CN106318557B - A kind of methanol-fueled engine lubricant oil composite and preparation method thereof - Google Patents
A kind of methanol-fueled engine lubricant oil composite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of methanol-fueled engine lubricant oil composites, on the basis of the weight of lubricant oil composite, the 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 0.02-5 weight %, the polyisobutene succinimide ashless dispersant of 0.5-10 weight % and the mixture of polyisobutylene succinic acid ester dispersing agent, the sodium sulfonate of 0.2-10 weight % and the mixture of calcium naphthenate, in terms of phosphorus≤zinc dialkyl dithiophosphate of 0.08 weight % and the compound friction improving agent of 0.01-5 weight %, the antioxygen multipurpose additive is the compound of structure shown in formula (I).Additionally provide the preparation method of lubricant oil composite.Lubricant oil composite of the invention has excellent wear-resistant and antioxygenic property, can inhibit the generation of high temperature deposition object, can be widely applied to methanol-fueled engine.
Description
Technical field
The present invention relates to lubricating oil fields, and in particular, to a kind of methanol-fueled engine profit containing special additive
Sliding oil composition and preparation method thereof.
Background technique
The methanol fuel alternative energy source novel as one is with a wide range of applications, and the by-product that methanol burning generates
Object is acid by force, it is rotten to easily lead to engine oil.Methanol gasoline in use, unavoidably has methanol to enter in lubricating oil.
Gas blowby in engine working process, the cooling procedure of engine working process are likely to make methanol condensed and enter lubricating oil.
Methanol can aoxidize generation formaldehyde in combustion, and formaldehyde is the intermediate product in methanol combustion process, and then aoxidize and generate first
Acid.Oxidation product formic acid will make each component of engine generate stronger corrosive wear.Therefore, it is fired using the methanol of 100% content
Material, or mixing different proportion carbinol gasoline fuel engine the high-temperature oxidation resistance of lubricating oil is proposed it is very high
Requirement.Methanol-fueled engine oil is easier to be diluted relative to normal engine oil, therefore it is required that having preferably wear-resistant
The requirement such as performance.Engine oil for methanol fuel has better deposit resistant to high temperatures and abrasion-resistance is in a research and development
Difficult point.
The high-temperature oxidation resistance of engine lubricating oil is always an important indicator in oil specification.Engine technology
Continuous development, the especially application of the gentle in-cylinder direct-jet technology of turbocharging technology, the temperature ratio at the positions such as engine piston
Pervious engine significantly improves, and the speed of engine oil aged deterioration is dramatically speeded up, and the consumption of engine oil increases, and especially exists
The generation of the key positions engine high-temperature deposit such as piston, combustion chamber, seriously affects the working performance of engine, causes to start
The problems such as machine difficulty in starting, unstable idle speed, driving are poor, acceleration is poor, power loss is serious.In new SN/GF-5 in 2010
Harsher requirement is proposed to the piston deposit of IIIG engine test test engine oil in specification, piston deposit is commented
Divide and promoted by 3.5 to 4 by index, severity greatly improves.This proposes new demand to the high temperature antioxygen property of antioxidant,
Develop direction of the novel high-temperature antioxidant as the research effort of those skilled in the art.
It mainly includes phenols and aminated compounds that the lube oil additive of antioxidation can be effectively played by, which being currently known,.
Phenolic compound contains one or more and is obstructed phenol functional group, and aminated compounds then contains one or more nitrogen-atoms, these are special
Different functional group can capture the free radical compounds of oxidation process generation, so that oxidation process be prevented to continue to occur.Due to
The operating condition of Current mechanical equipment tends to strongly, often accelerated oxidation rate, shortens the service life of lubricating oil, therefore right
More stringent requirements are proposed for the efficiency and economy of antioxidant.
United States Patent (USP) US4824601A reports diphenylamine and diisobutylene in the alkaline-earth metal catalyst of acid activation
The lower alkylated amines mixture formed of (earth catalyst) effect, its anti-oxidant energy in lubricating oil and other functional fluids
Power is excellent in.
