CN106318545A - Lubricating oil composition for diesel engine and preparation method thereof - Google Patents
Lubricating oil composition for diesel engine and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lubricating oil composition for a diesel engine, and the lubricating oil composition comprises, on the basis of the weight of the lubricating oil composition, the following components by weight: 75 to 95 wt% of lubricating oil base oil, 0.01 to 10 wt% of an antioxidant multi-effect additive, 0.02 to 8 wt% of a thio phenolic ester antioxidant, 0.5 to 10 wt% of a polyisobutylene succinimide ashless dispersant and boronized polyisobutylene succinimide dispersant mixture, 0.2 to 10 wt% of a high basic value magnesium salicylate and low basic value calcium sulfonate mixture, less than or equal to 0.15 wt% of zinc dialkyl dithiophosphate on the basis of phosphorus, and 0.01 to 5 wt% of an ashless friction modifier, and the antioxidant multi-effect additive is a compound with a formula (I) structure. The invention also provides a preparation method of the lubricating oil composition for the diesel engine. The lubricating oil composition for the diesel engine has excellent antiwear and oxidation resistance, and can inhibit the formation of high-temperature sediments.
Description
Technical field
The present invention relates to lubricating oil field, in particular it relates to a kind of diesel engine containing special additive
Machine lubricant oil composite and preparation method thereof.
Background technology
In recent years, the specification grade of diesel engine lubricant is along with Diesel engine structure, operating condition
With energy-saving and emission-reduction requirement and sustainable development, diesel engine oil frequently upgrades.Diesel engine oil product is advised
Lattice are gradually upgraded to CH-4, CI-4 and up-to-date CJ-4 from CF-4, and Diesel engine EGR exhaust follows
The application of loop systems, NOxDischarge reduce, bring the problem that soot amount in machine oil increases, a lot of diesel oil
In the lubricating oil that automotive engine test bench such as Mack T11 uses, the mass ratio Han soot can reach 6%.Send out
Motivation has multiple friction pair, such as piston and cylinder sleeve, crankshaft journal and bearing, cam and follower, tooth
Wheel etc..Soot particulates is very rigid, and its abrasive wear caused between engine friction pair will be to electromotor
Service life cause and have a strong impact on, lubricating oil is had higher requirement by this.
Additionally, engine fuel oil and unsaturated olefin, aromatic hydrocarbons and the sulfur-containing compound in base oil are at oxygen
Form colloid under gas effect, and ultimately form carbon distribution deposit, especially in the key such as piston, combustor portion
The generation of position meeting acceleration motor deposit, has a strong impact on the service behaviour of electromotor, causes electromotor to open
The problems such as dynamic difficulty, unstable idle speed, driving is poor, acceleration is poor, power loss is serious.Engine oil
Have excellence antioxidation and suppression high temperature deposition thing generate ability be this area research worker always with
The direction being continually striving to, develops the research mesh that novel more efficient antioxidant additive is those skilled in the art
Mark.Additionally due to diesel oil sulfur content is higher, the acidic materials generated after burning are more, Diesel engine work
The high temperature soot making to produce is the most more, uses the formula of protosulfate ash can effectively reduce coking and work
Plug top carbon deposit, reduces the abrasion of valve system, and the lowest ash can reduce corrosion resistance oxidation product, reduces and sends out
Motivation component corrosion is worn and torn, and extends safe operation cycle and spare part service life of electromotor.The lowest ash
Point I. C. engine oil is the developing direction of I. C. engine oil.
It is currently known and can effectively play the lube oil additive of antioxidation and mainly include phenols and amine
Compounds.Phenolic compound contains one or more hindered phenol functional group, and aminated compounds then contains one
Individual or multiple nitrogen-atoms, these special functional groups can catch the free radical chemical combination that oxidizing process generates
Thing, thus stop the continuation of oxidizing process to occur.Owing to the working condition of Current mechanical equipment tends to strong,
Often accelerated oxidation speed, shortens the service life of lubricating oil, therefore efficiency and the economy to antioxidant
Property is had higher requirement.
United States Patent (USP) US4824601A reports diphenylamine and the diisobutylene alkaline-earth metal in acid activation
The lower alkylated amines mixture formed of catalyst (earth catalyst) effect, it lubricating oil and other
Oxidation resistance performance excellence in functional fluid.
United States Patent (USP) US2005230664A1 reports the antioxidant 9,10-dihydro of a kind of below general formula
The synthetic method of acridine, it is to use alkylated diphenylamine and aldehydes or ketones to contract under acidic catalyst effect
Close preparation.
Patent CN1191340C uses the tert-butyl group phenols that is obstructed, aldehyde, Carbon bisulfide and dialkylamine to occur
Compound is prepared in condensation, and this compound has stronger seizure free radical and the ability of peroxynitrite decomposition compound,
More effectively protection can be provided to oil oxidation stability, may also function as wear-resistant effect.
Patent US4225450 reports a kind of by tert-butyl group phenols and the alkyl aminodithioformic acid of being obstructed
Polysulfide phenolic antioxidant prepared by reactant salt, has preferable antioxidation and wear-resistant effect.
Summary of the invention
The invention aims to meet to the antioxidation of diesel engine lubricating oil composite, wear-resistant and
The high request of ability that suppression high temperature deposition thing generates, it is provided that a kind of diesel engine lubricating oil composite and
Its preparation method.
The present inventor finds under study for action, and lubricant oil composite contains structure shown in formula (I)
Compound:
And this compound is combined with thiophenols ester type antioxidant, it is possible to make diesel engine lubricant combine
Thing has excellent antioxidation and the performance such as wear-resistant, it is possible to effectively suppress the generation of high temperature deposition thing.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of diesel engine lubrication
Fluid composition, on the basis of the weight of lubricant oil composite, described lubricant oil composite contains following components:
The lube base oil of 75-95 weight %, the antioxygen multipurpose additive of 0.01-10 weight %, 0.02-8 weight
Amount the thiophenols ester type antioxidant of %, the polyisobutene succinimide ashless dispersant of 0.5-10 weight %
Mixture, the high base number salicylic acid of 0.2-10 weight % with boronation polyisobutene succinimide dispersant
Magnesium 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 %, described antioxygen multipurpose additive is structure shown in formula (I)
Compound:
Preferably, on the basis of the weight of lubricant oil composite, described lubricant oil composite contains following group
Point: the lube base oil of 75-85 weight %, the antioxygen multipurpose additive of 0.1-4 weight %, 0.1-3 weight
Thiophenols ester type antioxidant, the polyisobutene succinimide ashless dispersant of 3-7 weight % and the boron of amount %
Change the mixture of polyisobutene succinimide dispersant, the high base number magnesium salicylate of 0.8-6 weight % and low
The mixture of base number calcium sulfonate, the zinc dialkyl dithiophosphate of weight % of 0.01-0.1 in terms of phosphorus and
The Ashless friction modifiers of 0.05-1.2 weight %.
