CN113493714B - Methanol engine lubricating oil composition and preparation method thereof - Google Patents

Methanol engine lubricating oil composition and preparation method thereof Download PDF

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CN113493714B
CN113493714B CN202010189030.7A CN202010189030A CN113493714B CN 113493714 B CN113493714 B CN 113493714B CN 202010189030 A CN202010189030 A CN 202010189030A CN 113493714 B CN113493714 B CN 113493714B
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methacrylate
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CN113493714A (en
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谢欣
陈晓伟
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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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular 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
    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • C10M2205/026—Butene
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/102—Polyesters
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal 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

Abstract

The invention provides a methanol engine lubricating oil composition and a preparation method thereof. The methanol engine lubricating oil composition comprises the following components: a) A viscosity index improver; b) A mixture of a complex antioxidant, alkylated diphenylamine and a thiophenol ester; c) A polyisobutylene succinimide dispersant and/or a polyisobutylene succinate dispersant; d) Mixtures of magnesium and sodium sulfonates; e) Zinc dialkyldithiophosphates; f) An organo-molybdenum friction modifier; g) A major amount of a lubricant base oil; wherein the component A) viscosity index improver has a structure shown in a general formula (I):

Description

Methanol engine lubricating oil composition and preparation method thereof
Technical Field
The invention relates to a lubricating oil composition, in particular to a lubricating oil composition for a methanol engine.
Background
The oxidation stability of engine lubricating oils is an extremely important control index. The oxidation resistance activity of the oil is gradually lost under the influence of factors such as operating temperature, combustion products, blow-by gas, metal catalysis and the like in the using process, and the oxidation deterioration is easy to occur, so that the properties such as detergency, dispersibility, abrasion resistance and the like of the oil are rapidly damaged, the viscosity is increased, acid products are increased, a paint film and sediments are formed, and the damage to engine equipment is caused.
The methanol fuel has wide application prospect as a novel alternative energy. Methanol gasoline inevitably enters lubricating oil in the using process. Blow-by gas during engine operation and cooling during engine operation may cause methanol to condense and enter the lubricating oil. Methanol is oxidized to form formaldehyde in the combustion process, and further, the formaldehyde is oxidized to form formic acid. Formic acid, being more acidic, reacts with the basic detergents in the lubricating oil. While formic acid has the potential to corrode and wear the engine when the base number of the lubricant is depleted. Therefore, the methanol gasoline engine has higher requirements on lubricating oil, and compared with the common engine lubricating oil, the methanol gasoline engine has the requirements on better acid neutralization and alkali retention capacity, better oxidation resistance, better abrasion resistance and the like.
In recent years, with the increasing demand for environmental protection, there is a further demand for energy saving of mechanical equipment. The low viscosity of the lubricating oil can effectively save energy, but the problems of liquid leakage and poor lubrication exist, the method for improving the viscosity index of the lubricating oil is considered to be a method for better solving the contradiction, and various polymers (such as polyisobutylene, ethylene propylene olefin polymers and the like) are widely applied to automobile engine lubricating oil as viscosity index improvers to improve the viscosity characteristics of the lubricating oil related to high and low temperatures. As the viscosity index improver which is used at the earliest, polymethacrylate (PMA) has excellent viscosity-temperature performance, oxidation stability and low-temperature performance, is widely applied to lubricating oil, but has poor shear stability and thickening capability.
CN 104178253A discloses methacrylic acid C 2 ～C 5 Alkyl esters, methacrylic acid C 7 ～C 10 Alkyl esters, methacrylic acid C 11 ～C 12 Alkyl esters and methacrylic acid C 13 ～C 16 The copolymer of alkyl ester has excellent shearing stability, low temperature performance, viscosity increasing performance and hydrolysis stability. CN 103965394B discloses the use of methacrylic acid C 8 ～C 12 Alkyl ester is used as monomer to obtain PMA viscosity index improver with average molecular weight, low acid value and low solidifying pointSmall low-temperature viscosity, good shearing stability, good viscosity-temperature performance and the like. CN 102295973A discloses the use of 20-80 mass% methacrylic acid C 1 ～C 25 Alkyl ester, 10 to 70 mass% of methacrylic acid C 1 ～C 20 The copolymer is prepared by copolymerizing alkyl ester and 1-10 mass percent of nitrogen-containing compound with carbon-carbon double bonds, and has better anti-wear performance and dispersion performance while keeping better pour point depression effect and shear stability. The viscosity index improver does not have oxidation resistance.
Disclosure of Invention
The invention provides a methanol engine lubricating oil composition and a preparation method thereof.
