CN106318559B - A kind of gas engine lubricant oil composite and preparation method thereof - Google Patents
A kind of gas engine lubricant oil composite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of gas engine lubricant oil composites, on the basis of the weight of lubricant oil composite, lubricant oil composite contains following components: the lube base oil of 75-95 weight %, the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.02-8 weight %, the polyisobutylene succinic acid ester dispersing agent of 0.5-10 weight %, the mixture of the high base number naphthenate of 0.2-10 weight % and middle base number naphthenate, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.15 weight % and the Ashless friction modifiers of 0.01-5 weight %, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I).The present invention also provides the preparation methods of gas engine lubricant oil composite.Gas engine lubricant oil composite of the invention has excellent wear-resistant and antioxygenic property, can inhibit the generation of high temperature deposition object, can be widely applied to gas engine field.
Description
Technical field
The present invention relates to lubricating oil fields, and in particular, to a kind of gas engine lubricating oil containing special additive
Composition and preparation method thereof.
Background technique
Low emission, low fuel expense and the reasonable fuel source configuration feature of compressed natural gas, as automobile engine
Fuel is paid more and more attention in the world, has also pushed the development of automobile with compressed natural gas, and technology development also reaches its maturity.By
The compressed natural gas repacked into using gasoline car/gasoline dual-purpose fuel vehicle is well received in big and medium-sized cities, development prospect
Also very bright.However, the original gasoline engine oil of this kind of vehicle occurs, carbon deposit is more, greasy filth is big, the drain period shortens etc. asks
Topic；Easily there is the problems such as premature wear and shortening of overhaul mileage in engine.Gasoline engine oil is in automobile compressed natural gas/gasoline dual-purpose
Using producing some problems on engine fuel.From service performance, gasoline engine oil does not meet the combustion of CNG/ gasoline dual-purpose yet
Expect requirement of the engine to lubricating oil.Compressed natural gas/gasoline dual purpose fuel engine use natural gas when, chamber temperature compared with
High, exhaust emissions temperature height requires the high-temperature oxidation resistance of engine oil under this operating condition higher.Simultaneously because containing metal
The additive of ash content easily in the hard deposit of engine components Surface Creation, causes piston and steel bushing component of engine etc. to rub
Being seriously worn of portion, piston region carbon deposit increases, burns phenomena such as valve, therefore gas engine oil wants high temperature wear resistance
It asks with the power parameter that gas engine is continuously improved and is continuously improved.Therefore developing novel has excellent high temperature antioxygen anti-
The gas engine lubricant oil composite for grinding performance becomes the striving direction of those skilled in the art.
It mainly includes phenols and aminated compounds that the lube oil additive of antioxidation can be effectively played by, which being currently known,.
Phenolic compound contains one or more and is obstructed phenol functional group, and aminated compounds then contains one or more nitrogen-atoms, these are special
Different functional group can capture the free radical compounds of oxidation process generation, so that oxidation process be prevented to continue to occur.Due to
The operating condition of Current mechanical equipment tends to strongly, often accelerated oxidation rate, shortens the service life of lubricating oil, therefore right
More stringent requirements are proposed for the efficiency and economy of antioxidant.
United States Patent (USP) US4824601A reports diphenylamine and diisobutylene in the alkaline-earth metal catalyst of acid activation
The lower alkylated amines mixture formed of (earth catalyst) effect, its anti-oxidant energy in lubricating oil and other functional fluids
Power is excellent in.
United States Patent (USP) US2005230664A1 reports a kind of synthesis of the antioxidant acridan of following general formula
Method, it is to be condensed preparation under acidic catalyst effect using alkylated diphenylamine and aldehydes or ketones.
Using the tert-butyl phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine condensation preparationization occurs for patent CN1191340C
Object is closed, which has the stronger ability for capturing free radical and peroxynitrite decomposition compound, can provide to oil oxidation stability
More effectively protection, may also function as wear-resistant effect.
Patent US4225450 reports one kind and reacts preparation with Diethyldithiocarbamate by the tert-butyl phenols that is obstructed
Polysulfide phenolic antioxidant, have preferable antioxidation and wear-resistant effect.
Summary of the invention
The purpose of the invention is to meet to the anti-oxidant, wear-resistant of gas engine lubricant oil composite and inhibit high temperature
The high request for the ability that deposit generates provides a kind of gas engine lubricant oil composite and preparation method thereof.
The present inventor has found that lubricant oil composite contains the compound of structure shown in formula (I) under study for action:
And the compound and thiophenols ester type antioxidant are combined, and gas engine lubricant oil composite can be made to have excellent
The good performances such as anti-oxidant and wear-resistant, can effectively inhibit the generation of high temperature deposition object.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of gas engine lubricant oil composite,
On the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: the lubrication oil base of 70-95 weight %
Thiophenols ester type antioxidant, the 0.5-10 of plinth oil, the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, 0.02-8 weight %
The polyisobutylene succinic acid ester dispersing agent of weight %, the high base number naphthenate of 0.2-10 weight % and middle base number naphthenate
Mixture, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.15 weight % and the Ashless friction modifiers of 0.01-5 weight %,
The wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 75-90
The thiophenols ester type of the lube base oil of weight %, the wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, 0.1-3 weight %
Antioxidant, the polyisobutylene succinic acid ester dispersing agent of 3-7 weight %, 0.8-6 weight % high base number naphthenate and middle base number
The nothing of the mixture of naphthenate, the zinc dialkyl dithiophosphate of the weight of the 0.01-0.1 in terms of phosphorus % and 0.05-1.2 weight %
Grey friction improver.
