CN106753699B - 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 present 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 > formula (I):B > boracic antioxidant polyisobutene succinimide ashless dispersant；C > polyisobutylene succinic acid ester ashless dispersant；D > at least one alkylsalicylate；E > at least one alkyl monosulfide phenates；F > at least one zinc dialkyl dithiophosphate；G > amine type antioxidant and/or phenolic ester type antioxidant；H > at least one oil-soluble organic molybdenum friction improver；The lube base oil of I > surplus.The phosphorus content that there is composition of the invention mass fraction to be no more than 0.08% has 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 compositions suitable for petrol engine
Object.
Background technique
The environmentally friendly and energy-efficient development for requiring to promote engine technology, the continuous upgrading for also promoting gasoline engine oil are changed
Generation, oil product are also higher and higher in the performance requirement of the various aspects such as antioxygen, wear-resistant, antifriction and peace and quiet, greasy filth dispersion.Gasoline at present
The highest quality level of engine lubricating oil is American Petroleum Institute (API) (API) and International Lubricant standardization and certification committee
(ILSAC) the SN/GF-5 rank formulated.
Modern gasoline machine power improves, and miniaturization, compression ratio improves, and thermic load increases, to oil product oxidation resistance and control
The requirement for the ability that deposit processed generates also is continuously improved.Its high-temperature oxidation resistant is evaluated in API petrol engine lubricating oil specification
Current procedure IIIG is arrived in 64 hours from program IIIE of engine test that viscosity increases, 80 hours for developing to program IIIF
100 hours, and the requirement that viscosity increases never exceeds 375% and is reduced to 275%, 150%, wants to high-temperature oxidation resistance
It asks and greatly improves.Requirement to detergency simultaneously is also increasingly harsher, and the TEOST-MHT test of simulation piston high temperature deposition object is wanted
It asks from SL and is no more than 45mg, develop to the 35mg of SM, SN specification, the requirement for inhibiting deposit to generate is significantly improved.
Modern gasoline machine load improves, and puts forward higher requirements to the abrasion resistance of gasoline engine oil, while power conservation requirement
It increasingly improves, it is desirable that oil product has better antifriction performance, there is more preferably fuel economy.GF-5 is entirely using gasoline engine oil
Fuel economy performance in service life proposes harsh requirement, and uses the higher harsh engine test program of test accuracy
VI D alternative program VI B evaluates engine oil fuel economy.
CN 00129836.4 discloses a kind of boracic antioxidant dispersant of phenol containing methoxy, have good antioxidant and
Detergent-dispersant performance.
US 4824601A reports diphenylamine and diisobutylene in the clay catalyst (earth of acid activation
Catalyst) the lower alkylated amines mixture formed of effect, its oxidation resistance in lubricating oil and other functional fluids show
Preferably.
Using the tert-butyl phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine condensation reaction preparation occurs for CN 1191340C
Compound has the stronger ability for capturing free radical and peroxynitrite decomposition compound, can provide to oil oxidation stability more effective
Protection, may also function as wear-resistant effect.
US 4225450, which is reported, a kind of reacts preparation by being obstructed tert-butyl phenols with Diethyldithiocarbamate
Polysulfide phenolic antioxidant has preferable antioxidation and wear-resistant effect.
Summary of the invention
The present 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 > formula (I):
B > boracic antioxidant polyisobutene succinimide ashless dispersant；
C > polyisobutylene succinic acid ester dispersing agent；
D > at least one alkylsalicylate；
E > at least one alkyl monosulfide phenates；
F > at least one zinc dialkyl dithiophosphate；
G > amine type antioxidant and/or phenolic ester type antioxidant；
H > at least one oil-soluble organic molybdenum friction improver；
The lube base oil of I > surplus；
There may also be other additives in lubricant oil composite of the invention, such as pour-point depressant, viscosity index improver
(VM), anti-foaming agent etc..