United States Patent (USP) US2005230664A1 reports a kind of synthesis of the antioxidant acridan of following general formula
Method, it is to be condensed preparation under acidic catalyst effect using alkylated diphenylamine and aldehydes or ketones.
Using the tert-butyl phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine condensation preparationization occurs for patent CN1191340C
Object is closed, which has the stronger ability for capturing free radical and peroxynitrite decomposition compound, can provide to oil oxidation stability
More effectively protection, may also function as wear-resistant effect.
Patent US4225450A report it is a kind of by the tert-butyl phenols that is obstructed with Diethyldithiocarbamate the system of reacting
Standby polysulfide phenolic antioxidant has 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 methanol-fueled engine lubricating oil and inhibit high temperature heavy
The high request for the ability that product object generates, provides a kind of methanol-fueled engine lubricant oil composite and preparation method thereof.
The present inventor has found that lubricant oil composite contains the compound of structure shown in formula (I) under study for action:
And the compound and thiophenols ester type antioxidant are combined, and methanol-fueled engine lubricant oil composite can be made to have
There are the excellent 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 methanol-fueled engine lubricating oil compositions
Object, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: the lubrication of 75-95 weight %
Oil base oil, the antioxygen multipurpose additive of 0.01-10 weight %, 0.02-5 weight % thiophenols ester type antioxidant, 0.5-10
The polyisobutene succinimide ashless dispersant of weight % and mixture, the 0.2-10 weight of polyisobutylene succinic acid ester dispersing agent
Measure the sodium sulfonate of % and the mixture of calcium naphthenate, in terms of phosphorus≤zinc dialkyl dithiophosphate and 0.01-5 of 0.08 weight %
The compound friction improving agent of weight %, the antioxygen multipurpose additive are the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 78-90
The lube base oil of weight %, the antioxygen multipurpose additive of 0.1-4 weight %, the thiophenols ester type of 0.2-1.5 weight % are anti-
Oxygen agent, the polyisobutene succinimide ashless dispersant of 3-6 weight % and polyisobutylene succinic acid ester dispersing agent mixture,
The dialkyl dithiophosphoric acid of the mixture of the sodium sulfonate of 1.2-6 weight % and calcium naphthenate, the weight of the 0.01-0.08 in terms of phosphorus %
The compound friction improving agent of zinc and 0.05-1.2 weight %.
On the other hand, the present invention provides a kind of preparation method of methanol-fueled engine lubricant oil composite, the sides
Method includes: that will contain lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, polyisobutene succinimide
Mixture, the dialkyl group two of the mixture of ashless dispersant and polyisobutylene succinic acid ester dispersing agent, sodium sulfonate and calcium naphthenate
The raw material of thiophosphoric acid zinc and compound friction improving agent is uniformly mixed and obtains lubricant oil composite, wherein with lubricant oil composite
Weight on the basis of, the dosage of lube base oil is 75-95 weight %, the dosage of antioxygen multipurpose additive be 0.01-10 weight
Measure %, the dosage of thiophenols ester type antioxidant is 0.02-5 weight %, polyisobutene succinimide ashless dispersant and is gathered different
The dosage of the mixture of butylene succinate dispersing agent is 0.5-10 weight %, the dosage of the mixture of sodium sulfonate and calcium naphthenate
For 0.2-10 weight %, the dosage of zinc dialkyl dithiophosphate be in terms of phosphorus≤0.08 weight %, compound friction improving agent
Dosage is 0.01-5 weight %, and the antioxygen multipurpose additive is the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 78-90 weight %, resists
The dosage of oxygen multipurpose additive is 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is 0.2-1.5 weight %, poly- isobutyl
The dosage of the mixture of alkene Ashless butyl diimide dispersant and polyisobutylene succinic acid ester dispersing agent is 3-6 weight %, sulfonic acid
The dosage of the mixture of sodium and calcium naphthenate is 1.2-6 weight %, and the dosage of zinc dialkyl dithiophosphate is the 0.01- in terms of phosphorus
0.08 weight %, the dosage of compound friction improving agent are 0.05-1.2 weight %.