On the other hand, the present invention provides a kind of preparation method of gas engine lubricant oil composite, the method packets
It includes: will be containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, polyisobutylene succinic acid ester point
Powder, the mixture of high base number naphthenate and middle base number naphthenate, zinc dialkyl dithiophosphate and Ashless friction improve
The raw material of agent is uniformly mixed and obtains lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, lube base oil
Dosage be 70-95 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-10 weight %, thiophenols ester type antioxidant
Dosage be 0.02-8 weight %, the dosage of polyisobutylene succinic acid ester dispersing agent is 0.5-10 weight %, high base number aphthenic acids
The dosage of the mixture of salt and middle base number naphthenate is 0.2-10 weight %, and the dosage of zinc dialkyl dithiophosphate is with phosphorus
≤ 0.15 weight % is counted, the dosage of Ashless friction modifiers is 0.01-5 weight %, and the wear-resistant multipurpose additive of antioxygen is formula
(I) compound of structure shown in:
Preferably, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 75-90 weight %, resists
The dosage of the wear-resistant multipurpose additive of oxygen is 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is 0.1-3 weight %, it is different to gather
The dosage of butylene succinate dispersing agent is 3-7 weight %, the mixture of high base number naphthenate and middle base number naphthenate
Dosage is 0.8-6 weight %, and the dosage of zinc dialkyl dithiophosphate is the weight % of the 0.01-0.1 in terms of phosphorus, and Ashless friction improves
The dosage of agent is 0.05-1.2 weight %.
Gas engine lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can inhibit height
The generation of warm deposit can be widely applied to combustion gas and start so as to avoid spark plug from blocking and engine advanced ignition
Machine field.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the reaction equation of (a) the step of preparing antioxygen wear-resistant multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing antioxygen wear-resistant multipurpose additive.
Fig. 3 is the hydrogen spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.
Fig. 4 is the carbon spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.
Fig. 5 is the mass spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
On the one hand, the present invention provides a kind of gas engine lubricant oil composites, are with the weight of lubricant oil composite
Benchmark, lubricant oil composite contain following components: lube base oil, the antioxygen of 0.01-10 weight % of 70-95 weight % is anti-
Grind the polyisobutylene succinic acid ester point of multipurpose additive, the thiophenols ester type antioxidant of 0.02-8 weight %, 0.5-10 weight %
Powder, the mixture of the high base number naphthenate of 0.2-10 weight % and middle base number naphthenate, in terms of phosphorus≤0.15 weight %
Zinc dialkyl dithiophosphate and 0.01-5 weight % Ashless friction modifiers, the wear-resistant multipurpose additive of antioxygen be formula (I)
The compound of shown structure:
In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably 75-90 weight
Measure %；The content of the wear-resistant multipurpose additive of antioxygen is preferably 0.02-5 weight %, more preferably 0.1-4 weight %；Sulfophenates
The content of type antioxidant is preferably 0.05-4 weight %, more preferably 0.1-3 weight %；Polyisobutylene succinic acid ester dispersing agent
Content is preferably 1.5-8 weight %, more preferably 3-7 weight %；The mixing of high base number naphthenate and middle base number naphthenate
The content of object is preferably 0.5-8 weight %, more preferably 0.8-6 weight %；The content of zinc dialkyl dithiophosphate is in terms of phosphorus
Preferably 0.01-0.1 weight %；The content of Ashless friction modifiers is preferably 0.02-2 weight %, more preferably 0.05-1.2
Weight %.
The present invention is directed to tie by the compound containing structure shown in formula (I) in lubricant oil composite, and shown in formula (I)
The compound of structure and thiophenols ester type antioxidant are combined and realize goal of the invention, though lubricant oil composite have it is excellent wear-resistant
With the performances such as anti-oxidant.Therefore, it for the selection of conventional constituents each in lubricant oil composite, does not limit specifically.
In the present invention, lube base oil can be lube base oil commonly used in the art, such as can be mine
Object lubricating oil and/or synthetic lubricant fluid.
Mineral lubricating oil in viscosity can from light fraction mineral oil to heavy distillat mineral oil, including saxol and plus
That hydrogen refines, the processed alkane of solvent, cycloalkanes and mixing par-affinic-naphthenic types mineral lubricating oil, are generally divided into I, II, Group III
Base oil, common trade names include I class 150SN, 600SN, II class 100N, 150N, 350N etc..
Synthetic lubricant fluid may include polymerization hydrocarbon ils, alkyl benzene and its derivative, polymerization hydrocarbon ils specific example include but
It is not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly- (1- hexene), poly- (1- octene), gathers
(1- decene), common trade names include PAO4, PAO6, PAO8, PAO10 etc., alkyl benzene and its derivative specific example
Including but not limited to detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethylhexyl) benzene, alkyl benzene derivate packet
Include alkylated diphenyl ether and alkylated diphenyl sulfide and its derivative, analog and homologue etc..
Another suitable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (such as phthalic acid, succinic acid, alkane
Base succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimerization
Object, malonic acid, alkyl malonic acid, alkenyl malonic) with various alcohol (such as butanol, hexanol, dodecyl alcohol, 2- ethylhexyl alcohol,
Ethylene glycol, propylene glycol) ester or complex ester that condensation reaction generates occurs.The specific example of these esters includes but is not limited to adipic acid
Dibutyl ester, decanedioic acid two (2- ethylhexyl) ester, the just own ester of fumaric acid acid two, dioctyl sebacate, azelaic acid two are different pungent
Ester, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, decanedioic acid two (larane base) ester, linoleic acid
2- ethylhexyl diester of dimer etc..
