CN102690711B - Lubricant composition for gasoline engine - Google Patents
Lubricant composition for gasoline engine Download PDFInfo
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Abstract
The invention relates to a lubricant composition for a gasoline engine. The lubricant composition contains: by mass, less than or equal to 0.08% of phosphorus and less than or equal to 0.9% of sulfate ash. The lubricant composition comprises A) a composite antioxidant comprising at least ingredients of 1, an alkylated diphenylamine antioxidant, 2, a thiophenolic ester antioxidant and 3, an unessential phenolic thioether antioxidant, B) a polyisobutylene succinimide ashless dispersant and/or a boronized polyisobutylene succinimide dispersant, C) one or more alkaline earth metal salicylate cleaning agents, D) at least one zinc dialkyl dithiophosphate, E) one or more oil-soluble organic molybdenum friction modifiers, F) one or more ashless friction modifiers, and G) a main amount of lubricating base oil. The lubricant composition for a gasoline engine has synergistic effect of the additives, can satisfy antioxidation requirements of a high-grade gasoline engine lubricant, and has excellent piston cleanliness, wear resistance and a viscosity increasing control capacity.
Description
Technical field
The present invention relates to lubricating oil composition, relate in particular to a kind of for petrolic lubricating oil composition.
Background technology
Petrolic high-power and miniaturization make engine around air-flow reduce, increased the requirement that engine oil resistance of oxidation and piston deposit is suppressed to ability.Along with the harshness day by day of Abgasgesetz, also more and more stricter to the requirement of engine discharge, thus the performance of engine oil is also had higher requirement.The requirement of the performances such as that the update of petrol engine lubricating oil also continues to have improved is anti-oxidant to oil product, piston is peace and quiet, greasy filth disperses, resistance to wear, the product specification of current high-grade petrol engine lubricating oil has been upgraded to SM/GF-4, the SN/GF-5 rank that international lubricant level and certification committee (ILSAC) and American Petroleum Institute (API) (API) are formulated.
Petrol engine oxidation of lubricating oil stability is extremely important one and controls index.Lubricating oil in use is subject to the impact of the factors such as service temperature, metal catalytic effect, products of combustion and gas blowby, lose gradually anti-oxidant activity, deterioration by oxidation easily occurs, cause detergency, dispersiveness and the resistance to abrasion etc. of oil product to suffer to destroy fast, viscosity increases, acid product increases, and forms paint film, settling, and engine parts are worked the mischief.
Zinc dialkyl dithiophosphate (ZDDP) is a kind of phosphorous multipurpose additive, has outstanding antioxygen, wear-resistant, Corrosion Protection.Because phosphor-included additive can enter catalytic converter by exhaust gas recirculation or gas blowby process, and accumulate at the reactive metal position, poison catalyzer, thereby reduce the catalyzer effect and shorten its work-ing life, thereby use phosphor-included additive to be subject to the restriction of specification standards as lubricating oil component.Requirement for restriction to phosphorus content in high-grade petrol engine lubricating oil standard is: in the SL oil product, the massfraction of phosphorus content requires the massfraction that is less than phosphorus content in 0.1%, SM and SN rank oil product to require to be less than 0.08%.
The engine evaluation test that the anti-oxidant viscosity of high-grade petrol engine lubricating oil increases was from 64 hours of program III E, develop into program III F 80 hours, 100 of program III G hours up till now, and the viscosity growth requires to be reduced to 275%, 150% from being no more than 375%, the requirement that suppresses the viscosity growth is significantly improved.Simultaneously also more and more harsher to the requirement of piston detergency, the TEOST-MHT test requirements document of simulation piston high temperature deposition thing, from the 45mg that is no more than of SL, develops into the 35mg of SM, SN specification, therefore the requirement of antioxidant property is significantly improved.
To the strict restriction of phosphorus content in high-grade petrol engine lubricating oil, make the ZDDP of simple use regulation content can not meet the requirement of oxidation stability, need to use auxiliary antioxidant in lubricant formula.Seek more efficiently antioxidant additive, be the target that those skilled in the art make great efforts always.
