CN102690711A - 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 petrolic lubricating oil composition that is used for.
Background technology
Petrolic high-power making with miniaturized increased the requirement to engine oil resistance of oxidation and piston deposit inhibition ability at mover air-flow minimizing on every side.Along with the harshness day by day of Abgasgesetz, also more and more stricter to the requirement of engine emission, thus the performance of engine oil is also had higher requirement.Performance demands 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 present high-grade petrol engine lubricating oil have been upgraded to SM/GF-4, the SN/GF-5 rank that international lubricant levelization and certification committee (ILSAC) and API (API) are formulated.
Petrol engine oxidation of lubricating oil stability is an extremely important controlling index.Lubricating oil in use receives the influence of factors such as service temperature, metal catalytic effect, products of combustion and gas blowby; Lose anti-oxidant activity gradually, be prone to deterioration by oxidation takes place, 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 get into catalytic converter through 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 receive the restriction of specification standards as lubricating oil component.Requirement for restriction to phosphorus content in the high-grade petrol engine lubricating oil standard is: the massfraction of phosphorus content requires less than 0.1% in the SL oil product, and the massfraction of phosphorus content requires less than 0.08% in SM and the SN rank oil product.
The mover 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%, and the requirement that suppresses the viscosity growth is significantly improved.Also more and more harsher to the requirement of piston detergency simultaneously, the TEOST-MHT TR of simulation piston high temperature deposition thing develops into the 35mg of SM, SN specification from the 45mg that is no more than of SL, and therefore the requirement to antioxidant property significantly improves.
To the strictness restriction of phosphorus content in the high-grade petrol engine lubricating oil, make the simple ZDDP of regulation content that uses satisfy not the requirement of oxidation stability, need to use auxiliary antioxidant in the 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 carbon deposit is too much in detonation and the combustion chamber, keep sparking plug clean.Low in addition ash content can reduce the corrosive oxidation product, reduces the engine parts corrosive wear, prolongs safe operation cycle and parts work-ing life of mover.The peace and quiet ability of good engine oil can prolong 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 low-phosphorous low zinc of low-sulfur that a kind of oil engine that uses low-sulfur fuel is suitable for; 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 satisfy 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 comprises following component at least: 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 earth alkali metal purification agents;
D＞at least a 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;
In lubricating oil composition of the present invention, can also there be other additive, like 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 comprises following component at least: (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, preferred C
4-C
9Alkyl, the position at place are in amino contraposition or ortho position, the preferably tertiary butyl and/or iso-octyl.
Alkylated diphenylamine accounts for the 50%-95% of total mass in the composite antioxidant, is preferably 60%-90%.IRGANOX L-01, IRGANOX L-57 that alkylated diphenylamine can select for use BASF Aktiengesellschaft to produce; The T534 that Beijing Xing Pu company produces; The LZ5150A that the blue refining of Lu Borun additive ltd 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 (the for example T534 of Beijing Xing Pu company production).
(2) structural formula of sulfophenates type oxidation inhibitor is:
R wherein
3, R
4H or C respectively do for oneself
1-C
12Alkyl, preferred C
1-C
9Alkyl is preferably the methyl and/or the tertiary butyl.Wherein m, n are the integer between the 0-10, are preferably 0,1 or 2.
Sulfophenates type oxidation inhibitor accounts for the 5%-50% of total mass in the composite antioxidant, is preferably 8%-30%.Preferred sulfophenates type oxidation inhibitor is 2,2 '-thiobis [3-(3, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate] (for example the Sichuan oxidation inhibitor 1035 produced of industry chemical industry ltd 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, preferred C
1-C
9Alkyl is preferably the methyl and/or the tertiary butyl.Wherein q is the integer between the 0-10, preferred 0,1 or 2.
The thioether phenol type antioxidant accounts for the 0-20% of total mass in the composite antioxidant, is preferably 1%-15%.Preferred thioether phenol type antioxidant is thiobis-(3,5-di-t-butyl-4-hydroxyl benzyl) (for example the methene 4426-S that produces of Changzhou Ling Chi chemical company, the Lowinox TBP-6 that U.S. big lake company produces, the Irganox 1081 that BASF Aktiengesellschaft produces).
In 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, the 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, preferred 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 the polyisobutene succinimide ashless dispersant (PIB) part is 800-4000, preferred 900-3000, preferably 1000-2400.The T161 that this component can select for use 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 ltd produces; LZ6418, LZ6420 that Lubrizol Corporation produces, the Hitec646 that Afton Corporation produces etc.
