CN106753699A - Lubricant composition for gasoline engine and preparation method thereof, purposes - Google Patents
Lubricant composition for gasoline engine and preparation method thereof, purposes Download PDFInfo
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Abstract
The invention provides a kind of Lubricant composition for gasoline engine and preparation method thereof, purposes.Lubricant composition for gasoline engine of the invention, including following components：The multipurpose additive of structure shown in A ＞ formulas (I)：B ＞ boracic antioxidant polyisobutene succinimide ashless dispersants；C ＞ polyisobutylene succinic acid ester ashless dispersants；D ＞ at least one alkylsalicylates；E ＞ at least one alkyl monosulfide phenates；F ＞ at least one zinc dialkyl dithiophosphates；G ＞ amine type antioxidant and/or phenolic ester type antioxidant；H ＞ at least one oil-soluble organic molybdenum friction improvers；The lube base oil of I ＞ surpluses.Composition of the invention has phosphorus content of the mass fraction no more than 0.08%, with excellent wear-resistant, antifriction, anti-oxidant and cleansing performance.
Description
Technical field
The present invention relates to a kind of lubricant oil composite, more particularly to a kind of lubricating oil suitable for petrol engine
Composition.
Background technology
Environmental protection and the requirement of energy-conservation promote the development of engine technology, also promote the continuous liter of gasoline engine oil
Level is regenerated, performance requirement of the oil product in each side such as antioxygen, wear-resistant, antifriction and peace and quiet, greasy filth dispersions
More and more higher.The highest quality level of current petrol engine lubricating oil is American Petroleum Institute (API) (API) and the world
The SN/GF-5 ranks that lubricant level and certification committee (ILSAC) formulate.
Modern gasoline acc power is improved, and miniaturization, compression ratio is improved, thermic load increase, anti-oxidant to oil product
The requirement of ability and the ability of control deposit generation is also improved constantly.In API petrol engine lubricating oil specifications
The engine test of its high-temperature oxidation resistant viscosity growth is evaluated from 64 hours of program IIIE, program IIIF is developed into
80 hours, by 100 hours of current procedure IIIG, and the requirement that viscosity increases never exceeded 375% and is reduced to
275%th, 150%, the requirement to high-temperature oxidation resistance is greatly improved.Requirement to detergency simultaneously is also got over
Come harsher, simulate piston high temperature deposition thing TEOST-MHT test requirements documents from SL no more than 45mg,
The 35mg of SM, SN specification is developed into, the requirement to suppressing deposit generation is significantly improved.
Modern gasoline machine load is improved, and the abrasion resistance to gasoline engine oil proposes requirement higher, while energy-conservation
It is required that increasingly raising, it is desirable to oil product has more preferable antifriction performance, there is more preferably fuel economy.GF-5 pairs
Fuel economy performance of the gasoline engine oil in whole service life proposes the requirement of harshness, and employs experiment
The precision harsh B of VI D alternative programs of engine test program VI higher enters to engine oil fuel economy
Row is evaluated.
CN 00129836.4 discloses a kind of boracic antioxidant dispersant containing methoxy phenol, with good antioxygen
Property and detergent-dispersant performance.
US 4824601A report the clay catalyst (earth of diphenylamine and diisobutylene in acid activation
Catalyst the lower alkylated amines mixture for being formed) is acted on, it is anti-oxidant in lubricating oil and other functional fluids
Ability performance is preferable.
To there is condensation in CN 1191340C anti-using the tert-butyl group phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine
The compound that should be prepared has the stronger ability for catching free radical and peroxynitrite decomposition compound, can give oil oxidation
Stability provides more effectively protection, may also function as wear-resistant effect.
US 4225450 reports a kind of reaction with Diethyldithiocarbamate by the tert-butyl group phenols that is obstructed and makes
Standby polysulfide phenolic antioxidant, with preferable antioxidation and wear-resistant effect.
The content of the invention
The invention provides a kind of Lubricant composition for gasoline engine and preparation method thereof, purposes.
Lubricant composition for gasoline engine of the invention, including following components：
The multipurpose additive of structure shown in A ＞ formulas (I)：
B ＞ boracic antioxidant polyisobutene succinimide ashless dispersants；
C ＞ polyisobutylene succinic acid ester dispersants；
D ＞ at least one alkylsalicylates；
E ＞ at least one alkyl monosulfide phenates；
F ＞ at least one zinc dialkyl dithiophosphates；
G ＞ amine type antioxidant and/or phenolic ester type antioxidant；
H ＞ at least one oil-soluble organic molybdenum friction improvers；
The lube base oil of I ＞ surpluses；
Can also there are other additives, such as pour-point depressant, Viscosity Index in lubricant oil composite of the invention
Modifier (VM), anti-foaming agent etc..