Because the lubricant formula of protosulfate ash content can effectively reduce coking and top land carbon deposit, reduce the wearing and tearing of valve system, prevent that in detonation and combustion chamber, carbon deposit is too much, the maintenance sparking plug is clean.Low ash content can reduce the corrosive oxidation product in addition, reduces the engine parts corrosive wear, extends safe operation cycle and parts work-ing life of engine.The peace and quiet ability of good engine oil can extend filter life, reduces maintenance cost.Therefore low ash content is the developing direction of petrol engine lubricating oil.
CN100460490C has introduced a kind of by the composite antioxidant component of alkylated diphenylamine and ester type shielding phenol, the resistance of oxidation of the raising oil product that it can be by a relatively large margin.The application of this patent not mentioned sulfophenates type oxidation inhibitor and thioether phenol type antioxidant.
US20080076686 has introduced the lubricating oil composition of the applicable low-phosphorous low zinc of low-sulfur of a kind of oil engine that uses low-sulfur fuel, comprise alkaline purification agent and dispersion agent, Hinered phenols antioxidant or alkylated diphenylamine oxidation inhibitor, have stronger high temperature detergency and fastness to wear.The application of this patent not mentioned sulfophenates type oxidation inhibitor and thioether phenol type antioxidant.
Summary of the invention
The invention provides a kind of petrol engine lubricating oil composition, said composition has excellent antioxidant property, high temperature detergent performance, wear resistance, can meet the performance requriements of SL/GF-3, SM/GF-4, the high-grade petrol engine lubricating oil of SN/GF-5 rank.
Petrol engine lubricating oil composition provided by the invention comprises following component:
A>composite antioxidant at least comprises following component: alkylated diphenylamine oxidation inhibitor, sulfophenates type oxidation inhibitor, non-essential thioether phenol type antioxidant;
B>polyisobutene succinimide ashless dispersant and/or boronation polyisobutene succinimide dispersion agent;
C>one or more salicylate alkaline-earth metal purification agents;
D>at least one zinc dialkyl dithiophosphate;
E>one or more oil-soluble organic molybdenum friction improvers;
F>one or more ashless friction improvers;
The lubricant base of G>main amount;
Can also there is other additive in lubricating oil composition of the present invention, as rust-preventive agent, pour point depressant, viscosity index improver (VM), kilfoam etc.
Specifically, petrol engine lubricating oil composition of the present invention comprises following component:
A>composite antioxidant at least comprises following component: (1) alkylated diphenylamine oxidation inhibitor; (2) sulfophenates type oxidation inhibitor; (3) non-essential thioether phenol type antioxidant.
(1) the alkylated diphenylamine structural formula is:
R wherein
1, R
2h or C respectively do for oneself
1-C
12alkyl, preferably C
4-C
9alkyl, the position at place is in amino contraposition or ortho position, preferably the tertiary butyl and/or iso-octyl.
Alkylated diphenylamine accounts for the 50%-95% of total mass in composite antioxidant, is preferably 60%-90%.IRGANOX L-01, IRGANOX L-57 that alkylated diphenylamine can select BASF Aktiengesellschaft to produce, the T534 that Beijing Xing Pu company produces, the LZ5150A that the blue refining of Lu Borun additive company limited produces, VANLUBE NA, VANLUBE 961, dioctyl diphenylamine VANLUBE 81 that U.S. Vanderbilt company produces, it is right that TUV chemical company produces, to ' di-iso-octyldiphenylamine RC7001.
Preferred alkylated diphenylamine oxidation inhibitor is the tertiary butyl/di-iso-octyldiphenylamine (T534 that for example Xing Pu company in Beijing produces).
(2) structural formula of sulfophenates type oxidation inhibitor is:
R wherein
3, R
4h or C respectively do for oneself
1-C
12alkyl, preferably C
1-C
9alkyl, be preferably methyl and/or the tertiary butyl.Wherein m, n are the integer between 0-10, are preferably 0,1 or 2.