On the other hand, the invention provides the preparation method of a kind of diesel engine lubricating oil composite, institute
The method of stating includes: will containing lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant,
Polyisobutene succinimide ashless dispersant and the mixing of boronation polyisobutene succinimide dispersant
Thing, high base number magnesium salicylate and the mixture of low alkali value sulfoacid calcium, zinc dialkyl dithiophosphate and ashless
The raw material mix homogeneously of friction improver obtains lubricant oil composite, wherein, with the weight of lubricant oil composite
On the basis of amount, the consumption of lube base oil is that 75-95 weight %, the consumption of antioxygen multipurpose additive are
0.01-10 weight %, the consumption of thiophenols ester type antioxidant are 0.02-8 weight %, polyisobutylene succinyl
The consumption of the mixture of imines ashless dispersant and boronation polyisobutene succinimide dispersant is 0.5-10
Weight %, the consumption of the mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium is 0.2-10 weight %,
The consumption of zinc dialkyl dithiophosphate in terms of phosphorus≤0.15 weight %, the consumption of Ashless friction modifiers
For 0.01-5 weight %, described antioxygen multipurpose additive is the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is 75-85
Weight %, the consumption of antioxygen multipurpose additive are that 0.1-4 weight %, the consumption of thiophenols ester type antioxidant are
0.1-3 weight %, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide divide
The consumption of the mixture of powder is 3-7 weight %, high base number magnesium salicylate and the mixing of low alkali value sulfoacid calcium
The consumption of thing is 0.8-6 weight %, and the consumption of zinc dialkyl dithiophosphate is the weight of 0.01-0.1 in terms of phosphorus
Amount %, the consumption of Ashless friction modifiers is 0.05-1.2 weight %.
The diesel engine lubricating oil composite of the present invention has abrasion resistance and the antioxygenic property of excellence,
Can suppress the generation of high temperature deposition thing, and there is the sulfur content less than 0.5%, phosphorus less than 0.1%
Content, meets CJ-4 and the requirement of above rank diesel engine lubricant.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is the reaction equation of the step (a) preparing antioxygen multipurpose additive.
Fig. 2 is the reaction equation of the step (b) preparing antioxygen multipurpose additive.
Fig. 3 is the reaction equation of the step (c) preparing antioxygen multipurpose additive.
Fig. 4 is the hydrogen spectrum spectrogram of antioxygen multipurpose additive prepared by preparation example.
Fig. 5 is the carbon spectrum spectrogram of antioxygen multipurpose additive prepared by preparation example.
Fig. 6 is the mass spectrogram of antioxygen multipurpose additive prepared by preparation example.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of diesel engine lubricating oil composite, with lubricant oil composite
Weight on the basis of, 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 %, 0.5-10
The polyisobutene succinimide ashless dispersant of weight % and the dispersion of boronation polyisobutene succinimide
The mixture of agent, the high base number magnesium salicylate of 0.2-10 weight % and the mixture of low alkali value sulfoacid calcium, with
The zinc dialkyl dithiophosphate of phosphorus meter≤0.15 weight % and the Ashless friction of 0.01-5 weight % improve
Agent, described antioxygen multipurpose additive is 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 %；The content of antioxygen multipurpose additive is preferably 0.02-5 weight %, more preferably 0.1-4
Weight %；The content of thiophenols ester type antioxidant is preferably 0.05-4 weight %, more preferably 0.1-3 weight
Amount %；Polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersant
The content of mixture is preferably 1.5-8 weight %, more preferably 3-7 weight %；High base number magnesium salicylate and
The content of 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
Content be preferably 0.02-2 weight %, more preferably 0.05-1.2 weight %.
It is contemplated that by lubricant oil composite contains the compound of structure shown in formula (I), and
The compound of structure shown in formula (I) is combined with thiophenols ester type antioxidant and realizes goal of the invention, even if
Lubricant oil composite has the performances such as excellent wear-resistant and antioxidation.Therefore, in lubricant oil composite
The selection of each conventional constituents, the most specifically limits.
In the present invention, lube base oil can be lube base oil commonly used in the art, such as
Can be mineral lubricating oil and/or synthetic lubricant fluid.
Mineral lubricating oil can be from light fraction mineral oil to heavy distillat mineral oil in viscosity, including liquid stone
Alkane, cycloalkanes and the mixing par-affinic-naphthenic types mineral lubricant that wax oil and hydrorefined, solvent processed
Oil, is generally divided into I, II, Group III base oil, and common trade names include I class 150SN, 600SN,
II class 100N, 150N, 350N etc..
Synthetic lubricant fluid can include being polymerized hydrocarbon ils, alkyl benzene and its derivative, the example that polymerization hydrocarbon ils is concrete
Son includes but not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly-(1-
Hexene), poly-(1-octene), poly-(1-decene), common trade names include PAO4, PAO6, PAO8,
PAO10 etc., alkyl benzene and its derivative specific example includes but not limited to detergent alkylate, the tetradecane
Base benzene, dinonyl benzene, two (2-ethylhexyl) benzene, alkyl benzene derivate includes alkylating diphenyl ether
With alkylating diphenyl sulfide and derivant, analog and homologue etc..
Another applicable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (as phthalic acid,
Succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, Azelaic Acid, suberic acid, decanedioic acid, anti-
Butene dioic acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic) with
Various alcohol (such as butanol, hexanol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, propylene glycol) are sent out
The ester of raw condensation reaction generation or complex ester.The object lesson of these esters includes but not limited to adipic acid two fourth
Ester, decanedioic acid two (2-ethylhexyl) ester, the most own ester of fumaric acid acid two, di-n-octyl sebacate, nonyl
Diacid di-isooctyl, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate,
Decanedioic acid two (larane base) ester, the 2-ethylhexyl diester etc. of linoleic acid dimer.
