CN106318545B - A kind of diesel engine lubricating oil composite and preparation method thereof - Google Patents
A kind of diesel engine lubricating oil composite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of diesel engine lubricating 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 antioxygen multipurpose additive of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.02-8 weight %, the polyisobutene succinimide ashless dispersant of 0.5-10 weight % and the mixture of boronation polyisobutene succinimide dispersing agent, the high base number magnesium salicylate of 0.2-10 weight % and the mixture of low alkali value sulfoacid calcium, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.15 weight % and the Ashless friction modifiers of 0.01-5 weight %, the antioxygen multipurpose additive is the compound of structure shown in formula (I).Additionally provide the preparation method of diesel engine lubricating oil composite.Diesel engine lubricating oil composite of the invention has excellent wear-resistant and antioxygenic property, can inhibit the generation of high temperature deposition object.
Description
Technical field
The present invention relates to lubricating oil fields, and in particular, to a kind of diesel engine lubricant containing special additive
Composition and preparation method thereof.
Background technique
In recent years, the specification grade of diesel engine lubricant subtracts with diesel engine structure, operating condition and energy conservation
Row requires and sustainable development, diesel engine oil frequently upgrade.Diesel engine oil product specification is gradually upgraded to CH- from CF-4
4, CI-4 and newest CJ-4, the application of the diesel engine EGR exhaust circulatory system, NOxDischarge reduce, bring cigarette in machine oil
The problem of soot amount increases, mass ratio containing soot can in the lubricating oil that many diesel engine testboard bays such as Mack T11 are used
Reach 6%.It is secondary that there are many frictions in engine, such as piston and cylinder sleeve, crankshaft journal and bearing, cam and follower, gear.
Soot particulates are very rigid, and caused abrasive wear will cause seriously the service life of engine between engine friction pair
It influences, to lubricating oil, more stringent requirements are proposed for this.
In addition, engine fuel oil and the unsaturated olefin in base oil, aromatic hydrocarbons and sulfur-containing compound are under oxygen effect
Colloid is formed, and ultimately forms carbon distribution deposit, especially in the key positions such as piston, combustion chamber meeting acceleration motor deposit
Generate, seriously affect the working performance of engine, cause engine start difficulty, unstable idle speed, driving is poor, acceleration is poor,
The problems such as power loss is serious.It is this field that engine oil, which has excellent ability that is anti-oxidant and inhibiting high temperature deposition object to generate,
The research that novel more efficient antioxidant additive is those skilled in the art is developed in the direction that researcher is continually striving to all the time
Target.Additionally due to diesel oil sulfur content is higher, the acidic materials generated after burning are more, the high temperature that diesel engine work generates
Soot is also more, can effectively reduce coking and top land carbon deposit using the formula of protosulfate ash content, reduces the abrasion of valve system,
In addition low ash point can reduce corrosion resistance oxidation product, reduce engine component corrosion abrasion, extend the safe operation of engine
Period and spare part service life.Therefore low ash divides I. C. engine oil to be the developing direction of I. C. engine oil.
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 diesel engine lubricating oil composite and inhibit high temperature
The high request for the ability that deposit generates provides a kind of diesel engine lubricating 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 diesel engine lubricating 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 diesel engine lubricating oil composite,
On the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: the lubrication oil base of 75-95 weight %
Plinth oil, the thiophenols ester type antioxidant of the antioxygen multipurpose additive of 0.01-10 weight %, 0.02-8 weight %, 0.5-10 weight
Measure the polyisobutene succinimide ashless dispersant of % and mixture, the 0.2- of boronation polyisobutene succinimide dispersing agent
The high base number magnesium salicylate of 10 weight % and the mixture of low alkali value sulfoacid calcium, in terms of phosphorus≤dialkyl disulfides of 0.15 weight %
For the Ashless friction modifiers of trbasic zinc phosphate and 0.01-5 weight %, the antioxygen multipurpose additive is the change of structure shown in formula (I)
Close object:
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 75-85
The lube base oil of weight %, the antioxygen multipurpose additive of 0.1-4 weight %, 0.1-3 weight % thiophenols ester type antioxygen
Agent, the polyisobutene succinimide ashless dispersant of 3-7 weight % and boronation polyisobutene succinimide dispersing agent it is mixed
Close object, the high base number magnesium salicylate of 0.8-6 weight % and the mixture of low alkali value sulfoacid calcium, the weight of the 0.01-0.1 in terms of phosphorus %
The Ashless friction modifiers of zinc dialkyl dithiophosphate and 0.05-1.2 weight %.