Sulfophenates type oxidation inhibitor accounts for the 5%-50% of total mass in composite antioxidant, is preferably 8%-30%.Preferred sulfophenates type oxidation inhibitor is 2,2 '-[3-(3 for thiobis, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate] (for example the Sichuan oxidation inhibitor 1035 that industry chemical industry company limited produces forever, the IRGANOX L115 that BASF Aktiengesellschaft produces).
(3) structural formula of thioether phenol type antioxidant is:
R wherein
5, R
6h or C respectively do for oneself
1-C
12alkyl, preferably C
1-C
9alkyl, be preferably methyl and/or the tertiary butyl.Wherein q is the integer between 0-10, preferably 0,1 or 2.
The thioether phenol type antioxidant accounts for the 0-20% of total mass in composite antioxidant, is preferably 1%-15%.Preferred thioether phenol type antioxidant is thiobis-(3,5-di-t-butyl-4-hydroxyl benzyl) (the methene 4426-S that for example Ling Chi chemical company in Changzhou produces, the Lowinox TBP-6 that U.S. big lake company produces, the Irganox 1081 that BASF Aktiengesellschaft produces).
In a preferred embodiment, composite antioxidant of the present invention is composed of the following components: (1) tertiary butyl/di-iso-octyldiphenylamine; (2) 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate]; (3) thiobis-(3,5-di-t-butyl-4-hydroxyl benzyl).
Component A composite antioxidant accounts for the 0.1%-10% of lubricating oil composition total mass of the present invention, preferably 0.2%-6%, preferably 0.3%-5%.
B>be selected from polyisobutene succinimide ashless dispersant and/or boronation polyisobutene succinimide dispersion agent.
The number-average molecular weight of polyisobutene in polyisobutene succinimide ashless dispersant (PIB) part is 800-4000, preferably 900-3000, preferably 1000-2400.The T161 that this component can select Suzhou specialty oil products factory to produce, T161A, T161B that Jinzhou Petrochemical Company additive factory produces, the LZL157 that the blue refining of Lu Borun additive company limited produces, LZ6418, LZ6420 that Lubrizol Corporation produces, the Hitec646 that Afton Corporation produces etc.
In boronation polyisobutene succinimide dispersion agent, the number-average molecular weight of polyisobutene part is 500-4000, and preferably 700-2500, be preferably 1000-2300.The MX3316 that this component can select Agip Petroli company to produce, the LZ935 that Hitec648, the Hitec7714 that Afton Corporation produces and Lubrizol Corporation produce etc.
The mixture of the preferred polyisobutene succinimide ashless dispersant of B component and boronation polyisobutene succinimide dispersion agent, the mass ratio between the two can be that preferred proportion is between 1: 1 to 3: 1 arbitrarily.
B component accounts for the 0.5%-10% of lubricating oil composition total mass of the present invention, preferably 1.5%-8%, preferably 3%-6%.
C>one or more salicylate alkaline-earth metal purification agents, described alkaline-earth metal can be magnesium, calcium, one or more in the salicylate alkaline-earth metal purification agent that preferably base number is (10-450) mgKOH/g, the mixture of the middle base number calcium salicylate that the high base number calcium salicylate that preferably base number is (200-450) mgKOH/g and base number are (100-<200) mgKOH/g, mass ratio between the two can be that preferred proportion is between 0.5: 1 to 4: 1 arbitrarily.LZL109A, LZL109B, LZL112 that component C can select the blue refining of Lu Borun additive company limited to produce, C9371, the C9372 that Infineum company produces, C9375, C9006, C9012 etc.
Component C accounts for 0.2%-10%, preferred 0.8%-8%, the preferably 1.2%-6% of lubricating oil composition total mass.