Another applicable type of synthetic lubricant fluid can be fischer tropsch process synthetic hydrocarbon oil and to this synthesis hydrocarbon
Oil by hydroisomerizing, be hydrocracked, lube base oil that the PROCESS FOR TREATMENT such as dewaxing obtains.
In the present invention, lube base oil preferred viscosities index more than 80, saturated hydrocarbon content is more than 90 weights
Amount %, sulfur content are 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,
Can be such as the double lauryl alcohol ester (DLTDP) of thio-2 acid, the double octadecyl ester of thio-2 acid
(DSTDP), 2,5-dimercapto-1,3,4-thiadiazoles (DMTD) and 2,2'-thiobis [3-(the tertiary fourth of 3,5-bis-
Base-4-hydroxy phenyl) ethyl propionate] at least one, preferably 2,2'-thiobis [3-(3,5-di-t-butyls
-4-hydroxy phenyl) ethyl propionate], the antioxidant 1035 that such as Yong Ye Chemical Co., Ltd. in Sichuan produces, moral
The IRGANOX L115 etc. that BASF AG of state produces.
In the present invention, the equal molecule of the number of polyisobutylene part in polyisobutene succinimide ashless dispersant
Amount is preferably 800-4000, more preferably 900-3000, more preferably 1000-2400.Poly-isobutyl
Alkene Ashless butyl diimide dispersant such as can select the T161 that Suzhou specialty oil factory produces, Jinzhou
T161A, T161B that additive factory of petrochemical industry branch company produces, Lu Borun Lan Lian additive company limited is raw
The LZLl57 produced, LZ6418, LZ6420 that Lubrizol Corp. produces, Afton Chemical Corp. produces
Hitec646 etc..
In the present invention, the equal molecule of number of polyisobutylene part in boronation polyisobutene succinimide dispersant
Amount is preferably 500-4000, more preferably 700-2500, more preferably 1000-2300.Boronation is gathered different
Butylene succinimide dispersant such as can select the MX3316, Ya Fu that Agip Petroli company produces
Hitec648, Hitec7714 that company produces and the LZ935 etc. that Lubrizol Corp. produces.
In the present invention, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide
Polyisobutene succinimide ashless dispersant and boronation polyisobutylene succinyl in the mixture of dispersant
The weight ratio of imine dispersants is preferably 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, the weight ratio of high base number magnesium salicylate and low alkali value sulfoacid calcium is preferably 0.1-10:1, more
It is preferably 0.6-3:1.The mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium such as can select Wuxi
South additive company produce T101, T102, T103, T104, Run Yinglian company produce C9006,
C9012 etc..
In the present invention, the alkyl in zinc dialkyl dithiophosphate is preferably the alkyl of C2-C12, more excellent
Elect the alkyl of C2-C8 as, more preferably ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group,
Sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, iso-octyl, 2-ethylhexyl,
Cyclohexyl or methylcyclopentyl.Zinc dialkyl dithiophosphate can select south, Wuxi petroleum additive to have
T202, T203 that limit company produces, primary alkyl T202 that Jinzhou Petrochemical Company additive factory produces,
Primary alkyl T203, brothers alkyl T204, secondary alkyl T205, Lubrizol Corp. produce LZ1371,
C9417, C9425, C9426 that LZ1375, Run Yinglian company produces, Afton Chemical Corp. produces
Hitec7169, Hitec1656 etc..
In the present invention, Ashless friction modifiers is preferably selected from polyol esters of fatty acids, aliphatic amine and fat
The mixture of one or more in race's amide, more preferably polyol esters of fatty acids and aliphatic amide,
The weight ratio of polyol esters of fatty acids and aliphatic amide is preferably 0.5-3:1, and the most aliphatic alkyl is excellent
Electing the carbon number saturated or unsaturated alkyl between 6-60 as, more preferably carbon number is at 10-50
Between saturated or unsaturated alkyl.
Described polyol esters of fatty acids is preferably selected from fatty glyceride, fatty acid pentaerythritol ester, fat
Acid glycol ester, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, fat
At least one in the monoesters of compound, dibasic acid esters and the polyester such as triethylenetetraminehexaacetic acid alkanolamine ester, is more preferably selected from single oil
Acid glyceride, double olein, stearic acid monopentaerythritol ester, lauric acid/dodecanoic acid diethylene glycol dilaurate, oleic acid
At least one in diethanolamine monoesters and triethanolamine oleate monoesters；Described aliphatic amine is preferably selected from hydrocarbon
Base replaces the alkyl of monoamine or polyamine, alkoxylate and replaces monoamine or polyamine and alkyl ether amine etc.
In at least one, the tallow amine of more preferably ethoxylation and/or the Adeps Bovis seu Bubali aliphatic ether of ethoxylation
Amine；Described aliphatic amide is preferably selected from oleamide, coconut oleoyl amine and oleic acid diethyl amide etc.
At least one.Ashless friction modifiers such as can select F10, F20 etc. of BASF Aktiengesellschaft.
The lubricant oil composite of the present invention can also contain in antirust agent, pour-point depressant, tackifier and anti-foaming agent
At least one.Antirust agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5-dihydro
At least one in imidazoles, alkenyl imidazoline succinate and alkenyl succinic acid ester, such as, can select brocade
T746, T703, T747 that state safe lube oil additive company limited produces.Pour-point depressant can be selected from
Poly alpha olefin, vinyl acetate copolymer and alkyl are the dialkyl fumarate of C8-C18, poly-alkyl
At least one in methacrylate, alkylnaphthalene, such as, can select south, Wuxi petroleum additive public
V385, Luo Mankesi VISCOPLEX1-248 etc. of T803, Run Yinglian company of department.Tackifier can
With in ethylene propylene copolymer, polymethyl methacrylate and hydrogenated styrene isoprene copolymer
At least one, such as can select T601, SV260, Lz7065 etc..Anti-foaming agent can be selected poly-
Silicone-type anti-foaming agent, such as, can be silicone oil and/or polydimethylsiloxane.For antirust agent, pour point depression
The content of agent, tackifier and anti-foaming agent, without particular/special requirement, can be the content of this area routine, and this is this
Well known to skilled person, do not repeat them here.