Specifically, Lubricant composition for gasoline engine of the invention includes following component：
A ＞ are the multipurpose additive of structure shown in formula (I)：
The present inventor has found under study for action, many containing structure shown in formula (I) in lubricant oil composite
Effect additive can make the lubricant oil composite have the performance such as excellent wear-resistant, antifriction, anti-oxidant.The present invention
In, the preparation method of the compound of structure will be described in detail in subsequent section shown in formula (I).
Component A accounts for the 0.05%-2% of lubricant oil composite gross mass of the present invention, preferably 0.1%-1.0%.
B ＞ are boracic antioxidant polyisobutene succinimide ashless dispersant, are by polyamines polyene, methoxyl group
Phenol, aldehyde, polyolefin-based succinic acid or acid anhydrides and acid reaction are obtained.Preparation method is in metoxyphenol
Amine condensation is obtained with addition aldehyde reaction in the mixture of polyamines polyene, then is sent out with polyolefin-based succinic acid or acid anhydrides
Raw dehydration obtains antioxidant dispersant, obtains final product boracic with fatty alcohol and acid reaction again afterwards
Antioxidant dispersant.The copolymer or homopolymers of the preferred C2-C4 alkene of polyolefin, can be poly- isobutyls
One or more in alkene, random polypropylene and ethylene-propylene copolymer, its number-average molecular weight is 850-5000, most
It is well 950-2500；Metoxyphenol is selected from p methoxy phenol, o-methoxyphenol and meta-methoxy phenol
One or more；Aldehyde be selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, salicylide and benzaldehyde in one kind or
It is various.Component B method can be obtained as disclosed in CN 00129836.4.
Component B accounts for the 0.5%-8% of lubricant oil composite gross mass of the present invention, preferably 1%-6%.
C ＞ polyisobutylene succinic acid esters dispersant can select polyisobutylene succinic acid pentaerythritol ester, poly- isobutyl
Alkene succinic acid glyceride, polyisobutylene succinic acid glycol ester etc..The component can select Lubrizol companies
LZ936 etc..
Component C accounts for the 0.5%-8% of lubricant oil composite gross mass of the present invention, preferably 0.8%-5%.
D ＞ are selected from one or more of alkylsalicylate alkaline-earth metal detersive, and the alkaline-earth metal can be
Magnesium, calcium, preferably base number are one or more of the high base number alkylsalicylate of (200-450) mgKOH/g.
Component D can select LZL109B, LZL112 of the production of Lu Borun Lan Lian additives Co., Ltd, Infineum
C9375, C9012 of company's production, the OSCA420 of OSCA companies production, the SAP007 of Shell companies production
Deng.
Component D accounts for the 0.1%-10% of lubricant oil composite gross mass of the present invention, preferably 0.2%-6%.
E ＞ are selected from one or more in sulfenyl phenolate saline-alkali soil metal detergent, and the alkaline-earth metal can be with
It is magnesium, calcium, preferably base number is one or more of the high-alkali calcium sulfenyl phenolate of (200-400) mgKOH/g.
Component E can select LZL115A, LZL115B of the production of Lu Borun Lan Lian additives Co., Ltd, Lubrizol
The OLOA219 of LZ6499, LZ6500 of Corporation productions, Chevron Oronite Company production,
C9391, C9394 of the production of Infineum companies etc..
Component E accounts for the 0.1%-10% of lubricant oil composite gross mass, preferably 0.2%-6%.
F ＞ are selected from one or more of zinc dialkyl dithiophosphate (ZDDP)；The dialkyl dithiophosphoric acid
Alkyl in zinc is, containing 2 to 12 alkyl of carbon atom, preferably to contain 2 to 8 alkane of carbon atom
Base, including but not limited to ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl,
One kind in isopentyl, n-hexyl, isohesyl, n-octyl, 2- ethylhexyls, cyclohexyl and methylcyclopentyl
Or it is various.
The zinc dialkyl dithiophosphate can be selected but be not limited to WUXI SOUTH PETROLEUM ADDITIVE Co., LTD.
T202, T203 of production, T202, T203, the brothers alkyl of the production of Jinzhou Petrochemical Company additive factory
T204, secondary alkyl T205, the C9417 of LZ1371, LZ1375, Infineum company of Lubrizol companies,
C9425, C9426, Hitec7169, Hitec1656 of Afton companies etc..
Additions of the component F in lubricant oil composite be no more than 0.08% in terms of the mass fraction of P elements
Preferably, preferably 0.06%-0.08%.
G ＞ are selected from amine type antioxidant and/or phenolic ester type antioxidant.
