CN112760154B - Natural gas engine lubricating oil composition and preparation method thereof - Google Patents

Abstract

The invention provides a natural gas engine lubricating oil composition and a preparation method thereof. The natural gas engine lubricating oil composition comprises a phosphorus-containing compound, a high-molecular-weight succinimide ashless dispersant, a mono-succinimide ashless dispersant, a calcium sulfonate detergent, a sulfurized calcium alkyl phenate detergent, a naphthylamine antioxidant, zinc dialkyl dithiophosphate, an organic molybdenum friction improver, a viscosity index improver and lubricating oil base oil, wherein the phosphorus-containing compound has the structure as follows:

Description

Natural gas engine lubricating oil composition and preparation method thereof

technical field

The invention relates to a lubricating oil composition, in particular to a natural gas engine lubricating oil composition with excellent biodegradability and oxidation resistance.

Background technique

At present, the environmental pollution caused by vehicle exhaust emissions is becoming more and more serious, and the development and application of clean energy has become the general trend. As a vehicle fuel, natural gas is safer to burn than traditional gasoline and diesel, and can reduce _CO emissions by 97%, HC emissions by 72%, NOx emissions by 39%, SO2 emissions by 90%, and produce a very small amount of emissions particulates. Therefore, gas vehicles are considered to be an effective way to solve the problem of vehicle emission pollution, and the development prospect is very bright.

Internal combustion engine oil is subject to high temperature oxidation, external fuel, moisture, metal, and mechanical impurities during use, and the oil will oxidize and deteriorate. Therefore, it must be replaced with new engine oil after a period of use. Waste internal combustion engine oil contains hydrocarbons, additives, sludge and other organic or inorganic substances harmful to animals and plants. In the "National List of Hazardous Wastes", waste engine oil belongs to hazardous waste (HW08), which is particularly serious for water and soil pollution. In my country, it is difficult to effectively recycle waste engine oil due to scattered distribution and difficulty in dispersion. Therefore, it is necessary to seek high-efficiency lubricating oil biodegradation accelerators and antioxidants to be applied to internal combustion engine oils to prolong the service life of oil products and reduce waste. The impact of engine oil on the environment has always been the goal of those skilled in the art.

Contents of the invention

The invention provides a natural gas engine lubricating oil composition and a preparation method thereof.

The natural gas engine lubricating oil composition of the present invention comprises phosphorus-containing compound, high molecular weight succinimide ashless dispersant, monosuccinimide ashless dispersant, calcium sulfonate detergent, sulfurized alkylphenate calcium detergent, Naphthylamine type antioxidant, zinc dialkyldithiophosphate, organic molybdenum friction modifier, viscosity index improver and lubricating base oil, wherein the structure of the phosphorus-containing compound is:

In formula I, n is an integer between 0 and 50 (preferably an integer between 0 and 20, more preferably an integer between 0 and 10); n+1 R groups are the same or different from each other, each independently selected from trivalent C ₁ -C ₃₀ hydrocarbon groups (preferably trivalent C ₁ -C ₁₀ alkyl groups, more preferably trivalent C ₁ -C ₄ alkyl groups); R _b group is H or C ₁ -C ₁₀ hydrocarbon group (preferably H or C ₁ to C ₆ straight chain or branched chain alkyl, more preferably H or C ₁ to C ₄ straight chain or branched chain alkyl);

(优选各自独立地选自H、C₁～C₁₀的直链或支链烷基和

更优选各自独立地选自H、C₁～C₄的直链或支链烷基和

且至少其中一个R₀为

)，其中x为0～5之间的整数(优选0～4之间的整数，更优选0、1、2或3)，y为1～5之间的整数(优选1～4之间的整数，更优选1、2或3)，x个R₁基团彼此相同或不同，各自独立地选自H、C₁～C₃₀的烃基(优选选自H、C₁～C₁₀的直链或支链烷基，更优选选自H、C₁～C₄的直链或支链烷基)，Ar基团为C₃～C₃₀的环基团(优选C₆～C₁₅的芳香环基团，更优选苯环、萘环或蒽环)，R₂基团为单键或C₁～C₁₀的亚烷基(优选单键或C₁～C₆的亚烷基，更优选单键或C₁～C₄的亚烷基)；Each R ₀ group is the same or different from each other, each independently selected from H, C ₁ -C ₃₀ hydrocarbon groups and

(preferably each independently selected from H, C ₁ to C ₁₀ linear or branched alkyl and

More preferably each independently selected from H, C ₁ to C ₄ linear or branched alkyl and

and at least one of R ₀ is

), wherein x is an integer between 0 and 5 (preferably an integer between 0 and 4, more preferably 0, 1, 2 or 3), and y is an integer between 1 and 5 (preferably an integer between 1 and 4 Integer, more preferably 1, 2 or 3), x R ₁ groups are the same or different from each other, each independently selected from H, C ₁ to C ₃₀ hydrocarbon groups (preferably selected from H, C ₁ to C ₁₀ straight chain or branched chain alkyl, more preferably selected from H, C ₁ to C ₄ straight chain or branched chain alkyl), Ar group is C ₃ to C ₃₀ ring group (preferably C ₆ to C ₁₅ aromatic ring group, more preferably benzene ring, naphthalene ring or anthracene ring), R2 group is a single bond or _{a C 1 to} C ₁₀ alkylene group (preferably a single bond or a C ₁ to C ₆ alkylene group, more preferably a single bond or C ₁ ~ C ₄ alkylene);

OH、C₁～C₃₀的烃基(优选C₁～C₁₀的直链或支链烷基，更优选C₁～C₄的直链或支链烷基)、C₁～C₃₀的烷氧基(优选C₁～C₁₀的直链或支链烷氧基，更优选C₁～C₄的直链或支链烷氧基)和H，其中至少一个A基团为

X基团为O或S，a为0或1，R’选自C₁～C₃₀的烃基(优选C₁～C₁₀的直链或支链烷基，更优选C₁～C₄的直链或支链烷基)、苄基、苯基、

R”选自C₁～C₃₀的烃基(优选C₁～C₁₀的直链或支链烷基，更优选C₁～C₄的直链或支链烷基)、C₁～C₃₀的烷氧基(优选C₁～C₁₀的直链或支链烷氧基，更优选C₁～C₄的直链或支链烷氧基)，其中各个R₀、R、R_b、n的定义同前所述；Each A group is the same or different from each other, each independently selected from

OH, C ₁ -C ₃₀ hydrocarbon group (preferably C ₁ -C ₁₀ straight chain or branched chain alkyl, more preferably C ₁ -C ₄ straight chain or branched chain alkyl), C ₁ -C ₃₀ alkoxy (preferably C ₁ to C ₁₀ straight or branched chain alkoxy, more preferably C ₁ to C ₄ straight or branched alkoxy) and H, wherein at least one A group is

The X group is O or S, a is 0 or 1, and R' is selected from C ₁ -C ₃₀ hydrocarbon groups (preferably C ₁ -C ₁₀ straight chain or branched chain alkyl groups, more preferably C ₁ -C ₄ straight chain chain or branched alkyl), benzyl, phenyl,

R" is selected from C ₁ to C ₃₀ hydrocarbon group (preferably C ₁ to C ₁₀ straight chain or branched chain alkyl, more preferably C ₁ to C ₄ straight chain or branched chain alkyl), C ₁ to C ₃₀ Alkoxy (preferably C ₁ to C ₁₀ linear or branched alkoxy, more preferably C ₁ to C ₄ linear or branched alkoxy), wherein each of R ₀ , R, R _b , n as defined above;

Optionally include the product of partial or complete condensation dehydration reaction between NH and COOH present in the compound of formula (I).

