CN108728215B

CN108728215B - Gasoline engine oil composition and preparation method thereof

Info

Publication number: CN108728215B
Application number: CN201710270689.3A
Authority: CN
Inventors: 成欣; 段庆华; 黄作鑫; 张建荣
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-04-24
Filing date: 2017-04-24
Publication date: 2020-11-13
Anticipated expiration: 2037-04-24
Also published as: CN108728215A

Abstract

The present invention provides a gasoline engine oil composition and its preparation method. The gasoline engine oil composition comprises a polyether amine compound, an antioxidant, a metal detergent, ZDDP, organic molybdenum, an ashless friction modifier and the balance of lubricating oil base oil, wherein the polyether amine compound has the structure:

Description

Gasoline engine oil composition and preparation method thereof

Technical Field

The invention relates to a lubricating oil composition, in particular to a gasoline engine oil composition.

Background

Unsaturated olefin, aromatic hydrocarbon and a small amount of sulfur-containing compounds in the lubricating oil base oil are easy to react with oxygen to form colloid, and finally form carbon deposit, and particularly, the generation of engine deposit can be accelerated at key parts such as an air inlet valve, a piston, an oil pan, a combustion chamber and the like. The working performance of the engine is seriously influenced, so that the problems of difficult starting of the engine, unstable idling, poor drivability, poor acceleration, serious power loss and the like are caused, and expensive maintenance cost is generated. A lubricating oil composition having detergent properties (deposit formation inhibiting properties) is produced by adding a detergent dispersant to a lubricating base oil. The lubricating oil composition with detergency can effectively reduce coking and carbon deposit on the top of a piston, reduce valve system abrasion, reduce corrosion abrasion of an engine part, and prolong the safe operation period of the engine and the service life of spare parts.

US 5112364 to BASF uses a nickel catalyzed process to form an amine based polymer which can be used for gasoline coke removal.

In recent years, the specification of gasoline engine oil products is gradually upgraded from SJ/GF-2 to SL/GF-3, SM/GF-4 and SN/GF-5. The performance of a detergent dispersant of engine lubricating oil is an important index in oil specifications all the time, in a 2010 new SN/GF-5 specification, a IIIG engine test puts forward a more rigorous requirement on the piston detergency of the engine lubricating oil, the piston deposit score is improved to 4 from 3.5 through the index, and a higher requirement is put forward on the evaluation of engine oil sludge score in a VG engine test, namely, less oil sludge is required to be generated under the more rigorous working condition, and the changes put forward a higher requirement on the detergent dispersant.

However, gasoline engine oil compositions made using the clean dispersants of the prior art have not fully met the requirements of such higher specification products.

In addition to the adverse effects of deposits, corrosion of the engine can severely shorten the life of the engine, and corrosion of critical parts can also affect the performance of the engine to a great extent. The prior art puts a lot of experience on the cleaning performance of the gasoline engine oil composition, but the attention on the rust prevention performance is far from enough.

Therefore, there is still a need in the art for a gasoline engine oil composition that not only meets the increasingly stringent requirements of today's higher specification products for clean dispersancy, but also exhibits excellent rust inhibition.

Disclosure of Invention

The present invention provides a gasoline engine oil composition and its preparation method.

The gasoline engine oil composition comprises a polyether amine compound, an antioxidant, a metal detergent, ZDDP, organic molybdenum, an ashless friction modifier and the balance of lubricating oil base oil, wherein the polyether amine compound has the structure:

wherein the radical R₀Selected from hydrogen atoms and optionally substituted C_1-40A hydrocarbon group, preferably selected from a hydrogen atom, C_1-20A straight chain or branched alkyl group, further preferably selected from a hydrogen atom, C_5-15A linear or branched alkyl group; y groups Ru, equal to or different from each other, are each independently selected from C_2-24Straight or branched alkylene, preferably each independently selected from C_2-12Straight or branched alkylene, more preferably each independently selected from C_2-6Straight or branched alkylene, more preferably each independently selected from-CH₂-CH₂-and-CH₂-CH(CH₃) -; y represents the average degree of polymerization of the polyether segment-O-Ru-, and is selected from any value between 1 and 200, preferably any value between 1 and 100, more preferably any value between 1 and 50, and still more preferably any value between 1 and 30; radical R₁And R₂Are identical or different from each other and are each independently selected from hydrogen and C_1-10Hydrocarbyl (preferably C)_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl); a radicals R₃Or a radicals R₄Are identical or different from each other and are each independently selected from hydrogen and C_1-10Hydrocarbyl (preferably C)_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl); a radicals R₆Or a radicals R₇Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C_1-10Hydrocarbyl (preferably optionally substituted C)_1-6Straight or branched alkyl, further preferably optionally substituted C_1-4Straight or branched alkyl) and

(wherein q groups R8, equal to or different from each other, are each independently selected from C_1-40Alkylene, preferably C_1-40Straight or branched alkylene, more preferably C_1-20Straight or branched alkylene, further preferably C_2-6A linear or branched alkylene group; q radicals R₉Are identical or different from each other and are each independently selected from hydrogen and C_1-10Hydrocarbyl (preferably C)_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl); radical R₁₀Selected from hydrogen and C_1-10Hydrocarbyl (preferably C)_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl); q is an integer between 1 and 50, preferably an integer between 1 and 10, more preferably 1,2, 3 or 4); a is an integer between 1 and 10, preferably an integer between 1 and 4, more preferably 1,2 or 3; a radicals R' identical or different from one another, each independently selected from the group consisting of a single bond and C_1-10Alkylene (preferably C)_1-6Straight or branched alkylene, further preferably C_1-4Linear or branched alkylene, more preferably methylene or ethylene); radical R₅Selected from hydrogen and C_1-10Hydrocarbyl (preferably C)_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl).