Another suitable type of synthetic lubricant fluid can be for fischer tropsch process synthetic hydrocarbon oil and to this synthetic hydrocarbon oil by adding
Hydrogen isomery such as is hydrocracked, dewaxes at the lube base oil that process obtain.
In the present invention, lube base oil preferred viscosities index is greater than 80, saturated hydrocarbon content and is greater than 90 weight %, sulfur content
Less than the lube base oil of 0.03 weight %.
In the present invention, thiophenols ester type antioxidant can be thiophenols ester type antioxidant commonly used in the art, such as can be with
For thiodipropionic acid bis-dodecanol ester (DLTDP), thio-2 acid double octadecyl esters (DSTDP), 2,5- dimercapto -1,3,4- thiophene two
Azoles (DMTD) and 2, at least one of 2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], preferably
2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], such as the production of Sichuan Yong Ye Chemical Co., Ltd.
Antioxidant 1035, the IRGANOX L115 etc. of BASF Aktiengesellschaft's production.
In the present invention, the number-average molecular weight of polyisobutene part is preferably 800- in polyisobutylene succinic acid ester dispersing agent
4000, more preferably 900-3000, further preferably 1000-2400.Polyisobutylene succinic acid ester dispersing agent can for example select
The LZ936 etc. produced with Lubrizol Corp..
In the present invention, high base number naphthenate is preferably the overbased calcium alkyl-salicylate that base number is 260-400mgKOH/g, in
Base number naphthenate is preferably the middle base number calcium naphthenate that base number is 150-250mgKOH/g, high base number naphthenate and middle base number
The weight ratio of naphthenate is preferably 0.1-12:1, more preferably 0.6-4:1.High base number naphthenate and middle base number naphthenate
Mixture T112, T113, the T114 etc. that can for example select Dushanzi petro-chemical corporation to produce.
In the present invention, the alkyl in zinc dialkyl dithiophosphate is preferably the alkyl of C2-C12, more preferably C2-C8's
Alkyl, further preferably ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, just oneself
Base, isohesyl, n-octyl, iso-octyl, 2- ethylhexyl, cyclohexyl or methylcyclopentyl.Zinc dialkyl dithiophosphate can be with
T202, the T203 for selecting WUXI SOUTH PETROLEUM ADDITIVE Co., LTD. to produce, the primary of the production of Jinzhou Petrochemical Company additive factory
Alkyl T202, primary alkyl T203, brothers alkyl T204, secondary alkyl T205, LZ1371, LZ1375 of Lubrizol Corp.'s production, profit
C9417, C9425, C9426 of Ying Lian company production, Hitec7169, Hitec1656 etc. of Afton Chemical Corp.'s production.
In the present invention, Ashless friction modifiers are preferably selected from polyol esters of fatty acids, aliphatic amine and aliphatic amide
One or more, the more preferably mixture of polyol esters of fatty acids and aliphatic amide, polyol esters of fatty acids and fat
The weight ratio of race's amide is preferably 0.5-3:1, wherein aliphatic alkyl be preferably saturation of the carbon atom number between 6-60 or
The saturation or unsaturated alkyl of unsaturated alkyl, more preferably carbon atom number between 10-50.
The polyol esters of fatty acids is preferably selected from fatty glyceride, fatty acid pentaerythritol ester, fatty acid ethylene glycol
The compounds such as ester, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, fatty acid triethanolamine ester
At least one of monoesters, dibasic acid esters and polyester are more preferably selected from glyceryl monooleate, double oleins, stearic acid single cropping penta
At least one of four alcohol esters, lauric acid/dodecanoic acid diethylene glycol dilaurate, oleic acid diethanol amine monoesters and triethanolamine oleate monoesters；The rouge
Fat race amine is preferably selected from alkyl and monoamine or polyamine, alkoxylated alkyl is replaced to replace monoamine or polyamine and alkyl ether
The butter fat ether amines of at least one of amine etc., the more preferably tallow amine of ethoxylation and/or ethoxylation；It is described
Aliphatic amide is preferably selected from least one of oleamide, coconut oleoyl amine and oleic acid diethyl amide etc..Ashless friction changes
F10, F20 etc. of BASF Aktiengesellschaft can be for example selected into agent.
Lubricant oil composite of the invention can also contain at least one in antirust agent, pour-point depressant, tackifier and anti-foaming agent
Kind.Antirust agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline fourth two
At least one of hydrochlorate and alkenyl succinic acid ester, such as Jinzhou Kangtai Lube Additive Co., Ltd. can be selected to produce
T746,T703,T747.The dialkyl group that pour-point depressant can be C8-C18 selected from poly alpha olefin, vinyl acetate copolymer and alkyl
At least one of fumarate, poly- alkylmethacrylate, alkylnaphthalene, such as Wuxi south petroleum additive can be selected
V385, Luo Mankesi VISCOPLEX1-248 of T803, Run Yinglian company of company etc..Tackifier can be total selected from ethylene, propylene
At least one of polymers, polymethyl methacrylate and hydrogenated styrene isoprene copolymer, for example, can select T601,
SV260, Lz7065 etc..Anti-foaming agent can select polysiloxane type anti-foaming agent, such as can be silicone oil and/or polydimethylsiloxanes
Alkane.For antirust agent, pour-point depressant, tackifier and anti-foaming agent content without particular/special requirement, can be the content of this field routine, this
Known to those skilled in the art, details are not described herein.