Specifically, Lubricant composition for gasoline engine of the invention includes following component:
A > is the multipurpose additive of structure shown in formula (I):
The present inventor has found that the multiple-effect containing structure shown in formula (I) in lubricant oil composite is added under study for action
Agent can make lubricant oil composite have the performances such as excellent wear-resistant, antifriction, anti-oxidant.In the present invention, structure shown in formula (I)
The preparation method of compound will be described in detail in subsequent section.
Component A accounts for the 0.05%-2% of lubricant oil composite gross mass of the present invention, preferably 0.1%-1.0%.
B > be boracic antioxidant polyisobutene succinimide ashless dispersant, be by polyamines polyene, metoxyphenol,
Aldehyde, polyolefin-based succinic acid or acid anhydrides and acid reaction are made.Preparation method is the mixing in metoxyphenol and polyamines polyene
Aldehyde reaction is added in object and obtains amine condensation, then dehydration occurs with polyolefin-based succinic acid or acid anhydrides and obtains antioxidant dispersion
Agent obtains final product boracic antioxidant dispersant with fatty alcohol and acid reaction again later.The preferred C2-C4 alkene of polyolefin
The copolymer or homopolymer of hydrocarbon, can be one of polyisobutene, random polypropylene and ethylene-propylene copolymer or a variety of, and number is equal
Molecular weight is 850-5000, preferably 950-2500；Metoxyphenol is selected from p methoxy phenol, o-methoxyphenol and first
Oxygroup phenol it is one or more；Aldehyde is selected from one of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, salicylide and benzaldehyde or a variety of.
Component B can be made by method 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 ester dispersing agent can select polyisobutylene succinic acid pentaerythritol ester, polyisobutene fourth
Diglyceride, polyisobutylene succinic acid glycol ester etc..The component can select the LZ936 etc. of Lubrizol company.
Component C accounts for the 0.5%-8% of lubricant oil composite gross mass of the present invention, preferably 0.8%-5%.
D > be selected from alkylsalicylate alkaline-earth metal detersive it is one or more, the alkaline-earth metal can be magnesium,
Calcium, preferably base number are the one or more of the high base number alkylsalicylate of (200-450) mgKOH/g.Component D can select road
LZL109B, LZL112 of Bo Runlanlian additive Co., Ltd production, C9375, C9012 of the production of Infineum company, OSCA
The OSCA420 of company's production, the SAP007 etc. of Shell company production.
Component D accounts for the 0.1%-10% of lubricant oil composite gross mass of the present invention, preferably 0.2%-6%.
E > is selected from one of sulfenyl phenolate saline-alkali soil metal detergent or a variety of, the alkaline-earth metal can be magnesium,
Calcium, preferably base number are the one or more of the high-alkali sulfurized alkylphenol calcium of (200-400) mgKOH/g.Component E can select road rich
The LZ6499 of LZL115A, LZL115B of Run Lanlian additive Co., Ltd production, Lubrizol Corporation production,
The OLOA219 of LZ6500, Chevron Oronite Company production, C9391, C9394 etc. of the production of Infineum company.
Component E accounts for the 0.1%-10% of lubricant oil composite gross mass, preferably 0.2%-6%.
F > is selected from the one or more of zinc dialkyl dithiophosphate (ZDDP)；In the zinc dialkyl dithiophosphate
Alkyl be the alkyl containing 2 to 12 carbon atoms, the preferably alkyl containing 2 to 8 carbon atoms, including but not limited to second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, 2- second
One of base hexyl, cyclohexyl and methylcyclopentyl are a variety of.
The zinc dialkyl dithiophosphate can be selected but be not limited to WUXI SOUTH PETROLEUM ADDITIVE Co., LTD.'s production
T202, T203, Jinzhou Petrochemical Company additive factory production T202, T203, brothers alkyl T204, secondary alkyl T205,
C9417, C9425, C9426 of LZ1371, LZ1375, Infineum company of Lubrizol company, Afton company
Hitec7169, Hitec1656 etc..
Additional amount of the component F in lubricant oil composite is no more than 0.08% in terms of the mass fraction of P elements and is advisable, excellent
Select 0.06%-0.08%.
G > is selected from amine type antioxidant and/or phenolic ester type antioxidant.