In the present invention, shown in formula (I), the preparation method of the compound of structure preferably includes:
A (), by 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene carry out condensation reaction, generate shown in formula (II)
Intermediate M,
B intermediate M that step (a) is obtained by () contacts with bromide reagent and carries out bromo-reaction, raw
Become the bromination product shown in formula (III),
C bromination product that () makes step (b) obtain contacts with the compound shown in formula (IV) and carries out idol
Connection reaction, generates the antioxidant shown in formula (I),
In step (a) of the present invention, the condition of condensation reaction preferably includes: under an inert atmosphere,
In one solvent, in the presence of the first catalyst, by 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene are at-20-0 DEG C
Rise to 15-30 DEG C after lower reaction 0.5-1.5h, be then heated to 70-80 DEG C of reaction 1-3h.
In the present invention, inert atmosphere can be the inert atmosphere that this area is conventional, such as can by nitrogen,
The gases such as argon provide.
It will be understood by those skilled in the art that to make stable reaction carry out, react at-20-0 DEG C
15-30 DEG C is risen to, it should be to slowly warm up to 15-30 DEG C after 0.5-1.5h, for example, it is possible to will be at-20-0 DEG C
System after lower reaction 0.5-1.5h is placed under the ambient temperature of 15-30 DEG C, makes reaction system self slow
It is warming up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from methanol, ethanol, DMF and acetonitrile
At least one, more preferably methanol and/or acetonitrile, the most preferably methanol.
In the present invention, the first catalyst can be mineral acid or organic acid, is preferably selected from acetic acid, to methyl
At least one in benzoic acid and benzenesulfonic acid, more preferably acetic acid.
In the present invention, the consumption of 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene is substantially equimolar amounts, but
Formaldehyde and benzene can be suitably excessive.The mol 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 consumption of the first catalyst can be catalytic amount, with 2, and the tertiary fourth of 6-bis-
On the basis of the molal quantity of base phenol, the consumption of the first catalyst is preferably 5-100 mole of %, more preferably
10-30 mole of %.
It will be understood by those skilled in the art that in step (a) of the present invention, purer in order to obtain
Intermediate M, in addition it is also necessary to reacted system is carried out post processing, and the mode of post processing can include subtracting
Pressure removes solvent, then through solvent dilution, wash, be dried, reduce pressure removes solvent again, such as, general is instead
System after should removes solvent at 0.01-0.05MPa, 40-60 DEG C, is subsequently poured into 1-10 times of volume
In ethyl acetate (or dichloromethane), respectively with distilled water and saturated aqueous common salt washing, then at 15-30 DEG C
The desiccant such as lower addition anhydrous calcium chloride or anhydrous sodium sulfate, keep 10-60min.It is filtered to remove dry
After agent, at 0.01-0.05MPa, 40-60 DEG C, remove solvent, to obtain intermediate M.
In step (a) of the present invention, 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction of condensation reaction
Equation is as it is shown in figure 1, in Fig. 1, the first solvent uses methanol, and the first catalyst uses
Acetic acid, purpose by way of example only, the scope of the present invention is not construed as limiting.
In step (b) of the present invention, the condition of bromo-reaction preferably includes: under an inert atmosphere,
In two solvents, in the presence of the second catalyst, under the conditions of lucifuge, during step (a) is obtained
Mesosome M and bromide reagent react 1-2h at 15-30 DEG C, then use quencher cancellation.
" inert atmosphere " be not as it was previously stated, repeat them here.
It will be understood by those skilled in the art that and more stably carry out, preferably to intermediate to react
M is slowly added to brominated reagent.
In the present invention, the second solvent is preferably selected from oxolane, dichloromethane, chloroform and ether extremely
Few one, more preferably oxolane.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azo
At least one in bis-isobutyronitrile (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, more excellent
Elect NBS as.
In step (b) of the present invention, carrying out cancellation with quencher, quencher can be commonly used in the art
Quencher, such as, can be saturated aqueous common salt.
In step (b) of the present invention, intermediate M is substantially equimolar amounts with the consumption of bromide reagent,
But bromide reagent typically can be suitably excessive, reaches 1.1-3 times of equivalent of reaction substrate.Intermediate M with
Bromide reagent mol ratio is preferably 0.9-1.2:0.9-3.0.
In step (b) of the present invention, the consumption of the second catalyst can be catalytic amount, with intermediate M's
On the basis of molal quantity, the consumption of the second catalyst is preferably 10-100 mole of %, more preferably 40-60 and rubs
You are %.
In the inventive method step (b), intermediate M contacts with bromide reagent and carries out the anti-of bromo-reaction
Answer equation as in figure 2 it is shown, in Fig. 2, bromide reagent uses NBS, mesh by way of example only
, the scope of the present invention is not construed as limiting.
In step (b) of the present invention, in addition to generating the bromination product shown in formula (III), also trace
The bromination product at ortho position generates, and does not has the bromination product of meta to generate, but the amount of the bromination product at ortho position is very
Pettiness, does not has materially affect to subsequent reactions, is negligible.
It will be understood by those skilled in the art that in step (b) of the present invention, purer in order to obtain
Bromination product, in addition it is also necessary to the system after cancellation is carried out post processing, and the mode of post processing can include water
Wash, be dried, removal of solvent under reduced pressure, such as, by the system distilled water wash after cancellation, then exist
Add the desiccant such as anhydrous calcium chloride or anhydrous sodium sulfate at 15-30 DEG C, keep 10-60min.Filter
After removing desiccant, at 0.01-0.05MPa, 40-60 DEG C, remove solvent, to obtain bromination product.
In step (c) of the present invention, the condition of coupling reaction preferably includes: under an inert atmosphere,
In three solvents, in the presence of the 3rd catalyst, the bromination product that step (b) is obtained and formula (IV)
Shown compound reacts 4-8h at 80-100 DEG C.
" inert atmosphere " be not as it was previously stated, repeat them here.
In the present invention, in order to make stable reaction carry out, preferably it is gradually heating to 80-100 DEG C, then exists
4-8h is reacted at 80-100 DEG C.
In the present invention, the 3rd solvent is preferably selected from dichloromethane, chloroform, toluene and oxolane extremely
Few one, more preferably dichloromethane.