In the present invention, the preparation method of the compound of structure shown in formula (I) is preferably included:
(a) aniline, sulfur chloride and 4- chloroaniline are reacted, generate intermediate M shown in formula (II),
(b) the intermediate M and dimercapto -1,3,4- thiadiazoles that step (a) obtains nucleophilic is carried out under alkaline condition to take
Generation reaction, generates multipurpose additive shown in formula (I),
In step (a) of the present invention, the concrete mode that aniline, sulfur chloride and 4- chloroaniline react is preferably included:
(i) under an inert atmosphere, in the first solvent, aniline is sufficiently reacted at -20-0 DEG C with sulfur chloride；
(ii) 4- chloroaniline is added in the reaction system of step (i), reacts 1-3h at 15-30 DEG C.
In the present invention, inert atmosphere can be the inert atmosphere of this field routine, such as can be by gases such as nitrogen, argon gas
It provides.
In step (i) of the present invention, the first solvent is preferably selected from methylene chloride, tetrahydrofuran, toluene, dimethylbenzene and dioxy six
At least one of ring, more preferably methylene chloride and/or tetrahydrofuran are still more preferably methylene chloride.
It in the present invention in step (i), is sufficiently reacted and refers to fully reacting, is i.e. reaction raw materials are reacted completely.
Reaction can be monitored using method commonly used in the art, to confirm fully reacting, such as thin layer chromatography can be used
(TLC) or the methods of gas-chromatography is monitored.
In step (ii) of the present invention, 1-3h is reacted at 15-30 DEG C, preferably after step (i) sufficiently reaction, by reactant
The temperature of system is gradually increased to 15-30 DEG C, adds 4- chloroaniline and carries out reaction 1-3h.It, can be further under the preferable case
Improve reaction yield.
In step (ii) of the present invention, the adding manner of 4- chloroaniline is preferably to be added by several times, such as can divide 3-4 times and add
Enter.Under the preferable case, reaction yield can be further improved.When gradation is added, each additional amount can be identical,
It can also be different, in order to easy to operate, preferably each additional amount is identical.
In step (ii) of the present invention, react 1-3h, stop reaction mode can for those skilled in the art it is contemplated that
Various modes, be quenched for example, quencher can be added, quencher can be quencher commonly used in the art, such as can
Think saturated salt solution.
In the present invention, the dosage of aniline, sulfur chloride and 4- chloroaniline is substantially equimolar amounts, but aniline and sulfur chloride can
With appropriate excessive.The molar ratio of aniline, sulfur chloride and 4- chloroaniline is preferably 0.9-1.5:0.9-1.5:0.8-1.2.
It will be understood by those skilled in the art that purer intermediate M, goes back in order to obtain in step (a) of the present invention
It needing to post-process the system after reaction, the mode of post-processing may include washing, drying, solvent be removed under reduced pressure, for example,
Reaction system after being quenched is used into distilled water and saturated common salt water washing respectively, anhydrous calcium chloride then is added at 15-30 DEG C
Or the desiccant such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain intermediate M.
In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4- chloroaniline are reacted is as shown in Figure 1, figure
In 1, the first solvent is using methylene chloride, and purpose by way of example only is not construed as limiting the scope of the present invention.
In step (b) of the present invention, the condition of nucleophilic substitution is preferably included: under an inert atmosphere, in the second solvent,
Dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed into 10-30min at 15-30 DEG C, intermediate is then added
M is sufficiently reacted.I.e. alkaline condition is provided by alkaline reagent.
" inert atmosphere ", " sufficiently being reacted " are as previously mentioned, details are not described herein.
In the present invention, intermediate M is preferably slowly added to, such as can be added by several times, and 3-4 addition can be generally divided.?
Under the preferable case, reaction yield can be further improved.When gradation is added, each additional amount can be identical, can also
With difference, in order to easy to operate, preferably each additional amount is identical.
In the present invention, the second solvent is preferably selected from methylene chloride, tetrahydrofuran, toluene, dimethylbenzene, N, N- dimethyl formyl
At least one of amine, more preferably methylene chloride and/or n,N-Dimethylformamide are still more preferably N, N- dimethyl
Formamide.
In the present invention, alkaline reagent is preferably selected from least one of inorganic bases such as potassium carbonate, sodium carbonate, sodium methoxide.
In the present invention, catalyst is preferably potassium sulfate.
In step (b) of the present invention, the dosage of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate M is substantially etc.
Mole, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Dimercapto -1,3,4- thiadiazoles, alkalinity examination
The molar ratio of agent and intermediate M are preferably 0.9-3.0:0.9-5.0:0.8-1.5.
In step (b) of the present invention, the dosage of catalyst can be catalytic amount, with mole of dimercapto-1,3,4-thiadiazole
On the basis of number, the dosage of catalyst is preferably 5-100 moles of %, more preferably 10-50 moles of %.
In step (b) of the present invention, reaction equation such as Fig. 2 that dimercapto-1,3,4-thiadiazole and intermediate M are reacted
Shown, in Fig. 2, alkaline reagent is using potassium carbonate, purpose by way of example only, does not constitute and limits to the scope of the present invention
System.
