CN102477340A - Lubricant composition for internal combustion engines - Google Patents
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Abstract
A lubricant composition for internal combustion engines is provided, which comprises a lubricant base oil and a sulfonate detergent, wherein the content of the sulfonate detergent is 0.8% to 1.5% (by weight) calculated on the basis of the composition; the sulfonate detergent comprises calcium sulfonate with a ultra-high base number more than 400 mg KOH/g, calcium sulfonate with a high base number of 300 to 350 mg KOH/g and lithium sulfonate with a base number less than 150 mg KOH/g. The lubricant composition has low contents of S, P and sulfuric ash, the additives used have a low cost and are easily available, and the economical efficiency is better. The lubricant composition can not only meet the requirements for normal operation of engines but also meet the requirements for normal operation of automobile exhaust gas recirculation (EGR) systems.
Description
Technical field
The present invention is the internal combustion engine lubrication oil compsns, specifically, is a kind of lubricating oil composition that is used for petrol motor and diesel engine.
Background technology
Along with the increase of China's automobile quantity, motor vehicle exhaust becomes the principal element of contaminate environment, contains the material of severe contamination air such as carbon monoxide, hydro carbons and oxynitride in the tail gas.Therefore it is very necessary vehicle exhaust to be filtered, absorb processing.The method of handling vehicle exhaust at present is through installation tail gas convertor, by the three-way catalyst in the convertor carbon monoxide in the tail gas and hydrocarbon compound is oxidized to carbonic acid gas and water, and oxynitride is reduced to nitrogen and oxygen.
Three-way catalyst is very responsive for the sulphur in the engine oil, phosphorus and ash content.The too high meeting of sulphur content causes mover inner acidic material to increase, and too high sulfated ash can form particle and be adsorbed on the particulate filter, and further assembles the back pressure rising that causes particle trapper, causes exhaust gas recirculation in the mover, the fuel consumption aggravation.The too high meeting of phosphorus content makes the three-way catalyst poisoning and deactivation in the particle trapper.Therefore, the sulphur, phosphorus content and the ash content that reduce in the engine oil are one of developing direction from now on.
At present in the low-sulfur of exploitation, the low-phosphorous and low ash content automobile engine lubricating oil compsn; Mainly contain no sulfur additives such as alkylsalicylate; Because of alkylsalicylate has excellent high temperature detergency, in prescription, can satisfy various performance requriementss with less dosage.
CN1493671A discloses and has been used for the diesel engine oil lubricating oil composition that sulphur content is lower than 50ppm fuel, wherein uses at least a metal detergent, and metal detergent generation ash content total amount is lower than 1.0wt%.Contain at least a alkylsalicylate in the purification agent.MackT-10 tests demonstration, and the result is better for its lead corrosion.
CN1746279A discloses a kind of lubricating oil composition, and wherein sulphur content is less than 0.3wt%, and phosphorus content is less than 0.08wt%, and ash content contains the salicylate fatty acid additive less than 0.8wt% in the prescription.
CN1746280A discloses a kind of low-sulfur, low-phosphorous and low-ash lubricating oil composition; Wherein sulphur content is less than 0.3wt%; Phosphorus content is less than 0.08wt%; Ash content is less than 0.8wt%, and having used the additive of boracic and total basicnumber in the prescription is the alkylsalicylate of 200～400mgKOH/g, and wherein the mass ratio of nitrogen in the ashless dispersant and boron is 3～5: 1.Compsn has the effect that reduces lubricating oil viscosity and raising piston detergency.
The base number of the disclosed lubricating oil composition of CN1754950A is 8～9mgKOH/g, and sulphur content is less than 0.3wt%, and phosphorus content is less than 0.08wt%, and ash content contains the nitrogenous dispersion agent of high alkalinity magnesium salts purification agent and 2.5～4% less than 0.8wt%.