In the present invention, the 3rd catalyst preferably includes palladium salt, part and alkali.Palladium salt is preferably selected from palladium
And/or palladium-dibenzalacetone complex [Pd2(dba)3]；Part is preferably selected from tri-tert phosphorus, dinaphthol
(BINAP) at least one and in double (diphenylphosphino) ferrocene (dppf)；Alkali is preferably selected from uncle
At least one in sodium butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate.
In step (c) of the present invention, the bromination product that step (b) obtains and the chemical combination shown in formula (IV)
The consumption of thing is substantially equimolar amounts, but the compound shown in formula (IV) can be suitably excessive.Step
B bromination product that () obtains is preferably 0.9-1.5:0.9-2.5 with the mol ratio of the compound shown in formula (IV).
In step (c) of the present invention, the consumption of catalyst can be catalytic amount, with bromination product mole
On the basis of number, the consumption of palladium salt is preferably 5-50 mole of %, more preferably 5-20 mole %, more enters one
Step is preferably 5-10 mole of %；The consumption of part is preferably 5-50 mole of %, more preferably 10-30 mole %；
The consumption of alkali is preferably 5-50 mole of %, more preferably 10-30 mole %.
In step (c) of the present invention, the bromination product that step (b) obtains and the chemical combination shown in formula (IV)
Thing contact carries out the reaction equation of coupling reaction as it is shown on figure 3, in Fig. 3, palladium salt uses acetic acid
Palladium, purpose by way of example only, the scope of the present invention is not construed as limiting.
It will be understood by those skilled in the art that to obtain purer end product, i.e. formula (I)
Shown antioxidant, the inventive method the most also includes reacted system is carried out post processing, post processing
Mode can include filtration, solvent dilution, wash, be dried, removal of solvent under reduced pressure, such as, will be anti-
The filtrate after system filtration after should is poured in the ethyl acetate (or dichloromethane) of 1-10 times of volume,
Then with distilled water wash, at 15-30 DEG C, anhydrous calcium chloride or anhydrous sodium sulfate etc. are then added dry
Drying prescription, keeps 10-60min.After being filtered to remove desiccant, remove at 0.01-0.05MPa, 40-60 DEG C
Remove solvent, to obtain the antioxidant shown in formula (I).
The present invention is prepared each step of the method for the compound of structure shown in formula (I) the most under agitation
Carry out, for mixing speed without particular/special requirement, can be the mixing speed of this area routine, such as, stir
Mixing speed can be 100-800rpm.
In the method for the compound that the present invention prepares structure shown in formula (I), for the first solvent, second
The amount of solvent and the 3rd solvent, without particular/special requirement, can be the solvent load of this area routine, and this is ability
Well known to field technique personnel, do not repeat them here.
As it has been described above, it is contemplated that by lubricant oil composite contains the change of structure shown in formula (I)
Compound, and the combination of the compound of structure shown in formula (I) and thiophenols ester type antioxidant and realize invention
Purpose, even if lubricant oil composite has the performances such as excellent wear-resistant and antioxidation, suppresses high temperature deposition thing
Generation.Therefore, for the preparation method of lubricant oil composite without particular/special requirement, this area can be used
Conventional use of method, such as, second aspect, present invention also offers a kind of diesel engine lubricant
The preparation method of compositions, the method includes: will containing lube base oil, antioxygen multipurpose additive,
Thiophenols ester type antioxidant, polyisobutene succinimide ashless dispersant and boronation polyisobutylene succinyl
The mixture of imine dispersants, high base number magnesium salicylate and the mixture of low alkali value sulfoacid calcium, dialkyl group two
The raw material mix homogeneously of D2EHDTPA zinc and Ashless friction modifiers obtains lubricant oil composite, wherein, with
On the basis of the weight of lubricant oil composite, the consumption of lube base oil is that 75-95 weight %, antioxygen are many
The consumption of effect additive be 0.01-10 weight %, the consumption of thiophenols ester type antioxidant be 0.02-8 weight
Amount %, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersant
The consumption of mixture is 0.5-10 weight %, the mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium
Consumption is 0.2-10 weight %, the consumption of zinc dialkyl dithiophosphate in terms of phosphorus≤0.15 weight %,
The consumption of Ashless friction modifiers is 0.01-5 weight %, and antioxygen multipurpose additive is structure shown in formula (I)
Compound:
In the inventive method, it is preferable that on the basis of the weight of lubricant oil composite, lube base oil
Consumption be 75-85 weight %, the consumption of antioxygen multipurpose additive is 0.02-5 weight %, more preferably
0.1-4 weight %, the consumption of thiophenols ester type antioxidant is 0.05-4 weight %, more preferably 0.1-3 weight
Amount %, polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersant
The consumption of mixture is 1.5-8 weight %, more preferably 3-7 weight %, high base number magnesium salicylate and low alkali
The consumption of the mixture of value sulfoacid calcium is 0.5-8 weight %, more preferably 0.8-6 weight %, dialkyl group two
The consumption of D2EHDTPA zinc is weight % of 0.01-0.1 in terms of phosphorus, and the consumption of Ashless friction modifiers is 0.02-2
Weight %, more preferably 0.05-1.2 weight %.
As it was previously stated, in the inventive method, raw material can also contain antirust agent, pour-point depressant, tackifier and
At least one in anti-foaming agent.
In the inventive method, for the mode of mixing without particular/special requirement, such as can be except lube base
Each raw material components of oil is added separately in lube base oil, it is also possible to each by except lube base oil
Component is mixed and made into concentrate and is then added in lube base oil.
In the inventive method, the condition of mixing preferably includes: temperature is 40-90 DEG C, and the time is 1-6h.
Lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, polyisobutylene succinyl
Imines ashless dispersant and the mixture of boronation polyisobutene succinimide dispersant, high base number salicylic acid
Magnesium and the mixture of low alkali value sulfoacid calcium, zinc dialkyl dithiophosphate, Ashless friction modifiers, antirust
Agent, pour-point depressant, tackifier and anti-foaming agent be not as it was previously stated, repeat them here.
Embodiment
The present invention is further illustrated for below example, but and is not so limited the present invention.
In the following Examples and Comparative Examples:
The physico-chemical analysis method of product: measure element by inductively coupled plasma ion emission spectroscopy method
Content.
Structure characterization methods: nuclear magnetic resonance method (1H hydrogen is composed,13C carbon is composed), high resolution mass spectrum.