基团中，Ar基团优选苯环，x优选为2，OH优选位于R₂基团的对位，两个R₁优选分别位于OH的两个邻位，两个R₁各自独立地选自C₁～C₄的直链或支链烷基，优选选自叔丁基。According to the present invention, in the compound of formula (I), preferably, in

In the group, the Ar group is preferably a benzene ring, x is preferably 2, OH is preferably located at the para position of the R2 group, and _two R1 are preferably located at two ortho positions _of the OH group, and the two _R1s are each independently selected from C ₁ -C ₄ linear or branched alkyl groups are preferably selected from t-butyl groups.

OH、C₁～C₁₀的直链或支链烷基、C₁～C₁₀的直链或支链烷氧基和H，更优选地，各个A基团各自独立地选自

OH、C₁～C₄的直链或支链烷基、C₁～C₄的直链或支链烷氧基和H。According to the present invention, in the compound of formula (I), preferably, each A group is independently selected from

OH, C ₁ to C ₁₀ straight chain or branched chain alkyl, C ₁ to C ₁₀ straight chain or branched chain alkoxy and H, more preferably, each A group is independently selected from

OH, C ₁ -C ₄ linear or branched alkyl, C ₁ -C ₄ linear or branched alkoxy, and H.

The phosphorus-containing compound of specific structure described in the present invention comprises one or more in the compound shown below:

According to the present invention, the preparation method of the phosphorus-containing compound comprises:

Step (1): reacting the compound represented by formula (II) and/or its inorganic acid salt with the compound represented by formula (III), and collecting the product of step (1);

In formula (II), n is an integer between 0 and 50 (preferably an integer between 0 and 20, more preferably an integer between 0 and 10); n+1 R groups are the same or different from each other, each independently selected from trivalent C ₁ -C ₃₀ hydrocarbon groups (preferably trivalent C ₁ -C ₁₀ alkyl groups, more preferably trivalent C ₁ -C ₄ alkyl groups); R _b groups are H, C ₁ ~C ₁₀ hydrocarbon group (preferably H or C ₁ ~C ₆ straight chain or branched chain alkyl, more preferably H or C ₁ ~C ₄ straight chain or branched chain alkyl) and benzyl;

Each R ₀ 'group is the same or different from each other, each independently selected from H, C ₁ to C ₃₀ hydrocarbon groups (preferably each independently selected from H, C ₁ to C ₁₀ linear or branched chain alkyl groups, more preferably each independently selected from H, C ₁ to C ₄ linear or branched alkyl), wherein x is an integer between 0 and 5 (preferably an integer between 0 and 4, more preferably 0, 1, 2 or 3), y is an integer between 1 and 5 (preferably an integer between 1 and 4, more preferably ₁ , 2 or 3), and x R groups are the same or different from each other, each independently selected from H, C ₁ to C ₃₀ hydrocarbon group (preferably selected from H, C ₁ to C ₁₀ straight chain or branched chain alkyl, more preferably selected from H, C ₁ to C ₄ straight chain or branched chain alkyl), Ar group is a C ₃ -C ₃₀ ring group (preferably a C ₆ -C ₁₅ aromatic ring group, more preferably a benzene ring, a naphthalene ring or an anthracene ring), and the R ₂ group is a single bond or a C ₁ -C ₁₀ sub Alkyl group (preferably a single bond or a C ₁ -C ₆ alkylene group, more preferably a single bond or a C ₁ -C ₄ alkylene group);

其中M为无机酸根，j为所述无机酸根电荷数的绝对值，z为1～10之间的整数(优选1～之间的整数，更优选1～3之间的整数)，其它各基团的定义同式(II)(所述式(II)所示化合物的无机酸盐优选其盐酸盐、其硝酸盐、或其硫酸盐，最优选其盐酸盐)；The A' groups are the same or different from each other, and are independently selected from OA"', C ₁ -C ₃₀ hydrocarbon groups (preferably C ₁ -C ₁₀ straight chain or branched chain alkyl groups, more preferably C ₁ -C ₄ straight or branched chain alkyl), C ₁ to C ₃₀ alkoxy (preferably C ₁ to C ₁₀ straight or branched alkoxy, more preferably C ₁ to C ₄ straight or branched alkoxy group) and H, A"' is selected from F, Cl, Br, I, H, wherein at least one A' group is OA"'; the structure of the inorganic acid salt of the compound shown in formula (II) is

Wherein M is an inorganic acid radical, j is the absolute value of the charge number of the inorganic acid radical, z is an integer between 1 and 10 (preferably an integer between 1 and 1, more preferably an integer between 1 and 3), and other groups The definition of the group is the same as that of formula (II) (the inorganic acid salt of the compound shown in the formula (II) is preferably its hydrochloride, its nitrate, or its sulfate, most preferably its hydrochloride);

In formula (III), the X group is O or S, a is 0 or 1, each R"' is the same or different from each other, each independently selected from A"', C ₁ -C ₃₀ hydrocarbon groups (preferably C ₁ ~C ₁₀ straight chain or branched chain alkyl, benzyl or phenyl, more preferably C ₁ ~C ₄ straight chain or branched chain alkyl), benzyl or phenyl;

And the optional (2) step: make the product of the (1) step react with the compound represented by formula (IV), and collect the product of the (2) step;

Wherein x is an integer between 0 and 5 (preferably an integer between 0 and 4, more preferably 0, 1, 2 or 3), and y is an integer between 1 and 5 (preferably an integer between 1 and 4, More preferably 1, 2 or 3), x R ₁ groups are the same or different from each other, each independently selected from H, C ₁ to C ₃₀ hydrocarbon groups (preferably selected from H, C ₁ to C ₁₀ straight chain or branched chain alkyl, more preferably selected from H, C ₁ to C ₄ straight chain or branched chain alkyl), Ar group is C ₃ to C ₃₀ ring group (preferably C ₆ to C ₁₅ aromatic ring group , more preferably a benzene ring, a naphthalene ring or an anthracene ring), the R ₂ group is a single bond or a C ₁ to C ₁₀ alkylene group (preferably a single bond or a C ₁ to C ₆ alkylene group, more preferably a single bond or C ₁ -C ₄ alkylene group), X' is F, Cl, Br, I or OH (preferably Cl, Br).