The preparation method of the polyether amine compound comprises the following steps:

1) reacting hydroxyl-containing polyether with alkenyl compound to generate alkenyl polymer;

2) reacting the product of step 1) with an oxidizing agent;

3) reacting the oxidation product obtained in the step 2) with an aminating agent, and collecting the product.

The hydroxyl-containing polyether in step 1) is preferably

The alkenyl compound is preferably

Wherein the radical R₀Selected from hydrogen atoms or C_1-40Hydrocarbyl, preferably C_1-20Straight or branched alkyl, especially C_5-15Straight or branched chain alkyl.

The y groups Ru, which are identical or different from one another, are each independently selected from C_2-24Straight or branched alkylene, preferably each independently selected from C_2-12Straight or branched alkylene, more preferably each independently selected from C_2-6Straight or branched alkylene, more preferably each independently selected from-CH₂-CH₂-and-CH₂-CH(CH₃) -, more preferably-CH₂-CH(CH₃)-。

Wherein the group G is capable of reacting with-OH to removeExcept for the functional group of compound GH, preferably halogen (more preferably chlorine) or hydroxyl; radical R₁And R₂Are identical or different from each other and are each independently selected from hydrogen and C_1-10Hydrocarbyl (preferably C)_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl); a radicals R₃Or a radicals R₄Are identical or different from each other and are each independently selected from hydrogen and C_1-10Hydrocarbyl (preferably C)_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl); a is an integer between 1 and 10, preferably an integer between 1 and 4, more preferably 1,2 or 3; a radicals R' identical or different from one another, each independently selected from the group consisting of a single bond and C_1-10Alkylene (preferably C)_1-6Straight or branched alkylene, further preferably C_1-4Linear or branched alkylene, more preferably methylene or ethylene); radical R₅Selected from hydrogen and C_1-10Hydrocarbyl (preferably C)_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl).

Examples of the alkenyl compound include allyl halide, 3-butene-1-halide, 3-butene-2-halide, 3-methyl-3-butene-1-halide, 4-pentene-2-halide, 4-pentene-3-halide, 3-methyl-4-pentene-1-halide, 2-methyl-4-pentene-1-halide, 3-ethyl-4-pentene-1-halide, 2-ethyl-4-pentene-1-halide, 3-isobutyl-4-pentene-1-halide, 2, 3-dimethyl-4-pentene-1-halide, 2-dimethyl-4-pentene-1-halide, 3-dimethyl-pentene-1-halide, 2-dimethyl-pentene-1-halide, 3-dimethyl-pentene-1-halide, and the, 3, 3-dimethyl-4-pentene-1-halogen, 5-hexene-1-halogen, 4-methyl-5-hexene-halogen, 3-methyl-5-hexene-halogen, 2-methyl-5-hexene-halogen, 3-ethyl-5-hexene-halogen, 5-hexene-2-halogen, 5-hexene-3-halogen, 5-hexene-4-halogen, 6-heptene-1-halogen, 2-methyl-6-heptene-1-halogen, 3-methyl-6-heptene-1-halogen, 4-methyl-6-heptene-1-halogen, 5-methyl-6-heptene-1-halogen, 2-methyl-5-heptene-1-halogen, 5-methyl-5-hexene-2-halogen, 5-methyl-5-hexene-1-halogen, 5-methyl-, 2-ethyl-6-hepten-1-yl halide, 3-ethyl-6-hepten-1-yl halide, 4-ethyl-6-hepten-1-yl halide, 5-ethyl-6-hepten-1-yl halide, 2-methyl-7-octene-1-yl halide, 3-methyl-7-octene-1-yl halide, 4-methyl-7-octene-1-yl halide, 5-methyl-7-octene-1-yl halide, 6-methyl-7-octene-1-yl halide, 3-ethyl-7-octene-1-yl halide, 9-decene-1-yl halide, 10-undecene-1-yl halide, 11-dodecene-1-yl halide, 3-ethyl-7-heptene-1-yl halide, 2-ethyl-6-heptene-1-yl halide, 4-ethyl, One or more of 5-chloro-1, 3-pentadiene, 6-chloro-1, 3-hexadiene, 5-chloro-1, 3-hexadiene, 6-chloro-2, 4-hexadiene and 5-chloro-2, 4-hexadiene.

According to the invention, the molar ratio of the hydroxyl-containing polyether to the alkenyl compound is generally 1: 1-1.5, preferably 1: 1-1.2, the reaction temperature is generally 50-150 ℃, the reaction pressure is generally normal pressure, and the reaction time is generally 2-10 h.

In the step 1), a catalyst may be used as needed. Examples of the catalyst include those generally used by those skilled in the art for this purpose, and specific examples thereof include basic catalysts, more specifically, alkali metals, alkali metal alkoxides and alkali metal hydroxides, and particularly potassium hydroxide and sodium methoxide. When used, the molar ratio of the catalyst to the alkenyl compound is generally from 1 to 2:1, preferably from 1 to 1.5:1, most preferably from 1 to 1.1: 1.

In the step 1), a solvent may be used or may not be used. When used, the solvent includes, for example, C_1-6The monohydric alcohol is more specifically exemplified by methanol, ethanol, isopropanol, and n-butanol. These solvents may be used alone or in combination of two or more.