CN1782047A discloses a kind of sulfated ash less than 1% lubricating oil composition; Comprising lubricant base; The alkyl sodium salicylate purification agent, the magnesium salts of 200ppm and low-molecular-weight ashless dispersant at least, said composition can reduce the wearing and tearing of engine piston apical ring among the MackT-10.
CN1782048A discloses a kind of sulfated ash less than 1% lubricating oil composition; Comprising lubricant base; The alkyl sodium salicylate purification agent; At least the high alkalinity magnesium sanitising agent of 200ppm and the molybdenum compound of the oil soluble sulfur-bearing of the molybdenum of 20ppm at least are at least the nitrogenous dispersion agent that lubricating oil provides 0.09% nitrogen, and said composition can reduce the wearing and tearing of engine piston apical ring in oil engine.
USP6569818 discloses a kind of lubricating oil composition, and compsn contains 0.01～0.3% sulphur, 0.01～0.1% phosphorus; 0.1～1% sulfated ash; 0.2～7% metal-salt, wherein the sulphur content of base oil is less than 0.1%, 0.01～0.3% ashless dispersant (in nitrogen atom content); Metal detergent is selected from basic metal or the alkylsalicylate of earth alkali metal that base number is the unvulcanised of 10～350mgKOH/g; Or the basic metal or the alkaline earth salt of the alkylphenol verivate with its (Mannich) alkali structure of Manny of unvulcanised, 0.01～0.1% dialkyl dithio zinc, 0.01～5% be selected from the inhibitor that contains amine and phenolic compound.
The disclosed lubricating oil composition of USP7563752 mainly comprises: 0.005～0.2% basic metal or earth alkali metal alkylsalicylate, and 0.005～0.2% phosphorous anti-wear agent, 0.01～1% amides, total sulfur content is 0.3% in the compsn.
Discover, in prescription, adopt alkylsalicylate and over base sulfosalt, phenates combination,, the high temperature detergency of lubricating oil composition is improved, guarantee to satisfy other requirement simultaneously again with other additive compound.
CN101108995A discloses phosphorus content less than 0.12%; Sulphur content is less than 0.4%; Sulfated ash is less than 1.0% lubricating oil composition; Total basicnumber is about 7～15, comprise main amount base oil, minor amount high alkalinity magnesium purification agent and at least 0.5wt% be selected from no sulphur phenolic antioxidant, contain the ashless oxidation inhibitor of amine oxidation inhibitor and their mixture, high alkalinity magnesium purification agent for the contribution of lubricating oil total basicnumber greater than 60%.Compsn has good oxidization resistance and resistance to abrasion.
CN1183237C discloses a kind of phosphorus content and has been lower than 0.1% large diesel engine lubricating oil composition; Mixture comprising ashless dispersant, neutral calcium phenylate, oil soluble high alkaline calcium sulfonate and overbased magnesium sulphonates; Zinc dialkyl dithiophosphate and ashless inhibitor, said composition have high temperature detergency, resistance to abrasion and anti-oxidative stability preferably.
USP6730638 discloses low ash content, low-phosphorous, doctor negative engine starts oil lubricating oil; Base oil by the sulphur content 300ppm of main amount; 0.5～10% boracic ashless dispersant, 0.05～1.5% the friction improver that contains molybdenum, 0.05～5.0% at least a be selected from sulphonate, alkylphenol or salicylate metal detergent; 0.1～0.75% thiophosphoric acid zinc, the wherein purification agent of the preferred alkaline including earth metal of purification agent.
USP5958848 discloses a kind of low chlorine, low-ash crankcase lubricating oil composition, contains 1.5% chloride ashless dispersant and purification agent system at least, and the purification agent system comprises sulphonate and a kind of phenates that is selected from alkylphenol, sulfenyl phenolate and alkyl salicylate; Described phenates provides the phenolic hydroxyl group of 0.0025g at least; Wherein sulphonate or metal-salt are high basicity salt, comprise the carbonate that is no more than 0.008g, and the gram equivalent ratio of phenolic hydroxyl group salt and sulphonate is 1.4: 1; Total organic metal salt is 0.5: 1 with the ratio of carbonate; Lubricating oil composition cl content 50ppm, sulfated ash 1.2% comprises a kind of oil-soluble magnesium salts at least in the metal detergent.
