Lubricating oil composition and preparation method thereof

Abstract

The invention provides a lubricating oil composition and a preparation method thereof. The lubricating oil composition provided by the invention comprises the following components: (A) bis-tertiary amine phosphate amine salt; (B) a dispersant; (C) a detergent; (D) zinc dialkyl dithiophosphate; (E) an antioxidant; (F) a friction modifier; (G) a metal deactivator; (H) a pour point depressant; (I) a viscosity index improver; (J) lubricant base oil; wherein the structure of the bis-tertiary amine type phosphate amine salt is shown as a formula (alpha) and / or a formula (beta), each R group is independently selected from C1-C4 straight chain or branched chain alkyl, an R0 group is selected from C2-C10 straight chain or branched chain alkylene, and an R'group is C1-C12 straight chain or branched chain alkyl. The lubricating oil composition disclosed by the invention has very excellent high-temperature oxidation resistance, cleaning performance and extreme pressure bearing performance, is long in oil change mileage, and can meet the requirements of lubricating oil for high-performance-grade gasoline and diesel passenger car engines such as ILSAC GF-7, ACEA C6, GLV-2 and the like.

Description

Technical Field

[0001] This invention relates to a lubricating oil composition, and more particularly to a gasoline and diesel passenger car engine lubricating oil composition with a long oil change interval. Background Technology

[0002] The specifications and performance of engine oils for passenger vehicles have continuously evolved with the design, operating conditions, and fuel efficiency of gasoline and diesel engines. Frequent upgrades and replacements of automotive lubricants place higher demands on lubricant additives. The anti-wear and anti-oxidation properties of engine oils have always been important indicators in oil specifications. Especially with the application of turbocharging and direct injection technologies, the temperature of engine pistons and other components is significantly higher than in previous engines, leading to a significantly faster rate of engine oil aging and deterioration, and increased oil consumption. High-temperature deposits, particularly in critical areas like pistons and combustion chambers, constantly place new demands on the anti-wear performance of engine oils. Engine oils with poor anti-wear properties severely impact engine performance. Simultaneously, the need for environmental protection and energy conservation has made extending engine oil mileage a primary market objective, further demanding higher levels of anti-wear and anti-oxidation performance from engine oils. Therefore, developing engine oil compositions for passenger vehicles with extended oil change intervals has become a research focus in this field. Summary of the Invention

[0003] This invention proposes a lubricating oil composition and its preparation method.

[0004] The lubricating oil composition of the present invention comprises the following components: (A) a bis-tertiary amine phosphate amine salt; (B) a dispersant; (C) a detergent; (D) zinc dialkyl dithiophosphate; (E) an antioxidant; (F) a friction modifier; (G) a metal deactivator; (H) a pour point depressant; (I) a viscosity index improver; and (J) a lubricating oil base oil.

[0005] The structure of the bis-tertiary amine phosphate amine salt is shown in formula (α) and / or formula (β):

[0006]

[0007] Each R group is independently selected from C1 to C4 straight-chain or branched alkyl groups, and the R0 group is selected from C2 to C4 straight-chain or branched alkyl groups. 10 Straight-chain or branched alkylene groups, with R' groups at C1-C1. 12 Straight-chain or branched alkyl groups.

[0008] According to the present invention, preferably, each R group is independently selected from methyl or ethyl, and the RO group is selected from C4 to C5. 10 Straight-chain or branched alkylene groups, with R' group at C4-C5. 10 Straight-chain or branched alkyl groups (preferably 2-ethylhexyl).

[0009] According to the present invention, in the bis-tertiary amine phosphate amine salt, the molar ratio between the compound shown in formula (α) and the compound shown in formula (β) can be 10 to 2000:1, preferably 30 to 1500:1.