One or more of D>be selected from zinc dialkyl dithiophosphate, alkyl in described zinc dialkyl dithiophosphate is the alkyl that contains 2 to 12 carbon atoms, the alkyl that preferably contains 2 to 8 carbon atoms can be ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, 2-ethylhexyl, cyclohexyl, methylcyclopentyl.T202, T203 that zinc dialkyl dithiophosphate can select WUXI SOUTH PETROLEUM ADDITIVE Co., LTD. to produce, primary alkyl T202, primary alkyl T203, brothers alkyl T204, secondary alkyl T205 that Jinzhou Petrochemical Company additive factory produces, LZ1371, LZ1375 that Lubrizol company produces, C9417, C9425, C9426 that Infineum company produces, Hitec7169, Hitec1656 etc. that Afton company produces.
The add-on of component D in lubricating oil composition is no more than 0.08% with the massfraction of phosphoric and is advisable, preferably 0.05%-0.08%.
One or more in the oil-soluble organic molybdenum friction improvers such as molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthogenic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex, molybdates esters of E>be selected from, in above-mentioned organic molybdenum, have comprise enough carbonatomss organic group so that organic molybdenum dissolves in or is scattered in base oil, general described carbonatoms is between 6-60, preferably between 10-50.The oil-soluble organic molybdenum friction improver can be selected from the MolyVan L, 822,855 that U.S. Vanderbilt company produces, Japanese rising sun electrification company produce 515,525,710 etc.
Component E accounts for the 0.01%-5% of lubricating oil composition total mass, and preferably 0.02%-2%, be preferably 0.05%-1.2%.
One or more of F>the be selected from ashless friction improvers such as polyol esters of fatty acids, fatty amine, aliphatic amide, wherein aliphatic alkyl is the saturated or unsaturated alkyl of carbonatoms between 6-60, preferably saturated the or unsaturated alkyl of carbonatoms between 10-50.Described polyol esters of fatty acids comprises glycerin fatty acid ester, fatty acid pentaerythritol ester, ethylene glycol fatty acid, the lipid acid succinate, fatty acid ethanolamide amine ester, the fatty acid diethanolamine ester, the monoesters of the compounds such as fatty acid triethanolamine ester, dibasic acid esters or polyester, as monoolein, the oleic acid double glyceride, stearic acid monopentaerythritol ester, the laurostearic acid diethylene glycol dilaurate, oleic acid diethanolamine monoesters, triethanolamine oleate monoesters etc., fatty amine comprises that alkyl replaces monoamine or polyamine, oxyalkylated alkyl replaces monoamine or polyamine and alkyl ether amine etc., as the tallow amine of ethoxylation and the butter aliphatic ether amine of ethoxylation, the example of aliphatic amide comprises amine hydroxybenzene, coconut oleoyl amine etc.Component F can select the F10 of BASF Aktiengesellschaft, F20 etc.
Component F accounts for the 0.02%-5% of lubricating oil composition total mass, and preferred amounts is 0.05%-2%, is preferably 0.1%-1%;
The lubricant base of G>main amount, can be selected from mineral oil and ucon oil or their mixture.
Described mineral oil can be from lighting end mineral oil to last running mineral oil on viscosity, comprise Witco 70 and hydrorefined, that solvent treatment is crossed alkane, cycloalkanes and mixing alkane-cycloalkanes type mineral lubricating oils, usually be divided into I, II, III class base oil, common trade names comprise I class 150SN, 600SN, II class 100N, 150N etc.
Ucon oil comprises polymerization hydrocarbon ils, alkyl benzene and its derivative, the concrete example of polymerization hydrocarbon ils includes but not limited to the polybutene of polybutene, polypropylene, propylene-isobutylene copolymers, chlorination, poly-(1-hexene), poly-(1-octene), poly-(1-decene), common trade names comprise PAO4, PAO6, PAO8, PAO10 etc., and the concrete example of alkyl benzene and its derivative includes but not limited to as dodecylbenzene, Tetradecylbenzene, dinonyl benzene, alkylating phenyl ether and alkylating diphenyl sulfide and derivative, analogue and homologue.