CN101108994A discloses a kind of lubricating oil composition; Wherein phosphorus content is less than 0.9%, and sulphur content is less than 0.3%, and sulfated ash is less than 1.0%; The ashless dispersant that adopts heat " alkene " reaction to process; High alkaline calcium sulfonate is as purification agent unique in the lubricating oil, and feedstock production lubricating oil compositions such as olefin copolymer vi modifiers, compsn have good oxidization resistance, resistance to abrasion and high temperature detergency.
USP5486300 discloses a kind of lubricating oil composition; Mainly comprise lubricant base, at least a high basicity organic acid alkali metal salt mainly is high basicity sulfonate sodium or sylvite; Its amount is to contain 0.005 normal an alkali metal salt in every 100g oil at least; The metal ratio of wherein high basicity salt is a kind of dispersion agent of 3～40, at least 1.13%, at least a dialkyl dithiophosphate.This patent is not confirmed sulphur content, the concrete numerical value of phosphorus content and sulfated ash.
USP6596672 discloses the low ash content lubricating oil composition that contains multiple high alkaline detergent and inhibitor; Comprise: lubricant base, the overbased calcium of 0.01～0.79% sulfated ash, magnesium, barium, strontium salt, 0.01～0.79% high basicity magnesium salts or sodium salt; 0.1 the shielding phenolic antioxidant of～1.5% thiazolinyl coupling; 0.1～6% at least a arylamine antioxidant, shielding phenol and arylamine content are at least 0.5%, lubricating oil composition sulfated ash 0.1～0.8%.
Prior art shows that the employing alkylsalicylate is a metal detergent, can be on the basis of satisfying each item performance, and the consumption of metal additive in the reduction system satisfies oil product low-sulfur, low-phosphorous and low-ash requirement.But alkylsalicylate prepares the process complicacy, and product cost is high.
With sulfonic acid calcium salt and the composite modulation lubricating oil composition of alkylsalicylate, though combined the advantage of the two, additive becomes turbid easily or precipitates in the storage of oil product and the use, influences its further use.
Be generally will introduce additives such as a spot of high basicity sulfonic acid magnesium, high basicity sodium sulfonate or high basicity potassium sulfonate in the compsn of metal detergent with the calcium sulfonate with high base number; The introducing of high basicity magnesium salts affects to the high temperature detergency of compsn; And the introducing of high basicity sodium sulfonate or potassium can make the resistance to abrasion of lubricating oil composition descend; Simultaneously; Because the limitation of high basicity sodium sulfonate or sylvite antioxidation property needs to introduce more inhibitor, makes the economy of prescription be affected.
Summary of the invention
The purpose of this invention is to provide a kind of internal combustion engine lubrication oil compsns, this lubricating oil composition has lower sulphur, p and s hydrochlorate ash oontent when guaranteeing to have preferably high temperature detergency, oxidation-resistance, resistance to abrasion and base number retentivity.
Internal combustion engine lubrication oil compsns provided by the invention; Comprise lubricant base and sulfonate detergent; Wherein the content of sulfonate detergent is that benchmark is calculated as 0.8～1.5 quality % with the compsn; Described sulfonate detergent comprises the overbased calcium sulphonate of base number greater than 400mgKOH/g, and base number is the calcium sulfonate with high base number of 300～350mgKOH/g and the sulfonic acid lithium that base number is lower than 150mgKOH/g.