The methanol engine lubricating oil composition comprises the following components:
a) A viscosity index improver;
b) Composite antioxidants including alkylated diphenylamines and thiophenol esters;
c) A polyisobutylene succinimide dispersant and/or a polyisobutylene succinate dispersant;
d) Mixtures of magnesium and sodium sulfonates;
e) Zinc dialkyldithiophosphates;
f) An organo-molybdenum friction modifier;
g) A major amount of a lubricant base oil;
the component A) viscosity index improver has a structure shown in a general formula (I):
Figure BDA0002415205530000021
wherein x sub-repeat units of the n repeat units may be the same or different, y sub-repeat units of the n repeat units may be the same or different, and z sub-repeat units of the n repeat units may be the same or different; r in x sub-repeating units 1 May be the same or different and are each independently selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R in x sub-repeat units 2 May be the same or different, eachIs independently selected from H and C 1 ～C 6 Alkyl (preferably C) 1 ～C 6 Straight chain alkyl); r in y sub-repeating units 1 May be the same or different and are each independently selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R in y sub-repeat units 4 May be the same or different and are each independently selected from H and C 1 ～C 4 Alkyl (preferably H), R in y sub-repeat units 5 May be the same or different and are each independently selected from H and C 1 ～C 20 Straight or branched alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R in y sub-repeat units 6 May be the same or different and are each independently selected from H and C 1 ～C 20 Straight or branched alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R in y repeating subunits 7 May be the same or different and are each independently selected from H and C 1 ～C 20 Straight or branched alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R in y repeating subunits 8 May be the same or different and are each independently selected from H and C 1 ～C 4 Alkyl (preferably selected from H and methyl); r in z sub-repeat units 1 May be the same or different and are each independently selected from H and C 1 ～C 4 Alkyl (preferably selected from H and methyl), R in z sub-repeat units 3 May be the same or different and are each independently selected from H and C 7 ～C 24 Alkyl (preferably selected from H and C) 8 ～C 18 Straight chain alkyl); x in the n repeating units may be the same or different and each independently selected from an integer of 0 to 3000 (preferably an integer of 10 to 1000), y in the n repeating units may be the same or different and each independently selected from an integer of 0 to 10000 (preferably an integer of 10 to 5000), and at least one y is a positive integer, and z in the n repeating units may be the same or different and each independently selected from an integer of 0 to 5000 (preferably an integer of 10 to 2000); n is a positive integer of 2 to 5000 (preferably an integer of 10 to 3000); in each of the n repeating units, the sum of x, y, z is a positive integer.
According to the invention, preferably, there are yIn each of the sub-repeating units of the sub-repeating unit, R 5 、R 6 、R 7 Wherein one group is C 1 ～C 20 Straight or branched alkyl (preferably C) 1 ～C 20 Straight chain alkyl), the other two groups are H; more preferably, in each of the y sub-repeating units, R 5 、R 7 Wherein one group is C 1 ～C 20 Straight or branched alkyl (preferably C) 1 ～C 20 Straight chain alkyl) and the other is H, R 6 The radical is H.
According to the present invention, the viscosity index improver preferably has a weight average molecular weight of 10000 to 1000000, more preferably 50000 to 800000, and still more preferably 200000 to 700000.
According to the present invention, the method for preparing the viscosity index improver comprises: carrying out polymerization reaction on optional a type monomers, optional b type monomers and c type monomers, and collecting polymerization products;
the structure of the a-type monomer is as follows:
Figure BDA0002415205530000031
wherein R is 1 Selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R 2 Selected from H and C 1 ～C 6 Alkyl (preferably C) 1 ～C 6 Straight chain alkyl). The monomer of the a type is preferably one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, and more preferably methyl methacrylate and/or butyl methacrylate.
The structure of the b-type monomer is as follows:
Figure BDA0002415205530000041
wherein R is 1 Selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R 3 Selected from H and C 7 ～C 24 Alkyl (preferably selected from H and C) 8 ～C 18 Straight chain alkyl). The b-type monomer is preferably one or more of hexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (wherein the isodecyl group is 2-ethyl-octyl), dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl mixed alkyl methacrylate, hexadecyl methacrylate and octadecyl methacrylate, and more preferably one or more of decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl mixed alkyl methacrylate and hexadecyl methacrylate.
The structure of the c-type monomer is as follows:
Figure BDA0002415205530000042
wherein R is 1 Selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R 4 Selected from H and C 1 ～C 4 Alkyl (preferably H), R 5 Selected from H and C 1 ～C 20 Straight or branched alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R 6 Selected from H and C 1 ～C 20 Straight or branched alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R 7 Selected from H and C 1 ～C 20 Straight or branched alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R 8 Is selected from H and C 1 ～C 4 Alkyl (preferably selected from H and methyl). The c-type monomer is preferably one or more of tetradecylphenyl methacrylate, tetradecylphenyl acrylate, pentadecylphenyl methacrylate, pentadecylphenyl acrylate, hexadecylphenyl methacrylate and hexadecylphenyl acrylate (more preferably 3-pentadecylphenyl methacrylate and/or 3-pentadecylphenyl acrylate).
The above-mentioned a-type monomer, b-type monomer and c-type monomer may be compounds having a single structure, or may be a mixture containing compounds having different structures.
According to the invention, preferably R 4 、R 8 Is H, R 5 、R 6 、R 7 Wherein one group is C 1 ～C 20 Straight or branched alkyl (preferably C) 1 ～C 20 Straight chain alkyl), the other two groups are H; more preferably, R 4 、R 6 、R 8 Is H, R 5 、R 7 Wherein one group is C 1 ～C 20 Straight or branched alkyl (preferably C) 1 ～C 20 Straight chain alkyl) and the other is H.