The applicable type of another of ucon oil is ester class oil, comprise that ester or the complex ester that condensation reaction generates occurs for dicarboxylic acid (as phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, FUMARIC ACID TECH GRADE, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid) and various alcohol (as butanols, hexanol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, propylene glycol).The object lesson of these esters includes but not limited to the 2-ethylhexyl diester of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, the just own ester of FUMARIC ACID TECH GRADE acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, sebacic acid two (larane base) ester, linoleic acid dimer.
The applicable type of another of ucon oil is Fischer-Tropsch method synthetic hydrocarbon oil and lubricant base that this synthetic hydrocarbon oil is obtained by art breading such as hydroisomerizing, hydrocracking, dewaxings.
The lubricant base that described base oil preferred viscosities index is greater than 80, the saturated hydrocarbon content massfraction is greater than 90%, the sulphur content massfraction is less than 0.03%.
Can also there is other following additive in lubricating oil composition of the present invention:
Rust-preventive agent can be used and be selected from nonionic polyoxyalkylene polyol and ester, polyoxyalkylene phenol negatively charged ion alkylsulphonic acid, Aliphatic monoacid or polyprotonic acid etc., and common example comprises dodecenylsuccinic acid, sorbitan list olein, sorbitan trioleate etc.
Pour point depressant or be called the lubricating oil flow improving agent, can reduce the minimum temperature that fluid flows and maybe can topple over.Typical additive is the alkyl dialkyl group fumarate/vinyl acetate copolymer that is C8 to C18, poly-alkylmethacrylate etc., and common trade names have T803, VX385 etc.
Applicable viscosity index improver is polyisobutene, the multipolymer of ethene and propylene and senior Q-alkene, polymethacrylate/salt, poly-alkylmethacrylate, methacrylic ester/salt copolymer, the multipolymer of unsaturated dicarboxylic acid and vinyl compound, the multipolymer of vinylbenzene and acrylate, styrene/isoprene, phenylethylene/butadiene, partially hydrogenated multipolymer with isoprene/butadiene, and the partially hydrogenated homopolymer of divinyl and isoprene and isoprene/Vinylstyrene, common trade names have the LZ7070 of Lubrizol company, LZ7065, LZ7067, LZ7077, the SV260 of Infineum company, SV261, T614 etc.They can form the 0.01%-20% of lubricating oil composition total mass.
Kilfoam can be selected polysiloxane type, as silicone oil or polydimethylsiloxane.
Lubricating oil composition of the present invention can adopt following methods preparation: each additive (comprise in composite antioxidant one or more) is joined respectively in base oil or additive is mixed and made into to enriched material and join heating in base oil again and mix, mixing temperature is between 40 ℃-90 ℃, and mixing time is between 1-6 hour.
The present invention brings into play the synergistic effect between additive, has improved antioxidant property, the high temperature wear resistance of lubricating oil composition, good piston detergency is provided simultaneously and has controlled the viscosity growing ability.Composition of the present invention has massfraction and is no more than 0.08% phosphorus content and massfraction and is no more than 0.9% sulfate ash content, can meet the requirement of the high-grade petrol engine lubricating oil of the ranks such as SL/GF-3, SM/GF-4, SN/GF-5.
Embodiment
Below with example, further describe characteristics of the present invention.
Composite antioxidant preparation example 1-5
Oxidation inhibitor T534,1035, methene 4426-S are joined in the mediation container in proportion, and under normal pressure, heating is 60 ℃-90 ℃, stirs 1 hour-2 hours, obtains the lurid thick liquid of homogeneous transparent and is component A composite antioxidant of the present invention.The proportion of composing (massfraction) of composite antioxidant preparation example 1-5 is in Table 1.
