is uniformly mixed and obtains lubricating oil group
Close object 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 1.5 parts by weight, 0.5 parts by weight dibutyl dithio amino first
Sour molybdenum, 0.3 parts by weight benzotriazole be added to the 100N lube base oil of 93.6 parts by weight (viscosity index (VI) 112, satisfy
It is 96 weight % with hydrocarbon content) 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 1000g, temperature are 80 DEG C, test period 120min, measure the mill formed on steel ball after the test
Spot diameter.It 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 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 wear-resistant multiple-effect of antioxygen of the lube base oil of 85-98 weight %, 0.01-10 weight %
Additive, the thiophenols ester type antioxidant of 0.01-5 weight %, the phosphate of 0-5 weight % and 0-5 weight % dialkyl group two
Thiocarbamate, the wear-resistant multipurpose additive of antioxygen 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 %, the wear-resistant multiple-effect of antioxygen of 0.1-4 weight % add
Add agent, the thiophenols ester type antioxidant of 0.1-3 weight %, the phosphate of 0.5-3 weight % and 0.5-2 weight % dialkyl group two
Thiocarbamate.
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 and dioxane
Base phosphorodithioate.
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 contain antirust agent,
At least one of dialkyl fumarate, pour-point depressant and anti-foaming agent of C8-C18.
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-
The poly- alkylmethacrylate and alkyl of C18 is at least one of the alkylnaphthalene of C8-C18.
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 14, 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
Lubricant base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, phosphate and dialkyl dithiocarbamate
Raw material be uniformly mixed obtain lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, lube base oil
Dosage is 85-98 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-10 weight %, thiophenols ester type antioxidant
Dosage is 0.01-5 weight %, the dosage of phosphate is 0-5 weight %, and the dosage of dialkyl dithiocarbamate is 0-5
Weight %, the wear-resistant multipurpose additive of antioxygen are 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 of the wear-resistant multipurpose additive of antioxygen is 0.1-4 weight %, thiophenols ester type antioxidant
Dosage is 0.1-3 weight %, the dosage of phosphate is 0.5-3 weight %, and the dosage of dialkyl dithiocarbamate is
0.5-2 weight %.
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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| CN1942564A (en) * | 2004-04-14 | 2007-04-04 | 科聚亚公司 | Ketone diarylamine condensates |
| EP1985690A2 (en) * | 2007-04-27 | 2008-10-29 | TonenGeneral Sekiyu Kabushiki Kaisha | Internal-combustion engine lubrican composition |
| CN102690711A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Lubricant composition for gasoline engine |
| CN103060058A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Antioxidant corrosion inhibitor composition and lubricating oil composition |
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|---|---|---|---|---|
| CN1942564A (en) * | 2004-04-14 | 2007-04-04 | 科聚亚公司 | Ketone diarylamine condensates |
| EP1985690A2 (en) * | 2007-04-27 | 2008-10-29 | TonenGeneral Sekiyu Kabushiki Kaisha | Internal-combustion engine lubrican composition |
| CN102690711A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Lubricant composition for gasoline engine |
| CN103060058A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Antioxidant corrosion inhibitor composition and lubricating oil composition |
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