On the other hand, the present invention provides a kind of preparation method of diesel engine lubricating oil composite, the method packets
It includes: lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, polyisobutene succinimide ashless will be contained
The mixture of dispersing agent and boronation polyisobutene succinimide dispersing agent, high base number magnesium salicylate and low alkali value sulfoacid calcium 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 the dosage of 75-95 weight %, antioxygen multipurpose additive
Dosage for 0.01-10 weight %, thiophenols ester type antioxidant is 0.02-8 weight %, polyisobutene succinimide ashless divides
The dosage of the mixture of powder and boronation polyisobutene succinimide dispersing agent is 0.5-10 weight %, high base number magnesium salicylate
Be 0.2-10 weight % with the dosage of the mixture of low alkali value sulfoacid calcium, 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 antioxygen multipurpose additive is knot shown in formula (I)
The compound of structure:
Preferably, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 75-85 weight %, resists
The dosage of oxygen multipurpose additive is 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is 0.1-3 weight %, polyisobutene
The dosage of the mixture of Ashless butyl diimide dispersant and boronation polyisobutene succinimide dispersing agent is 3-7 weight %,
The dosage of high base number magnesium salicylate and the mixture of low alkali value sulfoacid calcium is 0.8-6 weight %, zinc dialkyl dithiophosphate
Dosage is the weight % of the 0.01-0.1 in terms of phosphorus, and the dosage of Ashless friction modifiers is 0.05-1.2 weight %.
Diesel engine lubricating oil composite of the invention has excellent abrasion resistance and antioxygenic property, can inhibit height
The generation of warm deposit, and there is the sulfur content no more than 0.5%, the phosphorus content no more than 0.1%, meet CJ-4 and with higher level
The requirement of other diesel engine lubricant.
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 multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing antioxygen multipurpose additive.
Fig. 3 is the reaction equation of (c) the step of preparing antioxygen multipurpose additive.
Fig. 4 is the hydrogen spectrum spectrogram of the antioxygen multipurpose additive of preparation example preparation.
Fig. 5 is the carbon spectrum spectrogram of the antioxygen multipurpose additive of preparation example preparation.
Fig. 6 is the mass spectrogram of the antioxygen multipurpose additive 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 diesel engine lubricating 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 75-95 weight % is more
Imitate the polyisobutene succinimide ashless of additive, the thiophenols ester type antioxidant of 0.02-8 weight %, 0.5-10 weight %
The mixture of dispersing agent and boronation polyisobutene succinimide dispersing agent, the high base number magnesium salicylate of 0.2-10 weight % and low
The mixture of base number calcium sulfonate, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.15 weight % and 0.01-5 weight % it is ashless
Friction improver, the antioxygen multipurpose additive are the compound of structure shown in formula (I):
In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably 75-85 weight
Measure %；The content of antioxygen multipurpose additive is preferably 0.02-5 weight %, more preferably 0.1-4 weight %；Thiophenols ester type is anti-
The content of oxygen agent is preferably 0.05-4 weight %, more preferably 0.1-3 weight %；Polyisobutene succinimide ashless dispersant
Content with the mixture of boronation polyisobutene succinimide dispersing agent is preferably 1.5-8 weight %, more preferably 3-7 weight
Measure %；The content of high base number magnesium salicylate and the mixture of low alkali value sulfoacid calcium is preferably 0.5-8 weight %, more preferably 0.8-
6 weight %；The content of zinc dialkyl dithiophosphate is preferably 0.01-0.1 weight % in terms of phosphorus；Ashless friction modifiers contain
Amount 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 in polyisobutene succinimide ashless dispersant
800-4000, more preferably 900-3000, further preferably 1000-2400.Polyisobutene succinimide ashless dispersant
Such as the T161 that Suzhou specialty oil factory can be selected to produce, T161A, T161B of the production of Jinzhou Petrochemical Company additive factory,
The LZLl57 of Lu Borun Lan Lian additive Co., Ltd production, LZ6418, LZ6420 of Lubrizol Corp.'s production, Afton Chemical Corp.
The Hitec646 etc. of production.