According to the preparation method of the phosphorus-containing compound of the present invention, the inorganic acid salt of the compound represented by the formula (II) can be obtained by reacting the compound represented by the formula (II) with an inorganic acid to form a salt.

According to the preparation method of the phosphorus-containing compound of the present invention, the compound represented by the formula (II) and/or its inorganic acid salt can be selected from amino acid, amino acid condensate (partial condensation or full condensation), amino acid inorganic salt, amino acid One or more of the inorganic salts of the condensation products (partial condensation or full condensation). The compound represented by the formula (II) and/or its inorganic acid salt can be selected from one or more of the following specific compounds: L-serine and/or L-serine ester hydrochloride, L-leucine and/or or L-leucine ester hydrochloride, L-isoleucine and/or L-isoleucine ester hydrochloride, glycine and/or glycine ester hydrochloride, L-phenylalanine and/or L-phenylalanine ester hydrochloride, L-valine and/or L-valine ester hydrochloride.

According to the preparation method of the phosphorus-containing compound of the present invention, the compound represented by the formula (III) can be selected from phosphorous acid and/or phosphite, and the specific compounds that can be enumerated include phosphorous acid, dimethyl phosphite, diphosphite Ethyl ester, dipropyl phosphite, diisopropyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-tert-butyl phosphite, (2-ethylhexyl) phosphite, phosphorous acid One or more of dibenzyl ester and diphenyl phosphite.

According to the preparation method of the phosphorus-containing compound of the present invention, in step (1), the compound represented by the formula (II) and/or its inorganic acid salt (in OA"') and the compound represented by the formula (III) The reaction equivalence ratio between (based on P—H) is preferably 1:5 to 5:1, more preferably 1:3 to 3:1; the temperature of the reaction is preferably -40 to 80°C, more preferably - 20-40°C; generally speaking, the longer the reaction time, the better. In order to improve the reaction efficiency, the reaction time is preferably 0.5-30 hours, more preferably 1-8 hours.

According to the preparation method of the phosphorus-containing compound of the present invention, in step (1), in the reaction of the compound represented by the formula (II) and/or its inorganic acid salt with the compound represented by the formula (III), it can be added A solvent may not be added, but it is preferred to add a solvent. One or more of the preferred protic solvents, hydrocarbon solvents and furan solvents of the solvent, for example, one of normal hexane, benzene, toluene, tetrahydrofuran, dichloromethane, methanol, ethanol, isopropanol and water can be selected or more, more preferably a protic solvent, for example, one or more of methanol, ethanol, isopropanol and water can be selected. The added amount of the solvent is appropriate to promote the smooth progress of the reaction, and is not particularly limited.

According to the preparation method of the phosphorus-containing compound of the present invention, in step (1), in the reaction of the compound represented by the formula (II) and/or its inorganic acid salt with the compound represented by the formula (III), it can be A catalyst may or may not be added, but it is preferred to add a catalyst. The catalyst can be a phase transfer catalyst, and the phase transfer catalyst can be selected from quaternary ammonium salts and/or crown ethers, preferably tetrahydrocarbyl ammonium halides, such as tetrabutyl ammonium bromide, trioctyl ammonium chloride, cetyl One or more of alkyltrimethylammonium bromide, triethylbenzylammonium chloride and 18-crown-6, more preferably tetrabutylammonium bromide. The addition amount of the catalyst is preferably 0.1%-10% of the mass of the compound represented by the formula (II) and/or its inorganic acid salt.

According to the preparation method of the phosphorus-containing compound of the present invention, in step (1), chloride is preferably added when the compound represented by formula (II) and/or its inorganic acid salt reacts with the compound represented by formula (III). Said chloride is preferably an aqueous solution of hypochlorite and/or chlorinated alkanes, said hypochlorite is preferably one or more of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, said chlorinated alkanes are preferably chlorinated Methane, for example, can be selected from one or more of carbon monochloride, carbon dichloride, carbon trichloride and carbon tetrachloride. The chloride is preferably an aqueous solution of hypochlorite, and its concentration is preferably 5% to 80%, more preferably an aqueous solution of sodium hypochlorite. The added amount of the chloride is preferably 30-100 mL/100 mmol of the compound represented by formula (II) and/or its inorganic acid salt.

According to the preparation method of the phosphorus-containing compound of the present invention, in step (1), the reaction between the compound shown in the formula (II) and/or its inorganic acid salt and the compound shown in the formula (III) is preferably at pH The value is 8-10 (preferably 8.5-9.5). The pH value can be adjusted by adding an alkaline medium, the alkaline medium is preferably an alkaline solution, and the alkaline solution is preferably one or more alkalis in sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide of aqueous solution.

According to the preparation method of the phosphorus-containing compound of the present invention, in step (1), after the reaction of the compound represented by the formula (II) and/or its inorganic acid salt with the compound represented by the formula (III), the reaction The product is subjected to an optional extraction operation, an optional drying operation and an optional sonication operation.

Preferably, the reaction product is extracted with a solvent, more preferably, the reaction product is extracted with a solvent in an acidic environment. One or more of the preferred ether solvents, ester solvents, chlorinated alkane solvents and hydrocarbon solvents of the solvent, for example, one or more of sherwood oil, ether, ethyl acetate, dichloromethane, chloroform and toluene can be selected. one or more species. The extraction operation is preferably performed 1 to 3 times. The acidic environment is obtained by adding an acid solution to adjust the pH value of the system where the reaction product is located, the pH is preferably 2 to 5, more preferably 2.5 to 3.5; the acid solution is preferably hydrochloric acid, acetic acid, nitric acid and sulfuric acid Aqueous solution of one acid or multiple acids, the acid solution preferably has a concentration of 1-10 mol/liter. Preferably, inorganic salts are added during the extraction operation to improve extraction efficiency. The inorganic salt is preferably one or more of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.

Preferably, a desiccant is added to dry the reaction product. The desiccant can be selected from anhydrous magnesium chloride and/or anhydrous sodium sulfate.