Amine type antioxidant can be one of alkylation aniline, alkylated diphenylamine and phenyl-α-naphthylamine or a variety of,
In alkyl carbon number be C2-C12, such as dibutyl diphenylamines, dioctyl diphenylamine, dinonyldiphenylamine, Ding Xin can be selected
One of base diphenylamines and phenyl-α-naphthylamine are a variety of, preferably oil-soluble dialkyl diphenylamine, more preferable fourth octyl hexichol
Amine.IRGANOX L-01, the IRGANOX L-57 of alkylated diphenylamine available on the market such as BASF Corp. of Germany's production, north
The T534 of Jing Xingpu fine chemical technology development company production, the production of Lanzhou Lu Borun Lan Lian additive Co., Ltd
LZ5150A, the VANLUBE NA of R.T.Vanderbilt company, U.S. production, 961 VANLUBE, dioctyl diphenylamine
VANLUBE 81, pair of German Rhein Chemie company production, to ' di-iso-octyldiphenylamine RC7001.
Phenolic ester type antioxidant is the hydroxy phenyl carboxylate that molecular weight is 200-500, as BASF Corp. of Germany produces
The T512 that IRGANOX L-135, Beijing Xing Pu fine chemical technology development company produce.
Component G in the additional amount in lubricant oil composite between 0.1-6%, preferably 0.2%-3%.
H > is selected from molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen molybdenum, dialkyldithiocarbamacompositions
The oil-soluble organic molybdenums frictions such as molybdenum, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex, molybdates esters change
Into one of agent or a variety of, preferably organic molybdates esters.Have in above-mentioned organic molybdenum and includes enough carbon atom numbers
Organic group so that organic molybdenum is dissolved in or is scattered in base oil, the general carbon atom number 6-60 it
Between, between preferably 10-50.Oil-soluble organic molybdenum friction improver can be selected from the production of U.S. Vanderbilt company
Molyvan L, 822,855,515,525,710 etc. of the production of Japanese rising sun electrification company.
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 > surplus, selected from one of I class of API, II class, III class, IV class and V class base oil or
It is a variety of, preferred III class base oil of II class base oil of API and/or API.
There may also be following other additives in lubricant oil composite of the invention:
Pour-point depressant or make lube oil flow improvers, the minimum temperature that fluid flowing can be reduced or can be toppled over, packet
It includes but is not limited to dialkyl fumarate/vinyl acetate copolymer, polymethacrylates, poly- α-that alkyl is C8 to C18
Alkene, alkylnaphthalene etc., common trade names have T803, V385, PPT148 etc..
Suitable viscosity index improver includes but is not limited to the copolymerization of polyisobutene, ethylene and propylene and high alpha-olefin
Object, polymethacrylates, poly- alkylmethacrylate, methacrylate copolymer, unsaturated dicarboxylic and vinyl
The copolymer of compound, the copolymer of styrene and acrylate, partially hydrogenated (styrene/isoprene, styrene/fourth
Diene, isoprene/butadiene) copolymer and partially hydrogenated (butadiene and isoprene, isoprene/divinyl
Benzene) one of homopolymer or a variety of, common trade names have T613, T614, Lubrizol company LZ7070,
LZ7065, LZ7067, LZ7077, SV260, SV261 etc. of Infineum company.
Polysiloxane type can be selected in anti-foaming agent, such as silicone oil or dimethyl silicone polymer.
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 contain the chemical combination of structure shown in formula (I) by the additive in lubricant oil composite
Object and make lubricant oil composite that there are the performances such as excellent wear-resistant, antifriction, anti-oxidant.Therefore, for the system of lubricant oil composite
Preparation Method can use method commonly used in the art without particular/special requirement, for example, in order to manufacture the petrol engine lubrication
Fluid composition, using the multipurpose additive of structure shown in present invention formula (I) above-mentioned as one of lube oil additive, with lubricating oil
Base oil and dispersing agent, metal detergent, ZDDP, antioxidant, friction improver mix equal according to predetermined ratio or additive amount
It is even.