In the present invention, the number-average molecular weight of polyisobutene part is preferably in boronation polyisobutene succinimide dispersing agent
500-4000, more preferable 700-2500, further preferably 1000-2300.Boronation polyisobutene succinimide dispersing agent example
Can such as select Agip Petroli company produce MX3316, Afton Chemical Corp. production Hitec648, Hitec7714 and
The LZ935 etc. of Lubrizol Corp.'s production.
In the present invention, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersing agent
The weight ratio of polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersing agent is excellent in mixture
It is selected as 1-3:1.
In the present invention, the base number of high base number magnesium salicylate is preferably 100-450mgKOH/g, more preferably 300-
450mgKOH/g, the base number of low alkali value sulfoacid calcium preferably≤100mgKOH/g, more preferably≤50mgKOH/g, high base number salicylic acid
The weight ratio of magnesium and low alkali value sulfoacid calcium is preferably 0.1-10:1, more preferably 0.6-3:1.High base number magnesium salicylate and low alkali value
T101, T102, T103, T104 that the mixture of sulfoacid calcium can for example select Wuxi south additive company to produce, Run Yinglian
C9006, C9012 etc. of company's production.
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) 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are subjected to condensation reaction, generate intermediate M shown in formula (II),
(b) the intermediate M that step (a) obtains is contacted with bromide reagent and carries out bromo-reaction, generated shown in formula (III)
Bromination product,
(c) bromination product for obtaining step (b) is contacted with formula (IV) compound represented carries out coupling reaction, production
(I) antioxidant shown in,
In step (a) of the present invention, the condition of condensation reaction is preferably included: under an inert atmosphere, in the first solvent,
In the presence of one catalyst, 15- is risen to after 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene are reacted 0.5-1.5h at -20-0 DEG C
30 DEG C, it is then heated to 70-80 DEG C of reaction 1-3h.
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.
It will be understood by those skilled in the art that reacting 0.5-1.5h at -20-0 DEG C to carry out stable reaction
After rise to 15-30 DEG C, it should be to slowly warm up to 15-30 DEG C, for example, can by -20-0 DEG C react 0.5-1.5h after body
System is placed under 15-30 DEG C of environment temperature, and reaction system itself is made to be to slowly warm up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from least one in methanol, ethyl alcohol, n,N-Dimethylformamide and acetonitrile
Kind, more preferably methanol and/or acetonitrile, are still more preferably methanol.
In the present invention, the first catalyst can be inorganic acid or organic acid, be preferably selected from acetic acid, p-methylbenzoic acid and benzene
At least one of sulfonic acid, more preferably acetic acid.
In the present invention, the dosage of 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene is substantially equimolar amounts, but formaldehyde and benzene can
With appropriate excessive.The molar ratio of 2,6 di t butyl phenol, formaldehyde and benzene is preferably 0.9-1.5:0.9-10:0.9-10.
In step (a) of the present invention, the dosage of the first catalyst can be catalytic amount, with mole of 2,6- DI-tert-butylphenol compounds
On the basis of number, the dosage of the first catalyst is preferably 5-100 moles of %, more preferably 10-30 moles of %.
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 that solvent is removed under reduced pressure, then diluted through solvent,
Washing, dry, decompression remove solvent again, for example, the system after reaction is removed into solvent at 0.01-0.05MPa, 40-60 DEG C,
It is subsequently poured into the ethyl acetate (or methylene chloride) of 1-10 times of volume, uses distilled water and saturated common salt water washing respectively, then
The desiccant such as anhydrous calcium chloride or anhydrous sodium sulfate are added at 15-30 DEG C, keep 10-60min.It is filtered to remove desiccant
Afterwards, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain intermediate M.
In step (a) of the present invention, 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction equation of condensation reaction as schemed
Shown in 1, in Fig. 1, the first solvent is using methanol, and the first catalyst is using acetic acid, purpose by way of example only, no
The scope of the present invention is construed as limiting.
In step (b) of the present invention, the condition of bromo-reaction is preferably included: under an inert atmosphere, in the second solvent,
In the presence of two catalyst, under the conditions of being protected from light, the intermediate M that step (a) obtains is reacted at 15-30 DEG C with bromide reagent
Then 1-2h is quenched with quencher.
" inert atmosphere " is as previously mentioned, details are not described herein.