Methanol-fueled engine lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can press down
The generation of preparing high-temp deposit, can be widely applied to methanol-fueled engine.
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 methanol-fueled engine lubricant oil composites, with the weight of lubricant oil composite
On the basis of amount, the lubricant oil composite contains following components: lube base oil, the 0.01-10 weight % of 75-95 weight %
Antioxygen multipurpose additive, the thiophenols ester type antioxidant of 0.02-5 weight %, 0.5-10 weight % polyisobutene succinyl
The sodium sulfonate and calcium naphthenate of the mixture of imines ashless dispersant and polyisobutylene succinic acid ester dispersing agent, 0.2-10 weight %
Mixture, in terms of phosphorus≤compound friction of the zinc dialkyl dithiophosphate of 0.08 weight % and 0.01-5 weight % improves
Agent, 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 78-90 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 0.1-2 weight %, more preferably 0.2-1.5 weight %；Polyisobutene succinimide ashless dispersion
The content of the mixture of agent and polyisobutylene succinic acid ester dispersing agent is preferably 1.5-8 weight %, more preferably 3-6 weight %；
The content of the mixture of sodium sulfonate and calcium naphthenate is preferably 0.8-8 weight %, more preferably 1.2-6 weight %；Dialkyl group two
The content of thiophosphoric acid zinc is preferably 0.01-0.08 weight % in terms of phosphorus；The content of compound friction improving agent 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 800- in polyisobutylene succinic acid ester dispersing agent
4000, more preferably 900-3000, further preferably 1000-2400.Polyisobutylene succinic acid ester dispersing agent can for example select
The LZ936 etc. produced with Lubrizol Corp..
In the present invention, the weight ratio of polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent
Preferably 1-3:1.
In the present invention, the base number of sodium sulfonate is preferably 100-450mgKOH/g, more preferably 200-450mgKOH/g, cycloalkanes
The base number of sour calcium is preferably 100-200mgKOH/g, and the weight ratio of sodium sulfonate and calcium naphthenate is preferably 0.2-4:1, more preferably
0.5-2:1.The mixture of sodium sulfonate and calcium naphthenate can for example select Dushanzi petro-chemical corporation produce T112, T113,
T114, the KT5448 etc. of Jinzhou Kangtai Lube Additive Co., Ltd.'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, compound friction improving agent preferably comprises oil-soluble organic molybdenum friction improver and Ashless friction improves
Agent.
Oil-soluble organic molybdenum friction improver is preferably selected from molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen
Molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex and molybdenum
One of esters of gallic acid oil-soluble organic molybdenum friction improver is a variety of, has in above-mentioned organic molybdenum former comprising enough carbon
The organic group of subnumber is so that organic molybdenum is dissolved in or is scattered in base oil, and the general carbon atom number is in 6-
Between 60, between preferably 10-50.Oil-soluble organic molybdenum friction improver can for example select Vanderbilt company, the U.S. to produce
MolyVan L, 822,855, the Japanese rising sun electrification company production 515,525,710 etc..Oil-soluble organic molybdenum friction improver
It is preferred that accounting for the 5-50% of compound friction improving agent gross mass, more preferably 10-40%.
Ashless friction modifiers are preferably selected from one kind or more of polyol esters of fatty acids, aliphatic amine and aliphatic amide
Kind, wherein aliphatic alkyl is preferably saturation or unsaturated alkyl of the carbon atom number between 6-60, more preferably carbon atom
Saturation or unsaturated alkyl of the number between 10-50.The polyol esters of fatty acids is preferably selected from fatty glyceride, fatty acid
Pentaerythritol ester, ethylene glycol fatty acid, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, fat
At least one of monoesters, dibasic acid esters and polyester of the compounds such as triethylenetetraminehexaacetic acid alkanolamine ester are more preferably selected from glyceryl monooleate, double oil
Acid glyceride, stearic acid monopentaerythritol ester, lauric acid/dodecanoic acid diethylene glycol dilaurate, oleic acid diethanol amine monoesters and triethanolamine oleate list
At least one of ester；The aliphatic amine is preferably selected from alkyl and monoamine or polyamine, alkoxylated alkyl is replaced to replace
At least one of monoamine or polyamine and alkyl ether amine etc., the more preferably tallow amine and/or ethoxy of ethoxylation
The butter fat ether amines of base；The aliphatic amide is preferably selected from oleamide, coconut oleoyl amine and oleic acid diethyl amide etc.