Amine type antioxidant can be the one kind or many being alkylated in aniline, alkylated diphenylamine and PA
Kind, alkyl carbon number therein be C2-C12, for example can from dibutyl diphenylamines, dioctyl diphenylamine,
One or more in dinonyldiphenylamine, fourth octyl diphenylamine and PA, preferably oil-soluble two
Alkyl diphenylamine, more preferably fourth octyl diphenylamine.Alkylated diphenylamine on the market such as Germany BASF
IRGANOX L-01, the IRGANOX L-57 of company's production, Beijing Xing Pu fine chemical technologies development company
The T534 of production, the LZ5150A, U.S. R.T. of the production of Lanzhou Lu Borun Lan Lian additives Co., Ltd
VANLUBE NA, VANLUBE 961, the dioctyl diphenylamine of Vanderbilt companies production
VANLUBE 81, it is right that German Rhein Chemie companies produce, to ' di-iso-octyldiphenylamine RC7001.
Phenolic ester type antioxidant is the hydroxy phenyl carboxylate that molecular weight is 200-500, such as BASF Corp. of Germany's production
IRGANOX L-135, Beijing Xing Pu fine chemical technologies development company production T512.
Additions of the component G in lubricant oil composite between 0.1-6%, preferably 0.2%-3%.
H ＞ are selected from molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen molybdenum, dialkyl dithio amino
Formic acid molybdenum, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex, molybdates esters etc.
One or more in oil-soluble organic molybdenum friction improver, preferably organic molybdates esters.Above-mentioned organic-molybdenum
There is the organic group comprising enough carbon numbers in compound organic molybdenum is dissolved in or is disperseed
In base oil, general described carbon number between 6-60, between preferably 10-50.Oil-soluble organic molybdenum
Friction improver can be selected from Molyvan L, 822,855 of Vanderbilt companies of U.S. production, Japanese rising sun electricity
515,525,710 etc. of change company production.
Component H accounts for the 0.01%-5% of lubricant oil composite gross mass, preferably 0.02%-2%, preferably 0.05%
- 1.2%.
The lube base oil of I ＞ surpluses, selected from the classes of API I, II class, III class, IV class and V class base oil
In one kind of multiple, preferably the class base oils of API II and/or the class base oils of API III.
Can also there are other following additives in lubricant oil composite of the invention：
Pour-point depressant or make lube oil flow improvers, flow of fluid or the lowest temperature that can be toppled over can be reduced
Degree, including but not limited to alkyl are the dialkyl fumarate/vinyl acetate copolymer of C8 to C18, gather
Methacrylate, poly alpha olefin, alkylnaphthalene etc., common trade names have T803, V385, PPT148
Deng.
Suitable viscosity index improver includes but is not limited to polyisobutene, ethene and propylene and high alpha-olefin
Copolymer, polymethacrylates, poly- alkylmethacrylate, methacrylate copolymer, no
Copolymer of the saturated dicarboxylic acid with vinyl compound, the partly copolymer of styrene and acrylate, hydrogenation
(styrene/isoprene, phenylethylene/butadiene, isoprene/butadiene) copolymer and part hydrogenate
(butadiene and isoprene, isoprene/divinylbenzene) homopolymers in one or more, often
The trade names seen have LZ7070, LZ7065, LZ7067, LZ7077 of T613, T614, Lubrizol company,
SV260, SV261 of Infineum companies etc..
Anti-foaming agent can select polysiloxane type, such as silicone oil or dimethyl silicone polymer.
In the present invention, the preparation method of the compound of structure is preferably included shown in formula (I)：
A () is reacted aniline, sulfur chloride and 4- chloroanilines, the intermediate M shown in generation formula (II),
B intermediate M that () obtains step (a) enters in the basic conditions with dimercapto -1,3,4- thiadiazoles
Row nucleophilic substitution, the multipurpose additive shown in generation formula (I),
In step (a) of the present invention, the concrete mode that aniline, sulfur chloride and 4- chloroanilines are reacted is preferred
Including：
I () under an inert atmosphere, in the first solvent, aniline is fully carried out with sulfur chloride at -20-0 DEG C
Reaction；
(ii) 4- chloroanilines are added in the reaction system of step (i), 1-3h is reacted at 15-30 DEG C.
In the present invention, inert atmosphere can be the conventional inert atmosphere in this area, for example can be by nitrogen, argon
The gases such as gas are provided.
In step (i) of the present invention, the first solvent is preferably selected from dichloromethane, tetrahydrofuran, toluene, diformazan
At least one in benzene and dioxane, more preferably dichloromethane and/or tetrahydrofuran, still more preferably
It is dichloromethane.
In the present invention in step (i), it refers to complete reaction fully to be reacted, i.e., reaction raw materials enter completely
Row reaction.Reaction can be monitored using method commonly used in the art, to confirm that reaction is complete, for example
Can be monitored using methods such as TLC (TLC) or gas-chromatographies.
In step (ii) of the present invention, 1-3h is reacted at 15-30 DEG C, preferably after step (i) fully reaction,
The temperature of reaction system is gradually increased to 15-30 DEG C, adding 4- chloroanilines carries out reaction 1-3h.It is preferred at this
In the case of, can further improve reaction yield.