According to the present invention, it is preferable that the mass of the a-type monomer is 0 to 50% (preferably 5 to 30%) of the total mass, the mass of the b-type monomer is 0 to 80% (preferably 20 to 70%) of the total mass, and the mass of the c-type monomer is 10 to 60% (preferably 20 to 50%) of the total mass, based on the total mass of the a-type monomer, the b-type monomer, and the c-type monomer.
According to the invention, preferably, an initiator, preferably one or more of cumene hydroperoxide, 2,2 '-azobis (2,4-dimethylbutyronitrile) and 2,2' -azobis (2,4-dimethylvaleronitrile) (ADVN) may be added to the polymerization. The addition amount of the initiator is preferably 0.2-0.5% of the total mass of the a-type monomer, the b-type monomer and the c-type monomer.
According to the invention, a chain transfer agent, preferably an alkyl mercaptan, for example Dodecyl Mercaptan (DM) and/or hexadecyl mercaptan, may preferably be added to the polymerization. The addition amount of the chain transfer agent is preferably 0.1-0.25% of the total mass of the a-type monomer, the b-type monomer and the c-type monomer.
According to the present invention, a diluent, which may be mineral oil, ester oil and polyolefin, may be preferably added to the polymerization reaction. The amount of the diluent added is preferably 10 to 200%, more preferably 20 to 100% of the total mass of the a-type monomer, the b-type monomer and the c-type monomer.
According to the invention, the polymerization temperature is preferably between 60 ℃ and 140 ℃, preferably between 80 ℃ and 100 ℃; the polymerization time is 1 to 5 hours, preferably 2 to 4 hours. During the polymerization, an inert gas is preferably introduced, and for example, nitrogen gas may be introduced.
According to the invention, preferably, after the polymerization reaction is finished, the reaction product can be subjected to normal pressure or reduced pressure distillation to remove volatile monomers and unreacted monomers, and the viscosity index improver can be obtained by collecting.
According to the invention, the preferred preparation method of the c-type monomer is as follows:
a step of carrying out esterification reaction on the compound with the structure of formula (II) and the compound with the structure of formula (III);
Figure BDA0002415205530000051
wherein R is 1 Selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), X is selected from F, cl, br, I and OH (preferably Cl, br); r 4 Selected from H and C 1 ～C 4 Alkyl (preferably H), R 5 Selected from H and C 1 ～C 20 Straight or branched alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R 6 Selected from H and C 1 ～C 20 Straight or branched chain alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R 7 Is selected from H and C 1 ～C 20 Straight or branched alkyl (preferably selected from H and C) 1 ～C 20 Straight chain alkyl), R 8 Selected from H and C 1 ～C 4 Alkyl (preferably selected from H and methyl).
According to the invention, preferably R 4 、R 8 Is H, R 5 、R 6 、R 7 Wherein one group is C 1 ～C 20 Straight or branched alkyl (preferably C) 1 ～C 20 Straight chain alkyl), the other two groups are H; more preferably, R 4 、R 6 、R 8 Is H, R 5 、R 7 Wherein one group is C 1 ～C 20 Straight or branched alkyl (preferably C) 1 ～C 20 Straight chain alkaneGroup) and the other group is H.
According to the present invention, preferably, the molar ratio between the compound of formula (II) and the compound of formula (III) is 1:1 to 10, preferably 1:1 to 5.
According to the invention, preferably, the temperature of the esterification reaction is between 0 and 150 ℃, preferably between 30 and 80 ℃: in general, the reaction time is preferably as long as possible, and may be 2 to 10 hours, preferably 4 to 8 hours. According to the preparation method of the c-type monomer, preferably, in the esterification reaction, a catalyst can be added or not be added, and the catalyst is preferably added. The catalyst is preferably C 1 ～C 10 The organic amine and/or aqueous ammonia may be selected from one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine and aqueous ammonia. The amount of the catalyst added is preferably 0.1 to 20%, more preferably 1 to 15% of the amount of the compound having the structure of formula (III).
According to the invention, a polymerization inhibitor may or may not be added in the esterification reaction, and is preferably added. The polymerization inhibitor is preferably selected from the group consisting of metal chlorides, phenolic polymerization inhibitors, quinoid polymerization inhibitors and metal powders, and for example, one or more of cuprous chloride, ferric trichloride, hydroquinone, benzoquinone and copper powder may be used. The addition amount of the polymerization inhibitor is preferably 0.01 to 1 percent of the mass of the compound with the structure shown in the formula (III), and more preferably 0.05 to 0.5 percent.
According to the invention, in the esterification reaction, a solvent may or may not be added, preferably a solvent is added. The solvent is preferably one or more of methanol, toluene, ethanol, acetone, chloroform and petroleum ether; the amount of the solvent added is preferably 10% to 120%, more preferably 50% to 100%, of the amount of the compound of formula (III) in mass.
According to the invention, preferably, the compound with the structure of formula (III) is obtained by subjecting the compound with the structure of formula (IV) to hydrogenation reaction;
Figure BDA0002415205530000061
wherein R is 4 ' selected from H and C 1 ～C 4 Alkyl, alkenyl or alkynyl, R 5 ' selected from H and C 1 ～C 20 Straight-chain or branched alkyl, alkenyl or alkynyl, R 6 ' selected from H and C 1 ～C 20 Straight-chain or branched alkyl, alkenyl or alkynyl, R 7 ' selected from H and C 1 ～C 20 Straight-chain or branched alkyl, alkenyl or alkynyl, R 8 ' selected from H and C 1 ～C 4 Alkyl, alkenyl or alkynyl, wherein at least one group is selected from alkenyl or alkynyl.