[0010] According to the present invention, the bis-tertiary amine phosphate amine salt is selected from any one of the following single compounds or a composition obtained by mixing these single compounds in any proportion:

[0011]

[0012]

[0013] According to the present invention, the preparation method of the bis-tertiary amine phosphate amine salt includes:

[0014] React the compound shown in formula (X) with the compound shown in formula (Y) and collect the products;

[0015]

[0016] Each R group is independently selected from C1 to C4 straight-chain or branched alkyl groups, and the R0 group is selected from C2 to C4 straight-chain or branched alkyl groups. 10 Straight-chain or branched alkylene groups, with R' groups at C1-C1. 12 Straight-chain or branched alkyl groups.

[0017] According to the present invention, preferably, each R group is independently selected from methyl or ethyl, and the RO group is selected from C4 to C5. 10 Straight-chain or branched alkylene groups, with R' group at C4-C5. 10 Straight-chain or branched alkyl groups (preferably 2-ethylhexyl).

[0018] According to the present invention, the molar ratio between the compound shown in formula (X) and the compound shown in formula (Y) can be 1:0.5 to 5, preferably 1:1 to 2; the reaction temperature between the compound shown in formula (X) and the compound shown in formula (Y) can be 60 to 120°C, preferably 80 to 100°C; and the reaction time between the compound shown in formula (X) and the compound shown in formula (Y) can be 5 to 20 h, preferably 8 to 15 h.

[0019] According to the present invention, optionally, the compound represented by formula (X) is selected from N,N,N',N'-tetramethyl-1,2-ethylenediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,8-octanediamine, N,N,N',N'-tetramethyl-1,10-decanediamine, N,N,N',N'-tetraethyl- 1,2-Ethylenediamine, N,N,N',N'-Tetraethyl-1,4-Butanediamine, N,N,N',N'-Tetraethyl-1,6-Hexanediamine, N,N,N',N'-Tetraethyl-1,8-Octanediamine, N,N,N',N'-Tetraethyl-1,10-Decanediamine, N,N,N',N'-Tetrapropyl-1,2-Ethylenediamine, N,N,N',N'-Tetrapropyl-1,4-Butanediamine, N,N,N',N '-Tetrapropyl-1,6-hexanediamine, N,N,N',N'-tetrapropyl-1,8-octanediamine, N,N,N',N'-tetrapropyl-1,10-decanediamine, N,N,N',N'-tetrabutyl-1,2-ethylenediamine, N,N,N',N'-tetrabutyl-1,4-butanediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, N,N,N',N'-tetrabutyl-1,8-octanediamine, N One or more of N,N',N'-tetrabutyl-1,10-decanediamine, preferably one or more of N,N,N',N'-tetramethyl-1,2-ethylenediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,8-octanediamine, and N,N,N',N'-tetramethyl-1,10-decanediamine.

[0020] According to the present invention, optionally, the compound represented by formula (Y) is selected from one or more of dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, diisooctyl phosphate (i.e., di(2-ethylhexyl) phosphate), dinonyl phosphate, and didecyl phosphate, preferably one or more of dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, and diisooctyl phosphate.

[0021] According to the present invention, optionally, a solvent may be added to the reaction of the compound shown in formula (X) with the compound shown in formula (Y). The solvent may be one or more of xylene, hexane, cyclohexane, petroleum ether, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, and tetrahydrofuran. The amount of solvent used is preferably to promote the reaction and is not particularly limited. The solvent can be removed after the reaction is complete by conventional methods in the art, such as distillation or fractional distillation.

[0022] According to the present invention, optionally, the reaction between the compound shown in formula (X) and the compound shown in formula (Y) can be carried out under an inert gas protection environment or not.

[0023] According to the present invention, optionally, after the reaction between the compound shown in formula (X) and the compound shown in formula (Y) is completed, the reaction product can be purified. The purification method includes one or more of the following methods: washing with water, extraction, distillation, rectification, molecular distillation, filtration, drying and recrystallization, without particular limitation.