It more specifically, can be by above-mentioned each lubricating oil in order to manufacture Lubricant composition for gasoline engine of the invention
Additive is added separately in lube base oil, and heating is uniformly mixed.Mixing temperature at this time is generally 40 DEG C -90
DEG C, incorporation time is generally 1h-6h.
Present invention employs the multipurpose additives of structure shown in formula (I), while using boracic antioxidant ashless dispersant
With the optimum organization of other ashless dispersants, and the function such as suitable detersive, ZDDP, auxiliary antioxidant, friction improver are compounded
Can additive, played the synergistic effect between additive, made lubricant oil composite that there is excellent wear-resistant, antifriction, anti-oxidant
And cleansing performance.There is composition of the invention mass fraction to be no more than 0.08% phosphorus content, can satisfy SL/GF-3, SM/
The requirement of the ranks top grade petrol engine lubricating oil such as GF-4, SN/GF-5.
Detailed description of the invention
Fig. 1 is the reaction equation of (a) the step of preparing multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing multipurpose additive.
Fig. 3 is the hydrogen spectrum spectrogram of the multipurpose additive of preparation example preparation.
Fig. 4 is the carbon spectrum spectrogram of the multipurpose additive of preparation example preparation.
Fig. 5 is the mass spectrogram of the multipurpose additive of preparation example preparation.
Specific embodiment
The features of the present invention is further described with example below.
1 is shown in Table using the source of additive in embodiment and comparative example.
Table 1
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 × amine mole
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 1-4 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 reconciliation to hold
In device, 45 DEG C -80 DEG C are heated under normal pressure, is stirred -2 hours 1 hour, and the SN/GF-5 rank that viscosity rank is 5W-30 is prepared
Lubricant composition for gasoline engine.
Embodiment 1-3 and comparative example 1-3 is respectively provided with outside S1 multipurpose additive all identical formula compositions.Embodiment 4
There are whole identical formula compositions in addition to dispersing agent with comparative example 4-1, embodiment 4 is respectively provided with comparative example 4-2,4-3 to be removed
Whole identical formula compositions outside S1 multipurpose additive and organic anti-friction agent.Embodiment 1-4 and comparative example 1-3 and comparative example 4-1,
The respective composition ratio of 4-2,4-3 are shown in Table 2.
Table 2
Oil product is measured with pressure differential scanning calorimetry (PDSC) and ASTM D4742 oxide thin layer test (TFOUT)
Oxidation induction period evaluates the antioxygenic property of oil product, and induction period is longer, and oil product antioxygen property is better.The set temperature of PDSC is
220℃.The high temperature deposition object qualification test (TEOST-MHT) of oil product is carried out using ASTM D7097 method, deposition rod temperature is
285 DEG C, the reaction time is for 24 hours.
Embodiment 1-4, the oxidation induction period of comparative example 1-3 and 4-1 and high temperature deposition object 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 period of oil product is significantly better than that its comparative example in embodiment,
The TEOST deposit production quantity of oil product is significantly less than its comparative example in embodiment.Test data shows lubricating oil group of the invention
It closes object and uses S1 multipurpose additive, with the ability that excellent antioxygen property and control deposit generate, the present composition point
Compound boracic antioxidant polyisobutene succinimide also has better antioxidant than non-antioxidizing B-contained disperser in powder
Energy and deposit control capability.
The wear-resistant test of high temperature of oil product, experimental condition are carried out using high-frequency reciprocating frictional testing machine (HFRR) are as follows: load
800g, frequency 20Hz, stroke 1mm, temperature are 100 DEG C, test period 60min.Embodiment 1-4 and comparative example 1-3 and right
The HFRR wear test of ratio 4-2,4-3 the results are shown in Table 4.
From table 4, it can be seen that lubricant oil composite of the invention has excellent wear-resistant, antifriction quality compared with comparative example
Can, embodiment 4 shows that S1 multipurpose additive and organic molybdates esters have good synergistic effect compared with comparative example 4-2,4-3,
The two compounding has superior wear-resistant, friction reducing effect than being used alone.