The present invention selects three kinds of sulfonate detergents with different base numbers to combine sulfonate detergent; And do not adopt the alkylsalicylate purification agent; Be antifriction and the abrasion resistance that further improves lubricating oil composition; Select for use the friction improver and the above-mentioned sulfonate detergent that contain the ester class composite, with other additive, be modulated into lubricating oil composition again like inhibitor, ashless dispersant, viscosity index improver and pour point depressant and base oil; Said composition has high temperature detergency, anti-oxidative stability, antifriction antiwear property and base number retentivity preferably, and sulphur, phosphorus content are low.The used additive cost of the present invention is lower, be easy to obtain, and has better economic property, and the lubricating oil composition of preparation also can satisfy the works better of automobile-used tail gas circulation (EGR) system when satisfying the mover works better.
Embodiment
Lubricating oil composition of the present invention comprises lubricant base and three kinds of sulfonate detergents with different base numbers; Use these three kinds of sulphonate can satisfy the requirement of high temperature detergency, deacidification and the base number retentivity of lubricating oil composition; Can reduce simultaneously the usage quantity of metal additive; Thereby reduce ash content, sulphur and the phosphorus content of lubricating oil composition.For making compsn reach the use properties requirement of lubricating oil, preferred adding contains the friction improver and other additive of ester class.
Described three kinds of sulfonate detergents with different base numbers are the sulfonic acid lithium of overbased calcium sulphonate, calcium sulfonate with high base number and low alkali value.Preferred 400～the 500mgKOH/g of the base number of described overbased calcium sulphonate, the preferred 300～330mgKOH/g of the base number of calcium sulfonate with high base number, the preferred 50～180mgKOH/g of the base number of sulfonic acid lithium.
The mass ratio of described overbased calcium sulphonate, calcium sulfonate with high base number and sulfonic acid lithium is 1: 2～3: 1～2.
For improving the antifriction anti-friction property of lubricating oil composition; Preferably with sulfonate detergent of the present invention and the friction improver assembly that contains ester group functional group; Therefore; Preferably, the friction improver that contains ester group functional group that also comprises 0.1～0.4 quality %, preferred 0.15～0.3 quality % in the described lubricating oil composition.
The described friction improver that contains ester group functional group is by C
10～C
40Alkyl carboxylic acid or thiazolinyl carboxylic acid and C
2～C
5Alcohol make through esterification, described alcohol can be monohydroxy-alcohol, divalent alcohol or trivalent alcohol.The preferred C of described friction improver
16～C
24Alkyl carboxylic acid glycol ester, butyl stearate, oleic acid diethyl alcohol ester or olein.
Contained sulfonic acid is alkyl benzene sulphonate(ABS) or mahogany acid in the sulfonate detergent, and promptly sulphonate is synthetic by sulfonic acid.On the phenyl ring of described alkyl benzene sulphonate(ABS) or mahogany acid one or more alkyl substituent can be arranged, substituting group is the alkyl of straight or branched, and total carbon number of substituted alkyl on benzene ring is 10～30, preferred 12～28.
For making lubricating oil composition reach the performance index of regulation, also should contain an amount of ashless dispersant, oxidation inhibitor, tackifier and pour point depressant in the compsn.Preferably, also comprise the nitrogenous ashless dispersant of 1.0～3.0 quality %, the oxidation inhibitor of 0.5～1.5 quality %, the viscosity index improver of 5～10 quality % and the pour point depressant of 0.1～1.0 quality % in the compsn.
The preferred polyisobutene succinimide type of described nitrogenous ashless dispersant dispersion agent, its molecular weight preferred 1000～3000.This dispersion agent is through polyisobutene and maleic anhydride hydrocarbonylation, and and the compound that contains amine for example the polyamines polyene amination reaction make.Dispersion agent can be single, double or many Ashless butyl diimide dispersants.Ashless dispersant in lubricating oil effectively the jelly of barrier carbon distribution assemble each other, prevent that it is deposited on the metallic surface.
