CN107974328A - Lubricant oil composite and the method for improving lubrication oil antiwear antifriction performance - Google Patents

Lubricant oil composite and the method for improving lubrication oil antiwear antifriction performance Download PDF

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Publication number
CN107974328A
CN107974328A CN201610941461.8A CN201610941461A CN107974328A CN 107974328 A CN107974328 A CN 107974328A CN 201610941461 A CN201610941461 A CN 201610941461A CN 107974328 A CN107974328 A CN 107974328A
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peroxide
lubricant oil
oil composite
accordance
composite described
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CN107974328B (en
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张辉
段庆华
苏朔
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/22—Acids obtained from polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

A kind of method that the present invention proposes lubricant oil composite and raising lubrication oil antiwear antifriction performance.The lubricant oil composite of the present invention, includes the lubricating base oil of 0.1%~5% antioxygen antiwear additive, 3%~15% viscosity index improver, 1%~10% dispersant, 1%~15% detersive, 0.1%~5% antioxidant, 0.1%~5% oiliness improver and surplus；The preparation method of the antioxygen antiwear additive includes：By sulphur phosphoric acid and peroxide reactions, saponification then is carried out with zinc compound, collects oil phase product.The antioxygen antiwear additive and lubricant oil composite of the present invention has excellent antiwear and friction reduction property, can extend the service life of oil product.

Description

Lubricant oil composite and the method for improving lubrication oil antiwear antifriction performance
Technical field
The present invention relates to a kind of lubricant oil composite, the excellent lubricating oil composition of more particularly to a kind of antiwear and friction reduction property Thing.
Background technology
It is anti-that lubricating oil product inevitably contacts generation oxidation with the oxygen in air and metal surface in use Answer and go bad, increase oil viscosity, acid number increase, generates greasy filth and precipitation, and produces corrosion to metal parts and wear.For Extend the validity period of oil product, delay its oxidizing process, slow down the fretting wear of equipment, antioxidant can be added into oil product and is resisted Grinding agent, can effectively inhibit its oxidation reaction, improve the performance of oil product.
It is well known that zinc dialkyl dithiophosphate (ZDDP) has excellent anti-oxidant, anticorrosive, wear-resistant energy Power, after since last century, the forties develops, is just widely used, especially in internal combustion engine in various lubricating oil Have the function that in oil irreplaceable.In fact, " zinc dialkyl dithiophosphate " often said is to include a series of chemical combination Thing, the difference between the compound is mainly reflected in different alkyl components and the alkyl component surrounds the phase of phosphorus molecule To in spatial relationship.Therefore, the zinc dialkyl dithiophosphate of different structure can have different performance tables in the lubricant It is existing.In recent years, with the fast development of auto industry, increasingly harshness is proposed to lube oil additive (including ZDDP) and is wanted Ask, especially in terms of gasoline engine oil, phosphorus content progressively drops to 0.06% from 0.12%, and this requires will in I. C. engine oil The usage amount of ZDDP is reduced, also just there is an urgent need to develop going out all good dialkyl dithiophosphoric acid derivative of antioxidant and antiwear property energy, It is required that still there is good performance in the case where dosage reduces.Meanwhile excessive Zn/P ratios can cause to contain in the identical phosphorus of offer When amount so that lubricating oil product has more tenors, can cause to contain more particulate matters in exhaust emissions, unfavorable In environmental protection.
Chinese patent CN 101659896 is employed to solve the volatility problem of phosphorus, employs methyl isobutyl alcohol type Zinc dialkyl dithiophosphate, reduces the volatility of phosphorus, while reduces the growing amount of the deposit of engine oil, but it is former Expect the higher price of methyl isobutyl carbinol.
United States Patent (USP) US 5728656 discloses a kind of zinc dialkyl dithiophosphate of superneutrality, its Zn/P ratio exists Between 0.95-1.04.The product has more neutral salt component, has good wear-resistant corrosion resistance.
Chinese patent CN 1769405A disclose a kind of zinc dialkyl dithiophosphate for improving rubber seal compatibility performance Preparation method.By in the preparation process of dialkyl dithiophosphoric acid, introducing phosphorus pentoxide, final saponification obtains the patent To modified zinc dialkyl dithiophosphate product, which has preferable compatibility with rubber.
The content of the invention
A kind of method that the present invention proposes lubricant oil composite and raising lubrication oil antiwear antifriction performance.