Table 4
| Oil sample | HFRR mill class's 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 be use preparation method identical with preceding embodiment to obtain viscosity grade for the SN/ of 5W-40
GF-5 Lubricant composition for gasoline engine.Embodiment 5-8 and comparative example 9-10 is respectively provided in addition to dispersing agent all identical
Formula composition.Respectively composition ratio is shown in Table 5 for its.
Oil product is evaluated with spot distributed test to the dispersion performance of greasy filth, specific practice is as follows: by 30% program VG
Engine sludge is added in test oil, after ultrasonic disperse 6min, heats 2h in 200 DEG C of baking ovens, then by oil droplet on filter paper, 24
Measurement oil mark dispersion loop diameter and greasy filth circle of dispersion diameter ratio, as dispersion index after hour.Dispersion index is higher to illustrate oil
The dispersibility of product 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, the spot distributed test dispersion index of oil product is apparently higher than corresponding comparison in embodiment
Example shows that the present invention is had using boracic antioxidant ashless dispersant and succinate dispersing agent compounding than each individual dispersing agent
There is better dispersion performance.
Embodiment 9-12 and comparative example 13-15.
Embodiment 9-12 is the composition of petrol engine lubricating oil of the invention.Viscosity rank, which is prepared, in each component is
The SM/GF-4 grades of gasoline engine oil composition of 5W-30.Embodiment 9-12 and comparative example 13-15, which has, removes detersive
The identical formula composition of outer whole.Respectively composition ratio is shown in Table 7 to embodiment 9-12 with comparative example 13-15.
Table 7
QZX experiment has been carried out to the oil product of embodiment 9-12 and comparative example 13-15 modulation, what QZX experiment used
Equipment is the 25B-19 type coking plate instrument of Japanese Meitech company production, the test simulation engine crankcase and cylinder sleeve piston
The operating condition of ring lubrication oil circulation makes the process for testing the constantly heated oxidation coking of oil product.Test period is 6h, and oil temperature is
150 DEG C, plate temperature is 310 DEG C.
Table 8
By the test result of table 8 it is found that using high-alkali salicylate and high-alkali alkyl monosulfide phenates design of mixture
There is better cleansing performance compared with individual high-alkali salicylate or high-alkali alkyl monosulfide phenates.Lubricating oil group of the invention
Closing object has excellent high temperature detergent performance.
Although above, the present invention is described in detail with a general description of the specific embodiments, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention are fallen within the scope of the claimed invention.
Claims (22)
1. a kind of Lubricant composition for gasoline engine, including following components:
The multipurpose additive of structure shown in A > formula (I):
B > boracic antioxidant polyisobutene succinimide ashless dispersant；
C > polyisobutylene succinic acid ester ashless dispersant；
D > at least one alkylsalicylate；
E > at least one alkyl monosulfide phenates；
F > at least one zinc dialkyl dithiophosphate；
G > amine type antioxidant and/or phenolic ester type antioxidant；
H > at least one oil-soluble organic molybdenum friction improver；
The lube base oil of I > surplus.
2. composition described in accordance with the claim 1, which is characterized in that the component A accounts for the lubricant oil composite gross mass
0.05%-2%.
3. composition described in accordance with the claim 1, which is characterized in that the component B is boracic antioxidant polyisobutene fourth two
Acid imide ashless dispersant, preparation method are: aldehyde reaction being added in the mixture of metoxyphenol and polyamines polyene and obtains
Amine condensation, then dehydration occurs with polyolefin-based succinic acid or its acid anhydrides and obtains antioxidant dispersant, later again with fatty alcohol
It is obtained with acid reaction.
4. composition described in accordance with the claim 3, which is characterized in that the polyolefin is the copolymer or equal of C2-C4 alkene
Polymers, number-average molecular weight 850-5000；The metoxyphenol is selected from p methoxy phenol, o-methoxyphenol and first
Oxygroup phenol it is one or more.
5. composition described in accordance with the claim 1, which is characterized in that the component B accounts for the lubricant oil composite gross mass
0.5%-8%.