In step (ii) of the present invention, the feed postition of 4- chloroanilines is preferably and adds by several times, for example, can divide 3-4
Secondary addition.Under the preferable case, reaction yield can be further improved.When being added for gradation, every time
Addition can be with identical, it is also possible to it is different, in order to easy to operate, preferably each addition is identical.
In step (ii) of the present invention, 1-3h is reacted, the mode for stopping reaction can be those skilled in the art institute
Thinkable various modes, for example, quencher can be added to be quenched, quencher can be normal for this area
Quencher, for example, can be saturated aqueous common salt.
In the present invention, the consumption of aniline, sulfur chloride and 4- chloroanilines is substantially equimolar amounts, but aniline and
Sulfur chloride can be suitably excessive.The mol ratio of aniline, sulfur chloride and 4- chloroanilines 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, in order to obtain it is purer in
Mesosome M, in addition it is also necessary to post-processed to reacted system, the mode of post processing can include washing, do
Dry, removal of solvent under reduced pressure, for example, the reaction system after being quenched is washed with distilled water and saturated common salt respectively
Wash, the drier such as anhydrous calcium chloride or anhydrous sodium sulfate are then added at 15-30 DEG C, keep 10-60min.
After being filtered to remove drier, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain intermediate M.
In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4- chloroanilines are reacted is as schemed
Shown in 1, in Fig. 1, the first solvent uses dichloromethane, purpose by way of example only, not to this hair
Bright scope is construed as limiting.
In step (b) of the present invention, the condition of nucleophilic substitution is preferably included：Under an inert atmosphere,
In two solvents, dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed into 10-30min at 15-30 DEG C,
Intermediate M is subsequently adding, is fully reacted.I.e. alkalescence condition is provided by alkaline reagent.
" inert atmosphere ", " fully being reacted " are as it was previously stated, will not be repeated here.
In the present invention, intermediate M is preferably slowly added to, for example, can add by several times, can typically divide 3-4
Secondary addition.Under the preferable case, reaction yield can be further improved.When being added for gradation, every time
Addition can be with identical, it is also possible to it is different, in order to easy to operate, preferably each addition is identical.
In the present invention, the second solvent is preferably selected from dichloromethane, tetrahydrofuran, toluene, dimethylbenzene, N, N-
At least one in dimethylformamide, more preferably dichloromethane and/or DMF, more enter
One step is preferably N,N-dimethylformamide.
In the present invention, alkaline reagent is preferably selected from the inorganic bases such as potassium carbonate, sodium carbonate, sodium methoxide at least
It is a kind of.
In the present invention, catalyst is preferably potassium sulfate.
In step (b) of the present invention, the consumption base of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate M
It is equimolar amounts in sheet, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Dimercapto -1,3,4-
The mol ratio of 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-1,3,4-thiadiazole
Molal quantity on the basis of, the consumption of catalyst is preferably 5-100 moles of %, more preferably 10-50 moles %.
In step (b) of the present invention, the reactional equation that dimercapto-1,3,4-thiadiazole and intermediate M are reacted
Formula as shown in Fig. 2 in Fig. 2, alkaline reagent uses potassium carbonate, purpose by way of example only, no
The scope of the present invention is construed as limiting.
It will be understood by those skilled in the art that in order to obtain purer final product, i.e., it is of the invention
Multipurpose additive, after the method for preparing multipurpose additive of the invention preferably also includes carrying out reacted system
Treatment, the mode of post processing can include washing, dry, removal of solvent under reduced pressure, for example, will fully react
System afterwards is poured into the 1-10 times of ethyl acetate of volume (or dichloromethane), respectively with distilled water and saturation
Brine It, then adds the drier such as anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C, keeps
10-60min.After being filtered to remove drier, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain
Final product.
Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention is preferably carried out under agitation,
Can be the conventional mixing speed in this area, for example, mixing speed can for mixing speed without particular/special requirement
Think 100-800rpm.
In the present invention, for the first solvent and the second solvent amount without particular/special requirement, can be this area routine
Solvent load, this is known to those skilled in the art, will not be repeated here.
As described above, it is contemplated that containing structure shown in formula (I) by the additive in lubricant oil composite
Compound and make lubricant oil composite that there is the performance such as excellent wear-resistant, antifriction, anti-oxidant.Therefore, it is right
In lubricant oil composite preparation method without particular/special requirement, can use method commonly used in the art, example
Such as, in order to manufacture the Lubricant composition for gasoline engine, by structure shown in the foregoing formula (I) of the present invention
Multipurpose additive as one of lube oil additive, with lube base oil and dispersant, metal detergent
Agent, ZDDP, antioxidant, friction improver are well mixed according to predetermined ratio or addition.