The oxidizing agent in step 2) is preferably oxygen, ozone, hydrogen peroxide, a metal oxide, a metal peroxide, dichromic acid or a salt thereof, permanganic acid or a salt thereof, a peracid or a salt thereof, a hypohalous acid or a salt thereof, an organic hydroperoxide and an organic peroxide, and more specifically, there may be mentioned hydrogen peroxide, an organic hydroperoxide and an organic peroxide, and particularly, hydrogen peroxide, sodium hypochlorite, ammonium peroxodisulfate, benzoyl peroxide, N-methylmorpholine oxide, methylrhenium trioxide, osmium tetroxide, hypochlorous acid, KMnO₄、K₂Cr₂O₇、KNO₃、Na₂O₂、MnO₂Ozone and oxygen. More specifically, the organic hydroperoxide may be tert-butyl hydroperoxide. More specific example of the peroxygenated organic acid is C_3-12Peroxyorganic acids, preferably peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxybutyric acid, peroxybenzoic acid or m-chloroperoxybenzeneFormic acid. As the oxidizing agent, m-chloroperoxybenzoic acid and peracetic acid are particularly preferable, and m-chloroperoxybenzoic acid is most preferable. These oxidizing agents may be used alone or in combination of two or more.

In step 2), the molar ratio of the alkenyl compound to the oxidizing agent in step 1) is generally 1:1 to 100, preferably 1:10 to 40, the reaction temperature is generally 100 to 200 ℃, preferably 100 to 150 ℃, most preferably 100 to 120 ℃, the reaction pressure is generally 1 to 5 kg, preferably 1 to 3 kg, most preferably 1 to 2 kg, and the reaction time is generally 3 to 20 hours, preferably 3 to 11 hours.

In step 2), a catalyst may be used as needed. Examples of the catalyst include those generally used by those skilled in the art for this purpose, and specific examples thereof include basic catalysts, more specifically, alkali metals, alkali metal alkoxides and alkali metal hydroxides, and particularly potassium hydroxide and sodium methoxide. These catalysts may be used alone or in combination of two or more. When used, the molar ratio of the catalyst to the alkenyl compound is generally from 1 to 2:1, preferably from 1 to 1.5:1, most preferably from 1 to 1.1: 1. According to the invention, in step 2), a solvent may or may not be used. When used, the solvent includes, for example, C_1-6The monohydric alcohol is more specifically exemplified by methanol, ethanol, isopropanol, and n-butanol. These solvents may be used alone or in combination of two or more.

According to the invention, in step 3), the oxidation product obtained in step 2) is subjected to an amination reaction with an aminating agent, said group being obtained

Total amination to a radical

In step 3), the aminating agent may be, for example, an aminating agent represented by the following formula (II), specifically, ammonia or C₁-C₃₀Primary amine, C₃-C₃₀Secondary aminesAlcohol amines and polyene polyamines, preferably ammonia and C₁-C₃₀Examples of the primary amine include ammonia, ethylamine, propylamine, ethylenediamine, ethanolamine and triethylenetetramine. These aminating agents may be used alone or in combination of two or more.

In formula (II), the radical R₆And R₇Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C_1-10A hydrocarbon group and

here, as the C_1-10Examples of the hydrocarbon group include C_1-10Straight or branched alkyl, C_2-10Straight or branched alkenyl and C_2-10Straight-chain or branched alkynyl, preferably C_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl.

According to the invention, in

In which q radicals R are present₈. Here, the q radicals R₈Are the same or different from each other and are each independently selected from C_1-40Alkylene groups. As said C_1-40Alkylene group, for example, C_1-40Straight or branched alkylene, C_2-40Straight or branched alkenylene and C_2-40Straight-chain or branched alkynylene, preferably C_1-40Straight or branched alkylene, more preferably C_1-20Straight or branched alkylene, further preferably C_2-6Straight or branched chain alkylene.

According to the invention, in

In which q radicals R are present₉. Here, the q radicals R₉Are identical or different from each other and are each independently selected from hydrogen and C_1-10A hydrocarbyl group. Here, as the C_1-10Examples of the hydrocarbon group include C_1-10Straight or branched alkyl, C_2-10Straight or branched alkenyl and C_2-10Straight-chain or branched alkynyl, preferably C_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl.

According to the invention, in

In (1), the group R₁₀Selected from hydrogen and C_1-10A hydrocarbyl group. Here, as the C_1-10Examples of the hydrocarbon group include C_1-10Straight or branched alkyl, C_2-10Straight or branched alkenyl and C_2-10Straight-chain or branched alkynyl, preferably C_1-6Straight or branched alkyl, further preferably C_1-4Straight or branched chain alkyl.

According to the invention, in

Q is an integer between 1 and 50, preferably an integer between 1 and 10, more preferably 1,2, 3 or 4.

According to the invention, in step 3), the aminating agent is reacted with the oxidation product (as a radical)

By) is generally 1-4:1, preferably 1-2:1, most preferably 1-1.5: 1.

According to the invention, in step 3), the reaction temperature is generally from 100 to 180 ℃, preferably from 100 to 150 ℃, most preferably from 120 to 150 ℃, the reaction pressure is generally from 1 to 5 kg, preferably from 1 to 3 kg, most preferably from 1 to 2 kg, and the reaction time is generally from 1h to 8h, preferably from 2h to 6h, most preferably from 2h to 5 h.

According to the invention, in step 3), a solvent may or may not be added. Specific examples of the solvent include C₁-C₈More specific examples of the alcohol include n-propanol, n-butanol and n-hexanol.