The lubricant oil composite of the present invention, including：0.1%~5% antioxygen antiwear additive, 3%~15% Viscosity Index Modifier, 1%~10% dispersant, 1%~15% detersive, 0.1%~5% antioxidant, 0.1%~5% oil Property agent and the lubricating base oil of surplus.
The preparation method of the antioxygen antiwear additive includes：By sulphur phosphoric acid and peroxide reactions, then with zinc compound Saponification is carried out, collects oil phase product.
The structure of the sulphur phosphoric acid is：
R, R therein ' separately it is selected from C4~C30Alkyl, preferably C4~C12Alkyl.
The peroxide is selected from inorganic peroxide and/or organic peroxide, such as can select hydrogen peroxide, mistake Sodium oxide molybdena, potassium peroxide, calper calcium peroxide, peromag, zinc peroxide, potassium hydrogen peroxymonosulfate, 2,2- peroxidating dihydros propane, 2, 5- dimethyl -2,5- peroxidating dihydros hexane, 2,2- pairs-(tert-butyl peroxide) propane, 2,2- pairs-(tert-butyl peroxide) fourth Alkane, 2,5- dimethyl -2,5- be double-and (tert-butyl peroxide) hexane, 2,2- be double-(4,4- di-tert-butyl peroxides cyclohexyl) third - 2,5- couples alkane, -2,5- pairs-(peroxidating -2- ethyl hexanoyls) hexane of 2,5- dimethyl, 2,5- dimethyl-(peroxidating -3,5,5- Trimethyl acetyl) hexane, 2,5- dimethyl -2,5- be double-(the different nonanoyl of peroxidating) hexane and 2,5- dimethyl -2,5- it is double-(peroxide Change benzoyl) one or more in hexane, preferably hydrogen peroxide, sodium peroxide, potassium peroxide, 2,2- peroxidating dihydro third Alkane, 2,5- dimethyl -2,5- peroxidating dihydros hexane, 2,2- pairs-(tert-butyl peroxide) propane, 2,2- pairs-(the tertiary fourth of peroxidating Base) butane and 2,5- dimethyl -2,5- it is double-(tert-butyl peroxide) hexane in one or more.
The temperature of the sulphur phosphoric acid and peroxide reactions is 10~50 DEG C, preferably 20~40 DEG C.
One or more in the preferred zinc oxide of the zinc compound, zinc hydroxide and zinc acetate, most preferably aoxidize Zinc.
The temperature of the saponification is 70~100 DEG C, preferably 75~90 DEG C.The peroxide and zinc compound Total mole number is the 50~70% of sulphur phosphoric acid molal quantity, preferably 55~65%, wherein mole of peroxide and zinc compound Than for 1：20~20：1, preferably 1：10~10：1.
The mass ratio of Zn and P is between 0.01~0.95 in the antioxygen antiwear additive of the present invention, and preferably 0.1~0.95.
The antioxygen antiwear additive accounts for the 0.1%~5% of lubricant oil composite gross mass, preferably 0.2%~4%.
Viscosity index improver preferred ethylene-propylene copolymer, polyisobutene, styrene-butadiene copolymer and the poly- methyl One or more in acrylate, most preferably ethylene-propylene copolymer；The viscosity index improver accounts for the total matter of lubricant oil composite The 3%~15% of amount, preferably 5%~10%.
The preferred polyisobutene succinimide dispersant of the dispersant and/or boracic polyisobutene succinimide disperse Agent, the most preferably mixture of polyisobutene succinimide dispersant and boracic polyisobutene succinimide dispersant；It is described Dispersant accounts for the 1%~10% of lubricant oil composite gross mass, preferably 2%~8%.
One or more in the preferred sulfonate of the detersive, alkyl monosulfide phenates and salicylate, preferably sulfonate And/or alkyl monosulfide phenates；The detersive accounts for the 1%~15% of lubricant oil composite gross mass, preferably 2%~12%.
The preferred amine antioxidants of the antioxidant and/or phenolic antioxidant, most preferably amine antioxidants and phenolic antioxidant Mixture；The antioxidant accounts for the 0.1%~5% of lubricant oil composite gross mass, preferably 0.2%~3%.
One or more in the oiliness improver preferred fat acid esters, fatty amine, fatty alcohol and dimeric dibasic acid, such as can select With the one or more in olein, cetylamine, hexadecanol and dimer (fatty acid) yl；The oiliness improver accounts for lubricant oil composite The 0.1%~5% of gross mass, preferably 0.2%~3.5%.
One or more of the lubricating base oil in API I, II, III, IV and V class lubricating base oil, preferably One or more in API I, II, III and IV class lubricating base oil.