6. composition described in accordance with the claim 1, which is characterized in that the component C accounts for the lubricant oil composite gross mass
0.5%-8%.
7. composition described in accordance with the claim 1, which is characterized in that it is 200-450mgKOH/g's that the component D, which is base number,
High base number alkylsalicylate.
8. composition described in accordance with the claim 1, which is characterized in that the component D accounts for the lubricant oil composite gross mass
0.1%-10%.
9. composition described in accordance with the claim 1, which is characterized in that it is 200-400mgKOH/g's that the component E, which is base number,
High-alkali sulfurized alkylphenol calcium.
10. composition described in accordance with the claim 1, which is characterized in that the component E accounts for the lubricant oil composite gross mass
0.1%-10%.
11. composition described in accordance with the claim 1, which is characterized in that the alkyl in the zinc dialkyl dithiophosphate is
Alkyl containing 2 to 12 carbon atoms.
12. composition described in accordance with the claim 1, which is characterized in that the component F adding in the lubricant oil composite
Enter amount and is no more than 0.08% in terms of the mass fraction of P elements.
13. composition described in accordance with the claim 1, which is characterized in that the amine type antioxidant is selected from alkylation aniline, alkyl
One of diphenylamines and phenyl-α-naphthylamine are a variety of；The phenolic ester type antioxidant is the hydroxy benzenes that molecular weight is 200-500
Yl carboxylic acid ester.
14. composition described in accordance with the claim 1, which is characterized in that the component G accounts for the lubricant oil composite gross mass
0.1%-6%.
15. composition described in accordance with the claim 1, which is characterized in that the component H be selected from molybdenum dialkyl-dithiophosphate,
Dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulphur networks
Close one of object, molybdenum amine complex and molybdic acid esters oil-soluble organic molybdenum friction improver or a variety of.
16. composition described in accordance with the claim 1, which is characterized in that the component H accounts for the lubricant oil composite gross mass
0.01%-5%.
17. composition described in accordance with the claim 1, which is characterized in that the lube base oil of the component I is selected from API I
One of class, II class, III class, IV class and V class base oil are a variety of.
18. composition described in accordance with the claim 1, which is characterized in that pour-point depressant, viscosity are added in the lubricant oil composite
Index improver and anti-foaming agent it is one or more.
19. composition according to claim 18, which is characterized in that the pour-point depressant includes two that alkyl is C8 to C18
One of alkyl fumarate/vinyl acetate copolymer, polymethacrylates, poly alpha olefin and alkylnaphthalene is a variety of；
The viscosity index improver include the copolymer of polyisobutene, ethylene and propylene and high alpha-olefin, polymethacrylates,
Copolymer, the benzene second of poly- alkylmethacrylate, methacrylate copolymer, unsaturated dicarboxylic and vinyl compound
The copolymer of alkene and acrylate, the copolymer of partially hydrogenated styrene/isoprene, partially hydrogenated styrene/fourth two
The copolymer of alkene, partially hydrogenated isoprene/butadiene copolymer, partially hydrogenated butadiene and isoprene copolymerization
One of the copolymer or a variety of of object, partially hydrogenated isoprene/divinylbenzene；The anti-foaming agent is polysiloxanes
Type.
20. composition described in accordance with the claim 1, which is characterized in that the preparation method of structural compounds shown in the formula (I)
Include:
(a) aniline, sulfur chloride and 4- chloroaniline are reacted, generate intermediate M shown in formula (II),
(b) that the intermediate M and dimercapto -1,3,4- thiadiazoles that step (a) obtains is carried out nucleophilic displacement of fluorine under alkaline condition is anti-
It answers, generates multipurpose additive shown in formula (I).
21. the preparation method of lubricant oil composite described in one of claim 1-19, which is characterized in that by each lube oil additive
It is added in lube base oil, heating is uniformly mixed.
22. purposes of the lubricant oil composite described in one of claim 1-19 in petrol engine.
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| 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 |
| 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 |
| 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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| 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 |
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| 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 |
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