The number-average molecular weight of polyisobutene part is 500-4000 in the boronation polyisobutene succinimide dispersion agent, and preferred 700-2500 is preferably 1000-2300.The MX3316 that this component can select for use Agip Petroli company to produce, the LZ935 that the Hitec648 that Afton Corporation produces, Hitec7714 and Lubrizol Corporation produce etc.
The mixture of 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, preferred 1.5%-8%, preferably 3%-6%.
C＞one or more salicylate earth alkali metal purification agents; Said earth alkali metal can be magnesium, calcium; Preferably base number is one or more in the salicylate earth alkali metal purification agent of (10-450) mgKOH/g; Preferably base number is that high base number SAP 002 and the base number of (200-450) mgKOH/g are the mixture of the middle base number SAP 002 of (100-＜200) mgKOH/g, and the mass ratio between the two can be arbitrarily, and preferred proportion is between 0.5: 1 to 4: 1.LZL109A, LZL109B, LZL112 that component C can select for use the blue refining of Lu Borun additive ltd to produce, the C9371 that Infineum company produces, C9372, 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 the said 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 for use 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, the Hitec7169 that Afton company produces, Hitec1656 etc.
The add-on of component D in lubricating oil composition is no more than 0.08% with the massfraction of phosphoric and is advisable, preferred 0.05%-0.08%.
In the oil-soluble organic molybdenum friction improvers such as E＞be selected from molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthogenic acid molybdenum, sulfo-xanthogenic acid molybdenum, three nuclear molybdenum sulfide complexs, molybdenum amine complex, molybdates esters one or more; Have in the above-mentioned organic molybdenum comprise enough carbonatomss organic group so that organic molybdenum dissolves in or is scattered in the base oil; General described carbonatoms is between 6-60, between the preferred 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 preferred 0.02%-2% is preferably 0.05%-1.2%.
One or more of F＞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, the preferred saturated or unsaturated alkyl of carbonatoms between 10-50.Said polyol esters of fatty acids comprises monoesters, dibasic acid esters or the polyester of compounds such as glycerin fatty acid ester, fatty acid pentaerythritol ester, ethylene glycol fatty acid, lipid acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, fatty acid triethanolamine ester; Like monoolein, oleic acid double glyceride, Triple Pressed Stearic Acid monopentaerythritol ester, laurostearic acid diethylene glycol dilaurate, oleic acid diethylolamine monoesters, triethanolamine oleate monoesters etc.; Fatty amine comprises hydrocarbyl substituted monoamine or polyamine, oxyalkylated hydrocarbyl substituted monoamine or polyamine and alkyl ether amine etc.; Like 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. for use.
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 MO and ucon oil or their mixture.
Said MO can be from lighting end MO to last running MO 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, korenyl and verivate thereof; The concrete example of polymerization hydrocarbon ils includes but not limited to polybutylenes, Vestolen PP 7052, propylene-isobutylene copolymers, chlorating polybutylenes, gathers (1-hexene), gathers (1-octene), gathers (1-decene); Common trade names comprise PAO4, PAO6, PAO8, PAO10 etc., and the concrete example of korenyl and verivate thereof includes but not limited to like dodecylbenzene, tetradecyl benzene, dinonyl benzene, alkylating phenyl ether and alkylating diphenyl sulfide and verivate, analogue and homologue.
The suitable type of another of ucon oil is an ester class oil; Comprise that ester or the complex ester that condensation reaction generates takes place for dicarboxylicacid (like 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 (like butanols, hexanol, dodecyl alcohol, 2-ethylhexyl alcohol, terepthaloyl moietie, Ucar 35).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, FUMARIC ACID TECH GRADE acid two just own esters, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, DOP, didecyl phthalate, sebacic acid two (larane base) ester, linoleic acid dimer.
The suitable type of another of ucon oil is Fischer-Tropsch method synthetic hydrocarbon oil and lubricant base that this synthetic hydrocarbon oil is obtained through art breading such as hydroisomerizing, hydrogen cracking, dewaxings.
Said base oil preferred viscosities index greater than 80, the saturated hydrocarbon content massfraction greater than 90%, the sulphur content massfraction is less than 0.03% lubricant base.