Preparation example
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), it is filled with nitrogen protect
Protect, add the methanol of 150ml and the acetic acid of 0.01mol, sufficiently cool in ice-water bath after, then divide
Do not add the 2 of 0.1mol, 6-DI-tert-butylphenol compounds, the formaldehyde of 0.2mol and the benzene of 0.3mol.Reaction 1
Remove ice-water bath after hour, rise to stopped reaction after 25 DEG C of post-heating persistently reflux 2 hours to 75 DEG C,
By reacted system at 0.03MPa, steam solvent at 50 DEG C, be subsequently adding 250ml ethyl acetate,
And proceed in separatory funnel, respectively with 100ml distilled water (twice) and the washing of 50ml saturated aqueous common salt,
And adding 10g anhydrous calcium chloride dry 20min at 25 DEG C, the filtrate after filtration is at 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain midbody product M1.
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), it is filled with nitrogen protect
Protect, add the dry tetrahydrofuran of 150ml, then dissolve in midbody product M1, and add 0.05mol
Ammonium nitrate, under the conditions of lucifuge, be slowly added into 0.1mol brominated reagent NBS.At 25 DEG C, stirring is anti-
Answer 1.5h, then use saturated aqueous common salt cancellation, then wash with 100ml distilled water (twice), and add
Enter 10g anhydrous sodium sulfate at 25 DEG C, be dried 20min.Filtrate after filtration is at 40 DEG C, 0.03MPa
Under solvent is evaporated off, obtain bromination product.
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), it is filled with nitrogen protect
Protect, add the dichloromethane of 150ml as solvent, be separately added into above-mentioned bromination product and 0.12mol
Benzotriazole compound, is subsequently added the tri-tert phosphorus of 0.02mol, the sodium tert-butoxide of 0.02mol and
The Pd (OAc) of 0.005mol2.It is gradually heating to 90 DEG C, continuously stirred 6h.Then by reacted body
Filtrate after system filters adds 250ml ethyl acetate, and proceeds in separatory funnel, uses 100ml distilled water
(twice) washing, and add 10g anhydrous sodium sulfate dry 20min at 25 DEG C.Filtrate after filtration
40 DEG C, solvent is evaporated off under 0.03MPa, obtain end product S1.
The physico-chemical analysis data of S1 are as follows: nitrogen content, and 11.2%.
S1 is carried out structural characterization, respectively obtains hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectively
See Fig. 4, Fig. 5 and Fig. 6.
From the physico-chemical analysis data of above-mentioned preparation example, Fig. 4, Fig. 5 and Fig. 6 it can be seen that S1 has formula
(I) structure shown in.
Embodiment 1
The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.
By the S1 of 0.1 weight portion, the 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) of 3 weight portions
Ethyl propionate], the polyisobutene succinimide ashless dispersant of 1.5 weight portions (polyisobutylene part
Number-average molecular weight is 1600), boronation polyisobutene succinimide dispersant (the poly-isobutyl of 1.5 weight portions
The number-average molecular weight of alkene part is 1300, and Boron contents is 0.8 weight %), the high base number water of 4.5 weight portions
Poplar acid magnesium (base number is 300mgKOH/g), (base number is the low alkali value sulfoacid calcium of 1.5 weight portions
50mgKOH/g), two isohesyl zinc dithiophosphates of 0.11 weight portion, single oleic acid of 0.03 weight portion
Glyceride, the oleamide of 0.02 weight portion, the pour-point depressant VISCOPLEX1-248 of 0.3 weight portion (purchase
From Luo Mankesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S. of the U.S.) and the tackifier Lz7065 of 6.4 weight portions, join 81.04
The 600SN lube base oil of weight portion (viscosity index (VI) is 87, and saturated hydrocarbon content is 92 weight %,
Sulfur content is 0.02 weight %) in, at 60 DEG C, stirring 3h, mix homogeneously obtains viscosity rank and is
The diesel engine lubricating oil composite A1 of 15W-40.
Embodiment 2
The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.
By the S1 of 0.3 weight portion, the 2,2'-thiobis [3-(3,5-di-t-butyl-4-hydroxy benzenes of 0.3 weight portion
Base) ethyl propionate], polyisobutene succinimide ashless dispersant (the polyisobutylene portion of 5.25 weight portions
Point number-average molecular weight be 2300), the boronation polyisobutene succinimide dispersant of 1.75 weight portions (poly-
The number-average molecular weight of isobutene. part is 1000, and Boron contents is 0.8 weight %), 1.4 weight portions high-alkali
Value magnesium salicylate (base number is 350mgKOH/g), (base number is the low alkali value sulfoacid calcium of 0.6 weight portion
30mgKOH/g), double oil of the isohesyl iso-octyl zinc dithiophosphate of 1.1 weight portions, 0.2 weight portion
Acid glyceride, the coconut oleoyl amine of 0.4 weight portion, the pour-point depressant VISCOPLEX1-248 of 0.3 weight portion
(purchased from Luo Mankesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S. of the U.S.) and the tackifier Lz7065 of 6.4 weight portions, join
The II class 150N base oil (viscosity index (VI) is 117) of 68 weight portions and II class 600N of 14 weight portions
In the mixed lubrication oil base oil of base oil (viscosity index (VI) is 103), at 40 DEG C, stir 6h, mixing
Uniformly obtain the diesel engine lubricating oil composite A2 that viscosity rank is 15W-40.
Embodiment 3
The present embodiment is for lubricant oil composite that the present invention is described and preparation method thereof.
By the S1 of 4 weight portions, the 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) of 0.1 weight portion
Ethyl propionate], polyisobutene succinimide ashless dispersant (the polyisobutylene part of 3.34 weight portions
Number-average molecular weight be 1000), the boronation polyisobutene succinimide dispersant of 1.67 weight portions (poly-
The number-average molecular weight of isobutene. part is 2300, and Boron contents is 0.8 weight %), 0.3 weight portion high-alkali
Value magnesium salicylate (base number is 450mgKOH/g), (base number is the low alkali value sulfoacid calcium of 0.5 weight portion
40mgKOH/g), the n-hexyl n-octyl zinc dithiophosphate of 0.53 weight portion, the tristearin of 0.9 weight portion
Acid monopentaerythritol ester, the oleic acid diethyl amide of 0.3 weight portion, the pour-point depressant of 0.3 weight portion
VISCOPLEX1-248 (purchased from Luo Mankesi Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S. of the U.S.) and the adhesion-promoting of 6.4 weight portions
Agent Lz7065, join 81.66 weight portions 300SN lube base oil (viscosity index (VI) is 91,
Saturated hydrocarbon content is 92 weight %, and sulfur content is 0.01 weight %) in, at 90 DEG C, stir 1h, mixed
Close and uniformly obtain the diesel engine lubricating oil composite A3 that viscosity rank is 15W-40.