It will be understood by those skilled in the art that purer final product, i.e., multiple-effect of the invention add in order to obtain
Add agent, the present invention prepares the method for multipurpose additive it is also preferable to include post-processing to the system after reaction, the side of post-processing
Formula may include washing, drying, solvent be removed under reduced pressure, for example, the system after abundant reaction to be poured into the acetic acid of 1-10 times of volume
In ethyl ester (or methylene chloride), distilled water and saturated common salt water washing are used respectively, anhydrous calcium chloride then is added at 15-30 DEG C
Or the desiccant such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain final product.
Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention preferably carries out under stiring, for
Mixing speed can be the mixing speed of this field routine, for example, mixing speed can be 100-800rpm without particular/special requirement.
In the present invention, for the first solvent and the second solvent amount without particular/special requirement, can be the solvent of this field routine
Dosage, this is known to those skilled in the art, and details are not described herein.
As described above, the present invention is directed to the compound by containing structure shown in formula (I) in lubricant oil composite, and formula
(I) compound and thiophenols ester type antioxidant of structure shown in are combined and realize goal of the invention, even if lubricant oil composite has
The excellent performances such as wear-resistant and anti-oxidant, inhibit the generation of high temperature deposition object.Therefore, for the preparation method of lubricant oil composite
Without particular/special requirement, method commonly used in the art can be used, for example, second aspect, the present invention also provides a kind of combustion gas
The preparation method of engine oil composition, this method comprises: by being added containing lube base oil, the wear-resistant multiple-effect of antioxygen
Agent, thiophenols ester type antioxidant, polyisobutylene succinic acid ester dispersing agent, high base number naphthenate and middle base number naphthenate it is mixed
The raw material for closing object, zinc dialkyl dithiophosphate and Ashless friction modifiers, which is uniformly mixed, obtains lubricant oil composite, wherein with
On the basis of the weight of lubricant oil composite, the dosage of lube base oil is 70-95 weight %, the wear-resistant multipurpose additive of antioxygen
Dosage is 0.01-10 weight %, the dosage of thiophenols ester type antioxidant is 0.02-8 weight %, the dispersion of polyisobutylene succinic acid ester
The dosage of agent is 0.5-10 weight %, and the dosage of the mixture of high base number naphthenate and middle base number naphthenate is that 0.2-10 is weighed
Measure %, the dosage of zinc dialkyl dithiophosphate be in terms of phosphorus≤0.15 weight %, the dosage of Ashless friction modifiers is 0.01-
5 weight %, the wear-resistant multipurpose additive of antioxygen are the compound of structure shown in formula (I):
In the method for the present invention, it is preferable that on the basis of the weight of lubricant oil composite, the dosage of lube base oil is
80-95 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen are 0.02-5 weight %, more preferably 0.1-4 weight %, thiophenols
The dosage of ester type antioxidant is 0.05-4 weight %, more preferably 0.1-3 weight %, the use of polyisobutylene succinic acid ester dispersing agent
Measuring is 1.5-8 weight %, more preferably 3-7 weight %, the use of the mixture of high base number naphthenate and middle base number naphthenate
Amount is 0.5-8 weight %, and more preferably 0.8-6 weight %, the dosage of zinc dialkyl dithiophosphate is the 0.01-0.1 in terms of phosphorus
Weight %, the dosage of Ashless friction modifiers are 0.02-2 weight %, more preferably 0.05-1.2 weight %.
As previously mentioned, raw material can also be containing in antirust agent, pour-point depressant, tackifier and anti-foaming agent in the method for the present invention
It is at least one.
In the method for the present invention, for mixed mode without particular/special requirement, such as each original of lube base oil can will be removed
Material component is added separately in lube base oil, can also will be mixed and made into concentrate again except each component of lube base oil
It is added in lube base oil.
In the method for the present invention, mixed condition is preferably included: temperature is 40-90 DEG C, time 1-6h.
The wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, the dispersion of polyisobutylene succinic acid ester
Agent, the mixture of high base number naphthenate and middle base number naphthenate, zinc dialkyl dithiophosphate, Ashless friction modifiers,
Antirust agent, pour-point depressant, tackifier and anti-foaming agent are as previously mentioned, details are not described herein.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In the following Examples and Comparative Examples:
The method for monitoring fully reacting: thin-layer chromatography chromatography (TLC) fluorescence developing method.
Gross production rate=final product mole/aniline moles × 100%
The physico-chemical analysis method of product: constituent content is measured by inductively coupled plasma body ion emission spectroscopy method.
Structure characterization methods: nuclear magnetic resonance method (1H hydrogen spectrum,13C carbon spectrum), high resolution mass spectrum.
Preparation example
It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 300rpm), 150ml is added
Methylene chloride, then be added 0.2mol sulfur chloride, after being fully cooled in ice-water bath, the aniline of 0.2mol is added.Monitoring
Ice-water bath is moved back to fully reacting, is placed in 25 DEG C at room temperature, after reaction system is gradually increased to 25 DEG C, is added three times 4- chlorine
Aniline is reacted, and each additional amount is identical, and 4- chloroaniline 0.15mol is added altogether.30ml saturation is added after sustained response 2 hours
Reaction system, is then transferred in separatory funnel by saline solution quenching reaction, uses 50ml distilled water and 50ml saturated salt solution respectively
Washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is evaporated off molten under 40 DEG C, 0.05MPa
Agent obtains intermediate M1.