The invention also provides a kind of method for improving lubrication oil antiwear antifriction performance, it is characterised in that will be noted earlier Antioxygen antiwear additive, viscosity index improver, dispersant, detersive, antioxidant, oiliness improver be added in lubricating oil.
The antioxygen antiwear additive and lubricant oil composite of the present invention has excellent antiwear and friction reduction property, can extend oil product Service life.
Brief description of the drawings
Fig. 1 is that the nuclear-magnetism phosphorus of the antioxygen antiwear additive sample 1 of the present invention composes spectrogram.
Fig. 2 is that the nuclear-magnetism phosphorus of contrast sample 1 (T203) composes spectrogram.
Embodiment
Below by way of specific implementation row, the present invention is further explained, but the present invention is not limited thereto.
Raw material sources：
T202, butyl/iso-octyl zinc dithiophosphate, Wuxi south additive factory；
T203, di-isooctyl dithio zinc phosphate, Wuxi south additive factory；
Dimeric dibasic acid, dimerized linoleic acid, Mudanjiang Chemical Factory of Daily Use；
Oleic acid monoglyceride, standing grain major company of Britain；
Cetylamine, Beijing Reagent Company；
Hexadecanol, Beijing Reagent Company；
T618, ethylene propylene copolymer viscosity index improver, Refinery of Maoming Petrochemical Corporation；
T152, polyisobutene succinimide dispersant, Wuxi south additive factory；
T161B, boracic polyisobutene succinimide dispersant, Wuxi south additive factory；
T107, overbased magnesium sulfonate, Lanzhou Petrochemical additive factory；
T121, middle base number sulfurized alkylphenol calcium, Xinxiang Rui Feng new materials joint-stock company；
T534, amine antioxidants (butyl/octylated diphenylamine), Beijing Xing Pu Fine Chemical Co., Ltd；
T512,3, the 5- different monooctyl esters of di-t-butyl -4- hydroxy phenylpropionic acids, Beijing Xing Pu Fine Chemical Co., Ltd.
The preparation of 1 antioxygen antiwear additive of embodiment
In the 250ml there-necked flasks with agitating device, diisooctyl phosphordithiic acid 141.6g (0.4mol) is added, is protected Temperature is held at 60 DEG C, 30% hydrogen peroxide solution 5.7g (equivalent hydrogen peroxide is 0.05mol) was added dropwise in 30 minutes, after being added dropwise The reaction was continued 2 it is small when, then heat to 70 DEG C, add zinc oxide 13.4g (0.165mol), be warming up to 75~90 DEG C of reactions 3~5 Hour, 95~105 DEG C are continuously heating to, is evaporated under reduced pressure out remaining moisture, the antioxygen antiwear additive of the present invention is obtained by filtration, is denoted as Sample 1.
The preparation of embodiment 2-4 antioxygen antiwear additives
According to the method for embodiment 1, using the sulphur phosphoric acid of different structure, different sulphur phosphoric acid and hydrogen peroxide molar ratio, Different hydrogen peroxide and the molar ratio of zinc oxide prepare the antioxygen antiwear additive of the present invention, are denoted as sample 2-4 respectively, its reaction condition It is shown in Table 1.
Contrast sample 1-4 is also listed in table 1, wherein contrast sample 1 is the diisooctyl phosphordithiic acid of commercialization Zinc (C8 primary alconol ZDDP), domestic code name are T203；Contrast butyl/iso-octyl zinc dithiophosphate (C4/ that sample 2 is commercialization C8 primary alconol ZDDP), domestic code name is T202；Contrast sample 3 is C3/C6 secondary alcohol ZDDP, is prepared according to conventional ZDDP methods；Contrast Sample 4 is C6 secondary alcohol ZDDP, is prepared according to conventional ZDDP methods.
Sample 1 and contrast sample 1 (T203) to antioxygen antiwear additive have carried out the spectrum test of nuclear-magnetism phosphorus, test equipment and measure Condition is：FT-80A NMR instrument, solvent C CL4, concentration 50-80%, D2O locks field, resonant frequency 32.2MHZ, 5mm sample cell, 85%H3PO4For external standard.Fig. 1 is that the nuclear-magnetism phosphorus of the antioxygen antiwear additive sample 1 of the present invention composes spectrogram.Fig. 2 is contrast sample 1 (T203) nuclear-magnetism phosphorus spectrum spectrogram.Can be seen that displacement from the two phosphorus spectrogram has notable difference in 80~90ppm.