The preferred zinc dialkyl dithiophosphate of described oxidation inhibitor, its compound method is: earlier by alcohol and P
2S
5Reaction generates dialkyl dithiophosphoric acid, and reaction generates zinc dialkyl dithiophosphate with zinc oxide again, and said alkyl can be C
4Straight chained alkyl, C
8Straight chained alkyl, also can be C
4The isomery alkyl.Select the zinc salt of different alkyl according to the job requirement of lubricating oil composition.The main effect of zinc dialkyl dithiophosphate is the superoxide that forms in the decomposition reaction, suppresses oil oxidation.
Described viscosity index improver preferred number average molecular weight is 50000～100000 ethylene-propylene copolymer.Preferred 40～60 quality % of ethylene content in the ethylene-propylene copolymer, preferred 60～40 quality % of propylene content.Use viscosity index improver to regulate lubricating oil viscosity, can improve the working efficiency of oil engine, fuel economy.
The preferred C of described pour point depressant
8～C
12Alpha-olefin polymers, by C
8～C
12Alpha-olefin polymerization obtain.Pour point depressant can be adsorbed on the wax in the oil product, and the reticulated structure of wax when destroying low temperature guarantees that oil product can flow when low temperature.
The used base oil of the present composition is mainly hydro carbons lubricating oil, can be I class oil, II class oil; III class oil also can be IV class oil, also can be above several kinds mixture; Base oil mainly satisfies the viscosity requirement of lubricating oil composition, and 100 ℃ of viscosity of lubricant base are 3～20mm
2/ s, preferred 9～17mm
2/ s.The selection of base oil also will be considered other performance requriements of compsn, like Nock vaporization losses and viscosity index etc.
Lubricating oil composition provided by the invention is mainly used in the lubricated of petrol motor and diesel engine.
Pass through instance further explain the present invention below, but the present invention is not limited to this.
The method of evaluating performance of the compsn for preparing in the instance is following:
High temperature detergency:
On L-1 template formula coking device, carry out lacquering and coking is firm and hard tests.Coking: plate temperature/oil temperature=320 ℃/100 ℃, 2 hours time, stop/ETAD expected time of arrival and departure=45 seconds/15 seconds.Lacquering: plate temperature/oil temperature=300 ℃/150 ℃, 2 hours time, continuously.
On L-A type detergency tester, make an experiment, to investigate its high temperature detergency.Plate temperature/oil temperature=300 ℃/100 ℃, is stopped/ETAD expected time of arrival and departure=40 seconds/20 seconds at 1 hour time.Oil droplet speed 1.0ml/min.
Anti-oxidative stability:
Measure with the TA5000DSC2910 thermal analyzer, investigate the thermal oxidation stability of oil product with PDSC (Pressure Differential Scanning Calorimeter pressure differential scanning amount heat) method.
Rupture of oil film load and frictional coefficient:
The anti-wear and wear-resistant performance evaluation of GB/T3142-82 lubricant.
Wear scar diameter:
SH/T 0189 lubrication oil antiwear decreases performance measurement method (four-ball tester method).
The base number retentivity:
The 200ml test tube, in the time of oily warm 150 ℃, bubbling air, Ventilation Rate 10ml/min measures base number and changes after 2 hours.
Instance 1～3
Prepare compsn of the present invention.
With 150SN, 500SN, 150BS is modulated into base oil by 14: 5: 1 mass ratio, and 100 ℃ of viscosity are 14.5mm
2/ s, its performance satisfies the requirement of 15W/40 base oil.
Sulfonate detergent, friction improver, inhibitor, ashless dispersant, viscosity index improver and pour point depressant added in the base oil that modulates process lubricating oil composition, the additive title and the index of use are following:
Sulfonate detergent:
Overbased calcium sulphonate: base number 405mgKOH/g, calcium contents 14.5 quality %, sulphur content 1.43 quality %.
Calcium sulfonate with high base number: base number 311mgKOH/g, calcium contents 10.2 quality %, sulphur content 1.8 quality %.