Preferably, the reaction product is subjected to ultrasonic operation, more preferably in the presence of a solvent, which is preferably one or more of furan solvents, haloalkane solvents, ketone solvents, ester solvents and nitrile solvents, for example, Select one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate and acetonitrile, more preferably one or more of tetrahydrofuran, dichloromethane and acetonitrile. The time of the ultrasonic operation is preferably 1-10 hours, more preferably 2-8 hours.

According to the preparation method of the phosphorus-containing compound of the present invention, in step (1), after the reaction of the compound represented by the formula (II) and/or its inorganic acid salt with the compound represented by the formula (III), the (1) The reaction product of the step is further purified. The purification operation includes one or more of drying, evaporation, washing, distillation, recrystallization and centrifugation methods known in the prior art.

According to the preparation method of the phosphorus-containing compound of the present invention, in the optional step (2), the compound represented by the formula (IV) can be prepared by methods known in the prior art, and there is no special limitation . The compound shown in the formula (IV) can be selected from one or more of the following specific compounds: 3,5-bis(tert-butyl)-4-hydroxyphenylacetyl chloride, 3,5-bis(tert-butyl base)-4-hydroxyphenylpropionyl chloride, p-hydroxyphenylacetyl chloride, 3-hydroxyphenylacetyl chloride, 2-hydroxyphenylacetyl chloride, 3,4-dihydroxyphenylacetyl chloride, 3,5-dihydroxyphenylacetyl chloride, 3-Methyl-4-hydroxyphenylacetyl chloride, 3,5-dimethyl-4-hydroxyphenylacetyl chloride, 2,4-dihydroxyphenylpropionyl chloride, 3,4-dihydroxyphenylpropionyl chloride, 2-hydroxy - Naphthaleneacetyl chloride.

According to the preparation method of the phosphorus-containing compound of the present invention, in the optional step (2), the compound represented by the formula (IV) (in X') and the reaction product of (1) step (in NH) The reaction equivalent ratio between is preferably 5:1～1:5, more preferably 1:2～2:1; the temperature of the reaction is preferably -40～60°C, more preferably -20～20°C; the reaction time Generally speaking, the longer the better, in order to improve the reaction efficiency, the reaction time is preferably 1-20 hours, more preferably 3-8 hours.

According to the preparation method of the phosphorus-containing compound of the present invention, in the optional step (2), the compound represented by the formula (IV) (in X') and the reaction product of the (1) step (in the In the reaction between NH) a solvent can be added, or no solvent can be added, preferably a solvent is added. The solvent is preferably one or more of protic solvents, ether solvents, ester solvents, chlorinated alkanes solvents, furan solvents, ketone solvents and hydrocarbon solvents, such as water, methanol, ethanol, iso Propanol, dichloromethane, chloroform, diethyl ether, tetrahydrofuran, ethyl acetate, acetone and toluene, more preferably one or more of water, ethanol, diethyl ether, tetrahydrofuran and acetone. The added amount of the solvent is appropriate to promote the smooth progress of the reaction, and is not particularly limited.

According to the preparation method of the phosphorus-containing compound of the present invention, in the optional step (2), the compound represented by the formula (IV) (in X') and the reaction product of the (1) step (in the After the reaction between NH and NH, the reaction product of the (2) step is washed to improve the purity of the reaction product. It is preferred to use an acid solution to wash the reaction product of step (2). The acid solution is preferably an aqueous solution of one or more acids among hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the acid solution is preferably 1-12 mol/liter. According to the preparation method of the phosphorus-containing compound of the present invention, in the optional step (2), the compound represented by the formula (IV) (in X') and the reaction product of the (1) step (in the After the reaction between NH and NH, the reaction product of the (2) step is further purified. The purification operation includes one or more of washing, distillation, recrystallization and centrifugation methods known in the prior art.

The phosphorus-containing compound of the present invention has very excellent biodegradation performance and anti-oxidation performance, and is especially suitable for promoting the biodegradation of lubricating oil products. The preparation method of the phosphorus-containing compound of the invention is simple, efficient and has high yield.

According to the natural gas engine lubricating oil composition of the present invention, the phosphorus-containing compound accounts for 0.1%-10% (preferably 0.5%-3%) of the total mass of the lubricating oil composition; the high molecular weight succinimide has no The ash dispersant accounts for 1%-15% (preferably 2%-6%) of the total mass of the lubricating oil composition; the monosuccinimide ashless dispersant accounts for 1%-15% (preferably 2%-6%); the calcium sulfonate detergent accounts for 0.2%-10% (preferably 1%-4%) of the total mass of the lubricating oil composition; the sulfurized alkylphenate calcium detergent accounts for the lubricating oil composition 0.2%-10% (preferably 1%-4%) of the total mass; the naphthylamine type antioxidant accounts for 0.5%-10% (preferably 1%-4%) of the total mass of the lubricating oil composition; the two The alkyl zinc dithiophosphate accounts for 0.5%-10% (preferably 1%-5%) of the total mass of the lubricating oil composition; the organic molybdenum friction modifier accounts for 0.01%-5% of the total mass of the lubricating oil composition ( Preferably 0.05%-2%); the viscosity index improver accounts for 3%-15% (preferably 5%-10%) of the total mass of the lubricating oil composition; the lubricating oil base oil constitutes the main component of the lubricating oil composition .