At least one of.Ashless friction modifiers can for example select the F10 of BASF Aktiengesellschaft, F20 etc..Ashless friction improves
Agent preferably accounts for the 50-95% of compound friction improving agent gross mass, more preferably 60-90%.
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-butylphosphine, 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 methanol
The preparation method of engine fuel lubricant oil composite, this method comprises: by being added containing lube base oil, antioxygen multiple-effect
Agent, thiophenols ester type antioxidant, polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent it is mixed
The raw material mixing for closing object, the mixture of sodium sulfonate and calcium naphthenate, zinc dialkyl dithiophosphate and compound friction improving agent is equal
It is even to obtain lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 75-95
Weight %, antioxygen multipurpose additive dosage be 0.01-10 weight %, the dosage of thiophenols ester type antioxidant be 0.02-5 weight
The dosage for measuring the mixture of %, polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent is 0.5-
The dosage of the mixture of 10 weight %, sodium sulfonate and calcium naphthenate is 0.2-10 weight %, the use of zinc dialkyl dithiophosphate
Amount in terms of phosphorus≤0.08 weight %, the dosage of compound friction improving agent is 0.01-5 weight %, the antioxygen multipurpose additive
For 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
78-90 weight %, antioxygen multipurpose additive dosage be 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is 0.2-1.5
The dosage of the mixture of weight %, polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent is 3-
The dosage of the mixture of 6 weight %, sodium sulfonate and calcium naphthenate is 1.2-6 weight %, the dosage of zinc dialkyl dithiophosphate
For the weight % of the 0.01-0.08 in terms of phosphorus, the dosage of compound friction improving agent is 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
Mixture, the dialkyl dithio phosphorus of the mixture of powder and polyisobutylene succinic acid ester dispersing agent, sodium sulfonate and calcium naphthenate
Sour zinc, compound friction improving agent, antirust agent, pour-point depressant, tackifier and anti-foaming agent are as previously mentioned, details are not described herein.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In the following Examples and Comparative Examples:
The 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-butylphosphine 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, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 1.5 parts by weight
Acetoacetic ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 1.5 parts by weight
1000), the polyisobutylene succinic acid ester dispersing agent (number-average molecular weight of polyisobutene part is 1000) of 1.5 parts by weight, 1 weight
Part sodium sulfonate (base number 200mgKOH/g), the calcium naphthenates (base number 100mgKOH/g) of 1 parts by weight, 0.2 parts by weight
Two isohesyl zinc dithiophosphates, the dibutyl dithio molybdenum phosphate of 0.12 parts by weight, 1.08 parts by weight lauric acid/dodecanoic acid ethylene glycol
Dibasic acid esters, the pour-point depressant T803 (be purchased from Wuxi south petroleum additive company) of 0.2 parts by weight and the tackifier of 4.8 parts by weight
SV260, be added to 87 parts by weight 600SN lube base oil (viscosity index (VI) 87, saturated hydrocarbon content be 92 weight %, sulphur
Content is 0.02 weight %) in, 3h is stirred at 60 DEG C, is uniformly mixed and obtains lubricant oil composite A1.
Embodiment 2
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 0.6 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 0.6 parts by weight
Acetoacetic ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 3.5 parts by weight
1300), polyisobutylene succinic acid ester dispersing agent (number-average molecular weight of polyisobutene part is 1300), 0.5 weight of 1.5 parts by weight
Measure the sodium sulfonate (base number 300mgKOH/g) of part, the calcium naphthenate (base number 170mgKOH/g) of 1 parts by weight, 0.9 parts by weight
Two isohesyl zinc dithiophosphates, dibutyl dithiocaarbamate molybdenum, the single oleic acid of 0.2 parts by weight of 0.05 parts by weight it is sweet
Grease, the pour-point depressant T803 (be purchased from Wuxi south petroleum additive company) of 0.2 parts by weight and the tackifier of 4.8 parts by weight
SV260 is added to the Group III 150N base oil (viscosity index (VI) 124) of 49 parts by weight and the Group III 350N of 37.15 parts by weight
In the mixed lubrication oil base oil of base oil (viscosity index (VI) 126), 6h is stirred at 40 DEG C, is uniformly mixed and obtains lubricating oil group
Close object A2.