[0024] According to the present invention, a single bis-tertiary amine phosphate amine salt compound can be prepared as a reaction product, or a mixture of multiple bis-tertiary amine phosphate amine salt compounds can be prepared. These reaction products are all contemplated by the present invention, and their different forms do not affect the realization of the technical effects of the present invention. Therefore, in the context of this specification, these reaction products are collectively referred to as bis-tertiary amine phosphate amine salts without distinction. In view of this, according to the present invention, there is no absolute necessity for further purification of the reaction product, or for further separation of a bis-tertiary amine phosphate amine salt with a specific structure from the reaction product. Of course, such purification or separation is preferred for further enhancing the intended effects of the present invention, but is not necessary for the present invention. Nevertheless, methods for purification or separation, such as silica gel column chromatography or preparative chromatography, can be cited as examples.

[0025] According to the present invention, the bis-tertiary amine phosphate amine salt or the bis-tertiary amine phosphate amine salt prepared according to the preparation method of the present invention can be used as an extreme pressure anti-wear agent for lubricating oil.

[0026] The bis-tertiary amine phosphate amine salt of the present invention has excellent load-bearing capacity, corrosion resistance, oil solubility, anti-wear and friction-reducing properties and thermal stability.

[0027] According to the present invention, the bis-tertiary amine phosphate amine salt accounts for 0.1% to 10% (preferably 0.2% to 5%) of the total mass of the lubricating oil composition; the dispersant accounts for 1% to 15% (preferably 2% to 12%) of the total mass of the lubricating oil composition; the detergent accounts for 0.5% to 10% (preferably 1% to 8%) of the total mass of the lubricating oil composition; the dialkyl dithiophosphate zinc accounts for 0.05% to 3% (preferably 0.1% to 2%) of the total mass of the lubricating oil composition; and the antioxidant accounts for 0.1% to 6% (preferably...) of the total mass of the lubricating oil composition. The lubricating oil composition contains 0.2% to 5% of the lubricating oil composition; the friction modifier contains 0.02% to 3% (preferably 0.1% to 2.5%) of the total mass of the lubricating oil composition; the metal deactivator contains 0.02% to 3% (preferably 0.1% to 2.5%) of the total mass of the lubricating oil composition; the pour point depressant contains 0.1% to 3% (preferably 0.2% to 2%) of the total mass of the lubricating oil composition; the viscosity index improver contains 1% to 15% (preferably 2% to 12%) of the total mass of the lubricating oil composition; and the lubricating oil base oil constitutes the main component of the lubricating oil composition.

[0028] According to the present invention, the dispersant may be selected from one or more of monoisobutylene succinimide, diisobutylene succinimide, polyisobutylene succinimide, high molecular weight polyisobutylene succinimide, boronized polyisobutylene succinimide, and polyisobutylene succinate, wherein the number average molecular weight of the polyisobutylene group may be 500 to 4000, preferably 700 to 3000. The dispersant may be selected from T151, T152, T154 and T161 produced by Wuxi Nanfang Additives Co., Ltd., T161 produced by Suzhou Special Oil Products Plant, T155, T161A and T161B produced by Jinzhou Petrochemical Branch Additives Plant, LZ6418 and LZ6420 produced by Lubrizol, Hitec646, Hitec648 and Hitec7714 produced by Afton, MX3316 produced by Agip Petroli, and LZ935 and LZ936 produced by Lubrizol, etc.

[0029] According to the present invention, the detergent is selected from one or more of sulfonates, alkyl salicylates, and sulfoalkylphenol salts, preferably a mixture of sulfonates and sulfoalkylphenol salts, with a preferred mass ratio between the two being between 1:0.2 and 1. The detergent may be selected from T106B, T107, T121, and T122 produced by Xinxiang Ruifeng Chemical Co., Ltd.; T109A, T109B, T109C, S206, and T106 produced by Wuxi Nanfang Additives Co., Ltd.; LZ6499, LZ6500, LZ6477C, and LZ6478 produced by Lubrizol; E611 produced by Afton; OLOA219 produced by Chevron Oronite; C9375, C9012, C9391, C9330, and C9394 produced by Infineum; OSCA420 produced by OSCA; and SAP007 produced by Shell.