According to the natural gas engine lubricating oil composition of the present invention, the number average molecular weight of the polyisobutylene part in the high molecular weight succinimide ashless dispersant is preferably 1600-4000, more preferably 1800-2500, and the high molecular weight butane The imide ashless dispersant can be T161 produced by Wuxi Nanfang Additive Factory, T161A and T161B produced by Jinzhou Petrochemical Branch Additive Factory, LZL157 produced by Lubrizol Lanlian Additive Co., Ltd., LZ6418 and LZ6418B produced by Lubrizol Corporation, etc. ; The number average molecular weight of the polyisobutylene part in the monosuccinimide ashless dispersant is preferably 500 to 1500, more preferably 800 to 1200, and the monosuccinimide ashless dispersant can be produced by Wuxi Nanfang Additive Factory T151 produced by Jinzhou Petrochemical Branch Additive Factory, T151A and T151B produced by Additive Factory of Jinzhou Petrochemical Branch, LZL151A produced by Lubrizol Lanlian Additive Co., Ltd., LZ894 produced by Lubrizol Corporation, etc.; the calcium sulfonate detergent is preferably selected from low alkali value calcium sulfonate , one or more of medium-basic calcium sulfonate and high-basic calcium sulfonate. In order to better control the sulfated ash content of the oil, the calcium sulfonate is preferably a medium-basic calcium sulfonate with a base value of (130-200) mgKOH/g. The calcium sulfonate detergent can be selected from T105, T106, T104 produced by Jinzhou Petrochemical Branch Additive Factory, T102, T103, T107B produced by Shanghai Refining Additive Factory, LZ6478, LZ58B, LZ75, LZ6446 produced by Lubrizol Corporation, Infineum Company Produced C9353, C9330, etc.; the sulfurized alkyl phenate calcium detergent is selected from one or more of low alkali value sulfurized alkyl phenate calcium, medium alkali value sulfurized alkyl phenate calcium and high alkali value sulfurized alkyl phenate calcium kind. In order to better control the sulfated ash content of the oil, the sulfurized calcium alkylphenate with a medium alkali value of (130-200) mgKOH/g is preferred. The sulfurized calcium alkylphenate can be selected from S206 and T121 produced by Wuxi Nanfang Petroleum Additive Co., Ltd., LZL115A and LZL115B produced by Lubrizol Lanlian Additive Co., Ltd., LZ6499 and LZ6500 produced by Lubrizol Corporation, C9391 and C9394 produced by Infineum, etc. The alkyl group in the zinc dialkyl dithiophosphate is preferably C _1～12 alkyl, more preferably C _4～8 alkyl, and the zinc dialkyl dithiophosphate can be selected from Wuxi South Additive Factory, The T202, T203, T205 etc. that additive plant of Jinzhou petrochemical branch company produces; Described naphthylamine type antioxidant preferably selects the Irganox L106 that Ciba-Geigy Ltd company produces, the T531 etc. that Tianjin Wuyi chemical factory produces; Described organic molybdenum friction The improver is preferably selected from one or more of molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate, oxymolybdenum dialkyldithiophosphate, molybdenum xanthate and molybdate, The organic molybdenum friction modifier can be selected from Molyvan 807, Molyvan 822, Molyvan 855, Molyvan 856B, etc. produced by Vanderbilt Company; the viscosity index improver is preferably selected from OCP type viscosity index improver, for example, Jinzhou Lubricating Oil Additive Co., Ltd. JINEX 9100, JINEX 9300, JINEX 9600 produced by Lubrizol Corporation, LZ7065, LZ7067, LZ7077, LZ7070, etc. The lubricating base oil is preferably selected from one or more of API I, II, III, IV, and V base oils, more preferably selected from one or more of API III, IV, and V base oils , For example, one or more of hydrogenated base oil, polyolefin synthetic base oil, alkylbenzene base oil and ester synthetic base oil can be selected.

The present invention also provides a method for preparing a lubricating oil composition for a natural gas engine, comprising mixing the additive in the lubricating oil composition described in any aspect above with the lubricating oil base oil. The mixing temperature is preferably 40°C-90°C, and the mixing time is preferably 1 hour-6 hours.

The lubricating oil composition of the invention has excellent biodegradation performance, anti-wear performance, high-temperature oxidation resistance performance, dispersion performance and corrosion resistance performance, and can meet the requirements of high-performance natural gas engine lubricating oil.

Detailed ways

The method of the present invention will be described below through specific examples, but the present invention is not limited thereto.

The performance evaluation methods in Examples and Comparative Examples are shown below.

(1) Biodegradability

According to the OECD302B method, the lubricating oil compositions produced in the examples or comparative examples were used as test samples to evaluate the biodegradability.

(2) thermal oxidation stability

The lubricating oil composition that embodiment or comparative example manufacture is used as test sample, adopts pressurized differential scanning calorimetry test (PDSC) method to evaluate the thermo-oxidative stability performance of this test sample, evaluation index is the oxidation induction period of test sample (unit is min). The temperature of the PDSC test is 210° C., the pressure is 0.5 MPa, and the oxygen flow rate is 100 mL/min.

(3) Sludge dispersion performance

Mix the test oil and sludge evenly and drop it on the filter paper, measure the diameter of the sludge diffusion circle and the diameter of the lubricating oil diffusion circle after 24 hours, calculate the ratio of the diameter of the sludge diffusion circle and the diameter of the lubricating oil diffusion circle, and obtain the dispersion index for evaluation The dispersibility of the oil, the larger the ratio, the better the dispersibility.

(4) Evaluation of anti-friction performance

The lubricating oil compositions produced in Examples or Comparative Examples were used as test samples to perform a high-frequency reciprocating friction test. The test conditions of this method are load 1000g, frequency 20Hz, temperature 100°C, test time 60min, and record the friction coefficient. The smaller the coefficient of friction, the better the anti-friction performance of the test sample.

The experimental methods described in the following examples, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, can be obtained from commercial sources.

Example 1

Synthesis of O-dimethylphosphoryloxy-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine

(1) Add L-serine (shown in formula II-a) (100mmol, 10.5g) and 40mL water to the reactor successively, cool down to 0°C, adjust the pH to 9.0 with sodium hydroxide, add dimethyl phosphite Ester (represented by formula III-a) (130mmol, 14.3g) and tetrabutylammonium bromide (1mmol, 0.32g) were added dropwise with 50mL of 12% sodium hypochlorite solution under stirring. After reacting for 4 hours, it was extracted twice with ether, the aqueous layer was adjusted to pH=3 with hydrochloric acid, 8 g of sodium chloride was added, extracted twice with ethyl acetate, the organic phases were combined, dried with anhydrous magnesium chloride, and the solvent was distilled off under reduced pressure to obtain Color oil. Dissolve the colorless oil in 60 mL of acetonitrile, ultrasonicate at room temperature for 5 hours, and filter to obtain a white solid;

(2) Cool the above white solid (47.6mmol, 10.2g), 40mL acetone, 20mL water, sodium hydroxide (95.2mmol, 10g) to 0°C, add 3,5-bis(tert-butyl)-4 -Hydroxyphenylpropionyl chloride (47.6 mmol, 14.1 g). After reacting for 5 hours, use 6 mol/L hydrochloric acid solution to acidify to a pH value of 2, a large amount of white solid appears, filter with suction, wash the filter cake with water and petroleum ether, and obtain the reaction product of step (2), its structure and exemplary reaction formula As shown below, the structure of the reaction product of step (2) is the formula I-a in the exemplary reaction formula.

Wherein in step (2), the preparation method of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride is: 3,5-bis(tert-butyl)-4-hydroxyphenylpropionic acid (81mmol , 22.5g) was dissolved in 150mL chloroform, thionyl chloride (124mmol, 14.8g) was added, refluxed for 4 hours, and the solvent and excess thionyl chloride were removed by rotary evaporation to obtain a light yellow solid (ie 3,5-bis( tert-butyl)-4-hydroxyphenylpropionyl chloride).