Embodiment 3
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 4 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 0.2 parts by weight
Ethyl ester], (number-average molecular weight of polyisobutene part is for the polyisobutene succinimide ashless dispersants of 4.5 parts by weight
2400), the polyisobutylene succinic acid ester dispersing agent (number-average molecular weight of polyisobutene part is 2400) of 1.5 parts by weight, 4 weight
Part sodium sulfonate (base number 450mgKOH/g), the calcium naphthenates (base number 200mgKOH/g) of 2 parts by weight, 0.5 parts by weight
Two isohesyl zinc dithiophosphates, the dibutyl dithio phosphoric acid oxygen molybdenum of 0.02 parts by weight, 0.03 parts by weight stearic acid single cropping
Doutrate, the pour-point depressant T803 (be purchased from Wuxi south petroleum additive company) of 0.2 parts by weight and the tackifier of 4.8 parts by weight
SV260 is added to the 100N lube base oil of 78.25 parts by weight (viscosity index (VI) 112, saturated hydrocarbon content are 96 weight %)
In, 1h is stirred at 90 DEG C, is uniformly mixed and obtains lubricant oil composite A3.
Comparative example 1
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, S1 is replaced with etc. the 2,2'- of parts by weight
Thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], obtains lubricant oil composite D1.
Comparative example 2
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by 2,2'- thiobis [3- (3,5- bis- uncles
Butyl -4- hydroxy phenyl) ethyl propionate] S1 that the parts by weight such as replaces with, obtain lubricant oil composite D2.
Comparative example 3
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] zinc dibutyl dithiocarbamate that the parts by weight such as replaces with, it is lubricated
Fluid composition D3.
Comparative example 4
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the trimethylphenyl zinc phosphite that the parts by weight such as replaces with, obtain lubricating oil composition
Object D4.
Comparative example 5
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the fourth octyl diphenylamine that the parts by weight such as replaces with, obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively:
The measurement of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzer；
The measurement of oxidation induction period is carried out using high pressure differential scanning amount method (PDSC)；
Deposit production quantity is measured using crankcase QZX experiment method: QZX experiment instrument is added in 300mL oil sample,
Heating and keeping oil temperature is 130 DEG C, and aluminium sheet temperature is 290 DEG C, to the continuous spilled oil 6h of aluminium sheet, is generated on weighing aluminium sheet after test
Jiao Liang, as deposit production quantity.
Wear scar diameter is measured using SH/T 0189.It the results are shown in Table 1.
Table 1
| A1 | A2 | A3 | D1 | D2 | D3 | D4 | D5 | |
| Initial oxidation temperature, DEG C | 230 | 228 | 249 | 205 | 219 | 205 | 188 | 191 |
| Oxidation induction period, min | 54.7 | 53.5 | 62.1 | 33.6 | 42.7 | 31.4 | 19.4 | 18.7 |
| Deposit production quantity, mg | 26.8 | 22.6 | 16.1 | 51.9 | 32.7 | 54.7 | 89.1 | 82.2 |
| Wear scar diameter d60 40, μm | 635 | 561 | 524 | 703 | 613 | 652 | 669 | 776 |
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.
Methanol-fueled engine lubricant oil composite of the invention has excellent abrasion resistance and antioxygenic property, can press down
The generation of preparing high-temp deposit, can be widely applied to methanol-fueled engine.