[0030] According to the present invention, the alkyl group in the zinc dialkyl dithiophosphate can be C2-C3. 12 The alkyl group, preferably C2-C8, includes one or more of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, and 2-ethylhexyl. The dialkyl dithiophosphate zinc can be selected from T202 and T203 produced by Wuxi Southern Petroleum Additives Co., Ltd., T202, T203, primary and secondary alkyl T204, and secondary alkyl T205 produced by Jinzhou Petrochemical Branch Additives Plant, LZ1371 and LZ1375 from Lubrizol, C9417, C9425, and C9426 from Infineum, and Hitec7169 and Hitec1656 from Afton, etc.

[0031] According to the present invention, the antioxidant is selected from one or more of phenolic ester antioxidants, amine antioxidants, phenolic antioxidants, and thiophenolic ester antioxidants; the phenolic ester antioxidant is preferably a hydroxyphenyl carboxylic acid ester with a molecular weight of 200-500, such as IRGANOX L-135 produced by BASF GmbH, Germany, or T512 produced by Beijing Xingpu Fine Chemical Technology Development Co., Ltd. The amine antioxidant can be one or more of alkylaniline, alkyldiphenylamine, and phenyl-α-naphthylamine, such as dibutyldiphenylamine, dioctyldiphenylamine, dinonyldiphenylamine, butoctyldiphenylamine, and phenyl-α-naphthylamine. Commercially available alkylated diphenylamines can be selected from IRGANOX L-01 and IRGANOX XL-57 produced by BASF (Germany), T534 produced by Beijing Xingpu Fine Chemical Technology Development Co., Ltd., LZ5150A produced by Lanzhou Lubrizol Lanzhou Refinery Additives Co., Ltd., VANLUBE NA, VANLUBE 961, and dioctyl diphenylamine VANLUBE 81 produced by Vanderbilt (USA), p,p'-diisooctyl diphenylamine RC7001 produced by RheinChemie (Germany), and 438L produced by Chemtura, etc. The phenolic antioxidant can be selected from one or more of 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-p-cresol, 4,4'-methylenebis(2,6-di-tert-butylphenol), and 2,6-di-tert-butyl-4-alkoxyphenol. The thiophenol ester type antioxidant can be selected from 2,2'-thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], such as antioxidant 1035 produced by Sichuan Yongye Chemical Co., Ltd., IRGANOX L115 produced by BASF, and T535 produced by Xinxiang Ruifeng New Materials Co., Ltd.

[0032] According to the present invention, the friction modifier may be selected from oil-soluble organic molybdenum friction modifier and / or ashless friction modifier; the oil-soluble organic molybdenum friction modifier may be selected from one or more of dialkyl dithiophosphate molybdenum, dialkyl dithiophosphate oxymolybdenum, dialkyl dithiocarbamate molybdenum, xanthate molybdenum, thioxanthate molybdenum, trinuclear molybdenum-sulfur complex, molybdenum amine complex and molybdate ester, for example, MolyVan L, 822, 855 produced by Vanderbilt Corporation of the United States, and 515, 525, 710 produced by Asahi Denka Co., Ltd. of Japan. The ashless friction modifier can be selected from one or more of fatty acid polyol esters, aliphatic amines, and aliphatic amides; the fatty acid polyol ester can be selected from one or more of fatty acid glycerides, fatty acid pentaerythritol esters, fatty acid ethylene glycol esters, fatty acid succinates, fatty acid ethanolamine esters, fatty acid diethanolamine esters, and fatty acid triethanolamine esters; the aliphatic amine can be selected from one or more of hydrocarbon-substituted monoamines or polyamines, alkoxylated hydrocarbon-substituted monoamines or polyamines, and alkyl ether amines; the aliphatic amide can be selected from one or more of oleamide, cocoamide, and oleic acid diethanolamide. The ashless friction modifier can be selected from Croda's ATMER1006, BASF's Irgalube F10A, etc.