It will be understood by those skilled in the art that more stably being carried out to react, slowly add preferably into intermediate M
Enter brominated reagent.
In the present invention, the second solvent is preferably selected from least one of tetrahydrofuran, methylene chloride, chloroform and ether, more
Preferably tetrahydrofuran.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azodiisobutyronitrile
At least one of (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, more preferably NBS.
In step (b) of the present invention, it is quenched with quencher, quencher can be quencher commonly used in the art, such as
It can be saturated salt solution.
In step (b) of the present invention, the dosage of intermediate M and bromide reagent is substantially equimolar amounts, but bromide reagent one
As can be suitably excessive, reach 1.1-3 times of equivalent of reaction substrate.Intermediate M and bromide reagent molar ratio are preferably 0.9-
1.2:0.9-3.0。
In step (b) of the present invention, the dosage of the second catalyst can be catalytic amount, on the basis of the molal quantity of intermediate M,
The dosage of second catalyst is preferably 10-100 moles of %, more preferably 40-60 moles of %.
In the method for the present invention step (b), intermediate M contacts the reaction equation for carrying out bromo-reaction with bromide reagent as schemed
Shown in 2, in Fig. 2, bromide reagent is using NBS, 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, other than generating bromination product shown in formula (III), there are also the bromos at micro ortho position to produce
Object generates, and the bromination product of meta position does not generate, but the amount of the bromination product at ortho position very pettiness, to subsequent reactions without substantive shadow
It rings, can be ignored.
It will be understood by those skilled in the art that in step (b) of the present invention, purer bromination product in order to obtain,
It also needs to post-process the system after being quenched, the mode of post-processing may include washing, drying, solvent, example be removed under reduced pressure
Such as, the system after being quenched is washed with distilled water, it is dry that anhydrous calcium chloride or anhydrous sodium sulfate etc. is then added at 15-30 DEG C
Drying prescription keeps 10-60min.After being filtered to remove desiccant, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain bromine
For product.
In step (c) of the present invention, the condition of coupling reaction is preferably included: under an inert atmosphere, in third solvent,
In the presence of three catalyst, the bromination product that step (b) obtains is reacted at 80-100 DEG C with formula (IV) compound represented
4-8h。
" inert atmosphere " is as previously mentioned, details are not described herein.
In the present invention, in order to carry out stable reaction, it is preferably gradually heated to 80-100 DEG C, it is then anti-at 80-100 DEG C
Answer 4-8h.
In the present invention, third solvent is preferably selected from least one of methylene chloride, chloroform, toluene and tetrahydrofuran, more
Preferably methylene chloride.
In the present invention, third catalyst preferably includes palladium salt, ligand and alkali.Palladium salt is preferably selected from palladium acetate and/or palladium-two
BENZYLIDENE ACETONE complex compound [Pd2(dba)3]；Ligand is preferably selected from tri-tert phosphorus, dinaphthol (BINAP) and bis- (diphenylphosphines
At least one of base) ferrocene (dppf)；Alkali is preferably selected from sodium tert-butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate extremely
Few one kind.
In step (c) of the present invention, the dosage of bromination product and formula (IV) compound represented that step (b) obtains is substantially
For equimolar amounts, but formula (IV) compound represented can be suitably excessive.Shown in the bromination product and formula (IV) that step (b) obtains
The molar ratio of compound be preferably 0.9-1.5:0.9-2.5.
In step (c) of the present invention, the dosage of catalyst can be catalytic amount, on the basis of the molal quantity of bromination product, palladium
The dosage of salt is preferably 5-50 moles of %, more preferably 5-20 moles of %, is still more preferably 5-10 moles of %；The use of ligand
Amount is preferably 5-50 moles of %, more preferably 10-30 moles of %；The dosage of alkali is preferably 5-50 moles of %, more preferably 10-30
Mole %.
In step (c) of the present invention, the bromination product that step (b) obtains is contacted with formula (IV) compound represented to be coupled
The reaction equation of reaction is as shown in figure 3, in Fig. 3, and palladium salt is using palladium acetate, purpose by way of example only, not to this
The range of invention is construed as limiting.