In lubricating oil composition of the present invention, can also there be other following additive:
Rust-preventive agent can use and be selected from nonionic polyoxyalkylene polyol and ester, polyoxyalkylene phenol negatively charged ion alkylsulphonic acid, aliphatics monoprotic acid 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 improving agent that flows can reduce the minimum temperature that fluid flow maybe can be toppled over.Typical additive be alkyl be C8 to C18 dialkyl group fumarate/vinyl acetate copolymer, gather alkylmethacrylate etc., common trade names have T803, VX385 etc.
The viscosity index improver that is fit to is partially hydrogenated multipolymer and the partially hydrogenated homopolymer of divinyl and isoprene and isoprene/Vinylstyrene of multipolymer, styrene/isoprene, phenylethylene/butadiene and the isoprene/butadiene of multipolymer, the Rohm tech inc/salt of polyisobutene, ethene and propylene and senior Q-alkene, the multipolymer that gathers alkylmethacrylate, methacrylic ester/salt copolymer, unsaturated dicarboxylic acid and vinyl compound, vinylbenzene and propenoate; Common trade names have LZ7070, LZ7065, LZ7067, the LZ7077 of Lubrizol company; The SV260 of Infineum company, SV261, T614 etc.They can constitute the 0.01%-20% of lubricating oil composition total mass.
Kilfoam can be selected the ZGK 5 type for use, like silicone oil or YSR 3286.
Lubricating oil composition of the present invention can adopt the preparation of following method: each additive (comprise in the composite antioxidant one or more) is joined respectively in the base oil or additive is mixed and made into enriched material join that heating mixes in the base oil again; Mixing temperature is between 40 ℃-90 ℃, and mixing time is between 1-6 hour.
The present invention brings into play the synergistic effect between the additive, has improved antioxidant property, the high temperature wear resistance of lubricating oil composition, and good piston detergency and control viscosity growing ability is provided simultaneously.Compsn 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 satisfy the requirement of the high-grade petrol engine lubricating oil of ranks such as SL/GF-3, SM/GF-4, SN/GF-5.
Embodiment
Further describe characteristics of the present invention with instance below.
Composite antioxidant prepares routine 1-5
Oxidation inhibitor T534,1035, methene 4426-S are joined in the mediation container in proportion, and normal pressure heats 60 ℃-90 ℃ down, stirs 1 hour-2 hours, obtains the lurid thick liquid of homogeneous transparent and is component A composite antioxidant of the present invention.Composite antioxidant prepares the proportion of composing (massfraction) of routine 1-5 and sees 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 lubricated oil composition of petrol engine of the present invention and main character.Each component is joined in the mediation container in proportion, and normal pressure heats 45 ℃-80 ℃ down, stirs 1 hour-2 hours, and preparing viscosity grade is the low-phosphorous low ash content petrol engine lubricating oil of SM/GF-4 of 5W-30.In Comparative Examples 1,2,3-1, added single component oxidation inhibitor; Be respectively T534,1035, methene 4426-S; In Comparative Examples 3-2, added by the prepared two-pack composite antioxidant of patent CN100460490C method; Wherein embodiment 1 has prescription composition all identical except that oxidation inhibitor with Comparative Examples 1, embodiment 2 respectively with Comparative Examples 2, and embodiment 3 also has prescriptions all identical except that 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) is separately seen table 2.
Embodiment 1-7 and Comparative Examples 1,2,3-1 and 3-2 pressurization differential scanning calorimetric test (PDSC), high temperature deposition thing qualification test (TEOST-MHT), ASTM D4742 oxide thin layer test (TFOUT) and viscosity growth test (VIT) have been carried out.The PDSC design temperature is 220 ℃, and ASTM D7097 method is adopted in the TEOST-MHT test, and the deposition rod temperature is 285 ℃; Reaction times is 24h; The test conditions that viscosity increases test (VIT) is 160 ℃, and oxygen flow is 5L/h, and (Δ v) is 375% time to calculate viscosity growth velocity of variation.Concrete outcome is seen 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 |
Can find out from table 3; Under 220 ℃ of high temperature, lubricating oil composition has effectively improved the oxidation induction period (PDSC) of oil product, and oxidation induction period has improved 15%～25% than the oxidation induction period of oil product in the corresponding Comparative Examples among the embodiment; 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 superior to Comparative Examples.
The high temperature wear resistance result is as shown in table 4, the high temperature that adopts high frequency reciprocating friction trier (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.Can find out that from table 4 wear scar diameter of the embodiment of the invention is less than Comparative Examples, show fastness to wear preferably.