According to the present invention, preferably, the conditions of the hydrogenation reaction are: hydrogen pressure of 1.0-6.0 MPa (preferably 3.0-4.0 MPa), temperature of 60-260 deg.C (preferably 180-220 deg.C), and time of 0.5-10 h (preferably 3-5 h).
The phenol compound represented by formula (IV) of the present invention is preferably derived from a natural plant cashew nut, contains a large amount of cashew nut shell oil in the cashew nut shell, contains meta-phenol as a main component, is generally called cardanol, and has the following structure:
Figure BDA0002415205530000071
wherein R is C 15 H 31+x And x is 0, -2, -4 or-6. The viscosity index improver disclosed by the invention has excellent thickening performance, shear stability and oxidation resistance.
According to the invention, the component A) accounts for 0.01-6%, preferably 0.2-3% of the total mass of the composition.
According to the invention, the composite antioxidant of the component B) is a mixture of alkylated diphenylamine and thiophenol ester, wherein the alkylated diphenylamine accounts for 50-95%, preferably 60-90% of the total mass of the composite antioxidant; the thiophenol ester accounts for 5-50% of the total mass of the composite antioxidant, and preferably accounts for 10-40%. The alkyl group in the alkylated diphenylamine antioxidant is preferably C 1 ～C 12 Alkyl, more preferably C 4 ～C 9 Alkyl, more preferably tert-butyl and/or isooctylOne or more of tert-butyl/isooctyldiphenylamine, dioctyldiphenylamine, p' -diisooctyldiphenylamine and nonyldiphenylamine can be selected, and common commercial brands comprise IRGANOX L-01 and IRGANOX L-57 produced by Pasfu, germany, LZ5150A produced by Beijing Xinpu, LZ Lu Borun blue additive, LZ5150A produced by Vaubnlle, vanlle 961 and VANLube 81 produced by Vanderbilt, germany, and 700RC 1 produced by Rhine chemical company. The thiophenol ester can be 2,2' -thiobis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ethyl propionate]One or more of 2,2-thiobis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate and 3,3' -ditetradecyl thiodipropionate can be selected from, for example, DLTDP, DSTDP, DMTD manufactured by tianjin mechanical chemical co. The alkylated diphenylamine accounts for 0.01-5%, preferably 0.1-3% of the total mass of the composition; the content of the thiophenol ester is 0.1-5%, preferably 0.3-1.5% of the total weight of the composition.
According to the invention, the component C) is a polyisobutylene succinimide ashless dispersant and/or a polyisobutylene succinate dispersant. The number average molecular weight of the polyisobutylene part in the polyisobutylene succinimide ashless dispersant is 800-4000, preferably 900-3000, and most preferably 1000-2400, and T161 produced by Suzhou special oil product factory, T161A, T B produced by additive factory of Dan Huafen of Jinzhou, LZL 57 produced by Lu Borun blue additive limited company, LZ6418 and LZ6420 produced by Lu Bo Runck company, hitec646 produced by Yafton company and the like can be selected. The polyisobutylene succinate dispersant may be a polyisobutylene pentaerythritol succinate dispersant having a number average molecular weight of the polyisobutylene moiety of 500 to 4000, preferably 700 to 2500, and most preferably 1000 to 2300, for example LZ936 from luoborun. Component C) is preferably a mixture of an ashless polyisobutylene succinimide dispersant and a polyisobutylene succinate dispersant in a mass ratio of 1:1 to 3:1. The component C) accounts for 1-10 percent of the total mass of the composition, and preferably 2-8 percent.
According to the invention, the component D) is a mixture of magnesium sulfonate and sodium sulfonate, preferably a mixture of magnesium sulfonate with high base number of (200-450) mgKOH/g and sodium sulfonate with high base number of (200-450) mgKOH/g, and the preferred mixing ratio between the two is 1:1 to 3:1. The component D) may be KT5448 manufactured by KANTAI lube oil additives of Jinzhou, hitec7637 manufactured by Afton Corporation, C9340 manufactured by Infineum Corporation, or the like. The component D) accounts for 0.2-10 percent of the total mass of the composition, and preferably 0.8-8 percent.
According to the invention, component E) is a zinc dialkyldithiophosphate, the alkyl groups in the zinc dialkyldithiophosphate being alkyl groups having from 2 to 12 carbon atoms, preferably alkyl groups having from 2 to 8 carbon atoms, and being ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, 2-ethylhexyl, cyclohexyl, methylcyclopentyl. The zinc dialkyldithiophosphate may be selected from T202 and T203 produced by Wuxi south Petroleum additives Ltd, primary alkyl T202, primary alkyl T203, primary secondary alkyl T204 and secondary alkyl T205 produced by Dan Huafen additive factory, LZ1371 and LZ1375 produced by Lubrizol, C9417, C9425 and C9426 produced by Infineum, hitec7169 and Hitec1656 produced by Afton. The component E) accounts for 0.1-5 percent of the total mass of the composition, and preferably 0.3-3 percent.