Comparative example 1
Prepare lubricant oil composite according to the method for embodiment 2, except for the difference that, the weight such as S1 is replaced with
The 2 of amount part, 2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate], obtaining viscosity rank is
The diesel engine lubricating oil composite D1 of 15W-40.
Comparative example 2
Lubricant oil composite is prepared according to the method for embodiment 2, except for the difference that, by 2,2'-thiobis [3-(3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] S1 of weight portion such as replace with, obtaining viscosity rank is
The diesel engine lubricating oil composite D2 of 15W-40.
Comparative example 3
Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2
Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] dibutyl dithio of weight portion such as replace with
Carbaminate, obtains the diesel engine lubricating oil composite D3 that viscosity rank is 15W-40.
Comparative example 4
Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2
Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] the trimethylphenyl phosphorous of weight portion such as replace with
Acid zinc, obtains the diesel engine lubricating oil composite D4 that viscosity rank is 15W-40.
Comparative example 5
Lubricant oil composite is prepared, except for the difference that, by S1 and 2,2'-sulfur generation according to the method for embodiment 2
Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] the fourth octyl diphenylamine of weight portion such as replace with,
Obtain the diesel engine lubricating oil composite D5 that viscosity rank is 15W-40.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested the most as follows:
TA5000-DSC2910 differential thermal analyzer is used to carry out the mensuration of initial oxidation temperature；
High Pressure Difference heat scan mensuration (PDSC) is used to carry out the mensuration of oxidation induction period；
Crankcase QZX experiment method is used to measure deposit growing amount: to be added into by 300mL oil sample
Burnt plate tester, heating and keeping oil temperature is 120 DEG C, and aluminium sheet temperature is 320 DEG C, spatters continuously to aluminium sheet
Oil 6h, weighs the burnt amount generated on aluminium sheet, is deposit growing amount after test.
High-frequency reciprocating frictional testing machine (purchased from PCS company of Britain, HFRR) is used to carry out the height of oil product
The wear-resistant test of temperature, experimental condition is: load 1000g, and temperature is 100 DEG C, and test period is 120min,
Frequency is 10Hz, measures the wear scar diameter formed on steel ball after off-test.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 growing amount, 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 the highest, the heat stability of lubricating oil
The best；Oxidation induction period is the longest, and the antioxygenic property of lubricating oil is the best；Deposit growing amount is the highest, profit
The ability that lubricating oil suppression high temperature deposition thing generates is the poorest；Wear scar diameter is the least, the wear resistance of lubricating oil
The best.
A2 is compared with D1-D5 respectively it can be seen that the lubricant oil composite of the present invention has more
Good heat stability, non-oxidizability and abrasion resistance, has the energy that preferably suppression high temperature deposition thing generates
Power.
The diesel engine lubricating oil composite of the present invention has abrasion resistance and the antioxygenic property of excellence,
Can suppress the generation of high temperature deposition thing, and there is the sulfur content less than 0.5%, phosphorus less than 0.1%
Content, meets CJ-4 and the requirement of above rank diesel engine lubricant.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, but, the present invention does not limit
Detail in above-mentioned embodiment, in the technology concept of the present invention, can be to the present invention
Technical scheme carry out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a diesel engine lubricating oil composite, it is characterised in that with the weight of lubricant oil composite
On the basis of amount, described 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 %, 0.5-10
The polyisobutene succinimide ashless dispersant of weight % and the dispersion of boronation polyisobutene succinimide
The mixture of agent, the high base number magnesium salicylate of 0.2-10 weight % and the mixture of low alkali value sulfoacid calcium, with
The zinc dialkyl dithiophosphate of phosphorus meter≤0.15 weight % and the Ashless friction of 0.01-5 weight % improve
Agent, described antioxygen multipurpose additive is the compound of structure shown in formula (I):
Lubricant oil composite the most according to claim 1, wherein, with the weight of lubricant oil composite
On the basis of amount, described lubricant oil composite contains following components: the lube base oil of 75-85 weight %,
The antioxygen multipurpose additive of 0.1-4 weight %, the thiophenols ester type antioxidant of 0.1-3 weight %, 3-7 weight %
Polyisobutene succinimide ashless dispersant and boronation polyisobutene succinimide dispersant mixed
Compound, the high base number magnesium salicylate of 0.8-6 weight % and the mixture of low alkali value sulfoacid calcium, in terms of phosphorus
The zinc dialkyl dithiophosphate of 0.01-0.1 weight % and the Ashless friction modifiers of 0.05-1.2 weight %.
Lubricant oil composite the most according to claim 1 and 2, wherein, described lube base
Oil is mineral lubricating oil and/or synthetic lubricant fluid.
Lubricant oil composite the most according to claim 1 and 2, wherein, described thiophenols ester type
Antioxidant is the double lauryl alcohol ester of thio-2 acid, thio-2 acid double octadecyl ester, 2,5-dimercapto-1,3,4-
At least one in thiadiazoles and 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate].
Lubricant oil composite the most according to claim 1 and 2, wherein, described polyisobutylene fourth
In imidodicarbonic diamide ashless dispersant, the number-average molecular weight of polyisobutylene part is 800-4000, is preferably
900-3000, more preferably 1000-2400；Described boronation polyisobutene succinimide dispersant gathers
The number-average molecular weight of isobutene. part is 500-4000, preferably 700-2500, more preferably
1000-2300；Described polyisobutene succinimide ashless dispersant and described boronation polyisobutylene fourth two
The weight ratio of acid imide dispersant is 1-3:1.
Lubricant oil composite the most according to claim 1 and 2, wherein, described high base number bigcatkin willow
The base number of acid magnesium is 100-450mgKOH/g, preferably 300-450mgKOH/g；Described low alkali value sulphur
Base number≤the 100mgKOH/g, preferably≤50mgKOH/g of acid calcium；Described high base number magnesium salicylate and institute
The weight ratio stating low alkali value sulfoacid calcium is 0.1-10:1, preferably 0.6-3:1.