According to the invention, in step 3), a catalyst may or may not be added. Examples of the catalyst include tertiary amines and phenols, and tertiary amines are preferred. Examples of the tertiary amine include trihydrocarbyl tertiary amines having a molecular weight of 10 to 500 and amino derivatives thereof, more specifically include trimethylamine, triethylamine, tripropylamine, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylbutylamine, N-diethylpropylamine, N-dipropyl-1-propylamine, N-diethylbutylamine, N-dimethyl-1, 2-ethylenediamine, triphenylamine and N, N-2 methylbenzylamine, preferably trimethylamine, triethylamine and N, N' -2 methylbenzylamine, and most preferably trimethylamine and/or triethylamine. These tertiary amines may be used alone or in combination of two or more. Examples of the phenolic compound include monohydric, dihydric, polyhydric phenols and sodium phenolate having a molecular weight of 20 to 500, and electron donating groups such as alkoxy, phenyl and alkyl groups may be attached to the benzene ring. More specific examples of the phenol substance include phenol, sodium phenolate, hydroquinone, sodium hydroquinone, o-cresol, m-cresol, p-cresol, 2, 4-dimethylphenol, 2,4, 6-trimethylphenol, ethylphenol, sodium ethylphenol, 2, 4-diethylphenol, 2,4, 6-triethylphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, sodium m-methoxyphenol, sodium o-methoxyphenol, sodium phenyl phenol, preferably phenol and/or sodium phenolate, and most preferably sodium phenolate. These phenolic compounds may be used alone or in combination of two or more.

According to the invention, in step 3), the catalyst is used with the oxidation product (as a group)

Calculated as above) is 0.1 to 1:1, preferably 0.1 to 0.5:1, most preferably 0.3 to 0.5: 1.

According to the invention, after the end of the process for the preparation of the polyetheramines, the catalysts and the solvents which may be present are removed from the reaction mixture finally obtained in any manner known in principle, the polyetheramines are obtained. According to the invention, it is also possible to add further diluents to the polyetheramines in order to produce the detergents. Examples of the diluent include mineral base oils, polyolefins, and polyethers. These diluents may be used alone or in combination of two or more.

According to the present invention, there is further provided a gasoline engine oil composition comprising any of the polyether amine compounds described hereinbefore in the present invention or the polyether amine compound produced by the production process described hereinbefore in the present invention, an antioxidant, a metallic detergent, ZDDP, an organomolybdenum, an ashless friction modifier and the balance of a lubricating oil base stock.

The antioxidant is selected from alkylated diphenylamine and/or phenolic antioxidant (preferably a combination of alkylated diphenylamine and phenolic antioxidant), the metal detergent is selected from sulfonate (preferably calcium sulfonate), and the ZDDP is selected from C_2～12Alkyl ZDDP (preferably selected from C)_3～8Alkyl ZDDP), said organo-molybdenum being selected from one or more of molybdenum dialkyl dithiophosphate, oxymolybdenum dialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum xanthate, molybdenum thioxanthate, trinuclear molybdenum-sulfur complexes, molybdenum amine complexes, and molybdates (preferably from molybdenum dialkyl dithiocarbamates), and said ashless friction modifier being selected from one or more of fatty acid amides, fatty acid polyol esters, and fatty amines (preferably from fatty acid amides).

The polyether amine compound accounts for 0.01-20% (preferably 0.02-16%, more preferably 0.1-15%) of the total mass of the gasoline engine oil composition by mass; the antioxidant accounts for 0.1-8% (preferably 0.1-0.5%, more preferably 0.2-3%) of the total mass of the gasoline and engine oil composition; the metal detergent accounts for 0.2-15% (preferably 0.8-10%, more preferably 1.2-8%) of the total mass of the gasoline engine oil composition; the ZDDP accounts for 0.1-10% (preferably 0.05-5%, more preferably 0.1-2%) of the total mass of the gasoline engine oil composition; the organic molybdenum accounts for 0.01-10% (preferably 0.05-5%, more preferably 0.1-2%) of the total mass of the gasoline engine oil composition, and the ashless friction modifier accounts for 0.01-5% (preferably 0.02-4%, more preferably 0.05-3%) of the total mass of the gasoline engine oil composition.

The method for producing a gasoline/engine oil composition is characterized by comprising a step of mixing the polyether amine compound, the antioxidant, the metal detergent, ZDDP, the organic molybdenum, the ashless friction modifier, and the lubricating base oil.

The gasoline engine oil composition has excellent antioxidant property, wear resistance and detergency, and can meet the requirement of gasoline engine oil products of SL/GF-3, SM/GF-4, SN/GF-5 and above specifications.

Detailed Description

The deposit formation inhibiting properties relating to examples and comparative examples were evaluated as follows.

A gasoline engine air inlet valve deposit simulation test method is adopted (GB 19592-2004).

Specifically, a pipeline, an oil way and a sample bottle are respectively cleaned by dimethylbenzene and n-heptane; replacing sponge of an injection port in a sample bottle, adding a sample, inserting a deposition plate into a groove, clamping, inserting a thermocouple, and timing for 70 min; when the temperature is increased to 165 ℃, opening an air stop valve, controlling the air flow at 700L/h, and controlling the air pressure at 80 kPa; when the temperature reaches 175 ℃, a fuel valve is opened, air bubbles are firstly discharged until no breathing sound exists, and a floater is stabilized at the index of '30'; controlling the sample to be sprayed within 70-75 min; closing a fuel valve and an air valve, keeping the temperature at 175 ℃, timing again for 10min, closing heating, and naturally cooling; soaking the deposition plate in n-heptane for 6min, taking out the constant weight, weighing, and determining the difference with the blank plate as the amount of the deposit.