Table 1
| Sequence number | Oxidation inhibitor T534 | Oxidation inhibitor 1035 | Oxidation inhibitor methene 4426-S |
| Composite antioxidant preparation example 1 | 90％ | 10％ | |
| Composite antioxidant preparation example 2 | 80％ | 20％ | |
| Composite antioxidant preparation example 3 | 70％ | 30％ | |
| Composite antioxidant preparation example 4 | 70％ | 25％ | 5％ |
| Composite antioxidant preparation example 5 | 70％ | 20％ | 10％ |
Embodiment 1-7 and Comparative Examples 1,2,3-1,3-2
Embodiment 1-7 is the lubricated oil composition of petrol engine of the present invention and main character.Each component is joined in proportion and is in harmonious proportion in container, and under normal pressure, heating is 45 ℃-80 ℃, stirs 1 hour-2 hours, the low-phosphorous low ash content petrol engine lubricating oil of SM/GF-4 that to prepare viscosity grade be 5W-30.Added single component oxidation inhibitor in Comparative Examples 1,2,3-1, be respectively T534,1035, methene 4426-S, added the two-pack composite antioxidant prepared by patent CN100460490C method in Comparative Examples 3-2, wherein embodiment 1 has respectively whole identical formulas compositions except oxidation inhibitor with Comparative Examples 1, embodiment 2 with Comparative Examples 2, and embodiment 3 also has whole identical formulas except oxidation inhibitor with Comparative Examples 3-1,3-2 and forms.Embodiment 1-7 and Comparative Examples 1,2,3-1,3-2 proportion of composing (massfraction) separately is in Table 2.
Embodiment 1-7 and Comparative Examples 1,2,3-1 and 3-2 have been carried out to pressurization differential scanning calorimetry (PDSC), high temperature deposition thing qualification test (TEOST-MHT), the test of ASTM D4742 oxide thin layer (TFOUT) and viscosity growth test (VIT).The PDSC design temperature is 220 ℃, the TEOST-MHT test adopts ASTM D7097 method, the deposition rod temperature is 285 ℃, reaction times is 24h, the test conditions of viscosity growth test (VIT) is 160 ℃, oxygen flow is 5L/h, calculates viscosity and increases the time that velocity of variation (Δ v) is 375%.Concrete outcome is in Table 3.
Table 3
| Oil sample | PDSC/min | TEOST-MHT/mg | TFOUT/min | VIT-Δv(375％)/h |
| Embodiment 1 | 28.2 | 22.7 | 138 | 95 |
| Embodiment 2 | 31.4 | 23.2 | 146 | 94 |
| Embodiment 3 | 34.9 | 19.7 | 158 | 93 |
| Embodiment 4 | 35.3 | 21.7 | 158 | 92 |
| Embodiment 5 | - | - | 151 | - |
| Embodiment 6 | - | - | 167 | - |
| Embodiment 7 | - | - | 146 | - |
| Comparative Examples 1 | 24.4 | 27.6 | 129 | 84 |
| Comparative Examples 2 | 26.7 | 26.8 | 131 | 86 |
| Comparative Examples 3-1 | 28.5 | 26.0 | 134 | 87 |
| Comparative Examples 3-2 | 29.8 | 25.4 | 143 | 92 |
As can be seen from Table 3, under 220 ℃ of high temperature, lubricating oil composition has effectively improved the oxidation induction period (PDSC) of oil product, in embodiment, oxidation induction period has improved 15%～25% than the oxidation induction period of oil product in corresponding Comparative Examples, aspect the sedimental growing amount of control (TEOST), the settling growing amount of lubricating oil composition has reduced by 15%, and, aspect oxide thin layer (TFOUT) and control viscosity growth (VIT), slightly is better than Comparative Examples.
The high temperature wear resistance result is as shown in table 4, the high temperature that adopts high-frequency reciprocating frictional testing machines (HFRR) the to carry out oil product test of resistance to wearing, and test conditions is 150 ℃ of load 1000g, frequency 20Hz, stroke 1mm, temperature.As can be seen from Table 4, the wear scar diameter of the embodiment of the present invention is less than Comparative Examples, shows fastness to wear preferably.
Table 4
Embodiment 8-13
Adopt the preparation method identical with front embodiment to obtain the low-phosphorous low ash content petrol engine lubricating oil composition of SM/GF-4 that viscosity grade is 5W-40.Embodiment 8-13 has been carried out to the spot distributed test, and its formula forms and distributed test the results are shown in Table 5.What wherein in embodiment 8-11, add is the mixture of polyisobutene succinimide and boracic polyisobutene succinimide, and what in embodiment 12,13, add is the dispersion agent of single component.