According to the invention, said component F) is an organomolybdenum friction modifier, preferably selected from one or more of the group consisting of molybdenum dialkyldithiophosphates, oxymolybdenum dialkyldithiophosphates, molybdenum dialkyldithiocarbamates, molybdenum xanthates, molybdenum thioxanthates, trinuclear molybdenum-sulfur complexes, molybdenum amine complexes, and molybdates, said organomolybdenum compound having an organic group containing a sufficient number of carbon atoms to render the organomolybdenum compound soluble or dispersible in a base oil, generally said number of carbon atoms being between 6 and 60, preferably between 10 and 50. The organo-molybdenum friction modifier may be selected from the group consisting of MolyVan L, 822, 855, manufactured by Vanderbilt corporation, usa, 515, 525, 710, manufactured by asahi electric company, japan, and the like. The component F) accounts for 0.01-5 percent of the total mass of the composition, and preferably 0.1-2 percent.
According to the invention, the component G) is a major amount of a lubricant base oil and may be selected from mineral oils and/or synthetic lubricating oils. The mineral oils may range in viscosity from light distillate mineral oils to heavy distillate mineral oils, including liquid paraffinic oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types, and are generally classified as group I, II, III base oils, with common commercial designations including group I150 SN, 600SN, HVI 500, HVI 750, group II 100N, 150N, group III base oil S-8, and the like. The synthetic lubricating oil comprises one or more of polymerized hydrocarbon oil, alkylbenzene and derivatives thereof and ester oil. Specific examples of such polymeric hydrocarbon oils include, but are not limited to, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutene, poly (1-hexene), poly (1-octene), poly (1-decene), and common commercial designations including PAO4, PAO6, PAO8, PAO10, and the like. Specific examples of the alkylbenzene include, but are not limited to, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene, for example. Derivatives of said alkylbenzenes include alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof. The ester-based oils include esters or complex esters formed by condensation of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids) with alcohols (e.g., butanol, hexanol, dodecanol, 2-ethylhexyl alcohol, ethylene glycol, propylene glycol), and specific examples of such esters include, but are not limited to, dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, di (eicosyl) sebacate, 2-ethylhexyl diester of linoleic acid dimer.
The preparation method of the methanol engine lubricating oil composition comprises the step of mixing the components. The mixing temperature is preferably between 40 ℃ and 90 ℃ and the mixing time is preferably between 1 hour and 6 hours.
The methanol engine lubricating oil composition has excellent antioxidant performance, high temperature antiwear performance and piston detergency performance, and can meet the lubricating requirement of methanol fuel engine.
Detailed Description
The present invention will be described in more detail with reference to examples. The invention is not so limited. All proportions and parts are by mass unless otherwise specified.
In the context of the present invention, the straight or branched hydrocarbon group may be a straight or branched alkyl group, may also be a straight or branched alkenyl group comprising one or more (e.g. 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon double bonds, may also be a straight or branched alkynyl group comprising one or more (e.g. 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon triple bonds, may also be a straight or branched hydrocarbon group comprising one or more (e.g. 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon double bonds and carbon-carbon triple bonds.
The main raw materials used are as follows:
cardanol, shanghai Bingshi Binghe chemical science & technology Limited, industrial products
Methacryloyl chloride, national pharmaceutical group chemical reagents, analytical purity
Acryloyl chloride, national chemical group chemical reagent Limited, analytical pure
Triethylamine, chemical reagent of national drug group, analytical purity
Alkyl methacrylate, national pharmaceutical group chemical reagents, ltd, analytical purity
Cuprous chloride, chemical reagents of national drug group, chemical purity
2,2' -azobis (2,4-dimethylvaleronitrile), bailingwei Chemicals, inc., analytical purity
Palladium carbon catalyst (active carbon loaded with 10% of metal palladium), xian Kaili chemical Co., ltd., industrial methanol, chemical reagents Co., ltd., analytical purity
The aforementioned c-type monomer can be selected
Figure BDA0002415205530000101
Wherein R is 1 Selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R 5 Is C 15 Linear alkyl group of (1). The compound can be obtained by hydrogenation of cardanol.
The structure of the cardanol is shown as the following formula:
Figure BDA0002415205530000102
wherein R is C 15 H (31-X) And X is 0, 2,4 or 6. The cardanol is a compound with a single structure or a mixture containing a plurality of compounds with different structures.
EXAMPLE 1 preparation of m-pentadecylphenol
100g of cardanol and 1.5g of palladium-carbon catalyst are put into a 200ml high-pressure reaction kettle, the high-pressure kettle is sealed, hydrogen is introduced to 3.5MPa, and stirring and heating are started. The temperature was 200 ℃ and the reaction was carried out for 4.5 hours. And after the reaction is finished, cooling to 60 ℃, taking out the viscous reaction mixture, carrying out reduced pressure distillation for 1h at the temperature of 100Pa and 160 ℃, cooling to obtain a milky white solid, dissolving the milky white solid with petroleum ether, and then crystallizing and purifying to obtain the m-pentadecylphenol with the purity of more than 98%, wherein the reaction conversion rate is 83.6%.