The deposit reduction rate is an important index for evaluating detergency of a detergent, and the larger the value, the stronger the detergency. Deposit formation amount (m) measured based on gasoline engine intake valve deposit simulation test method (GB19592-2004)_IVDMg), the deposit reduction (%) was calculated according to the following formula:

wherein m is_IVD,0And m_IVDRespectively blank gasoline and gasoline with detergentIntake valve deposit formation was simulated in mg.

Example 1

1) And (3) preparing polyether. Adding a mixture of 220g of nonyl phenol and 2.0g of potassium hydroxide into a reaction kettle, replacing air in the reactor with nitrogen, sealing the reactor, heating to 110 ℃, reducing the pressure to 2000 Pa, steaming out water, introducing nitrogen into the reactor to restore normal pressure, raising the temperature to about 140 ℃, and continuously pressing 696g of propylene oxide into the reaction kettle for reaction until the pressure is not changed any more. After completion of the reaction, the reaction was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. And (4) evaporating water and volatile matters under reduced pressure to obtain the nonyl phenol polyether product.

The chemical formula of the obtained polyether is as follows:

2) adding 59g of sodium methoxide into 898g of polyether obtained in the step 1), reacting to generate sodium polyether alkoxide, then adding 76.5g of allyl chloride, reacting for 2-10h at 50-150 ℃, removing unreacted allyl chloride under reduced pressure after the reaction is finished, and refining the crude product. The structure of the obtained alkenyl terminated polyether is as follows:

3) and (3) epoxidation of the alkenyl-terminated polyether. Under the protection of nitrogen, 939g of polyether and 75g of formic acid are added into a four-neck flask, the temperature is raised to 60 ℃, 453g of hydrogen peroxide is mixed and then is dripped into the four-neck flask within two hours, the reaction is carried out for 2 to 8 hours, the product is washed by NaOH water until the pH value is about 7.0, and then is washed by clean water for three times, and the epoxy polyether is obtained by rotary evaporation after drying. The obtained epoxy polyether has the chemical formula:

4) and (3) pumping the treated materials into an amination reaction kettle, adding 60g of ethylenediamine and 10g of n-butanol, and reacting at the temperature of 150 ℃ for 2-6 hours to obtain a polyetheramine crude product. And washing and rotary steaming the product to obtain a polyetheramine product, wherein the nitrogen content of the product is 2.15%, and the total conversion rate is 77%. The obtained polyetheramine has the chemical formula:

example 2

1) And (3) preparing polyether. Adding a mixture of 220g of nonyl phenol and 2.0g of potassium hydroxide into a reaction kettle, replacing air in the reactor with nitrogen, sealing the reactor, heating to 110 ℃, reducing the pressure to 2000 Pa, evaporating water, introducing nitrogen into the reactor to restore normal pressure, raising the temperature to about 140 ℃, and continuously pressing 864g of epoxy butane into the reaction kettle for reaction until the pressure is not changed any more. After completion of the reaction, the reaction was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. And (4) evaporating water and volatile matters under reduced pressure to obtain the nonyl phenol polyether product.

2) Adding 44g of sodium hydroxide into 1066g of polyether obtained in the step 1) to react to generate sodium polyether alkoxide, then adding 76.5g of allyl chloride, reacting for 2-10h at 50-150 ℃, decompressing after the reaction is finished to remove unreacted allyl chloride, and refining the crude product.

3) And (3) epoxidation of the alkenyl-terminated polyether. 1121g of terminal alkenyl polyether was added to a four-necked flask under nitrogen protection. 172.57g of m-chloroperoxybenzoic acid are added into a four-neck flask within two hours and reacted for 2 to 8 hours, and the product is added with 5 percent NaSO₃Solution and 5% NaHCO₃And (3) cleaning the solution, washing the solution for 5-6 times until the pH value is about 7.0, drying, and performing rotary evaporation to obtain the epoxy polyether.

4) And (3) pumping the treated materials into an amination reaction kettle, adding 61g of ethanolamine and 10g of triethylamine, reacting at the temperature of 150 ℃ for 2-6 hours to obtain a polyetheramine crude product. Washing and rotary steaming the product to obtain the polyether amine product. The nitrogen content of the product was 0.98%, and the total conversion was 83%.

Example 3

1) And (3) preparing polyether. Adding a mixture of 220g of nonyl phenol and 2.0g of potassium hydroxide into a reaction kettle, replacing air in the reactor with nitrogen, sealing the reactor, heating to 110 ℃, reducing the pressure to 2000 Pa, steaming out water, introducing nitrogen into the reactor to restore normal pressure, raising the temperature to about 140 ℃, and continuously pressing 696g of propylene oxide into the reaction kettle for reaction until the pressure is not changed any more. After completion of the reaction, the reaction was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. Decompressing and distilling to remove water and volatile matters to obtain a nonyl phenol polyether product,

2) adding 59g of sodium methoxide into 898g of polyether obtained in the step 1), reacting to generate sodium polyetheralkoxide, then adding 103.5g of 5-chloro-1, 3-pentadiene, reacting for 2-10h at 50-150 ℃, decompressing after the reaction is finished, removing unreacted allyl chloride, and refining the crude product. The structure of the obtained alkenyl terminated polyether is as follows:

3) and (3) epoxidation of the alkenyl-terminated polyether. Adding 966g of polyether and 150g of formic acid into a four-neck flask under the protection of nitrogen, heating to 60 ℃, mixing 906g of hydrogen peroxide, dropwise adding into the four-neck flask within two hours, reacting for 2-8 hours, washing a product with NaOH water until the pH value is about 7.0, washing with clean water for three times, drying, and performing rotary evaporation to obtain the epoxy polyether.