Using the antioxygen antiwear additive sample 1-4 and contrast sample of the ICP method inductively coupled plasma spectrometer measure present invention Zn content, the phosphorus content of 1-4, obtains the mass ratio of the Zn/P of each sample after being computed, its result is same to be shown in Table 1.
1 antioxygen antiwear additive sample 1-4 of table and contrast sample 1-4
Sample 1-4 and contrast sample 1-4 are added in 150SN base oils by 0.5% dosage respectively, are configured to test With the embodiment 5-8 and comparative example 5-8 of lubricating oil.
The antioxygen property of each sample is measured according to SH/T0193 lubricating oil oxidation stabilities determination method (rotary bomb oxidation test). The maximum nonseizure load of each sample is measured according to GB/T3142 lubricating oil bearing capacity determination methods (four ball method).According to SH/ T0189 lubrication oil antiwears damage performance measurement method (four-ball tester method) measures the wear resistance of each sample.
2 are shown in Table to the test result of each lubricating oil sample.
2 assessment of performance of table
From table 2 it can be seen that by the low Zn/P for preparing of the present invention than antioxygen antiwear additive have it is preferably anti-oxidant, anti- The ability of abrasion, hence it is evident that better than existing zinc dialkyl dithiophosphate (ZDDP) product.
The sample 1-4 of 0.8% antioxygen antiwear additive and contrast sample 1-4,7.0% ethylene propylene copolymer are sticked respectively Spend index improver T618,3.5% polyisobutene succinimide dispersant T152,1.0% boracic polyisobutene fourth two Acid imide dispersant T161B, 1.0% overbased magnesium sulfonate T107,1.5% middle base number sulfurized alkylphenol calcium T121,0.3% Amine antioxidants T534,0.3% phenolic antioxidant T512,0.5% oleic esters oiliness improver, the 150SN of surplus Mineral base oil is modulated to obtain the embodiment 9-12 of the lubricating oil of full formula and comparative example 9-12, and these lubricating oil are resisted Oxidation test and abrasion resistance experiment.
The antioxygenic property of lubricating oil is measured according to ASTM D7098 methods.
According to the abrasion resistance of SH/T0188 methods measure lubricating oil, test condition is：54 DEG C, load 1335N of oil temperature, Run time is 60min.
Oxidation Resistance Test and the abrasion resistance experiment of the embodiment 9-12 and comparative example 9-12 of lubricating oil the results are shown in Table 3.
3 antioxygenic property of table and abrasion resistance test result
Preferably resist from table 3 it can be seen that the antioxygen antiwear additive of the low Zn/P prepared by the present invention has in formula Oxygen and abrasion resistance.
The antioxygen antiwear additive sample 1-4 of the present invention and contrast sample 1-4,7.0% ethylene propylene copolymer are sticked respectively Spend index improver T618,3.5% polyisobutene succinimide dispersant T152,1.0% boracic polyisobutene fourth two Acid imide dispersant T161B, 1.0% overbased magnesium sulfonate T107,1.5% middle base number sulfurized alkylphenol calcium T121,0.3% Amine antioxidants T534,0.3% phenolic antioxidant T512, the 150SN mineral base oil tune of different oiliness improvers and surplus Be made the embodiment 13-16 and comparative example 13-16 of the lubricant oil composite of full formula, in these compositions antioxygen antiwear additive and The species and content of oiliness improver are shown in Table 4.These lubricating oil are carried out with antiwear and friction reduction property experiment, result of the test is same to be shown in Table 4.
The measure of friction coefficient is carried out using high-frequency reciprocating tester (HFRR), test condition is：Frequency 20HZ, temperature 50 DEG C, load 400g, time 60min.
According to the abrasion resistance of SH/T0188 methods measure lubricating oil, test condition is：54 DEG C, load 1335N of oil temperature, Run time is 60min.
Table 4
From table 4, it can be seen that the lubricant oil composite of the present invention has more preferable antiwear and friction reduction property.

Claims (13)

  1. A kind of 1. lubricant oil composite, wherein being improved containing 0.1%~5% antioxygen antiwear additive, 3%~15% Viscosity Index Agent, 1%~10% dispersant, 1%~15% detersive, 0.1%~5% antioxidant, 0.1%~5% oiliness improver With the lubricating base oil of surplus；The preparation method of the antioxygen antiwear additive includes：By sulphur phosphoric acid and peroxide reactions, Ran Houyu Zinc compound carries out saponification, collects oil phase product.
  2. 2. lubricant oil composite described in accordance with the claim 1, it is characterised in that the structure of the sulphur phosphoric acid is：
    R, R therein ' separately it is selected from C4~C30Alkyl.