Example 2 preparation of 3-pentadecylphenyl acrylate (PDPA)
30g of m-pentadecylphenol is dissolved in 100ml of methanol, the solution is placed into a 250ml three-neck reaction flask, 0.05g of cuprous chloride is added, and stirring and heating are started. Maintaining the reaction temperature at 50 ℃, slowly dropping 9g of acryloyl chloride into the reaction flask, dropping 4g of triethylamine again after the dropping is finished, and then heating to 60 ℃ to continue the reaction for 5 hours. And cooling after the reaction is finished to obtain yellow transparent liquid. The reaction product was filtered and recrystallized to give a pale yellow solid with a product conversion of 60.1%.
Example 3 preparation of 3-pentadecylphenyl Methacrylate (MDPA)
30g of m-pentadecylphenol is dissolved in 100ml of methanol, the solution is placed into a 250ml three-neck reaction flask, 0.025g of cuprous chloride is added, stirring is started, and heating is carried out. Maintaining the reaction temperature at 60 ℃, slowly dropping 10g of methacryloyl chloride into the reaction flask, dropping 2g of triethylamine again after the dropping is finished, and then heating to 60 ℃ to continue the reaction for 7 hours. And cooling after the reaction is finished to obtain yellow transparent liquid. The reaction product was filtered and recrystallized to give a pale yellow solid with 58.2% product conversion.
The monomers of class a used in the polymerization reaction include: MMA, methyl methacrylate; BMA, butyl methacrylate; the b-type monomers used in the polymerization reaction include: DMA, decyl methacrylate; nTM, tetradecyl methacrylate; nDM, dodecyl methacrylate; nHM, cetyl methacrylate.
Examples 4 to 8 and comparative example 1
75 parts of Shanghai Gaoqiao No. 6 hydrogenated oil (diluent) was charged into a reactor equipped with a stirring, heating and cooling device, a dropping funnel, a thermometer, and a nitrogen line. In another reaction flask, 100 parts in total of the monomers shown in Table 1, and the amounts of the initiator and the chain transfer agent shown in Table 1 were charged, and the mixture was stirred at room temperature and charged into a dropping funnel. Starting a reactor to stir, heating the reactor to 90 ℃, opening a dropping funnel under the protection of nitrogen, slowly dropping the solution, finishing dropping within 5 hours, continuing to react for 2 hours at 90 ℃ after dropping, then carrying out reduced pressure distillation on the reaction product at the vacuum degree of 100Pa and the distillation temperature of 120 ℃, removing volatile monomers and unreacted monomers, obtaining uniform solution containing 57% of viscosity index improver and 43% of diluent, and respectively naming the viscosity index improver therein as S-1-S-5 and B-1.
TABLE 1
Figure BDA0002415205530000121
Viscosity measurement and shear stability test
In examples 9 to 13 and comparative examples 2 to 3 in which lubricating oil compositions were obtained by adding the viscosity index improver solutions obtained in examples 4 to 8 and comparative example 1 to a base liquid using PAO2 as the base liquid, respectively, these lubricating oil compositions contained the base liquid, a diluent and a viscosity index improver in the viscosity index improver solution, wherein the mass fractions of the viscosity index improvers S-1 to S-5 and B-1 to the lubricating oil compositions are shown in table 2. The resulting lubricating oil compositions were subjected to viscosity measurement and shear stability tests. Measuring the change of the viscosity of the lubricating oil composition along with the temperature according to GB/T265 'petroleum product kinematic viscosity determination method and dynamic viscometer algorithm', and measuring the kinematic viscosity at 100 ℃; the shear stability test is carried out by adopting SH/T0505 'method for measuring shear stability of polymer-containing oil', and the measuring method comprises the following steps: respectively carrying out radiation treatment on the lubricating oil composition in an ultrasonic oscillator for 15 minutes, measuring the liquid viscosity before and after ultrasonic shearing, and determining the shearing stability index (SSI value), wherein the lower the SSI value is, the better the shearing stability of the measured polymer solution is.
The SSI values and viscosity measurements of the respective lubricating oil compositions are shown in Table 2.
As can be seen from Table 2, the viscosity index improver of the present invention has strong thickening ability at low dosage, good low temperature fluidity, and good shear stability.
TABLE 2
Figure BDA0002415205530000131
Test for Oxidation resistance
The viscosity index improvers of examples 4 to 8 and the viscosity index improver of comparative example 1 were dissolved in shanghai bridge 6# hydrogenated oil to prepare solutions having a viscosity index improver content of 10% (mass fraction), and the solutions were subjected to an oxidation resistance test using a TA5000 DSC instrument, a test condition: 180 ℃, the oxygen pressure of 0.5MPa and the heating speed of 10 ℃/min. The test results are shown in Table 3.
TABLE 3
Figure BDA0002415205530000132
As can be seen from Table 3, the viscosity index improver of the present invention has better antioxidant properties than conventional viscosity index improvers.
Methanol Engine lubricating oil compositions of examples 14 to 16 and comparative examples 4 to 5
The formulation composition of the methanol engine lubricating oil compositions of examples 14 to 16 and comparative examples 4 to 5 is shown in Table 4 (wherein the mass fraction of the viscosity index improver in the products of example 4, example 5 and comparative example 1 is 57%). The components are added into a mixing container according to the proportion, heated and stirred for 2 hours at 50 ℃, and the methanol engine lubricating oil composition with the viscosity grade of 5W-40 is prepared respectively.