4) And (3) pumping the treated materials into an amination reaction kettle, adding 120g of ethylenediamine and 20g of n-butanol, and reacting at the temperature of 150 ℃ for 2-6 hours to obtain a polyetheramine crude product. Washing and rotary steaming the product to obtain the polyether amine product, wherein the nitrogen content of the product is 3.96 percent, and the total conversion rate is 79 percent. The obtained polyetheramine has the chemical formula:

comparative example 1

1) And (3) preparing polyether. 1.5g of potassium hydroxide mixture was placed in a reaction vessel, the temperature in the reaction vessel was increased to about 140 ℃ with nitrogen, about 696g of propylene oxide were continuously forced into the reaction vessel until the pressure did not change, and the mixture was allowed to continue to react at 140 ℃ until the pressure did not change. After completion of the reaction, the reaction was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. And (3) evaporating under reduced pressure to remove water and volatile matters to obtain a polyether product, wherein the polyether hydroxyl value of the product is 136mgKOH/g, and the molecular weight is 696.

2) Putting the polyether prepared in the step 1), 45g of modified Raney nickel catalyst and 60g of ethylenediamine into a 1L autoclave, filling hydrogen to an initial pressure of 10.0-14.0Mpa, starting heating, keeping the temperature at the reaction temperature of 200-240 ℃ for several hours, cooling to room temperature after the reaction is finished, evacuating the gas in the autoclave, opening the autoclave, discharging, filtering to remove the catalyst, and then carrying out reduced pressure distillation on the liquid to remove water and excessive liquid ammonia to obtain the product polyetheramine. Through analysis, the nitrogen content of the product is 3.51%, the conversion rate is 93%, and the structural formula is as follows:

comparative example 2

2) Putting the polyether prepared in the step 1), 45g of modified Raney nickel catalyst and two kilograms of ammonia gas into a 1L autoclave, filling hydrogen to an initial pressure of 10.0-14.0Mpa, starting heating, keeping the temperature at the reaction temperature of 200-240 ℃ for several hours, cooling to room temperature after the reaction is finished, emptying the autoclave, discharging, filtering to remove the catalyst, and then carrying out reduced pressure distillation on the liquid to remove water and excessive liquid ammonia to obtain the product polyetheramine. Through analysis, the nitrogen content of the product is 3.77%, the conversion rate is 98.43%, and the structural formula is as follows:

comparative example 3

1) And (3) preparing polyether. A mixture of 220g of nonylphenol and 2.0g of potassium hydroxide was placed in a reaction vessel, the temperature of the reactor was raised to about 140 ℃ with nitrogen, about 696g of propylene oxide was continuously forced into the reaction vessel until the pressure did not change, and the mixture was allowed to continue to react at 140 ℃ until the pressure did not change. After completion of the reaction, the reaction was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. And (3) evaporating under reduced pressure to remove water and volatile matters to obtain the polyether product with the molecular weight of 898.

2) Putting the polyether prepared in the step 1), 45g of modified Raney nickel catalyst and two kilograms of ammonia gas into a 1L autoclave, filling hydrogen to an initial pressure of 10.0-14.0Mpa, starting heating, keeping the temperature at the reaction temperature of 200-240 ℃ for several hours, cooling to room temperature after the reaction is finished, emptying the autoclave, discharging, filtering to remove the catalyst, and then removing water and excessive liquid ammonia by reduced pressure distillation of liquid to obtain the product polyetheramine. Through analysis, the nitrogen content of the product is 1.35%, the conversion rate is 88%, and the structural formula is as follows:

comparative example 4

2) Putting the polyether prepared in the step 1), 45g of modified Raney nickel catalyst and 30g of ethylenediamine into a 1L autoclave, filling hydrogen to an initial pressure of 10.0-14.0Mpa, starting heating, keeping the temperature at the reaction temperature of 200-240 ℃ for several hours, cooling to room temperature after the reaction is finished, evacuating the gas in the autoclave, opening the autoclave, discharging, filtering to remove the catalyst, and then carrying out reduced pressure distillation on the liquid to remove water and excessive liquid ammonia to obtain the product polyetheramine. Through analysis, the nitrogen content of the product is 1.12%, the conversion rate is 58%, and the structural formula is as follows:

according to the present invention, in order to produce the gasoline engine oil composition, the polyether amine compound of the present invention, the antioxidant, the metal detergent, ZDDP, the organomolybdenum, the ashless friction modifier, and the lubricant base oil may be uniformly mixed in a predetermined ratio.

Some of the lubricating oil additives specifically used are as follows:

antioxidant, butyl octyl diphenylamine, marked as KY-1, produced by Beijing coupling technology company;

antioxidant, 2, 2-methylene bis (4-methyl-6-tert-butylphenol), designated KY-2, produced by Beijing coupled technologies;

a detergent, high base number calcium sulfonate (TBN300), Liaoning Tianhe Fine chemical Co., Ltd;

a detergent, low base number calcium sulfonate (TBN40), Liaoning Nintenghe Fine chemical Co., Ltd;

ZDDP, n-butyl n-octyl dithiophosphate, labeled ZDDP-1, Liaoning Tianhe Fine chemical Co., Ltd;

organo molybdenum, molybdenum dialkyl dithiocarbamate, trade designation mollyyan 822;

ashless friction modifiers, oleamide, Haian petrochemical plants of Jiangsu province;

lubricating base oil, II base oil 100N (viscosity index 115), Dalian petrochemicals;

lubricating base oil, II base oil 150N (viscosity index 109), Dalian petrochemical company.