It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 400rpm), 150ml is added
DMF (n,N-Dimethylformamide), be then added 0.2mol dimercapto-1,3,4-thiadiazole and 0.2mol potassium carbonate,
The potassium sulfate of 0.05mol stirs 20 minutes at 25 DEG C, is added three times above-mentioned intermediate M1, and each additional amount is identical, is added altogether
Intermediate M10.12mol.Then to fully reacting 250ml ethyl acetate is added in reaction system by monitoring, and be transferred to separatory funnel
In, 100ml distilled water (twice) and 50ml saturated common salt water washing are used respectively, and 15g anhydrous sodium sulfate is added and does at 25 DEG C
Dry 20min.Solvent is evaporated off at 40 DEG C, 0.03MPa in filtered filtrate, obtains final product S1.Calculating gross production rate is 76%.
The physico-chemical analysis data of product are as follows: sulfur content, and 41.3%；Nitrogen content, 13.9%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 3, Fig. 4 and
Fig. 5.
It can be seen that S1 with knot shown in formula (I) from the physico-chemical analysis data of above-mentioned preparation example, Fig. 3, Fig. 4 and Fig. 5
Structure.
Embodiment 1
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 0.1 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 3 parts by weight
Ethyl ester], the polyisobutylene succinic acid ester dispersing agent of 7 parts by weight (number-average molecular weight of polyisobutene part is 2400), 2 parts by weight
Overbased calcium alkyl-salicylate (base number 260mgKOH/g), 1 parts by weight middle base number calcium naphthenate (base number 200mgKOH/g),
Two isohesyl zinc dithiophosphates of 0.12 parts by weight, the glyceryl monooleate of 0.03 parts by weight, 0.02 parts by weight oleic acid acyl
Amine, the pour-point depressant VISCOPLEX1-248 (be purchased from U.S. Luo Mankesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S.) of 0.3 parts by weight and 6.5 parts by weight
Tackifier SV260 is added to 600SN lube base oil (viscosity index (VI) 87, the saturated hydrocarbon content 92 of 79.93 parts by weight
Weight %, sulfur content are 0.02 weight %) in, 3h is stirred at 60 DEG C, is uniformly mixed and obtains lubricant oil composite A1.
Embodiment 2
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 0.4 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 0.4 parts by weight
Acetoacetic ester], the polyisobutylene succinic acid ester dispersing agent of 3 parts by weight (number-average molecular weight of polyisobutene part is 1300), 0.3 weight
Measure the overbased calcium alkyl-salicylate (base number 300mgKOH/g) of part, (base number is the middle base number calcium naphthenate of 0.5 parts by weight
150mgKOH/g), the isobutyl group n-octyl zinc dithiophosphate, the isopropyl hexyl two of 0.4 parts by weight of 0.2 parts by weight are thio
Trbasic zinc phosphate, double oleins of 0.1 parts by weight, the coconut oleoyl amine of 0.2 parts by weight, 0.3 parts by weight pour-point depressant
The tackifier SV260 of VISCOPLEX1-248 (being purchased from U.S. Luo Mankesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S.) and 6.5 parts by weight, is added to 78
(viscosity index (VI) is the Group III 350N base oil of the Group III 150N base oils (viscosity index (VI) 128) of parts by weight and 9.7 parts by weight
126) in mixed lubrication oil base oil, 6h is stirred at 40 DEG C, is uniformly mixed and obtains lubricant oil composite A2.
Embodiment 3
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 4 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 0.1 parts by weight
Ethyl ester], the polyisobutylene succinic acid ester dispersing agent of 5 parts by weight (number-average molecular weight of polyisobutene part is 1000), 4.8 weight
Part overbased calcium alkyl-salicylate (base number 400mgKOH/g), 1.2 parts by weight middle base number calcium naphthenate (base number is
250mgKOH/g), two isohesyl zinc dithiophosphates of 1.1 parts by weight, the stearic acid monopentaerythritol ester of 0.9 parts by weight, 0.3
The oleic acid diethyl amide of parts by weight, 0.3 parts by weight pour-point depressant VISCOPLEX1-248 (combining purchased from U.S. Luo Mankesi has
Limit company) and 6.5 parts by weight tackifier SV260, being added to the 100N lube base oils of 75.8 parts by weight, (viscosity index (VI) is
112, saturated hydrocarbon content is 96 weight %) in, 1h is stirred at 90 DEG C, is uniformly mixed and obtains lubricant oil composite A3.
Comparative example 1
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, S1 is replaced with etc. the 2,2'- of parts by weight
Thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], obtains lubricant oil composite D1.
Comparative example 2
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by 2,2'- thiobis [3- (3,5- bis- uncles
Butyl -4- hydroxy phenyl) ethyl propionate] S1 that the parts by weight such as replaces with, obtain lubricant oil composite D2.
Comparative example 3
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] zinc dibutyl dithiocarbamate that the parts by weight such as replaces with, it is lubricated
Fluid composition D3.
Comparative example 4
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the trimethylphenyl zinc phosphite that the parts by weight such as replaces with, obtain lubricating oil composition
Object D4.
Comparative example 5
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the fourth octyl diphenylamine that the parts by weight such as replaces with, obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively:
The measurement of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzer；
The measurement of oxidation induction period is carried out using high pressure differential scanning amount method (PDSC)；
Deposit production quantity is measured using crankcase QZX experiment method: QZX experiment instrument is added in 300mL oil sample,
Heating and keeping oil temperature is 130 DEG C, and aluminium sheet temperature is 290 DEG C, to the continuous spilled oil 6h of aluminium sheet, is generated on weighing aluminium sheet after test
Jiao Liang, as deposit production quantity.