The structure confirmation results of the reaction product in step (2) are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ12.19(br,1H),8.71(s,1H),6.96(s,2H),5.97(br,1H ), 4.66(d, J=6.4Hz, 2H), 4.07(t, J=6.8Hz, 1H), 3.79(s, 6H), 2.87(t, J=6.8Hz, 2H), 2.49(t, J =6.8Hz, 2H), 1.31(s, 18H); HRMS (FT-ICRMS) calcd for C ₂₂ H ₃₅ NO ₈ P ^- (MH): 472.2106, found: 472.2109.

The compound synthesized through structural identification is indeed the target compound O-dimethylphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (see structural formula I-a).

Example 2

Synthesis of O-diisopropyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine

(1) Add L-serine (shown in formula II-a) (100mmol, 10.5g) and 40mL water to the reactor in sequence, cool down to 0°C, adjust the pH to 9.0 with sodium hydroxide, add diisophosphorous acid Propyl ester (represented by formula III-b) (130mmol, 21.7g) and tetrabutylammonium bromide (1mmol, 0.32g) were added dropwise with 50mL of 12% sodium hypochlorite solution under stirring. After reacting for 4 hours, it was extracted twice with ether, the aqueous layer was adjusted to pH=3 with hydrochloric acid, 8 g of sodium chloride was added, extracted twice with ethyl acetate, the organic phases were combined, dried with anhydrous magnesium chloride, and the solvent was distilled off under reduced pressure to obtain Color oil. Dissolve the colorless oil in 60 mL of acetonitrile, ultrasonicate at room temperature for 5 hours, and filter to obtain a white solid;

(2) Cool the above white solid (47.6mmol, 12.8g), 40mL acetone, 20mL water, sodium hydroxide (95.2mmol, 10g) to 0°C, add 3,5-bis(tert-butyl)-4 -Hydroxyphenylpropionyl chloride (47.6 mmol, 14.1 g). After reacting for 5 hours, use 6 mol/L hydrochloric acid solution to acidify to a pH value of 2, a large amount of white solid appears, filter with suction, wash the filter cake with water and petroleum ether, and obtain the reaction product of step (2), its structure and exemplary reaction formula As shown below, the structure of the reaction product of step (2) is the formula I-b in the exemplary reaction formula.

Wherein in step (2), the preparation method of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride is: 3,5-bis(tert-butyl)-4-hydroxyphenylpropionic acid (81mmol , 22.5g) was dissolved in 150mL chloroform, thionyl chloride (124mmol, 14.8g) was added, refluxed for 4 hours, and the solvent and excess thionyl chloride were removed by rotary evaporation to obtain a light yellow solid (ie 3,5-bis( tert-butyl)-4-hydroxyphenylpropionyl chloride).

The structure confirmation results of the reaction product in step (2) are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ12.10(br,1H),8.55(s,1H),6.88(s,2H),5.85(br,1H ), 4.61(d, J=6.4Hz, 2H), 4.09(t, J=6.8Hz, 1H), 3.99-3.89(m, 2H), 2.81(t, J=6.8Hz, 2H), 2.44(t ,J＝6.8Hz,2H),1.31(s,18H),1.25(s,12H); HRMS(FT-ICRMS) calcd for C ₂₆ H ₄₃ NO ₈ P ^- (MH):528.2732,found:528.2737.

The compound synthesized by structural identification is indeed the target compound O-diisopropyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (see structural formula I-b) .

Example 3

Synthesis of O-benzhydryloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine

(1) Add L-serine (shown in formula II-a) (100mmol, 10.5g) and 40mL water to the reactor successively, cool down to 0°C, adjust the pH to 9.0 with sodium hydroxide, add dibenzyl phosphite Ester (represented by formula III-c) (130mmol, 34.0g) and tetrabutylammonium bromide (1mmol, 0.32g) were added dropwise with 50mL of 12% sodium hypochlorite solution under stirring. After reacting for 4 hours, it was extracted twice with ether, the aqueous layer was adjusted to pH=3 with hydrochloric acid, 8 g of sodium chloride was added, extracted twice with ethyl acetate, the organic phases were combined, dried with anhydrous magnesium chloride, and the solvent was distilled off under reduced pressure to obtain Color oil. Dissolve the colorless oil in 60 mL of acetonitrile, ultrasonicate at room temperature for 5 hours, and filter to obtain a white solid;

(2) Cool the above white solid (47.6mmol, 17.4g), 40mL acetone, 20mL water, sodium hydroxide (95.2mmol, 10g) to 0°C, add 3,5-bis(tert-butyl)-4 -Hydroxyphenylpropionyl chloride (47.6 mmol, 14.1 g). After reacting for 5 hours, use 6 mol/L hydrochloric acid solution to acidify to a pH value of 2, a large amount of white solid appears, filter with suction, wash the filter cake with water and petroleum ether, and obtain the reaction product of step (2), its structure and exemplary reaction formula As shown below, the structure of the reaction product of step (2) is formula I-c in the exemplary reaction formula.

Wherein in step (2), the preparation method of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride is: 1) 3,5-bis(tert-butyl)-4-hydroxyphenylpropionic acid (81mmol, 22.5g) was dissolved in 150mL chloroform, thionyl chloride (124mmol, 14.8g) was added, refluxed for 4 hours, and the solvent and excess thionyl chloride were removed by rotary evaporation to obtain a light yellow solid (ie 3,5- bis(tert-butyl)-4-hydroxyphenylpropionyl chloride).

The structure confirmation results of the reaction product in step (2) are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ12.27(br,1H),8.64(s,1H),7.55-7.26(m,10H),6.91(s ,2H),5.71(br,1H),5.17(s,4H),4.61(d,J=6.4Hz,2H),4.01(t,J=6.8Hz,1H),2.81(t,J=6.8Hz ,2H),2.44(t,J＝6.8Hz,2H),1.32(s,18H); HRMS(FT-ICRMS)calcd for C ₃₄ H ₄₃ NO ₈ P ^- (MH):624.2732,found:624.2730.

The compound synthesized by structural identification is indeed the target compound O-benzhydryloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (see structural formula I-c) .

Example 4

Synthesis of O-dimethylphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine methyl ester

(1) Add L-serine methyl ester hydrochloride (shown in formula II-b) (100mmol, 15.5g) and 40mL water to the reactor successively, cool down to 0°C, adjust to pH=9.0 with sodium hydroxide, Dimethyl phosphite (formula III-a) (130 mmol, 14.3 g) and tetrabutylammonium bromide (1 mmol, 0.32 g) were added, and 50 mL of 12% sodium hypochlorite solution was added dropwise with stirring. After reacting for 4 hours, it was extracted twice with ether, the aqueous layer was adjusted to pH = 3 with hydrochloric acid, 8 g of sodium chloride was added, extracted twice with ethyl acetate, the organic phases were combined, dried with anhydrous magnesium chloride, and the solvent was distilled off under reduced pressure to obtain a white solid. Dissolve the white solid in 60 mL of acetonitrile, ultrasonicate at room temperature for 5 hours, and filter to obtain a white solid;

(2) Cool the above white solid (47.6mmol, 10.8g), 40mL acetone, 20mL water, sodium hydroxide (95.2mmol, 10g) to 0°C, add 3,5-bis(tert-butyl)-4 -Hydroxyphenylpropionyl chloride (47.6 mmol, 14.1 g). After reacting for 5 hours, use 6 mol/L hydrochloric acid solution to acidify to a pH value of 2, a large amount of white solid appears, filter with suction, wash the filter cake with water and petroleum ether, and obtain the reaction product of step (2), its structure and exemplary reaction formula As shown below, the structure of the reaction product of step (2) is the formula I-d in the exemplary reaction formula.