Examples 4 to 6 and comparative examples 5 to 8 of the gasoline engine oil composition were prepared according to the formulation composition shown in Table 1.

These gasoline engine oil compositions were used as test samples for an engine crankcase coking simulation test simulating piston deposits. The method comprises the steps of adding a 300mL sample into a coke-forming plate simulator, heating to 150 ℃, splashing oil onto an aluminum plate with the temperature of 310 ℃ in a continuous mode, weighing the coke amount generated on the aluminum plate after 6 hours, and simulating the deposit on a piston. The higher the coke formation, the poorer the piston cleanliness of this test sample.

The results of the deposits from the coke forming tests of the gasoline engine oil compositions are shown in Table 1.

The compositions of examples 4 to 6 and comparative examples 5 to 8 were subjected to a high-temperature abrasion resistance test of an oil product using a high-frequency reciprocating friction tester under the following test conditions: the load is 1000g, the frequency is 20Hz, the temperature is 100 ℃, and the test time is 60 min. The high temperature antiwear results are shown in table 2. As can be seen from Table 2, the compositions of the present invention have better antiwear properties and lower coefficients of friction.

TABLE 1

TABLE 2

Claims

1. A gasoline engine oil composition comprising a polyetheramine compound, an antioxidant, a metallic detergent, ZDDP, an organomolybdenum, an ashless friction modifier, and a balance of a lubricating base oil, the polyetheramine compound having the structure:

wherein the radical R₀Selected from hydrogen atoms, C_1-20A linear or branched alkyl group; y groups Ru, equal to or different from each other, are each independently selected from C_2-24A linear or branched alkylene group; y represents the average degree of polymerization of the polyether segment-O-Ru-, and is selected from any value between 1 and 200; radical R₁And R₂Are identical or different from each other and are each independently selected from hydrogen and C_1-6A linear or branched alkyl group; a radicals R₃Or a radicals R₄Are identical or different from each other and are each independently selected from hydrogen and C_1-6A linear or branched alkyl group; a radicals R₆Or a radicals R₇Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C_1-6Straight or branched alkyl and

wherein q radicals R₈Are the same or different from each other and are each independently selected from C_1-40A linear or branched alkylene group; q radicals R₉Are identical or different from each other and are each independently selected from hydrogen and C_1-6A linear or branched alkyl group; radical R₁₀Selected from hydrogen and C_1-6A linear or branched alkyl group; q is an integer between 1 and 50; a is an integer between 1 and 10; a radicals R' identical or different from one another, each independently selected from the group consisting of a single bond and C_1-6A linear or branched alkylene group; radical R₅Selected from hydrogen and C_1-6Straight or branched chain alkyl.

2. The gasoline engine oil composition according to claim 1, wherein the group R₀Is selected from C_5-15A linear or branched alkyl group; y groups Ru are each independently selected from C_2-12A linear or branched alkylene group; y is selected from any number between 1 and 100; radical R₁And R₂Each independently selected from hydrogen and C_1-4A linear or branched alkyl group; radical R₃Or a radical R₄Each independently selected from hydrogen and C_1-4A linear or branched alkyl group; radical R₆Or a radical R₇Each independently selected from hydrogen, optionally substituted C_1-4Straight or branched alkyl and

wherein the radical R₈Are the same or different from each other and are each independently selected from C_1-20A linear or branched alkylene group; radical R₉Each independently selected from hydrogen and C_1-4A linear or branched alkyl group; radical R₁₀Selected from hydrogen and C_1-4A linear or branched alkyl group; q is an integer between 1 and 10; a is an integer between 1 and 4; the radicals R' are each independently selected from the group consisting of a single bond and C_1-4A linear or branched alkylene group; radical R₅Selected from hydrogen and C_1-4Straight or branched chain alkyl.

3. The gasoline engine oil composition according to claim 2, wherein a is 1,2 or 3.

4. The gasoline engine oil composition according to claim 1, wherein R is₀Is selected from C_5-15Straight or branched chain alkyl.

5. The gasoline engine oil composition according to claim 1, wherein the polyether amine compound is prepared by a method comprising:

2) reacting the product of step 1) with an oxidizing agent;

3) reacting the oxidation product obtained in the step 2) with an aminating agent, and collecting the product;

the hydroxyl-containing polyether in the step 1) is

The alkenyl compound is

Wherein the radical R₀Selected from hydrogen atoms or C_1-20A linear or branched alkyl group; radical (I)G represents a functional group capable of reacting with-OH to remove the compound GH.

6. The gasoline engine oil composition of claim 5 wherein the y groups Ru are the same or different from each other and are each independently selected from C_2-24A linear or branched alkylene group; group G is selected from halogen or hydroxy; radical R₁And R₂Are identical or different from each other and are each independently selected from hydrogen and C_1-6A linear or branched alkyl group; a radicals R₃Or a radicals R₄Are identical or different from each other and are each independently selected from hydrogen and C_1-6A linear or branched alkyl group; a is an integer between 1 and 10; a radicals R' identical or different from one another, each independently selected from the group consisting of a single bond and C_1-6A linear or branched alkylene group; radical R₅Selected from hydrogen and C_1-6Straight or branched chain alkyl.