Wear scar diameter is measured using SH/T 0189.It the results are shown in Table 1.
Table 1
| A1 | A2 | A3 | D1 | D2 | D3 | D4 | D5 | |
| Initial oxidation temperature, DEG C | 241 | 232 | 256 | 208 | 221 | 206 | 190 | 208 |
| Oxidation induction period, min | 46.3 | 48.2 | 63.8 | 31.5 | 41.6 | 30.9 | 17.5 | 36.8 |
| Deposit production quantity, mg | 25.8 | 20.7 | 14.5 | 38.1 | 29.5 | 42.4 | 70.1 | 66.8 |
| Wear scar diameter d60 40, mm | 0.60 | 0.54 | 0.49 | 0.75 | 0.55 | 0.75 | 0.62 | 0.77 |
It will be understood by those skilled in the art that initial oxidation temperature is higher, the thermal stability of lubricating oil is better；Oxidation
Induction period is longer, and the antioxygenic property of lubricating oil is better；Deposit production quantity is higher, and lubricating oil inhibits high temperature deposition object to generate
Ability is poorer；Wear scar diameter is smaller, and the wear resistance of lubricating oil is better.
A2 is compared with D1-D5 respectively as can be seen that lubricant oil composite of the invention has better thermostabilization
Property, inoxidizability and abrasion resistance, there is the ability for preferably high temperature deposition object being inhibited to generate.
Gas engine lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can inhibit height
The generation of warm deposit can be widely applied to combustion gas and start so as to avoid spark plug from blocking and engine advanced ignition
Machine field.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (28)
1. a kind of gas engine lubricant oil composite, which is characterized in that on the basis of the weight of lubricant oil composite, the profit
Sliding oil composition contains following components: the wear-resistant multiple-effect of antioxygen of the lube base oil of 70-95 weight %, 0.01-10 weight %
Additive, the thiophenols ester type antioxidant of 0.02-8 weight %, 0.5-10 weight % polyisobutylene succinic acid ester dispersing agent,
The mixture of the high base number naphthenate of 0.2-10 weight % and middle base number naphthenate, in terms of phosphorus≤dioxane of 0.15 weight %
The Ashless friction modifiers of base zinc dithiophosphate and 0.01-5 weight %, the wear-resistant multipurpose additive of antioxygen are formula (I) institute
Show the compound of structure:
2. lubricant oil composite according to claim 1, wherein on the basis of the weight of lubricant oil composite, the profit
Sliding oil composition contains following components: the lube base oil of 75-90 weight %, the wear-resistant multiple-effect of antioxygen of 0.1-4 weight % add
Add agent, the thiophenols ester type antioxidant of 0.1-3 weight %, the polyisobutylene succinic acid ester dispersing agent of 3-7 weight %, 0.8-6 weight
Measure the dialkyl disulfides of the high base number naphthenate of % and the mixture of middle base number naphthenate, the weight of the 0.01-0.1 in terms of phosphorus %
For the Ashless friction modifiers of trbasic zinc phosphate and 0.05-1.2 weight %.
3. lubricant oil composite according to claim 1 or 2, wherein the lube base oil be mineral lubricating oil and/
Or synthetic lubricant fluid.
4. lubricant oil composite according to claim 1 or 2, wherein the thiophenols ester type antioxidant is that 2,2'- is thio
Bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionates].
5. lubricant oil composite according to claim 1 or 2, wherein gather in the polyisobutylene succinic acid ester dispersing agent
The number-average molecular weight of isobutene part is 800-4000.
6. lubricant oil composite according to claim 5, wherein poly- isobutyl in the polyisobutylene succinic acid ester dispersing agent
The number-average molecular weight of alkene part is 900-3000.
7. lubricant oil composite according to claim 6, wherein poly- isobutyl in the polyisobutylene succinic acid ester dispersing agent
The number-average molecular weight of alkene part is 1000-2400.
8. lubricant oil composite according to claim 1 or 2, wherein it is 260- that the high base number naphthenate, which is base number,
The overbased calcium alkyl-salicylate of 400mgKOH/g, the middle base number naphthenate are the middle base number ring that base number is 150-250mgKOH/g
The weight ratio of alkanoic acid calcium, the high base number naphthenate and the middle base number naphthenate is 0.1-12:1.
9. lubricant oil composite according to claim 8, wherein the high base number naphthenate and the middle base number cycloalkanes
The weight ratio of hydrochlorate is 0.6-4:1.
10. lubricant oil composite according to claim 1 or 2, wherein the alkyl in the zinc dialkyl dithiophosphate
For the alkyl of C2-C12.
11. lubricant oil composite according to claim 10, wherein the alkyl in the zinc dialkyl dithiophosphate is
The alkyl of C2-C8.
12. lubricant oil composite according to claim 11, wherein the alkyl in the zinc dialkyl dithiophosphate is
Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl or
2- ethylhexyl.
13. lubricant oil composite according to claim 1 or 2, wherein it is more that the Ashless friction modifiers are selected from fatty acid
One of first alcohol ester, aliphatic amine and aliphatic amide are a variety of, the weight ratio of polyol esters of fatty acids and aliphatic amide
For 0.5-3:1, the carbon atom number of polyol esters of fatty acids, aliphatic amine and aliphatic amide is 6-60.
14. lubricant oil composite according to claim 13, wherein the Ashless friction modifiers are fatty polyol
The mixture of ester and aliphatic amide.