More specifically, in order to manufacture Lubricant composition for gasoline engine of the invention, can be above-mentioned each
Lube oil additive is added separately in lube base oil, and heating is well mixed.Mixing temperature now
Generally 40 DEG C -90 DEG C of degree, incorporation time is generally 1h-6h.
Present invention employs the multipurpose additive of structure shown in formula (I), while it is ashless to employ boracic antioxidant
The optimum organization of dispersant and other ashless dispersants, and compound suitable detersive, ZDDP, auxiliary antioxygen
The functional additives such as agent, friction improver, have played the cooperative effect between additive, make lubricating oil composition
Thing has excellent wear-resistant, antifriction, anti-oxidant and cleansing performance.Composition of the invention has mass fraction
Phosphorus content no more than 0.08%, disclosure satisfy that the ranks such as SL/GF-3, SM/GF-4, SN/GF-5 top grade gasoline
The requirement of engine lubricating oil.
Brief description of the drawings
Fig. 1 is the reaction equation of the step of preparing multipurpose additive (a).
Fig. 2 is the reaction equation of the step of preparing multipurpose additive (b).
Fig. 3 is the hydrogen spectrum spectrogram of multipurpose additive prepared by preparation example.
Fig. 4 is the carbon spectrum spectrogram of multipurpose additive prepared by preparation example.
Fig. 5 is the mass spectrogram of multipurpose additive prepared by preparation example.
Specific embodiment
Below the features of the present invention is further described with example.
Source in embodiment and comparative example using additive is shown in Table 1.
Table 1
In the following Examples and Comparative Examples：
The complete method of monitoring reaction：Thin-layer chromatography chromatogram (TLC) fluorescence developing method.
Gross production rate=final product mole/aniline moles × amine mole
The physico-chemical analysis method of product：Element is determined by inductively coupled plasma ion emission spectroscopy method to contain
Amount.
Structure characterization methods：Nuclear magnetic resonance method (1H hydrogen is composed,13C carbon is composed), high resolution mass spectrum.
Preparation example
Nitrogen protection is filled with the 500ml flasks with electromagnetic agitation (mixing speed is 300rpm),
Add the dichloromethane of 150ml, be subsequently adding the sulfur chloride of 0.2mol, it is sufficiently cool in the ice-water bath after,
Add the aniline of 0.2mol.Monitoring removes ice-water bath to after reacting completely, is placed in 25 DEG C at room temperature, question response
After system is gradually increased to 25 DEG C, point 3 addition 4- chloroanilines are reacted, and each addition is identical, adds altogether
Enter 4- chloroanilines 0.15mol.Sustained response adds 30ml saturated aqueous common salts that reaction is quenched after 2 hours, then
Reaction system is transferred in separatory funnel, respectively with 50ml distilled water and 50ml saturated common salt water washings, and
10g anhydrous sodium sulfates are added to dry 20min at 25 DEG C.Filtrate after filtering at 40 DEG C, under 0.05MPa
Solvent is evaporated off, intermediate M1 is obtained.
Nitrogen protection is filled with the 500ml flasks with electromagnetic agitation (mixing speed is 400rpm),
The DMF (DMF) of 150ml is added, 0.2mol dimercapto -1,3,4- thiophenes two is subsequently adding
The potassium carbonate of azoles and 0.2mol, the potassium sulfate of 0.05mol, stir 20 minutes at 25 DEG C, in point 3 additions
Intermediate M1 is stated, each addition is identical, intermediate M10.12mol is added altogether.Monitoring is complete to reaction,
Then reaction system is added into 250ml ethyl acetate, and is transferred in separatory funnel, distilled with 100ml respectively
Water (twice) and 50ml saturated common salt water washings, and add 15g anhydrous sodium sulfates to dry 20min at 25 DEG C.
Filtrate after filtering is evaporated off solvent under 40 DEG C, 0.03MPa, obtains final product S1.Calculating gross production rate is
76%.
The physico-chemical analysis data of product are as follows：Sulfur content, 41.3%；Nitrogen content, 13.9%.
S1 is carried out into structural characterization, hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram is respectively obtained, figure is seen respectively
3rd, Fig. 4 and Fig. 5.
Physico-chemical analysis data, Fig. 3, Fig. 4 and Fig. 5 from above-mentioned preparation example can be seen that S1 has formula (I)
Shown structure：
Embodiment 1-4 and comparative example 1-3 and comparative example 4-1,4-2,4-3.
Embodiment 1-4 is the composition of petrol engine lubricating oil of the invention.Each component is proportionally added into tune
In container, 45 DEG C -80 DEG C are heated under normal pressure, stirred -2 hours 1 hour, preparing viscosity rank is
The Lubricant composition for gasoline engine of the SN/GF-5 ranks of 5W-30.