TABLE 4
Figure BDA0002415205530000141
The compositions of examples 14 to 16 and comparative examples 4 to 5 were subjected to a pressure differential scanning calorimetry test (PDSC) and a high temperature deposit evaluation test (TEOST-MHT), respectively. PDSC was set at 220 ℃ and the TEOST-MHT test was conducted by ASTM D7097, the deposition bar temperature was 285 ℃ and the reaction time was 24 hours, the results are shown in Table 5.
TABLE 5
Oil sample PDSC/min TEOST-MHT/mg
Example 14 32.7 34.8
Example 15 33.4 31.2
Example 16 34.9 29.7
Comparative example 4 23.3 51.6
Comparative example 5 25.7 45.3
As can be seen from Table 5, at a high temperature of 220 ℃, the oxidation induction period in the examples is significantly increased compared to that of the oil in the comparative example, and the amount of deposit formation in the examples is significantly decreased in terms of controlling the amount of deposit formation (TEOST), indicating that the composition of the present invention has excellent antioxidant properties.
The compositions of examples 14 to 16 and comparative examples 4 to 5 were subjected to a high-temperature abrasion resistance test of oil products using an SRV friction tester under conditions of a load of 300N, a frequency of 50Hz, a stroke of 1mm and a temperature of 120 ℃ respectively, and the test results are shown in Table 6. As can be seen from Table 6, the wear-leveling diameters of the inventive examples were smaller than those of the comparative examples, and exhibited better wear resistance.
TABLE 6
Oil sample SRV grinding diameter/mm
Example 14 0.62
Example 15 0.65
Example 16 0.63
Comparative example 4 0.72
Comparative example 5 0.68
Examples 17, 18 and comparative examples 6, 7 of methanol engine lubricating oil compositions
The formulation compositions of examples 17 and 18 and comparative examples 6 and 7 of the methanol engine lubricating oil composition are shown in Table 7. The components are added into a mixing container according to the proportion, heated and stirred for 2 hours at 50 ℃, and the methanol engine lubricating oil composition with the viscosity grade of 5W-40 is prepared respectively.
TABLE 7
Figure BDA0002415205530000161
The compositions of examples 17 and 18 and comparative examples 6 and 7 were subjected to coke-forming tests, respectively. The device adopted in the coke forming plate test is a 25B-19 type coke forming plate instrument produced by Meitech company in Japan, and the test simulates the working conditions of the lubricating oil circulation of the crankcase and the piston ring of the cylinder sleeve of the engine so as to lead the tested oil product to be continuously oxidized by heat and coked. The test time is 6h, the oil temperature is 150 ℃, and the plate temperature is 320 ℃. The results of the coke-forming plate test are shown in Table 7. In examples 17 and 18, a mixture of a magnesium overbased sulfonate and a sodium overbased sulfonate was added, and in comparative examples 6 and 7, a single-component magnesium overbased sulfonate and a single-component sodium overbased sulfonate were added.
As can be seen from Table 7, the mixture of overbased magnesium sulfonate and overbased sodium sulfonate has better detergency performance than either the overbased magnesium sulfonate or the overbased sodium sulfonate alone.
BRT ball Corrosion test
The BRT ball rust test is an engine bench test that replaces procedure ID and is used primarily to evaluate the corrosion resistance and rust resistance of engine oils. The test oil protected metal spheres were continuously exposed to the acidic liquid and air throughout the 18 hour bench test. After the test is finished, the gray level test is carried out through the strength of the metal spherical reflecting surface to determine the corrosion area, so that the anti-corrosion capability of the test oil is evaluated. In this test, the injection rate of acetic acid/hydrobromic acid/hydrochloric acid/deionized water was 0.19 ml/hour, the air flow was 40 ml/min, and the oil temperature was 48 ℃.
The above-described ball rust test was carried out on the compositions of examples 17 and 18 and comparative examples 6 and 7, respectively, and the test results are shown in Table 8. The higher the ball rust test score, the stronger the rust resistance, and as can be seen from table 8, the composition of the present invention has excellent base number retention and rust resistance.