Table 5
Spot distributed test method is that 30% program VG engine sludge is added in test oil, after ultrasonic dispersion 6min, in 200 ℃ of baking ovens, heat 2h, then by oil droplet on filter paper, measure oil mark circle of dispersion diameter and greasy filth circle of dispersion diameter ratio after 24 hours, be dispersion index.The dispersiveness of the higher explanation oil product of dispersion index is better.
As seen from the results in Table 5, adopt the design of mixture oil product of dispersion agent to compare and there is better dispersing property with independent dispersion agent formula oil product.
Embodiment 14-17
Adopt preparation method identical with front embodiment to obtain the low-phosphorous low ash content petrol engine lubricating oil composition of SM/GF-4 that viscosity grade is 5W-30.Embodiment 14-17 has been carried out to the test of coking plate, and its formula composition and coking plate test-results are in Table 6.What wherein in embodiment 14,15, add is the mixture of high base number calcium salicylate and middle base number calcium salicylate, and what in embodiment 16,17, add respectively is high base number calcium salicylate and the middle base number calcium salicylate of single component.
Table 6
The equipment that coking plate test adopts is the 25B-19 type coking plate instrument that Japanese Meitech company produces, and the working conditions of this test simulation base chamber and cylinder liner piston ring lubrication oil circulation makes to test constantly the be heated process of oxidation coking of oil product.Test period is 6h, and oil temperature is 150 ℃, and the plate temperature is 310 ℃.
As seen from the results in Table 6, the formula oil product that adopts high base number calcium salicylate and the mixture of middle base number calcium salicylate is compared and is had better cleansing performance with the formula oil product of independent high base number calcium salicylate or middle base number calcium salicylate.
Embodiment 18
The SL/GF-3 of ILSAC and API specification, SM/GF-4, SN/GF-5 require by program III G bench testing, and purpose is high temperature oxidation thickening, high temperature piston deposit and the high temperature cam follower polishing machine of test engine lubricating oil.This testing of engine adopts 1996 General Motors 3800ml series II, water-cooling type 4 circulation V-6 petrol engines as testing apparatus.Program IIIG test engine is the overhead-valve design, uses white gasoline.Engine operation 100 hours under 125bhp, 3600rpm and 150 ℃ of oil temperatures, take and carry out the oil level inspection as interval interrupt in 20 hours.Last in test, as to measure cam lobe and push rod wearing and tearing.
In order to meet SL/GF-3 and the requirement of SM/GF-4 specification standards, the waste oil after test finishes will meet viscosity and increase and be no more than 150%, and the scoring of weighted mean piston deposit is not less than 3.5, average cam lobe and push rod wearing and tearing and be no more than 60 microns.The requirement of SN/GF-5 specification standards, the waste oil after test finishes will meet viscosity and increase and be no more than 150%, and the scoring of weighted mean piston deposit is not less than 4.0, average cam lobe and push rod wearing and tearing and be no more than 60 microns.The test-results of the III G engine pedestal that the 5W-30SM/GF-4 petrol engine lubricating oil that adopts embodiment 3 to allocate carries out is in Table 7.
Table 7
As seen from the results in Table 7, the III G engine pedestal result of embodiment 3 lubricating oil compositions not only meets SL/GF-3, SM/GF-4 specification requirement, meet the SN/GF-5 specification requirement simultaneously, shown that this lubricating oil composition has excellent high-temperature oxidation resistance, suppressed significantly ability and the high temperature fastness to wear of high temperature deposition thing.