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 (33)
1. a kind of methanol-fueled engine lubricant oil composite, which is characterized in that on the basis of the weight of lubricant oil composite, institute
It states lubricant oil composite and contains following components: the antioxygen multiple-effect of the lube base oil of 75-95 weight %, 0.01-10 weight %
Additive, the thiophenols ester type antioxidant of 0.02-5 weight %, 0.5-10 weight % polyisobutene succinimide ashless point
The mixture of powder and polyisobutylene succinic acid ester dispersing agent, the sodium sulfonate of 0.2-10 weight % and calcium naphthenate mixture,
In terms of phosphorus≤and the zinc dialkyl dithiophosphate of 0.08 weight % and the compound friction improving agent of 0.01-5 weight %, 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 78-90 weight %, 0.1-4 weight % antioxygen multipurpose additive,
The thiophenols ester type antioxidant of 0.2-1.5 weight %, the polyisobutene succinimide ashless dispersant of 3-6 weight % and gather different
The mixture of butylene succinate dispersing agent, the sodium sulfonate of 1.2-6 weight % and mixture, the 0.01- in terms of phosphorus of calcium naphthenate
The zinc dialkyl dithiophosphate of 0.08 weight % and the compound friction improving agent of 0.05-1.2 weight %.
3. lubricant oil composite according to claim 1 or 2, wherein the lube base oil be mineral lubricating oil and/
Or synthetic lubricant fluid.
4. lubricant oil composite according to claim 1 or 2, wherein the thiophenols ester type antioxidant is that 2,2'- is thio
Bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionates].
5. lubricant oil composite according to claim 1 or 2, wherein the polyisobutene succinimide ashless dispersion
The number-average molecular weight of polyisobutene part is 800-4000 in agent；Polyisobutene portion in the polyisobutylene succinic acid ester dispersing agent
The number-average molecular weight divided is 800-4000；The polyisobutene succinimide ashless dispersant and the polyisobutylene succinic acid
The weight ratio of ester dispersing agent 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.
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.
8. lubricant oil composite according to claim 5, wherein poly- isobutyl in the polyisobutylene succinic acid ester dispersing agent
The number-average molecular weight of alkene part is 900-3000.
9. lubricant oil composite according to claim 8, wherein poly- isobutyl in the polyisobutylene succinic acid ester dispersing agent
The number-average molecular weight of alkene part is 1000-2400.
10. lubricant oil composite according to claim 1 or 2, wherein the base number of the sodium sulfonate is 100-
450mgKOH/g, the base number of the calcium naphthenate are 100-200mgKOH/g, the weight of the sodium sulfonate and the calcium naphthenate
Than for 0.2-4:1.
11. lubricant oil composite according to claim 10, wherein the base number of the sodium sulfonate is 200-450mgKOH/
g。
12. lubricant oil composite according to claim 10, wherein the weight ratio of the sodium sulfonate and the calcium naphthenate
For 0.5-2:1.
13. lubricant oil composite according to claim 1 or 2, wherein the alkyl in the zinc dialkyl dithiophosphate
For the alkyl of C2-C12.
14. lubricant oil composite according to claim 13, wherein the alkyl in the zinc dialkyl dithiophosphate is
The alkyl of C2-C8.
15. lubricant oil composite according to claim 14, 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.
16. lubricant oil composite according to claim 1 or 2, wherein the compound friction improving agent, which contains oil-soluble, to be had
Machine molybdenum friction improver and Ashless friction modifiers, the oil-soluble organic molybdenum friction improver are selected from dialkyl dithiophosphoric acid
Molybdenum, dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulphur
One of complex compound, molybdenum amine complex and molybdic acid esters oil-soluble organic molybdenum friction improver or a variety of, carbon atom number 6-
60, the oil-soluble organic molybdenum friction improver accounts for the 5-50% of the compound friction improving agent gross mass；The Ashless friction
Modifier is selected from one of polyol esters of fatty acids, aliphatic amine and aliphatic amide or a variety of, carbon atom number 6-60, institute
State the 50-95% that Ashless friction modifiers account for the compound friction improving agent gross mass.
17. lubricant oil composite according to claim 16, wherein the oil-soluble organic molybdenum friction improver is selected from two
Alkyl dithiophosphoric acid molybdenum, dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, xanthic acid molybdenum, thio Huang
One of ortho acid molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex and molybdic acid esters oil-soluble organic molybdenum friction improver are more
Kind, carbon atom number 10-50.