Lubricant oil composite the most according to claim 1 and 2, wherein, described dialkyl disulfides
For the alkyl that the alkyl in zinc phosphate is the alkyl of C2-C12, preferably C2-C8, more preferably ethyl,
N-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, different
Hexyl, n-octyl, 2-ethylhexyl, cyclohexyl or methylcyclopentyl.
Lubricant oil composite the most according to claim 1 and 2, wherein, described Ashless friction changes
Enter one or more in polyol esters of fatty acids, aliphatic amine and aliphatic amide of agent, be preferably
Polyol esters of fatty acids and the weight of the mixture of aliphatic amide, polyol esters of fatty acids and aliphatic amide
Amount ratio is 0.5-3:1, and the carbon number of polyol esters of fatty acids, aliphatic amine and aliphatic amide is 6-60,
It is preferably 10-50.
Lubricant oil composite the most according to claim 8, wherein, described polyol esters of fatty acids
Selected from fatty glyceride, fatty acid pentaerythritol ester, ethylene glycol fatty acid, fatty acid succinate,
Fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, the monoesters of fatty acid triethanolamine ester, dibasic acid esters and many
At least one in ester, described aliphatic amine is selected from the substituted monoamine of alkyl or polyamine, alkoxylate
The substituted monoamine of alkyl or polyamine and alkyl ether amine at least one, described aliphatic amide selects
At least one in oleamide, coconut oleoyl amine and oleic acid diethyl amide.
Lubricant oil composite the most according to claim 9, wherein, described polyol esters of fatty acids
Selected from glyceryl monooleate, double olein, stearic acid monopentaerythritol ester, lauric acid/dodecanoic acid ethylene glycol bis
At least one in ester, oleic acid diethanolamine monoesters and triethanolamine oleate monoesters；Described aliphatic amine is
The tallow amine of ethoxylation and/or the Adeps Bovis seu Bubali fat ether amines of ethoxylation.
11. lubricant oil composites according to claim 1 and 2, wherein, described lubricating oil composition
Thing is possibly together with at least one in antirust agent, pour-point depressant, tackifier and anti-foaming agent.
12. lubricant oil composites according to claim 11, wherein, described antirust agent is selected from miaow
Azole and/or alkenyl succinic acid esters, preferably 4,5-glyoxalidine, alkenyl imidazoline succinate and alkene
At least one in base succinate.
13. lubricant oil composites according to claim 11, wherein, described pour-point depressant selected from poly-α-
Alkene, vinyl acetate copolymer and alkyl are the dialkyl fumarate of C8-C18, poly-alkyl methyl
At least one in acrylate, alkylnaphthalene.
14. lubricant oil composites according to claim 11, wherein, described tackifier is ethylene
In propylene copolymer, polymethyl methacrylate and hydrogenated styrene isoprene copolymer at least one
Kind.
15. lubricant oil composites according to claim 11, wherein, described anti-foaming agent is poly-silicon
Oxygen alkane type anti-foaming agent, preferably silicone oil and/or polydimethylsiloxane.
The preparation method of 16. 1 kinds of diesel engine lubricating oil composites, it is characterised in that described method
Including: will be containing lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, poly-isobutyl
Alkene Ashless butyl diimide dispersant and the mixture of boronation polyisobutene succinimide dispersant, high-alkali
Value magnesium salicylate and the mixture of low alkali value sulfoacid calcium, zinc dialkyl dithiophosphate and Ashless friction improve
The raw material mix homogeneously of agent obtains lubricant oil composite, wherein, on the basis of the weight of lubricant oil composite,
The consumption of lube base oil be 75-95 weight %, the consumption of antioxygen multipurpose additive be 0.01-10 weight
Amount %, the consumption of thiophenols ester type antioxidant are 0.02-8 weight %, polyisobutene succinimide ashless
The consumption of the mixture of dispersant and boronation polyisobutene succinimide dispersant is 0.5-10 weight %,
The consumption of the mixture of high base number magnesium salicylate and low alkali value sulfoacid calcium is 0.2-10 weight %, dialkyl group two
The consumption of D2EHDTPA zinc in terms of phosphorus≤0.15 weight %, the consumption of Ashless friction modifiers is 0.01-5
Weight %, described antioxygen multipurpose additive is the compound of structure shown in formula (I):
17. methods according to claim 16, wherein, with the weight of lubricant oil composite as base
Standard, the consumption of lube base oil be 75-85 weight %, the consumption of antioxygen multipurpose additive be 0.1-4
Weight %, the consumption of thiophenols ester type antioxidant are 0.1-3 weight %, polyisobutene succinimide ashless
The consumption of the mixture of dispersant and boronation polyisobutene succinimide dispersant is 3-7 weight %, high
The consumption of the mixture of base number magnesium salicylate and low alkali value sulfoacid calcium is 0.8-6 weight %, dialkyl disulfides
Consumption for zinc phosphate is weight % of 0.01-0.1 in terms of phosphorus, and the consumption of Ashless friction modifiers is 0.05-1.2
Weight %.
18. according to the method described in claim 16 or 17, and wherein, the condition of described mixing includes:
Temperature is 40-90 DEG C, and the time is 1-6h.
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Cited By (2)
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| CN107129840A (en) * | 2017-04-19 | 2017-09-05 | 江苏科创石化有限公司 | One kind hydrogenation low sulfur diesel lubricity additive and preparation method thereof |
| CN113462441A (en) * | 2020-03-30 | 2021-10-01 | 中国石油化工股份有限公司 | Diesel antiwear agent composition, preparation method thereof and diesel composition |
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| CN107129840B (en) * | 2017-04-19 | 2018-07-27 | 江苏科创石化有限公司 | One kind plus hydrogen low sulfur diesel lubricity additive and preparation method thereof |
| CN113462441A (en) * | 2020-03-30 | 2021-10-01 | 中国石油化工股份有限公司 | Diesel antiwear agent composition, preparation method thereof and diesel composition |
| CN113462441B (en) * | 2020-03-30 | 2023-01-13 | 中国石油化工股份有限公司 | Diesel oil antiwear agent composition, preparation method thereof and diesel oil composition |
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| CN106318545B (en) | 2019-04-16 |
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