Embodiment 1-3 and comparative example 1-3 has whole identical formula compositions outside S1 multipurpose additives respectively.
Embodiment 4 has whole identical formula compositions, embodiment 4 and comparative example in addition to dispersant with comparative example 4-1
4-2,4-3 have whole identical formula compositions in addition to S1 multipurpose additives and organic anti-friction agent respectively.Implement
Example 1-4 and comparative example 1-3 and comparative example 4-1,4-2, the respective proportion of composing of 4-3 are shown in Table 2.
Table 2
(TFOUT) is tested with pressure differential scanning calorimetry (PDSC) and ASTM D4742 oxide thin layers
The oxidation induction period of oil product is determined, the antioxygenic property of oil product is evaluated, induction period is more long, oil product antioxygen property
Better.The design temperature of PDSC is 220 DEG C.The high temperature deposition of oil product is carried out using ASTM D7097 methods
Thing qualification test (TEOST-MHT), deposition rod temperature is 285 DEG C, and the reaction time is 24h.
Embodiment 1-4, the oxidation induction period of comparative example 1-3 and 4-1 and high temperature deposition thing the results are shown in Table 3.
Table 3
| Oil sample | TFOUT/min | PDSC/min | TEOST-MHT/mg |
| Embodiment 1 | 175 | 41.0 | 16.5 |
| Embodiment 2 | 188 | 45.4 | 15.8 |
| Embodiment 3 | 190 | 46.3 | 15.4 |
| Embodiment 4 | 185 | 43.7 | 17.0 |
| Comparative example 1 | 146 | 29.5 | 25.8 |
| Comparative example 2 | 141 | 26.2 | 26.0 |
| Comparative example 3 | 137 | 23.0 | 27.4 |
| Comparative example 4-1 | 166 | 37.8 | 20.3 |
From table 3 it can be seen that TFOUT the and PDSC oxidation induction periods of oil product are significantly better than that in embodiment
Its comparative example, the TEOST deposit growing amounts of oil product are significantly less than its comparative example in embodiment.Test data
Show, lubricant oil composite of the invention uses S1 multipurpose additives, with excellent antioxygen property and control
The ability of deposit generation, is combined boracic antioxidant polyisobutene succinyl sub- in present composition dispersant
Amine also has more preferable antioxygen property and deposit control capability than non-antioxidizing B-contained disperser.
The wear-resistant experiment of high temperature of oil product is carried out using high-frequency reciprocating frictional testing machine (HFRR), experimental condition is：
Load 800g, frequency is 20Hz, and stroke 1mm, temperature is 100 DEG C, and test period is 60min.Implement
The HFRR wear tests of example 1-4 and comparative example 1-3 and comparative example 4-2,4-3 the results are shown in Table 4.
From table 4, it can be seen that compared with comparative example, lubricant oil composite of the invention have it is excellent it is wear-resistant,
Antifriction performance, embodiment 4 relatively shows S1 multipurpose additives with organic molybdates esters with comparative example 4-2,4-3
There is good cooperative effect, both compound has more excellent wear-resistant, friction reducing effect than exclusive use.
Table 4
| Oil sample | HFRR mills class diameter/μm | HFRR coefficient of friction |
| Embodiment 1 | 151 | 0.077 |
| Embodiment 2 | 146 | 0.064 |
| Embodiment 3 | 138 | 0.058 |
| Embodiment 4 | 158 | 0.066 |
| Comparative example 1 | 220 | 0.108 |
| Comparative example 2 | 227 | 0.110 |
| Comparative example 3 | 248 | 0.115 |
| Comparative example 4-2 | 218 | 0.095 |
| Comparative example 4-3 | 205 | 0.088 |
Embodiment 5-8 and comparative example 9-10.
Embodiment 5-8 is that to use the viscosity grade obtained with preceding embodiment identical preparation method be 5W-40's
SN/GF-5 Lubricant composition for gasoline engine.Embodiment 5-8 and comparative example 9-10 has in addition to dispersant respectively
Whole identical formula compositions.Its each proportion of composing be shown in Table 5.
Dispersive property of the oil product to greasy filth is evaluated with spot distributed test, specific practice is as follows：By 30%
Program VG engine sludges are added in experiment oil, after ultrasonic disperse 6min, heat 2h in 200 DEG C of baking ovens, so
Oil mark dispersion loop diameter and greasy filth circle of dispersion diameter ratio are measured afterwards by oil droplet on filter paper, after 24 hours, i.e.,
It is dispersion index.The dispersiveness of dispersion index explanation oil product higher is better.
Table 5
The spot distributed test of embodiment 5-8 and comparative example 9-10 the results are shown in Table 6.