15. lubricant oil composite according to claim 13, wherein polyol esters of fatty acids, aliphatic amine and aliphatic
The carbon atom number of amide is 10-50.
16. lubricant oil composite according to claim 13, wherein the polyol esters of fatty acids is selected from fatty acid glycerine
At least one of ester, fatty acid pentaerythritol ester, the monoesters of ethylene glycol fatty acid, dibasic acid esters and polyester, the aliphatic amine
In monoamine or polyamine and alkyl ether amine selected from monoamine or polyamine, the substitution of alkoxylated alkyl that alkyl replaces
At least one, the aliphatic amide are selected from least one of oleamide, coconut oleoyl amine and oleic acid diethyl amide.
17. lubricant oil composite according to claim 16, wherein the polyol esters of fatty acids is selected from single oleic
At least one of ester, double oleins, stearic acid monopentaerythritol ester and lauric acid/dodecanoic acid diethylene glycol dilaurate；The aliphatic amine
For the tallow amine of ethoxylation and/or the butter fat ether amines of ethoxylation.
18. lubricant oil composite according to claim 1 or 2, wherein the lubricant oil composite also contain antirust agent,
At least one of pour-point depressant, tackifier, the dialkyl fumarate that alkyl is C8-C18 and anti-foaming agent.
19. lubricant oil composite according to claim 18, wherein the antirust agent is selected from imidazoles antirust agent, alkenyl
At least one of succinic acid esters antirust agent and alkenyl imidazoline succinate.
20. lubricant oil composite according to claim 19, wherein the antirust agent is 4,5- glyoxalidine and allyl butyrate
At least one of two acid esters.
21. lubricant oil composite according to claim 18, wherein the pour-point depressant is selected from poly alpha olefin, poly- alkyl first
At least one of base acrylate, alkylnaphthalene.
22. lubricant oil composite according to claim 18, wherein the tackifier is ethylene propylene copolymer, poly- first
At least one of base methyl acrylate and hydrogenated styrene isoprene copolymer.
23. lubricant oil composite according to claim 18, wherein the anti-foaming agent is polysiloxane type anti-foaming agent.
24. lubricant oil composite according to claim 23, wherein the anti-foaming agent is silicone oil.
25. lubricant oil composite according to claim 23, wherein the anti-foaming agent is dimethyl silicone polymer.
26. a kind of preparation method of gas engine lubricant oil composite, which is characterized in that the described method includes: profit will be contained
Lubricant base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, polyisobutylene succinic acid ester dispersing agent, high base number
The raw material of the mixture of naphthenate and middle base number naphthenate, zinc dialkyl dithiophosphate and Ashless friction modifiers mixes
Uniformly obtain lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 70-
95 weight %, the wear-resistant multipurpose additive of antioxygen dosage be 0.01-10 weight %, the dosage of thiophenols ester type antioxidant is
0.02-8 weight %, polyisobutylene succinic acid ester dispersing agent dosage be 0.5-10 weight %, high base number naphthenate and middle alkali
The dosage for being worth the mixture of naphthenate is 0.2-10 weight %, the dosage of zinc dialkyl dithiophosphate be in terms of phosphorus≤0.15
Weight %, the dosage of Ashless friction modifiers are 0.01-5 weight %, and the wear-resistant multipurpose additive of antioxygen is knot shown in formula (I)
The compound of structure:
27. according to the method for claim 26, wherein on the basis of the weight of lubricant oil composite, lube base oil
Dosage be 75-90 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.1-4 weight %, thiophenols ester type antioxidant
Dosage is 0.1-3 weight %, the dosage of polyisobutylene succinic acid ester dispersing agent is 3-7 weight %, and high base number naphthenate is in
The dosage of the mixture of base number naphthenate is 0.8-6 weight %, and the dosage of zinc dialkyl dithiophosphate is the 0.01- in terms of phosphorus
0.1 weight %, the dosage of Ashless friction modifiers are 0.05-1.2 weight %.
28. the method according to claim 26 or 27, wherein the mixed condition includes: that temperature is 40-90 DEG C, when
Between be 1-6h.
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| CN1356382A (en) * | 2001-12-27 | 2002-07-03 | 上海交通大学 | Dithioamino acid triazine derivative as additive for antioxidizing extreme pressure lubricating oil |
| CN1453347A (en) * | 2002-04-26 | 2003-11-05 | 中国石油化工股份有限公司 | Prepn of antioxidant for lubricant oil |
| CN101880586A (en) * | 2010-06-29 | 2010-11-10 | 江苏龙蟠石化有限公司 | Composite of engine lubricant and preparation method thereof |
| CN102690709A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Lubricant composition for gas engine |
| CN102994193A (en) * | 2011-09-14 | 2013-03-27 | 中国石油天然气股份有限公司 | Gas engine lubricating oil composition |
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|---|---|---|---|---|
| CN1356382A (en) * | 2001-12-27 | 2002-07-03 | 上海交通大学 | Dithioamino acid triazine derivative as additive for antioxidizing extreme pressure lubricating oil |
| CN1453347A (en) * | 2002-04-26 | 2003-11-05 | 中国石油化工股份有限公司 | Prepn of antioxidant for lubricant oil |
| CN101880586A (en) * | 2010-06-29 | 2010-11-10 | 江苏龙蟠石化有限公司 | Composite of engine lubricant and preparation method thereof |
| CN102690709A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Lubricant composition for gas engine |
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