7. The gasoline engine oil composition of claim 5, wherein the alkenyl compound is selected from the group consisting of allyl halide, 3-butene-1-halide, 3-butene-2-halide, 3-methyl-3-butene-1-halide, 4-pentene-2-halide, 4-pentene-3-halide, 3-methyl-4-pentene-1-halide, 2-methyl-4-pentene-1-halide, 3-ethyl-4-pentene-1-halide, 2-ethyl-4-pentene-1-halide, 3-isobutyl-4-pentene-1-halide, 2, 3-dimethyl-4-pentene-1-halide, 2-isobutyl-4-pentene-1-halide, and mixtures thereof, 2, 2-dimethyl-4-pentene-1-halogen, 3-dimethyl-4-pentene-1-halogen, 5-hexene-1-halogen, 4-methyl-5-hexene-halogen, 3-methyl-5-hexene-halogen, 2-methyl-5-hexene-halogen, 3-ethyl-5-hexene-halogen, 5-hexene-2-halogen, 5-hexene-3-halogen, 5-hexene-4-halogen, 6-heptene-1-halogen, 2-methyl-6-heptene-1-halogen, 3-methyl-6-heptene-1-halogen, 4-methyl-6-heptene-1-halogen, 2-methyl-5-heptene-1-halogen, 5-methyl-5-hexene-2-halogen, 5-hexene-4-halogen, 6-heptene-1-halogen, 5-methyl-6-hepten-1-yl halide, 2-ethyl-6-hepten-1-yl halide, 3-ethyl-6-hepten-1-yl halide, 4-ethyl-6-hepten-1-yl halide, 5-ethyl-6-hepten-1-yl halide, 2-methyl-7-octene-1-yl halide, 3-methyl-7-octene-1-yl halide, 4-methyl-7-octene-1-yl halide, 5-methyl-7-octene-1-yl halide, 3-ethyl-7-octene-1-yl halide, 9-decene-1-yl halide, 10-undecene-1-yl halide, 11-dodecene-1-yl halide, 2-ethyl-6-heptene-1-yl halide, 3-ethyl-7-octene-1-yl halide, 3-methyl-7, One or more of 5-chloro-1, 3-pentadiene, 6-chloro-1, 3-hexadiene, 5-chloro-1, 3-hexadiene, 6-chloro-2, 4-hexadiene and 5-chloro-2, 4-hexadiene.

8. The gasoline engine oil composition of claim 5, wherein the molar ratio of the hydroxyl-containing polyether to the alkenyl compound in the step 1) is 1:1 to 1.5, the reaction temperature is 50 to 150 ℃, and the reaction time is 2 to 10 hours; the oxidant in the step 2) is selected from one or more of oxygen, ozone, hydrogen peroxide, metal oxide, metal peroxide, dichromic acid or salt thereof, permanganic acid or salt thereof, peracid or salt thereof, hypohalous acid or salt thereof and organic peroxide; in the step 2), the molar ratio of the alkenyl compound to the oxidant in the step 1) is 1:1-100, the reaction temperature is 100-200 ℃, and the reaction time is 3-20 h; in step 3), the oxidation product obtained in step 2) is subjected to amination reaction with an aminating agent to form a group

Total amination to a radical

In step 3), the aminating agent is selected from aminating agents represented by the following formula (II):

in formula (II), the radical R₆And R₇Are the same or different from each other and are each independently selected from hydrogen, optionally substituted C_1-6Straight or branched alkyl and

in-situ type

In (b), q R's are present₈Q of R₉And 1R₁₀Said group R₈Are the same or different from each otherEach independently selected from C_1-40A linear or branched alkylene group; the group R₉Are identical or different from each other and are each independently selected from hydrogen and C_1-6A linear or branched alkyl group; radical R₁₀Selected from hydrogen and C_1-6A linear or branched alkyl group; q is an integer between 1 and 50; in the step 3), the molar ratio of the aminating agent to the oxidation product is 1-4:1, the reaction temperature is 100-180 ℃, and the reaction time is 1-8 h.

9. The gasoline engine oil composition of claim 5 wherein the oxidizing agent in step 2) is an organic hydroperoxide.

10. The gasoline engine oil composition of claim 8, wherein a catalyst selected from the group consisting of tertiary amines and phenols is added in step 3), the molar ratio of the catalyst to the oxidation product is 0.1-1:1, and the number of moles of the oxidation product is the same as the number of moles of the oxidation product

To calculate.

11. The gasoline engine oil composition according to claim 1, wherein said antioxidant is selected from alkylated diphenylamine and/or phenolic antioxidant, said metal detergent is selected from sulfonate, and said ZDDP is selected from C_2～12An alkyl ZDDP, the organo-molybdenum being selected from one or more of molybdenum dialkyldithiophosphates, oxymolybdenum dialkyldithiophosphates, molybdenum dialkyldithiocarbamates, molybdenum xanthates, molybdenum thioxanthates, trinuclear molybdenum sulfur complexes, molybdenum amine complexes, and molybdates, and the ashless friction modifiers being selected from one or more of fatty acid amides, fatty acid polyol esters, and fatty amines.

12. The gasoline engine oil composition according to claim 1, characterized in that the polyether amine compound accounts for 0.01 to 20% by mass of the total mass of the gasoline engine oil composition; the antioxidant accounts for 0.1-8% of the total mass of the gasoline and engine oil composition; the metal detergent accounts for 0.2-15% of the total mass of the gasoline and engine oil composition; the ZDDP accounts for 0.1-10% of the total mass of the gasoline engine oil composition; the organic molybdenum accounts for 0.01-10% of the total mass of the gasoline engine oil composition, and the ashless friction modifier accounts for 0.01-5% of the total mass of the gasoline engine oil composition.

13. A method for producing a gasoline engine oil composition, comprising the step of mixing the polyetheramine compound according to any one of claims 1 to 12, an antioxidant, a metal detergent, ZDDP, organomolybdenum, an ashless friction modifier, and a lubricating oil base oil.