TABLE 8
Oil name Ball rust test results
Example 17 128
Example 18 126
Comparative example 6 98
Comparative example 7 91

Claims (6)

1. A methanol engine lubricating oil composition comprising the following components:
a) A viscosity index improver;
b) Composite antioxidants including alkylated diphenylamines and thiophenol esters;
c) A polyisobutylene succinimide dispersant and/or a polyisobutylene succinate dispersant;
d) Mixtures of magnesium and sodium sulfonates;
e) Zinc dialkyldithiophosphates;
f) An organo-molybdenum friction modifier;
g) A major amount of a lubricant base oil;
the component A) viscosity index improver has a structure shown in a general formula (I):
Figure DEST_PATH_IMAGE002
（I）
wherein x sub-repeat units of the n repeat units are the same or different from each other, y sub-repeat units of the n repeat units are the same or different from each other, and z sub-repeat units of the n repeat units are the same or different from each other; r in x sub-repeating units 1 Identical to or different from each other, each independently selected from H and methyl, R in x sub-repeating units 2 Are the same or different from each other and are each independently selected from C 1 ～C 6 A linear alkyl group; r in y sub-repeat units 1 Are identical or different from each other and are each independently selected from H and methyl, R in y sub-repeat units 4 R selected from H, y sub-repeat units 5 Are the same or different from each other and are each independently selected from C 1 ～C 20 Straight chain alkyl, R in y sub-repeat units 6 R selected from H, y sub-repeat units 7 R selected from H, y sub-repeat units 8 Is selected from H; r in z sub-repeat units 1 Identical or different from each other, each independently selected from H and methyl, R in z sub-repeating units 3 Are the same or different from each other and are each independently selected from C 8 ～C 18 A linear alkyl group; x in the n repeating units are the same or different from each other and are each independently selected from an integer of 10 to 1000, y in the n repeating units are the same or different from each other and are each independently selected from an integer of 10 to 5000, and z in the n repeating units are the same or different from each other and are each independently selected from an integer of 10 to 2000; n is an integer of 10 to 3000; the preparation method of the viscosity index improver comprises the following steps: carrying out polymerization reaction on a type monomer, a type monomer and a type c monomer, and collecting a polymerization product; the structure of the a-type monomer is as follows:
Figure DEST_PATH_IMAGE004
wherein R is 1 Selected from H and methyl, R 2 Is selected from C 1 ～C 6 A linear alkyl group;
the structure of the b-type monomer is as follows:
Figure DEST_PATH_IMAGE006
wherein R is 1 Selected from H and methyl, R 3 Is selected from C 8 ～C 18 A linear alkyl group;
the structure of the c-type monomer is as follows:
Figure DEST_PATH_IMAGE008
wherein R is 1 Selected from H and methyl, R 4 Selected from H, R 5 Is selected from C 1 ～C 20 Straight chain alkyl radical, R 6 Is selected fromH，R 7 Selected from H, R 8 Is selected from H; according to the total mass of the a-type monomer, the b-type monomer and the c-type monomer, the mass of the a-type monomer is 5-30% of the total mass, the mass of the b-type monomer is 20-70% of the total mass, and the mass of the c-type monomer is 20-50% of the total mass; the component A) accounts for 0.01-6% of the total mass of the composition; the alkylated diphenylamine accounts for 0.01-5% of the total mass of the composition, and the thiophenol ester accounts for 0.1-5% of the total mass of the composition; the component C) accounts for 1-10% of the total mass of the composition; the component D) accounts for 0.2-10% of the total mass of the composition; the component E) accounts for 0.1-5% of the total mass of the composition; the component F) accounts for 0.01-5% of the total mass of the composition; the component G) is a major amount of a lubricant base oil.
2. The composition of claim 1 wherein the group a monomers are selected from one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate; the b-type monomer is selected from one or more of octyl methacrylate, decyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl mixed alkyl methacrylate, hexadecyl methacrylate and octadecyl methacrylate; the c-type monomer is selected from one or more of tetradecylphenyl methacrylate, tetradecylphenyl acrylate, pentadecylphenyl methacrylate, pentadecylphenyl acrylate, hexadecylphenyl methacrylate and hexadecylphenyl acrylate.
3. The composition of claim 1, wherein the c-type monomer is prepared by: a step of carrying out esterification reaction on the compound with the structure of formula (II) and the compound with the structure of formula (III);
Figure DEST_PATH_IMAGE010
（II），
Figure DEST_PATH_IMAGE012
（III），
wherein R is 1 Selected from H and methyl, X is selected from Cl and Br; r 4 Selected from H, R 5 Is selected from C 1 ～C 20 Straight chain alkyl radical, R 6 Selected from H, R 7 Selected from H, R 8 Is selected from H.
4. The composition of claim 3, wherein the compound of formula (III) is obtained by hydrogenation of a compound of formula (IV);
Figure DEST_PATH_IMAGE014
（IV）
wherein R is 4 ' is selected from H, R 5 ' selected from C 1 ～C 20 Straight-chain alkenyl radical, R 6 ' is selected from H, R 7 ' is selected from H, R 8 ' is selected from H.
5. The composition of claim 1~4 wherein the complex antioxidant of component B) is a mixture of alkylated diphenylamine and a thiophenol ester, wherein the alkylated diphenylamine comprises 50% to 95% and the thiophenol ester comprises 5% to 50% of the total mass of the complex antioxidant; the number average molecular weight of a polyisobutylene part in the polyisobutylene succinimide ashless dispersant is 800-4000, and the polyisobutylene succinate dispersant is selected from polyisobutylene succinic acid pentaerythritol ester dispersant; the component D) is a mixture of high-base-number magnesium sulfonate with the base number of 200mgKOH/g to 450mgKOH/g and high-base-number sodium sulfonate with the base number of 200mgKOH/g to 450 mgKOH/g; the alkyl group in the zinc dialkyldithiophosphate of component E) is an alkyl group containing 2 to 12 carbon atoms; the component F) is selected from one or more of molybdenum dialkyldithiophosphates, molybdenum oxydithiophosphates, molybdenum dialkyldithiocarbamates, molybdenum xanthates, molybdenum thioxanthates, trinuclear molybdenum-sulfur complexes, molybdenum amine complexes, and molybdates; the component G) is selected from mineral oils and/or synthetic lubricating oils.
6. The method of making the methanol engine lubricating oil composition of any one of claims 1~5 comprising the step of combining the components therein.
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