Low alkali value sulfonic acid lithium: base number 135mgKOH/g, lithium content 1.91 quality %, sulphur content 2.07 quality %.
Friction improver:
The dimeracid glycol ester adopts 1014 dimeracid synthetic C of Emery company
18Alkyl carboxylic acid glycol ester, acid number are 26mgKOH/g.
Oleic acid diethyl alcohol ester, acid number are 38mgKOH/g.
Inhibitor:
Zinc dialkyl dithiophosphate (T202), zinc content 8.2 quality %, sulphur content 15.1 quality %, phosphorus content 8.2 quality %, content is 0.9 quality % in compsn.
Ashless dispersant:
Mono butonediimide (T151), nitrogen content 2.1 quality %, base number is 50mgKOH/g, content is 1.5 quality % in compsn.
Viscosity index improver (T613):
Ethylene-propylene copolymer, molecular weight Mn are 85000, ethylene content 51 quality %, and propylene content 49 quality %, ethylene-propylene copolymer content in compsn is 7.0 quality %.
Pour point depressant (T803):
Alpha-olefinic polymer, the Mn molecular weight is 2352, content is 0.3 quality % in compsn.
The used sulfonate detergent of each instance, the content of friction improver in compsn are seen table 1, the sulphur of compsn, phosphorus content, and detergency, oxidation-resistance, antifriction and resistance to abrasion and base number retentivity evaluation result are seen table 2.
Comparative Examples 1～5
Press the method compositions formulated of instance 1; Different is that the purification agent that adds is different with friction improver; The used sulfonate detergent of each Comparative Examples, the content of friction improver in compsn are seen table 1, the sulphur of compsn, phosphorus content, detergency; Oxidation-resistance, antifriction and resistance to abrasion and base number retentivity evaluation result are seen table 2.
The base number of the sulfonate with high base number magnesium that adopts in the Comparative Examples is 402mgKOH/g, Mg content 9.3 quality %, and sulphur content 1.42 quality %,
The base number of sulfonate with high base number sodium is 407mgKOH/g, sodium content 17.0 quality %, sulphur content 1.53 quality %.
Table 1
Table 2
Can know by table 2 data; The lubricating oil composition sulfated ash of the present invention's preparation is less than 0.8 quality %; Phosphorus content is less than 0.08 quality %; Sulphur content has excellent high temperature detergency, anti-oxidative stability, antifriction antiwear property and base number retentivity less than 0.2 quality %, and the instance 1 composition prepared antifriction antiwear property that does not wherein add friction improver is poor slightly.Comparative Examples 1 composition prepared does not adopt the sulfonic acid lithium as purification agent, and high temperature detergency is relatively poor, and Comparative Examples 2 composition prepared do not adopt overbased calcium sulphonate, and the base number retentivity descends very fast.Comparative Examples 3 composition prepared are owing to only adopt overbased calcium sulphonate, and its high temperature detergency is relatively poor.Comparative Examples 4 composition prepared adopt sulfonate with high base number magnesium to replace the sulfonic acid lithium, and its high temperature detergency is relatively poor, and Comparative Examples 5 composition prepared adopt sulfonate with high base number sodium to replace the sulfonic acid lithium, and high temperature detergency and anti-oxidative stability are relatively poor, and sulfated ash is maximum.
Claims (13)
1. internal combustion engine lubrication oil compsns; Comprise lubricant base and sulfonate detergent; Wherein the content of sulfonate detergent is that benchmark is calculated as 0.8～1.5 quality % with the compsn; Described sulfonate detergent comprises the overbased calcium sulphonate of base number greater than 400mgKOH/g, and base number is the calcium sulfonate with high base number of 300～350mgKOH/g and the sulfonic acid lithium that base number is lower than 150mgKOH/g.
2. according to the described compsn of claim 1, the mass ratio that it is characterized in that described overbased calcium sulphonate, calcium sulfonate with high base number and sulfonic acid lithium is 1: 2～3: 1～2.