Table 4
Embodiment 8-13
Adopt the preparation method identical to obtain the low-phosphorous low ash content petrol engine lubricating oil composition of SM/GF-4 that viscosity grade is 5W-40 with front embodiment.Embodiment 8-13 has been carried out the spot distributed test, and its prescription forms and the distributed test result sees table 5.What wherein add among the embodiment 8-11 is the mixture of polyisobutene succinimide and boracic polyisobutene succinimide, and what add among the embodiment 12,13 is the dispersion agent of single component.
Table 5
Spot distributed test method is with in 30% the program VG engine sludge adding test oil; Behind the ultra-sonic dispersion 6min, heat 2h in 200 ℃ of baking ovens, then with 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 high more explanation oil product of dispersion index is good more.
Can know that by table 5 result the design of mixture oil product of employing dispersion agent is compared with independent dispersion agent prescription oil product has better dispersing property.
Embodiment 14-17
Adopt identical preparation method to obtain the low-phosphorous low ash content petrol engine lubricating oil composition of SM/GF-4 that viscosity grade is 5W-30 with front embodiment.Embodiment 14-17 has been carried out the test of coking plate, and its prescription forms and coking plate test-results is seen table 6.What wherein add among the embodiment 14,15 is the mixture of high base number SAP 002 and middle base number SAP 002, and what add respectively among the embodiment 16,17 is the high base number SAP 002 and the middle base number SAP 002 of single component.
Table 6
The equipment that coking plate test is adopted is the 25B-19 type coking plate appearance that Japanese Meitech company produces, and the working conditions of this test simulation base chamber and cylinder liner piston ring oil circulation makes constantly the be heated process of oxidation coking of oil product of testing.Test period is 6h, and oily temperature is 150 ℃, and the plate temperature is 310 ℃.
Can know that by table 6 result the prescription oil product of the employing high base number SAP 002 and the mixture of middle base number SAP 002 is compared with the prescription oil product of independent high base number SAP 002 or middle base number SAP 002 has better cleansing performance.
Embodiment 18
The SL/GF-3 of ILSAC and API specification, SM/GF-4, SN/GF-5 require through 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.Mover moves 100 hours under 125bhp, 3600rpm and 150 ℃ of oil temperature, be that interval interrupt is carried out the oil level inspection with 20 hours.Last in test, as to measure cam lobe and push rod wearing and tearing.
In order to satisfy SL/GF-3 and the requirement of SM/GF-4 specification standards, the waste oil behind the EOT will satisfy the viscosity growth and be no more than 150%, and the scoring of weighted mean piston deposit is not less than 3.5, and average cam lobe and push rod wear and tear and be no more than 60 microns.The requirement of SN/GF-5 specification standards, the waste oil behind the EOT will be satisfied the viscosity growth and be no more than 150%, and the scoring of weighted mean piston deposit is not less than 4.0, and average cam lobe and push rod wear and tear 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 seen table 7.
Table 7
Can know by table 7 result; The III G engine pedestal result of embodiment 3 lubricating oil compositions not only satisfies SL/GF-3, SM/GF-4 specification requirement; Satisfy the SN/GF-5 specification requirement simultaneously; Shown that this lubricating oil composition has excellent high-temperature oxidation resistance, suppresses the ability and the high temperature fastness to wear of high temperature deposition thing significantly.
Claims (20)
1. petrol engine lubricating oil composition comprises following component:
A＞composite antioxidant wherein comprises following component at least: alkylated diphenylamine oxidation inhibitor, and sulfophenates type oxidation inhibitor and non-essential thioether phenol type antioxidant, said composite antioxidant accounts for the 0.1%-10% of lubricating oil composition total mass;
B＞polyisobutene succinimide ashless dispersant and/or boronation polyisobutene succinimide dispersion agent account for the 0.5%-10% of lubricating oil composition total mass;
C＞one or more salicylate earth alkali metal purification agents accounts for the 0.2%-10% of lubricating oil composition total mass;
D＞at least a zinc dialkyl dithiophosphate accounts for the 0.1%-5% of lubricating oil composition total mass;
E＞one or more oil-soluble organic molybdenum friction improvers accounts for the 0.01%-5% of lubricating oil composition total mass;
F＞one or more ashless friction improvers accounts for the 0.02%-5% of lubricating oil composition total mass;
The lubricant base of G＞main amount.