Table 6
| Oil sample | Spot distributed test dispersion index |
| Embodiment 5 | 83 |
| Embodiment 6 | 88 |
| Embodiment 7 | 86 |
| Embodiment 8 | 80 |
| Comparative example 9 | 76 |
| Comparative example 10 | 73 |
As can be seen from Table 6, in embodiment the spot distributed test dispersion index of oil product apparently higher than corresponding
Comparative example, show the present invention using boracic antioxidant ashless dispersant and succinate dispersant compounding than each
Individual single dispersant has more preferable dispersive property.
Embodiment 9-12 and comparative example 13-15.
Embodiment 9-12 is the composition of petrol engine lubricating oil of the invention.Each component is prepared into viscosity
Rank is the SM/GF-4 grades of gasoline engine oil compositions of 5W-30.Embodiment 9-12 and comparative example
13-15 has whole identical formula compositions in addition to detersive.The respective group of embodiment 9-12 and comparative example 13-15
It is proportional to be shown in Table 7.
Table 7
Oil product to embodiment 9-12 and comparative example 13-15 modulation has carried out QZX experiment, QZX experiment
The equipment of use is the 25B-19 type coking plate instrument of Japanese Meitech companies production, the test simulation engine
The condition of work of crankcase and cylinder liner piston ring lubrication oil circulation, makes test oil product constantly be heated and aoxidizes coking
Process.Test period is 6h, and oil temperature is 150 DEG C, and plate temperature is 310 DEG C.
Table 8
From the result of the test of table 8, using the mixing of high-alkali salicylate and high-alkali alkyl monosulfide phenates
Composition formula has more preferable cleansing performance compared with single high-alkali salicylate or high-alkali alkyl monosulfide phenates.
Lubricant oil composite of the invention has excellent high temperature detergent performance.
Although the present invention is described in detail with a general description of the specific embodiments for the above,
But on the basis of the present invention, it can be made some modifications or improvements, this is to those skilled in the art
Obviously.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention,
Belong to the scope of protection of present invention.
Claims (22)
1. a kind of Lubricant composition for gasoline engine, including following components：
The multipurpose additive of structure shown in A ＞ formulas (I)：
B ＞ boracic antioxidant polyisobutene succinimide ashless dispersants；
C ＞ polyisobutylene succinic acid ester ashless dispersants；
D ＞ at least one alkylsalicylates；
E ＞ at least one alkyl monosulfide phenates；
F ＞ at least one zinc dialkyl dithiophosphates；
G ＞ amine type antioxidant and/or phenolic ester type antioxidant；
H ＞ at least one oil-soluble organic molybdenum friction improvers；
The lube base oil of I ＞ surpluses.
2. according to the composition described in claim 1, it is characterised in that the component A accounts for the lubricating oil group
The 0.05%-2% of compound gross mass.
3. according to the composition described in claim 1, it is characterised in that the component B is poly- for boracic antioxidant
Isobutene Ashless butyl diimide dispersant, is by polyamines polyene, metoxyphenol, aldehyde, polyolefin
Base succinic acid or acid anhydrides and acid reaction are obtained.
4. according to the composition described in claim 3, it is characterised in that the polyolefin is C2-C4 alkene
Copolymer or homopolymers, its number-average molecular weight are 850-5000；The metoxyphenol is selected to methoxy
One or more of base phenol, o-methoxyphenol and meta-methoxy phenol.
5. according to the composition described in claim 1, it is characterised in that the component B accounts for the lubricating oil group
The 0.5%-8% of compound gross mass.
6. according to the composition described in claim 1, it is characterised in that the component C accounts for the lubricating oil group
The 0.5%-8% of compound gross mass.
7. according to the composition described in claim 1, it is characterised in that the component D is for base number
The high base number alkylsalicylate of (200-450) mgKOH/g.
8. according to the composition described in claim 1, it is characterised in that the component D accounts for the lubricating oil group
The 0.1%-10% of compound gross mass.
9. according to the composition described in claim 1, it is characterised in that the component E is for base number
The high-alkali calcium sulfenyl phenolate of (200-400) mgKOH/g.
10. according to the composition described in claim 1, it is characterised in that the component E accounts for the lubricating oil group
The 0.1%-10% of compound gross mass.
11. according to the composition described in claim 1, it is characterised in that in the zinc dialkyl dithiophosphate
Alkyl be to contain 2 to 12 alkyl of carbon atom.
12. according to the composition described in claim 1, it is characterised in that the component F is in the lubricating oil group
Addition in compound is in terms of the mass fraction of P elements no more than 0.08%.
13. according to the composition described in claim 1, it is characterised in that the amine type antioxidant is selected from alkylation
One or more in aniline, alkylated diphenylamine and PA；The phenolic ester type antioxidant is
Molecular weight is the hydroxy phenyl carboxylate of 200-500.
14. according to the composition described in claim 1, it is characterised in that the component G accounts for the lubricating oil group
The 0.1%-6% of compound gross mass.