It will be understood by those skilled in the art that purer final product, i.e. antioxygen shown in formula (I) in order to obtain
Agent, for the method for the present invention it is also preferable to include post-processing to the system after reaction, the mode of post-processing may include filtering, solvent
Washing, drying, solvent is removed under reduced pressure in dilution, for example, the filtered filtrate of system after reaction to be poured into the second of 1-10 times of volume
It in acetoacetic ester (or methylene chloride), is then washed with distilled water, anhydrous calcium chloride or anhydrous sulphur is then added at 15-30 DEG C
The desiccant such as sour sodium keep 10-60min.After being filtered to remove desiccant, solvent is removed at 0.01-0.05MPa, 40-60 DEG C,
To obtain antioxidant shown in formula (I).
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.
The present invention is prepared in the method for the compound of structure shown in formula (I), molten for the first solvent, the second solvent and third
The amount of agent can be the solvent usage of this field routine, this is known to those skilled in the art, herein no longer without particular/special requirement
It repeats.
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 diesel oil
The preparation method of engine oil composition, this method comprises: lube base oil, antioxygen multipurpose additive, sulphur will be contained
For the mixed of phenolic ester type antioxidant, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersing agent
Close mixture, zinc dialkyl dithiophosphate and the Ashless friction modifiers of object, high base number magnesium salicylate and low alkali value sulfoacid calcium
Raw material be uniformly mixed obtain lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, lube base oil
The dosage that dosage is 75-95 weight %, the dosage of antioxygen multipurpose additive is 0.01-10 weight %, thiophenols ester type antioxidant
For the mixed of 0.02-8 weight %, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersing agent
The dosage of object is closed as 0.5-10 weight %, the dosage of the mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium is 0.2-10 weight
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 %, antioxygen multipurpose additive 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
75-85 weight %, the dosage of antioxygen multipurpose additive are 0.02-5 weight %, more preferably 0.1-4 weight %, thiophenols ester type
The dosage of antioxidant be 0.05-4 weight %, more preferably 0.1-3 weight %, polyisobutene succinimide ashless dispersant and
The dosage of the mixture of boronation polyisobutene succinimide dispersing agent is 1.5-8 weight %, more preferably 3-7 weight %, height
The dosage of base number magnesium salicylate and the mixture of low alkali value sulfoacid calcium is 0.5-8 weight %, more preferably 0.8-6 weight %, two
The dosage of alkyl zinc dithiophosphate is the weight % of the 0.01-0.1 in terms of phosphorus, and the dosage of Ashless friction modifiers is 0.02-2 weight
Measure %, 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.
Lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, polyisobutene succinimide ashless point
The mixing of the mixture, high base number magnesium salicylate and low alkali value sulfoacid calcium of powder and boronation polyisobutene succinimide dispersing agent
Object, zinc dialkyl dithiophosphate, Ashless friction modifiers, antirust agent, pour-point depressant, tackifier and anti-foaming agent as previously mentioned,
This is repeated no more.
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 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 200rpm), 150ml is added
Methanol and 0.01mol acetic acid, after being fully cooled in ice-water bath, be then respectively adding 2, the 6- di-tert-butyl of 0.1mol
Phenol, the formaldehyde of 0.2mol and the benzene of 0.3mol.Reaction moves back ice-water bath in 1 hour, and 75 DEG C are heated to after rising to 25 DEG C and is persistently returned
Stream stops reaction after 2 hours, the system after reaction is steamed solvent at 0.03MPa, 50 DEG C, and 250ml acetic acid second is then added
Ester, and be transferred in separatory funnel, 100ml distilled water (twice) and 50ml saturated common salt water washing are used respectively, and it is anhydrous that 10g is added
Calcium chloride dry 20min, filtered filtrate at 25 DEG C are evaporated off solvent at 40 DEG C, 0.03MPa, obtain midbody product
M1。
It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 200rpm), 150ml is added
Dry tetrahydrofuran, then dissolve in midbody product M1, and the ammonium nitrate of 0.05mol is added, under the conditions of being protected from light slowly plus
Enter 0.1mol brominated reagent NBS.It is stirred to react 1.5h at 25 DEG C, is then quenched with saturated salt solution, is then distilled with 100ml
Water (twice) washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is in 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain bromination product.
It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 200rpm), 150ml is added
Methylene chloride as solvent, be separately added into above-mentioned bromination product and the benzotriazole compound of 0.12mol, then be added
The tri-tert phosphorus of 0.02mol, the sodium tert-butoxide of 0.02mol and the Pd (OAc) of 0.005mol2.90 DEG C are gradually heated to, is continued
Stir 6h.Then 250ml ethyl acetate is added in the filtered filtrate of system after reaction, and be transferred in separatory funnel, used
100ml distilled water (twice) washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is 40
DEG C, solvent is evaporated off under 0.03MPa, obtain final product S1.