Wherein in step (2), the preparation method of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride is: 3,5-bis(tert-butyl)-4-hydroxyphenylpropionic acid (81mmol , 22.5g) was dissolved in 150mL chloroform, thionyl chloride (124mmol, 14.8g) was added, refluxed for 4 hours, and the solvent and excess thionyl chloride were removed by rotary evaporation to obtain a light yellow solid (ie 3,5-bis( tert-butyl)-4-hydroxyphenylpropionyl chloride).

The structure confirmation results of the reaction product in step (2) are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ8.54(s,1H),6.91(s,2H),5.77(br,1H),4.60(d,J =6.4Hz,2H),4.11(t,J=6.8Hz,1H),3.73(s,6H),3.61(s,3H),2.80(t,J=6.8Hz,2H),2.52(t,J =6.8Hz, 2H), 1.35(s, 18H); HRMS (FT-ICRMS) calcd for C ₂₃ H ₃₇ NO ₈ P ^- (MH): 486.2262, found: 486.2268.

The compound synthesized by structural identification is indeed the target compound O-dimethylphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine methyl ester (see structural formula I-d ).

The sources of additives used in the lubricating oil composition of the present invention are as follows:

T161, high molecular weight succinimide ashless dispersant, Wuxi South Additive Factory

T151, monosuccinimide ashless dispersant, Wuxi Nanfang Additive Factory

T105, medium alkali value calcium sulfonate, Jinzhou Petrochemical Company

T121, medium alkali value sulfurized calcium alkylphenate, Wuxi South Additive Factory

Irganox L106, naphthylamine type antioxidant, Ciba-Geigy Ltd company

T202, butyl/isooctyl zinc dithiophosphate, Wuxi South Additive Factory

Molyvan 855, organic molybdenum friction modifier, Vanderbilt Corporation

LZ 7067, OCP viscosity index improver, Lubrizol Corporation company

Embodiment 1-1 to embodiment 1-4 and comparative example ID-1 to comparative example ID-3

The formula composition of embodiment I-1 to embodiment I-4 and comparative example ID-1 to ID-3 is shown in table 1. Comparative examples ID-1 and ID-2 are natural gas engine oils of different brands on the market.

Table 1

The lubricating oil compositions of the above examples and the lubricating oil compositions of the comparative examples were evaluated for biodegradation performance, anti-wear performance, high-temperature oxidation resistance performance, dispersion performance and corrosion resistance performance, and the measurement results are shown in Table 2.

Table 2

It can be known from Table 2 that the lubricating oil composition of the present invention has excellent biodegradability, antiwear performance, high temperature oxidation resistance, dispersion performance and corrosion resistance.

Claims (17)

1. A natural gas engine lubricating oil composition, comprising phosphorus compound, high molecular weight succinimide ashless dispersant, monosuccinimide ashless dispersant, calcium sulfonate detergent, sulfurized alkylphenate calcium detergent , naphthylamine type antioxidant, dialkyl zinc dithiophosphate, organic molybdenum friction modifier, viscosity index improver and lubricating oil base oil, wherein the structure of the phosphorus-containing compound is:

In formula I, n is 0; the R group is selected from trivalent C ₁ -C ₃₀ hydrocarbon groups; the R _b group is H or C ₁ -C ₁₀ hydrocarbon groups; each R ₀ group is the same or different from each other, each independently selected from H, C ₁ -C ₃₀ hydrocarbon groups and

and at least one of R ₀ is

Wherein x is 2, y is ₁ , x R1 groups are the same or different from each other, each independently selected from _{C1 - C4} linear or branched chain alkyl groups, Ar group is a benzene ring, R2 group It is a single bond or C ₁ ~ C ₁₀ alkylene group; OH is located at the para position of R ₂ group, and two R ₁ are respectively located at two ortho positions of OH; The A group is selected from

The X group is O or S, a is 1, and R' is selected from C ₁ -C ₃₀ hydrocarbon groups. 2. according to the described lubricating oil composition of claim 1, it is characterized in that, in formula (I) structure compound, in

In the group, two R ₁ are tert-butyl. 3. The lubricating oil composition according to claim 1, wherein the phosphorus-containing compound comprises one or more of the following compounds:

4. according to the described lubricating oil composition of claim 1, it is characterized in that, the preparation method of described phosphorus-containing compound comprises: Step (1): reacting the compound represented by formula (II) and/or its inorganic acid salt with the compound represented by formula (III), and collecting the product of step (1);

In formula (II), n is 0; R group is selected from trivalent C ₁ -C ₃₀ hydrocarbon groups; R _b group is H, C ₁ -C ₁₀ hydrocarbon groups; Each R ₀ 'group is the same or different from each other, each independently selected from H, C ₁ -C ₃₀ hydrocarbon groups; A' group is selected from OA "', and A "' is selected from F, Cl, Br, I, H; The structure of the inorganic acid salt of the compound shown in formula (II) is

Wherein M is an inorganic acid radical, j is the absolute value of the charge number of the inorganic acid radical, z is an integer between 1 and 10, n is 0, and the R group is selected from trivalent C ₁ -C ₃₀ hydrocarbon groups, R _b group is H, C ₁ ~ C ₁₀ hydrocarbon group; each R ₀ 'group is the same or different from each other, each independently selected from H, C ₁ ~ C ₃₀ hydrocarbon group; A' group is selected from OA"', A"' is selected from F, Cl, Br, I, H; In formula (III), the X group is O or S, a is 1, each R"' is the same or different from each other, each independently selected from A"', C ₁ ~ C ₃₀ hydrocarbon groups, and A"' is selected from F, Cl, Br, I, H; Step (2): making the product of step (1) react with the compound shown in formula (IV), and collecting the product of step (2);