Claims (8)
1. a petrol engine lubricating oil composition comprises following component:
A > composite antioxidant, account for the 0.2%-6% of lubricating oil composition total mass, at least comprise following component: (1) alkylated diphenylamine oxidation inhibitor; (2) sulfophenates type oxidation inhibitor; (3) thioether phenol type antioxidant; Said alkylated diphenylamine is the tertiary butyl/di-iso-octyldiphenylamine, accounts for the 60-90% of composite antioxidant total mass;
Said sulfophenates type oxidation inhibitor is 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate], account for the 8-30% of composite antioxidant total mass;
Said thioether phenol type antioxidant is thiobis-(3,5-di-t-butyl-4-hydroxyl benzyl), accounts for the 1-15% of composite antioxidant total mass;
B > polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersion agent, account for the 1.5%-8% of lubricating oil composition total mass, the mass ratio between polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersion agent is between 1:1 to 3:1;
C > mixture of high base number calcium salicylate and middle base number calcium salicylate, account for the 0.2%-8% of lubricating oil composition total mass, the mass ratio of high base number calcium salicylate and middle base number calcium salicylate is between 0.5:1 to 4:1, the base number of high base number calcium salicylate is 200-450mgKOH/g, and the base number of middle base number calcium salicylate is 100-<200mgKOH/g;
D > at least one zinc dialkyl dithiophosphate, account for the 0.1%-5% of lubricating oil composition total mass;
E > one or more oil-soluble organic molybdenum friction improvers, account for the 0.01%-5% of lubricating oil composition total mass;
F > one or more ashless friction improvers, described ashless friction improver is selected from one or more in aliphatic polyol ester, fatty amine and aliphatic amide, accounts for the 0.02%-5% of lubricating oil composition total mass;
G > the main lubricant base of measuring.
2. according to lubricating oil composition claimed in claim 1, it is characterized in that, in described polyisobutene succinimide ashless dispersant, the number-average molecular weight of polyisobutene part is 800-4000, and in described boronation polyisobutene succinimide dispersion agent, the number-average molecular weight of polyisobutene part is 500-4000.
3. according to lubricating oil composition claimed in claim 1, it is characterized in that, the alkyl of described zinc dialkyl dithiophosphate is the alkyl that contains 2 to 12 carbon atoms.
4. according to lubricating oil composition claimed in claim 1, it is characterized in that, the add-on of described zinc dialkyl dithiophosphate in lubricating oil composition calculated between 0.05%-0.08% with the massfraction of phosphoric.
5. according to lubricating oil composition claimed in claim 1, it is characterized in that, described oil-soluble organic molybdenum friction improver is selected from one or more in molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthogenic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex and molybdates esters.
6. according to lubricating oil composition claimed in claim 1, it is characterized in that, described oil-soluble organic molybdenum friction improver accounts for the 0.02%-2% of lubricating oil composition total mass.
7. according to lubricating oil composition claimed in claim 1, it is characterized in that, described ashless friction improver accounts for the 0.05%-2% of lubricating oil composition total mass.
8. according to lubricating oil composition claimed in claim 1, it is characterized in that, the viscosity index of described lubricant base is greater than 80, and the saturated hydrocarbon content massfraction is greater than 90%, and the sulphur content massfraction is less than 0.03%.
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| CN 201110071817 CN102690711B (en) | 2011-03-24 | 2011-03-24 | Lubricant composition for gasoline engine |
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| CN 201110071817 CN102690711B (en) | 2011-03-24 | 2011-03-24 | Lubricant composition for gasoline engine |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822839A (en) * | 1987-11-25 | 1989-04-18 | Hercules Incorporated | Polyunsaturated hydrocarbon polymer-compatible antioxidant compositions |
| CN1611589A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Lubricating oil composition |
| CN101851549A (en) * | 2010-07-05 | 2010-10-06 | 中国人民解放军后勤工程学院 | Engine oil of long-service life gasoline engine |
-
2011
- 2011-03-24 CN CN 201110071817 patent/CN102690711B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822839A (en) * | 1987-11-25 | 1989-04-18 | Hercules Incorporated | Polyunsaturated hydrocarbon polymer-compatible antioxidant compositions |
| CN1611589A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Lubricating oil composition |
| CN101851549A (en) * | 2010-07-05 | 2010-10-06 | 中国人民解放军后勤工程学院 | Engine oil of long-service life gasoline engine |
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