The physico-chemical analysis data of S1 are as follows: nitrogen content, and 11.2%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 4, Fig. 5 and
Fig. 6.
It can be seen that S1 with knot shown in formula (I) from the physico-chemical analysis data of above-mentioned preparation example, Fig. 4, Fig. 5 and Fig. 6
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], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 1.5 parts by weight
1600), 1.5 parts by weight boronation polyisobutene succinimide dispersing agent (number-average molecular weight of polyisobutene part be 1300,
Boron content be 0.8 weight %), the high base number magnesium salicylate (base number 300mgKOH/g) of 4.5 parts by weight, 1.5 parts by weight it is low
Base number calcium sulfonate (base number 50mgKOH/g), two isohesyl zinc dithiophosphates of 0.11 parts by weight, the list of 0.03 parts by weight are oily
Acid glyceride, the oleamide of 0.02 parts by weight, 0.3 parts by weight pour-point depressant VISCOPLEX1-248 (be purchased from U.S. Luo Manke
This Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S.) and 6.4 parts by weight tackifier Lz7065, be added to the 600SN lube base oil of 81.04 parts by weight
In (viscosity index (VI) 87, saturated hydrocarbon content are 92 weight %, and sulfur content is 0.02 weight %), 3h is stirred at 60 DEG C, is mixed
Uniformly obtain the diesel engine lubricating oil composite A1 that viscosity rank is 15W-40.
Embodiment 2
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 0.3 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 0.3 parts by weight
Acetoacetic ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 5.25 parts by weight
2300), (number-average molecular weight of polyisobutene part is the boronation polyisobutene succinimide dispersing agent of 1.75 parts by weight
1000, boron content is 0.8 weight %), the high base number magnesium salicylate (base number 350mgKOH/g) of 1.4 parts by weight, 0.6 parts by weight
Low alkali value sulfoacid calcium (base number 30mgKOH/g), the isohesyl iso-octyl zinc dithiophosphate of 1.1 parts by weight, 0.2 parts by weight
Double oleins, the coconut oleoyl amines of 0.4 parts by weight, 0.3 parts by weight pour-point depressant VISCOPLEX1-248 (be purchased from U.S. sieve
Man Kesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S.) and 6.4 parts by weight tackifier Lz7065, be added to the II class 150N base oil of 68 parts by weight
In the mixed lubrication oil base oil of the II class 600N base oil (viscosity index (VI) 103) of (viscosity index (VI) 117) and 14 parts by weight,
6h is stirred at 40 DEG C, is uniformly mixed and obtains the diesel engine lubricating oil composite A2 that viscosity rank is 15W-40.
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], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 3.34 parts by weight
1000), (number-average molecular weight of polyisobutene part is the boronation polyisobutene succinimide dispersing agent of 1.67 parts by weight
2300, boron content is 0.8 weight %), the high base number magnesium salicylate (base number 450mgKOH/g) of 0.3 parts by weight, 0.5 parts by weight
Low alkali value sulfoacid calcium (base number 40mgKOH/g), the n-hexyl n-octyl zinc dithiophosphate of 0.53 parts by weight, 0.9 weight
Part stearic acid monopentaerythritol ester, the oleic acid diethyl amides of 0.3 parts by weight, 0.3 parts by weight pour-point depressant VISCOPLEX1-
The tackifier Lz7065 of 248 (being purchased from U.S. Luo Mankesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S.) and 6.4 parts by weight, is added to 81.66 parts by weight
300SN lube base oil (viscosity index (VI) 91, saturated hydrocarbon content be 92 weight %, sulfur content be 0.01 weight %) in,
1h is stirred at 90 DEG C, is uniformly mixed and obtains the diesel engine lubricating oil composite A3 that viscosity rank is 15W-40.
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 the diesel engine that viscosity rank is 15W-40
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 the diesel engine that viscosity rank is 15W-40
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, obtain viscosity
Rank is the diesel engine lubricating oil composite D3 of 15W-40.
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 phosphites of parts by weight such as replace with, obtaining viscosity rank is
The diesel engine lubricating oil composite D4 of 15W-40.