18. lubricant oil composite according to claim 16, wherein the oil-soluble organic molybdenum friction improver accounts for described
The 10-40% of compound friction improving agent gross mass.
19. lubricant oil composite according to claim 16, wherein the Ashless friction modifiers are selected from aliphatic polybasic acid
One of alcohol ester, aliphatic amine and aliphatic amide are a variety of, carbon atom number 10-50.
20. lubricant oil composite according to claim 16, wherein the Ashless friction modifiers account for the compound friction
The 60-90% of modifier gross mass.
21. lubricant oil composite according to claim 16, 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.
22. lubricant oil composite according to claim 21, 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.
23. 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.
24. lubricant oil composite according to claim 23, wherein the antirust agent is selected from imidazoles and/or allyl butyrate
Two esters of gallic acid.
25. lubricant oil composite according to claim 24, wherein the antirust agent is selected from 4,5- glyoxalidine, alkenyl
At least one of imidazoline succinate and alkenyl succinic acid ester.
26. lubricant oil composite according to claim 23, wherein the pour-point depressant is selected from poly alpha olefin, alkyl C8-
At least one of the dialkyl fumarate of C18, poly- alkylmethacrylate, alkylnaphthalene.
27. lubricant oil composite according to claim 23, wherein the tackifier is ethylene propylene copolymer, poly- first
At least one of base methyl acrylate and hydrogenated styrene isoprene copolymer.
28. lubricant oil composite according to claim 23, wherein the anti-foaming agent is polysiloxane type anti-foaming agent.
29. lubricant oil composite according to claim 28, wherein the anti-foaming agent is silicone oil.
30. lubricant oil composite according to claim 28, wherein the anti-foaming agent is dimethyl silicone polymer.
31. a kind of preparation method of methanol-fueled engine lubricant oil composite, which is characterized in that the described method includes: will contain
Have lube base oil, antioxygen multipurpose additive, thiophenols ester type antioxidant, polyisobutene succinimide ashless dispersant and
The mixture of polyisobutylene succinic acid ester dispersing agent, the mixture of sodium sulfonate and calcium naphthenate, zinc dialkyl dithiophosphate and
The raw material of compound friction improving agent is uniformly mixed and obtains lubricant oil composite, wherein on the basis of the weight of lubricant oil composite,
The dosage of lube base oil is 75-95 weight %, the dosage of antioxygen multipurpose additive is 0.01-10 weight %, sulfophenates
The dosage of type antioxidant is 0.02-5 weight %, polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester point
The dosage of the mixture of powder is 0.5-10 weight %, and the dosage of the mixture of sodium sulfonate and calcium naphthenate is that 0.2-10 is weighed
Measure %, the dosage of zinc dialkyl dithiophosphate be in terms of phosphorus≤0.08 weight %, the dosage of compound friction improving agent is 0.01-
5 weight %, the antioxygen multipurpose additive are the compound of structure shown in formula (I):
32. according to the method for claim 31, wherein on the basis of the weight of lubricant oil composite, lube base oil
Dosage be 78-90 weight %, the dosage that the dosage of antioxygen multipurpose additive is 0.1-4 weight %, thiophenols ester type antioxidant
For 0.2-1.5 weight %, the mixture of polyisobutene succinimide ashless dispersant and polyisobutylene succinic acid ester dispersing agent
Dosage be 3-6 weight %, the dosage of the mixture of sodium sulfonate and calcium naphthenate is 1.2-6 weight %, dialkyl dithio phosphorus
The dosage of sour zinc is the weight % of the 0.01-0.08 in terms of phosphorus, and the dosage of compound friction improving agent is 0.05-1.2 weight %.
33. the method according to claim 31 or 32, wherein the mixed condition includes: that temperature is 40-90 DEG C, when
Between be 1-6h.
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| CN110862855B (en) * | 2019-12-09 | 2022-02-01 | 辽宁三特石油化工有限公司 | Anti-foam methanol automobile engine lubricating oil |
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