15. according to the composition described in claim 1, it is characterised in that the component H is selected from dialkyl disulfides
For molybdenum phosphate, dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthic acid molybdenum,
Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex and molybdic acid esters oil-soluble organic molybdenum rub
Wipe one or more in modifier.
16. according to the composition described in claim 1, it is characterised in that the component H accounts for the lubricating oil group
The 0.01%-5% of compound gross mass.
17. according to the composition described in claim 1, it is characterised in that the lube base oil of the component I
Selected from one kind of multiple in the classes of API I, II class, III class, IV class and V class base oil.
18. according to the composition described in claim 1, it is characterised in that drop is added in the lubricant oil composite
One or more of solidifying agent, viscosity index improver and anti-foaming agent.
19. according to the composition described in claim 18, it is characterised in that the pour-point depressant includes that alkyl is C8
Dialkyl fumarate/vinyl acetate copolymer, polymethacrylates, poly- α-alkene to C18
One or more in hydrocarbon and alkylnaphthalene；The viscosity index improver include polyisobutene, ethene with
The copolymer of propylene and high alpha-olefin, polymethacrylates, poly- alkylmethacrylate, first
The copolymer of base acrylate copolymer, unsaturated dicarboxylic and vinyl compound, styrene and third
The copolymer of olefin(e) acid ester, partially hydrogenated (styrene/isoprene, phenylethylene/butadiene, isoamyl
Diene/butadiene) copolymer and partially hydrogenated (butadiene and isoprene, isoprene/bis-
Vinyl benzene) homopolymers in one or more；The anti-foaming agent is polysiloxane type.
20. according to the composition described in claim 1, it is characterised in that structural compounds shown in the formula (I)
Preparation method include：
A () is reacted aniline, sulfur chloride and 4- chloroanilines, the intermediate M shown in generation formula (II),
B intermediate M that () obtains step (a) enters in the basic conditions with dimercapto -1,3,4- thiadiazoles
Row nucleophilic substitution, the multipurpose additive shown in generation formula (I).
The preparation method of one of the 21. claim 1-19 lubricant oil composite, it is characterised in that by each lubrication
Oil additive is added in lube base oil, and heating is well mixed.
One of 22. claim 1-19 purposes of the lubricant oil composite in petrol engine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679719A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Lubricant composition for gasoline engine and preparation method thereof |
| CN110317663A (en) * | 2018-03-28 | 2019-10-11 | 中国石油化工股份有限公司 | Lubricant composition for gasoline engine and preparation method thereof |
| CN112442413A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | High-cleanness engine oil composition and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5177212A (en) * | 1991-07-26 | 1993-01-05 | R.T. Vanderbilt Company, Inc. | Phenolic derivatives of 2,5-dimercapto-1,3,4-thiadiazoles |
| US5336420A (en) * | 1991-05-08 | 1994-08-09 | Mobil Oil Corporation | Antioxidants for functional fluids |
| CN101830865A (en) * | 2010-03-19 | 2010-09-15 | 华东交通大学 | Hydroxyl-containing thiadiazole derivate as well as preparation method and application thereof |
| CN102690703A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Extreme-pressure long-life industrial lubricant composition |
| CN103320199A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Screen phenol-containing thiadiazole type antioxygen antiwear additive and preparation method thereof |
-
2015
- 2015-11-23 CN CN201510815160.6A patent/CN106753699B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336420A (en) * | 1991-05-08 | 1994-08-09 | Mobil Oil Corporation | Antioxidants for functional fluids |
| US5177212A (en) * | 1991-07-26 | 1993-01-05 | R.T. Vanderbilt Company, Inc. | Phenolic derivatives of 2,5-dimercapto-1,3,4-thiadiazoles |
| CN101830865A (en) * | 2010-03-19 | 2010-09-15 | 华东交通大学 | Hydroxyl-containing thiadiazole derivate as well as preparation method and application thereof |
| CN102690703A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Extreme-pressure long-life industrial lubricant composition |
| CN103320199A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Screen phenol-containing thiadiazole type antioxygen antiwear additive and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679719A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Lubricant composition for gasoline engine and preparation method thereof |
| CN109679719B (en) * | 2017-10-18 | 2022-06-28 | 中国石油化工股份有限公司 | Gasoline engine lubricating oil composition and preparation method thereof |
| CN110317663A (en) * | 2018-03-28 | 2019-10-11 | 中国石油化工股份有限公司 | Lubricant composition for gasoline engine and preparation method thereof |
| CN110317663B (en) * | 2018-03-28 | 2022-07-12 | 中国石油化工股份有限公司 | Gasoline engine lubricating oil composition and preparation method thereof |
| CN112442413A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | High-cleanness engine oil composition and preparation method thereof |
| CN112442413B (en) * | 2019-08-30 | 2022-09-16 | 中国石油化工股份有限公司 | High-cleanness engine oil composition and preparation method thereof |
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