3. according to the described compsn of claim 1, it is characterized in that also comprising in the described lubricating oil composition friction improver that contains ester group functional group of 0.15～0.3 quality %.
4. according to the described compsn of claim 3, it is characterized in that described friction improver is by C
10～C
40Alkyl carboxylic acid or thiazolinyl carboxylic acid and C
2～C
5Alcohol make through esterification.
5. according to the described compsn of claim 3, it is characterized in that described friction improver is C
16～C
24Alkyl carboxylic acid glycol ester, butyl stearate, oleic acid diethyl alcohol ester or olein.
6. according to the described compsn of claim 1, it is characterized in that sulfonic acid used in the sulfonate detergent is alkyl benzene sulphonate(ABS) or mahogany acid.
7. according to the described compsn of claim 1, the total carbon number that it is characterized in that the substituted alkyl on benzene ring of alkyl benzene sulphonate(ABS) or mahogany acid is 10～40.
8. according to claim 1 or 3 described compsns, it is characterized in that also comprising in the compsn the nitrogenous ashless dispersant of 1.0～3.0 quality %, the oxidation inhibitor of 0.5～1.5 quality %, the viscosity index improver of 5～10 quality % and the pour point depressant of 0.1～1.0 quality %.
9. according to the described compsn of claim 8, it is characterized in that described nitrogenous ashless dispersant is a polyisobutene succinimide type dispersion agent.
10. according to the described compsn of claim 8, it is characterized in that described oxidation inhibitor is zinc dialkyl dithiophosphate.
11., it is characterized in that described viscosity index improver is that number-average molecular weight is 50000～100000 ethylene-propylene copolymer according to the described compsn of claim 8.
12., it is characterized in that described pour point depressant is C according to the described compsn of claim 8
8～C
12Alpha-olefin polymers.
13., it is characterized in that 100 ℃ of viscosity of lubricant base are 3～20mm according to claim 1 or 3 described compsns
2/ s.
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| CN104449964A (en) * | 2014-10-28 | 2015-03-25 | 无锡乐华自动化科技有限公司 | Automotive antirust lubricating oil |
| CN104911001A (en) * | 2015-06-05 | 2015-09-16 | 广西大学 | Lubricant composition for Miller cycle engines |
| CN105524681A (en) * | 2014-10-23 | 2016-04-27 | 中国石油化工股份有限公司 | Gasoline engine oil friction modifier and use thereof |
| CN105722964A (en) * | 2013-11-25 | 2016-06-29 | 出光兴产株式会社 | Lubricating oil composition for spark ignition internal combustion engine |
| CN107001972A (en) * | 2014-12-11 | 2017-08-01 | 国际壳牌研究有限公司 | Lubricant oil composite for explosive motor |
| CN107312593A (en) * | 2017-06-09 | 2017-11-03 | 中国石油化工股份有限公司 | Diesel engine oil compositions of CF 4 and application thereof |
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| CN105722964A (en) * | 2013-11-25 | 2016-06-29 | 出光兴产株式会社 | Lubricating oil composition for spark ignition internal combustion engine |
| CN105524681A (en) * | 2014-10-23 | 2016-04-27 | 中国石油化工股份有限公司 | Gasoline engine oil friction modifier and use thereof |
| CN104449964A (en) * | 2014-10-28 | 2015-03-25 | 无锡乐华自动化科技有限公司 | Automotive antirust lubricating oil |
| CN107001972B (en) * | 2014-12-11 | 2020-03-06 | 国际壳牌研究有限公司 | Lubricating oil composition for internal combustion engine |
| CN107001972A (en) * | 2014-12-11 | 2017-08-01 | 国际壳牌研究有限公司 | Lubricant oil composite for explosive motor |
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| CN114752425A (en) * | 2021-01-11 | 2022-07-15 | 中国石油天然气股份有限公司 | Additive composition |
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