Wherein x is 2, y is ₁ , x R1 groups are the same or different from each other, each independently selected from _{C1 - C4} linear or branched chain alkyl groups, Ar group is a benzene ring, R2 group It is a single bond or C ₁ ~ C ₁₀ alkylene group, OH is located at the para position of R ₂ group, and two R ₁ are respectively located at two ortho positions of OH; X' is F, Cl, Br, I or OH. 5. The lubricating oil composition according to claim 4, characterized in that, the compound represented by the formula (II) and/or its inorganic acid salt is one or more of amino acids and inorganic salts of amino acids. 6. according to the described lubricating oil composition of claim 4, it is characterized in that, the compound shown in described formula (II) and/or its inorganic acid salt are selected from one or more in the following specific compounds: L-serine and/or L-serine ester hydrochloride, L-leucine and/or L-leucine ester hydrochloride, L-isoleucine and/or L-isoleucine ester hydrochloride, glycine And/or glycine ester hydrochloride, L-phenylalanine and/or L-phenylalanine ester hydrochloride, L-valine and/or L-valine ester hydrochloride. 7. The lubricating oil composition according to claim 4, characterized in that, the compound represented by the formula (III) is selected from phosphorous acid and/or phosphorous acid ester. 8. according to the described lubricating oil composition of claim 4, it is characterized in that, the compound shown in described formula (III) is selected from phosphorous acid, dimethyl phosphite, dimethyl thiophosphite, diethyl phosphite Ester, dipropyl phosphite, diisopropyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-tert-butyl phosphite, (2-ethylhexyl) phosphite, diphosphite One or more of benzyl ester and diphenyl phosphite. 9. According to the described lubricating oil composition of claim 4, it is characterized in that, in step (1), the compound shown in the formula (II) and/or its inorganic acid salt are calculated in OA "', the formula The compound shown in (III) is based on P-H, and the reaction equivalent ratio between the compound shown in the formula (II) and/or its inorganic acid salt and the compound shown in the formula (III) is 1:5～5:1 ; The temperature of the reaction is -40 to 80°C. 10. The lubricating oil composition according to claim 4, characterized in that, in step (1), the compound represented by the formula (II) and/or its inorganic acid salt are calculated in OA "', the formula The compound shown in (III) is based on P-H, and the reaction equivalent ratio between the compound shown in the formula (II) and/or its inorganic acid salt and the compound shown in the formula (III) is 1:3～3:1 ; The temperature of the reaction is -20 to 40°C. 11. according to the described lubricating oil composition of claim 4, it is characterized in that, in step (2), the compound shown in described formula (IV) is selected from one or more in the following specific compounds: 3,5 - Bis(tert-butyl)-4-hydroxyphenylacetyl chloride, 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride. 12. according to the described lubricating oil composition of claim 4, it is characterized in that, in step (2), in step (2), the compound shown in described formula (IV) is calculated as X ', and the reaction product of described (1) step is expressed as NH In other words, the reaction equivalent ratio between the compound represented by the formula (IV) and the reaction product of step (1) is 5:1 to 1:5; the temperature of the reaction is -40 to 60°C. 13. according to the described lubricating oil composition of claim 4, it is characterized in that, in step (2), the compound shown in described formula (IV) is calculated as X ', and the reaction product of described (1) step is calculated as NH In other words, the reaction equivalent ratio between the compound represented by the formula (IV) and the reaction product of step (1) is 1:2 to 2:1; the temperature of the reaction is -20 to 20°C. 14. The lubricating oil composition according to any one of claims 1 to 13, wherein the phosphorus-containing compound accounts for 0.1%-10% of the total mass of the lubricating oil composition; the high molecular weight succinimide The ashless dispersant accounts for 1%-15% of the total mass of the lubricating oil composition; the monosuccinimide ashless dispersant accounts for 1%-15% of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 1%-15% of the total mass of the lubricating oil composition; 0.2%-10% of the total mass of the lubricating oil composition; the sulfurized alkylphenate calcium detergent accounts for 0.2%-10% of the total mass of the lubricating oil composition; the naphthylamine type antioxidant accounts for the total mass of the lubricating oil composition 0.5%-10% of the mass; the zinc dialkyldithiophosphate accounts for 0.5%-10% of the total mass of the lubricating oil composition; the organic molybdenum friction modifier accounts for 0.01%-10% of the total mass of the lubricating oil composition 5%; the viscosity index improver accounts for 3%-15% of the total mass of the lubricating oil composition; the lubricating oil base oil constitutes the main component of the lubricating oil composition. 15. The lubricating oil composition according to any one of claims 1 to 13, wherein the phosphorus-containing compound accounts for 0.5%-3% of the total mass of the lubricating oil composition; the high molecular weight succinimide The ashless dispersant accounts for 2%-6% of the total mass of the lubricating oil composition; the monosuccinimide ashless dispersant accounts for 2%-6% of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 2%-6% of the total mass of the lubricating oil composition; 1%-4% of the total mass of the lubricating oil composition; the sulfurized alkylphenate calcium detergent accounts for 1%-4% of the total mass of the lubricating oil composition; the naphthylamine type antioxidant accounts for the total mass of the lubricating oil composition 1%-4% of the mass; the zinc dialkyl dithiophosphate accounts for 1%-5% of the total mass of the lubricating oil composition; the organic molybdenum friction modifier accounts for 0.05%-5% of the total mass of the lubricating oil composition 2%; the viscosity index improver accounts for 5%-10% of the total mass of the lubricating oil composition; the lubricating oil base oil constitutes the main component of the lubricating oil composition. 16. The lubricating oil composition according to any one of claims 1 to 13, characterized in that, the number average molecular weight of the polyisobutylene part in the high molecular weight succinimide ashless dispersant is 1600 to 4000; The number-average molecular weight of the polyisobutylene part in the monosuccinimide ashless dispersant is 500-1500; the calcium sulfonate detergent is selected from the group consisting of low-basic calcium sulfonate, medium-basic calcium sulfonate and high-basic sulfonic acid One or more of calcium; the sulfurized alkyl phenate calcium detergent is selected from one of low alkali value sulfurized alkyl phenate calcium, medium alkali value sulfurized alkyl phenate calcium and high alkali value sulfurized alkyl phenate calcium or more; the alkyl group in the zinc dialkyldithiophosphate is selected from C _1～12 alkyl; the organic molybdenum friction modifier is selected from molybdenum dialkyl dithiocarbamate, dialkyl One or more of molybdenum thiophosphate, oxymolybdenum dialkyl dithiophosphate, molybdenum xanthate and molybdate; the viscosity index improver is selected from OCP type viscosity index improver; the lubricating oil The base oil is selected from one or more of API I, II, III, IV, and V base oils. 17. A method for preparing a lubricating oil composition for a natural gas engine, comprising mixing the additive in the lubricating oil composition according to any one of claims 1 to 16 with a lubricating oil base oil.