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, obtaining viscosity rank is 15W-
40 diesel engine lubricating 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 120 DEG C, and aluminium sheet temperature is 320 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.
The wear-resistant test of high temperature of oil product is carried out using high-frequency reciprocating frictional testing machine (being purchased from Britain PCS company, HFRR),
Experimental condition are as follows: load 1000g, temperature are 100 DEG C, test period 120min, frequency 10Hz and measure steel after the test
The wear scar diameter formed on ball.It the results are shown in Table 1.
Table 1
| A1 | A2 | A3 | D1 | D2 | D3 | D4 | D5 | |
| Initial oxidation temperature, DEG C | 235 | 228 | 247 | 202 | 214 | 193 | 187 | 185 |
| Oxidation induction period, min | 51.6 | 46.3 | 64.1 | 26.3 | 35.6 | 27.7 | 16.4 | 15.2 |
| Deposit production quantity, mg | 28.2 | 27.4 | 16.8 | 44.3 | 37.8 | 48.6 | 65.1 | 53.2 |
| Wear scar diameter, mm | 0.52 | 0.51 | 0.43 | 0.72 | 0.55 | 0.74 | 0.64 | 0.71 |
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.
Diesel engine lubricating oil composite of the invention has excellent abrasion resistance and antioxygenic property, can inhibit height
The generation of warm deposit, and there is the sulfur content no more than 0.5%, the phosphorus content no more than 0.1%, meet CJ-4 and with higher level
The requirement of other diesel engine lubricant.
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 (27)
1. a kind of diesel engine lubricating 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 antioxygen multiple-effect addition of the lube base oil, 0.01-10 weight % of 75-95 weight %
Agent, the thiophenols ester type antioxidant of 0.02-8 weight %, 0.5-10 weight % polyisobutene succinimide ashless dispersant
With the high base number magnesium salicylate and low alkali value sulphur of the mixture of boronation polyisobutene succinimide dispersing agent, 0.2-10 weight %
The mixture of sour calcium, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.15 weight % and the Ashless friction of 0.01-5 weight % change
Into agent, the antioxygen multipurpose additive is the compound of structure shown in formula (I):
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 75-85 weight %, 0.1-4 weight % antioxygen multipurpose additive,
The thiophenols ester type antioxidant of 0.1-3 weight %, the polyisobutene succinimide ashless dispersant of 3-7 weight % and boronation are poly-
The mixture of isobutene succinimide dispersant, the high base number magnesium salicylate of 0.8-6 weight % and low alkali value sulfoacid calcium it is mixed
The Ashless friction for closing object, the zinc dialkyl dithiophosphate of the weight of the 0.01-0.1 in terms of phosphorus % and 0.05-1.2 weight % improves
Agent.
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 the polyisobutene succinimide ashless dispersion
The number-average molecular weight of polyisobutene part is 800-4000 in agent；Gather in the boronation polyisobutene succinimide dispersing agent different
The number-average molecular weight of butylene part is 500-4000；The polyisobutene succinimide ashless dispersant and the boronation are gathered different
The weight ratio of butylene succinimide dispersant is 1-3:1.
6. lubricant oil composite according to claim 5, wherein in the polyisobutene succinimide ashless dispersant
The number-average molecular weight of polyisobutene part is 900-3000；Polyisobutene in the boronation polyisobutene succinimide dispersing agent
Partial number-average molecular weight is 700-2500.
7. lubricant oil composite according to claim 6, wherein in the polyisobutene succinimide ashless dispersant
The number-average molecular weight of polyisobutene part is 1000-2400；Poly- isobutyl in the boronation polyisobutene succinimide dispersing agent
The number-average molecular weight of alkene part is 1000-2300.
8. lubricant oil composite according to claim 1 or 2, wherein the base number of the high base number magnesium salicylate is 100-
450mgKOH/g；Base number≤100mgKOH/g of the low alkali value sulfoacid calcium；The high base number magnesium salicylate and the low alkali value
The weight ratio of sulfoacid calcium is 0.1-10:1.
9. lubricant oil composite according to claim 8, wherein the base number of the high base number magnesium salicylate is 300-
450mgKOH/g；Base number≤50mgKOH/g of the low alkali value sulfoacid calcium；The high base number magnesium salicylate and the low alkali value sulphur
The weight ratio of sour calcium is 0.6-3:1.