2. according to the described lubricating oil composition of claim 1, it is characterized in that the structural formula of said alkylated diphenylamine oxidation inhibitor is:
R wherein
1, R
2H or C respectively do for oneself
1-C
12Alkyl;
The structural formula of said sulfophenates type oxidation inhibitor is:
R wherein
3, R
4H or C respectively do for oneself
1-C
12Alkyl, m, n are the integer between the 0-10;
The structural formula of said thioether phenol type antioxidant is:
R wherein
5, R
6H or C respectively do for oneself
1-C
12Alkyl, q are the integer between the 0-10.
3. according to the described lubricating oil composition of claim 2, it is characterized in that described R
1, R
2Be C
4-C
9Alkyl, described R
3, R
4Be C
1-C
9Alkyl, described R
5, R
6Be C
1-C
9Alkyl.
4. according to the described lubricating oil composition of one of claim 1-3; It is characterized in that; Said alkylated diphenylamine accounts for the 50%-95% of composite antioxidant total mass; Said sulfophenates type oxidation inhibitor accounts for the 5%-50% of composite antioxidant total mass, and said thioether phenol type antioxidant accounts for the 0-20% of composite antioxidant total mass.
5. according to the described lubricating oil composition of one of claim 1-3; It is characterized in that; Said alkylated diphenylamine accounts for the 60%-90% of composite antioxidant total mass; Said sulfophenates type oxidation inhibitor accounts for the 8%-30% of composite antioxidant total mass, and said thioether phenol type antioxidant accounts for the 1%-15% of composite antioxidant total mass.
6. according to the described lubricating oil composition of one of claim 1-3, it is characterized in that said composite antioxidant accounts for the 0.2%-6% of lubricating oil composition total mass.
7. according to the described lubricating oil composition of claim 1; It is characterized in that; The number-average molecular weight of polyisobutene part is 800-4000 in the said polyisobutene succinimide ashless dispersant, and the number-average molecular weight of polyisobutene part is 500-4000 in the said boronation polyisobutene succinimide dispersion agent.
8. according to the described lubricating oil composition of claim 1, it is characterized in that the mass ratio between said polyisobutene succinimide ashless dispersant and the boronation polyisobutene succinimide dispersion agent is between 1: 1 to 3: 1.
9. according to the described lubricating oil composition of claim 1, it is characterized in that said polyisobutene succinimide ashless dispersant and/or boronation polyisobutene succinimide dispersion agent account for the 1.5%-8% of lubricating oil composition total mass.
10. according to the described lubricating oil composition of claim 1, it is characterized in that said salicylate earth alkali metal purification agent is selected from magnesium salicylate and/or SAP 002.
11. according to the described lubricating oil composition of claim 1; It is characterized in that it is the mixture of the middle base number SAP 002 of 100-＜200mgKOH/g that said salicylate earth alkali metal purification agent is selected from high base number SAP 002 and the base number that base number is 200-450mgKOH/g.
12., it is characterized in that the mass ratio of high base number SAP 002 and middle base number SAP 002 is between 0.5: 1 to 4: 1 according to the described lubricating oil composition of claim 11.
13., it is characterized in that said salicylate earth alkali metal purification agent accounts for the 0.8%-8% of lubricating oil composition total mass according to the described lubricating oil composition of one of claim 1,10-12.
14., it is characterized in that the alkyl of said zinc dialkyl dithiophosphate is the alkyl that contains 2 to 12 carbon atoms according to the described lubricating oil composition of claim 1.
15., it is characterized in that the add-on of said zinc dialkyl dithiophosphate in lubricating oil composition calculated between 0.05%-0.08% with the massfraction of phosphoric according to the described lubricating oil composition of claim 1.
16. according to the described lubricating oil composition of 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, sulfo-xanthogenic acid molybdenum, three nuclear molybdenum sulfide complexs, molybdenum amine complex and the molybdates esters.
17., it is characterized in that described oil-soluble organic molybdenum friction improver accounts for the 0.02%-2% of lubricating oil composition total mass according to the described lubricating oil composition of claim 1.
18., it is characterized in that said ashless friction improver is selected from one or more in aliphatic polyol ester, fatty amine and the aliphatic amide according to the described lubricating oil composition of claim 1.
19., it is characterized in that said ashless friction improver accounts for the 0.05%-2% of lubricating oil composition total mass according to claim 1 or 18 described lubricating oil compositions.
20., it is characterized in that the viscosity index of said lubricant base is greater than 80 according to the described lubricating oil composition of claim 1, the saturated hydrocarbon content massfraction is greater than 90%, the sulphur content massfraction is less than 0.03%.
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