  3. 3. lubricant oil composite described in accordance with the claim 1, it is characterised in that the peroxide is selected from inorganic peroxide And/or organic peroxide.
  4. 4. lubricant oil composite described in accordance with the claim 1, it is characterised in that the peroxide is selected from hydrogen peroxide, mistake Sodium oxide molybdena, potassium peroxide, calper calcium peroxide, peromag, zinc peroxide, potassium hydrogen peroxymonosulfate, 2,2- peroxidating dihydros propane, 2, 5- dimethyl -2,5- peroxidating dihydros hexane, 2,2- pairs-(tert-butyl peroxide) propane, 2,2- pairs-(tert-butyl peroxide) fourth Alkane, 2,5- dimethyl -2,5- be double-and (tert-butyl peroxide) hexane, 2,2- be double-(4,4- di-tert-butyl peroxides cyclohexyl) third - 2,5- couples alkane, -2,5- pairs-(peroxidating -2- ethyl hexanoyls) hexane of 2,5- dimethyl, 2,5- dimethyl-(peroxidating -3,5,5- Trimethyl acetyl) hexane, 2,5- dimethyl -2,5- be double-(the different nonanoyl of peroxidating) hexane and 2,5- dimethyl -2,5- it is double-(peroxide Change benzoyl) one or more in hexane.
  5. 5. lubricant oil composite described in accordance with the claim 1, it is characterised in that the temperature of the sulphur phosphoric acid and peroxide reactions Spend for 10~50 DEG C.
  6. 6. lubricant oil composite described in accordance with the claim 1, it is characterised in that the zinc compound is zinc oxide, hydrogen One or more in zinc oxide and zinc acetate.
  7. 7. lubricant oil composite described in accordance with the claim 1, it is characterised in that the temperature of the saponification is 70~100 ℃。
  8. 8. lubricant oil composite described in accordance with the claim 1, it is characterised in that the peroxide and zinc compound it is total Molal quantity is the 50~70% of sulphur phosphoric acid molal quantity, and wherein the molar ratio of peroxide and zinc compound is 1：20~20：1.
  9. 9. lubricant oil composite described in accordance with the claim 1, it is characterised in that the peroxide and zinc compound it is total Molal quantity is the 55~65% of sulphur phosphoric acid molal quantity, and wherein the molar ratio of peroxide and zinc compound is 1：10~10：1.
  10. 10. lubricant oil composite described in accordance with the claim 1, it is characterised in that the quality of Zn and P in the antioxygen antiwear additive Than between 0.01~0.95.
  11. 11. lubricant oil composite described in accordance with the claim 1, it is characterised in that the viscosity index improver is selected from second third One or more in copolymer, polyisobutene, styrene-butadiene copolymer and polymethacrylates；The dispersant It is selected from selected from polyisobutene succinimide dispersant and/or boracic polyisobutene succinimide dispersant, the detersive One or more in sulfonate, alkyl monosulfide phenates and salicylate；The antioxidant is selected from amine antioxidants and/or phenols Antioxidant；One or more of the oiliness improver in fatty acid ester, fatty amine, fatty alcohol and dimeric dibasic acid.
  12. 12. lubricant oil composite described in accordance with the claim 1, it is characterised in that the lubricating base oil be selected from API I, II, One or more in III, IV and V class lubricating base oil.
  13. A kind of 13. method for improving lubrication oil antiwear antifriction performance, it is characterised in that described in one of claim 1-12 Antioxygen antiwear additive, viscosity index improver, dispersant, detersive, antioxidant, oiliness improver are added in lubricating oil.
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CN110845528A (en) * 2019-12-04 2020-02-28 锦州康泰润滑油添加剂股份有限公司 Preparation method of zinc dialkyl dithiophosphate and application of hydrogen peroxide
CN111704897A (en) * 2020-04-30 2020-09-25 中石化石油工程技术服务有限公司 Temperature-resistant and salt-resistant lubricating drag reducer for drilling fluid and preparation method thereof
CN113372979A (en) * 2021-05-28 2021-09-10 中国石油化工股份有限公司 Automobile steering ball joint lubricating grease composition and preparation method thereof
CN114480798A (en) * 2022-02-17 2022-05-13 马鞍山金泉工业介质科技有限公司 Quenching oil with strong quenching capacity and preparation method thereof

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CN113372979A (en) * 2021-05-28 2021-09-10 中国石油化工股份有限公司 Automobile steering ball joint lubricating grease composition and preparation method thereof
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