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, polyol esters of fatty acids, aliphatic amine and aliphatic amide
Carbon atom number be 6-60.
14. lubricant oil composite according to claim 13, wherein the Ashless friction modifiers are fatty polyol
The weight ratio of the mixture of ester and aliphatic amide, polyol esters of fatty acids and aliphatic amide is 0.5-3:1, aliphatic polybasic acid
The carbon atom number of alcohol ester, aliphatic amine and aliphatic amide is 10-50.
15. lubricant oil composite according to claim 14, 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.
16. lubricant oil composite according to claim 15, 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.
17. 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 and anti-foaming agent.
18. lubricant oil composite according to claim 17, wherein the antirust agent is selected from imidazoles and/or allyl butyrate
Two esters of gallic acid.
19. lubricant oil composite according to claim 18, wherein the antirust agent is 4,5- glyoxalidine, alkenyl miaow
At least one of oxazoline succinate and alkenyl succinic acid ester.
20. lubricant oil composite according to claim 17, wherein the pour-point depressant is selected from poly alpha olefin, alkyl C8-
The poly- alkylmethacrylate and alkyl of C18 is at least one of the alkylnaphthalene of C8-C18.
21. lubricant oil composite according to claim 17, wherein the tackifier is ethylene propylene copolymer, poly- first
At least one of base methyl acrylate and hydrogenated styrene isoprene copolymer.
22. lubricant oil composite according to claim 17, wherein the anti-foaming agent is polysiloxane type anti-foaming agent.
23. lubricant oil composite according to claim 22, wherein the anti-foaming agent is silicone oil.
24. lubricant oil composite according to claim 23, wherein the silicone oil is dimethyl silicone polymer.
25. a kind of preparation method of diesel engine lubricating oil composite, which is characterized in that the described method includes: profit will be contained
Lubricant base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, polyisobutene succinimide ashless dispersant and boronation
The mixture of polyisobutene succinimide dispersing agent, the mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium, dialkyl group
The raw material of zinc dithiophosphate and Ashless friction modifiers is uniformly mixed and obtains lubricant oil composite, wherein with lubricating oil composition
On the basis of the weight of object, the dosage of lube base oil is 75-95 weight %, the dosage of antioxygen multipurpose additive is 0.01-10
Weight %, thiophenols ester type antioxidant dosage be 0.02-8 weight %, polyisobutene succinimide ashless dispersant and boron
The dosage for changing the mixture of polyisobutene succinimide dispersing agent is 0.5-10 weight %, high base number magnesium salicylate and low alkali value
The dosage of the mixture of sulfoacid calcium is 0.2-10 weight %, the dosage of zinc dialkyl dithiophosphate be in terms of phosphorus≤0.15 weight
% is measured, the dosage of Ashless friction modifiers is 0.01-5 weight %, and the antioxygen multipurpose additive is the change of structure shown in formula (I)
Close object:
26. according to the method for claim 25, wherein on the basis of the weight of lubricant oil composite, lube base oil
Dosage be 75-85 weight %, the dosage that the dosage of antioxygen multipurpose additive is 0.1-4 weight %, thiophenols ester type antioxidant
For the mixed of 0.1-3 weight %, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersing agent
The dosage of object is closed as 3-7 weight %, the dosage of the mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium is 0.8-6 weight
% is measured, the dosage of zinc dialkyl dithiophosphate is the weight % of the 0.01-0.1 in terms of phosphorus, and the dosage of Ashless friction modifiers is
0.05-1.2 weight %.
27. the method according to claim 25 or 26, wherein the mixed condition includes: that temperature is 40-90 DEG C, when
Between be 1-6h.
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| CN101528668A (en) * | 2006-10-17 | 2009-09-09 | 雅宝公司 | Macromolecular amine-phenolic antioxidant compositions, process technology thereof, and uses thereof |
| CN102757847A (en) * | 2012-07-25 | 2012-10-31 | 江苏龙蟠石化有限公司 | Anhydrous albany grease and preparation method thereof |
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| CN102757847A (en) * | 2012-07-25 | 2012-10-31 | 江苏龙蟠石化有限公司 | Anhydrous albany grease and preparation method thereof |
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| 润滑油抗氧剂的研究现状与进展;薛卫国等;《合成润滑材料》;20130620;第40卷(第2期);第7-13页 |
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