[0033] According to the present invention, the metal deactivator can be selected from one or more of triazole derivatives, thiazole derivatives, and thiadiazole derivatives, such as benzothiazole, toluenetriazole, octyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbon-substituted-1,3,4-thiadiazole, 2-dimercapto-5-dithio-1,3,4-thiadiazole, N,N'-dihexylaminomethylenetriazole, and 2-mercaptobenzothiazole. The metal deactivator can be selected from T551, T561, T706, etc., produced by Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.

[0034] According to the present invention, the pour point depressant is selected from polyα-olefins, vinyl acetate copolymers, and alkyl groups having C8 to C6 Å. 18 One or more of dialkyl fumarate, polyalkyl methacrylate, and alkyl naphthalene can be selected, such as T803 from Wuxi Southern Petroleum Additives Company or V385 from Runyinglian Company.

[0035] According to the present invention, the viscosity index improver may be selected from one or more of the following: ethylene-propylene copolymer, polymethacrylate, polyalkylmethacrylate, styrene-acrylate copolymer, hydrogenated or partially hydrogenated styrene / isoprene copolymer, hydrogenated or partially hydrogenated styrene / butadiene copolymer, and hydrogenated or partially hydrogenated isoprene / butadiene copolymer; for example, Lubrizol's LZ7070, LZ7065, LZ7067, and LZ7077, and Infineum's SV260, SV261, and SV203 may be selected.

[0036] According to the present invention, the lubricating oil base oil is selected from one or more of API Group I, II, III, IV and V base oils, preferably API Group III base oil.

[0037] Rust inhibitors, antifoaming agents, etc., may also be added to the lubricating oil composition of the present invention, and there are no particular limitations.

[0038] The method for preparing the lubricating oil composition of the present invention includes the step of mixing the above-mentioned components. The mixing temperature is between 40°C and 90°C, and the mixing time is between 1 hour and 6 hours.

[0039] The lubricating oil composition of the present invention has excellent high-temperature oxidation resistance, detergency and extreme pressure carrying capacity, long oil change interval, and can meet the requirements of high-performance gasoline and diesel passenger car engine lubricating oils such as ILSAC GF-7, ACEA C6, and GLV-2. Attached Figure Description

[0040] Figure 1 This is the mass spectrometry spectrum of product 1 in Example 1 of the present invention.

[0041] Figure 2 This is the mass spectrum of product 2 in Example 2 of the present invention.

[0042] Figure 3 This is the mass spectrometry spectrum of product 3 in Example 3 of the present invention.

[0043] Figure 4 This is the mass spectrometry spectrum of product 4 in Example 4 of the present invention. Detailed Implementation

[0044] The present invention will be explained and illustrated below through specific embodiments, but these do not constitute a limitation on the present invention.

[0045] Unless otherwise specified, all percentages mentioned below are percentages by mass.

[0046] The main raw materials used and their sources:

[0047] N,N,N',N'-Tetramethyl-1,2-ethylenediamine (99%, Beijing Inokai Technology Co., Ltd.), N,N,N',N'-Tetramethyl-1,4-butanediamine (98%, Shanghai Maclean Biochemical Technology Co., Ltd.), N,N-dimethylethylamine (99%, Beijing Inokai Technology Co., Ltd.), N,N,N',N'-Tetramethyl-1,6-hexanediamine (99%, Shanghai Aladdin Biochemical Technology Co., Ltd.), N,N-dimethylpropylamine (98%, Shanghai Aladdin Biochemical Technology Co., Ltd.), N,N-dimethyln-octylamine (95%, Shanghai Aladdin Biochemical Technology Co., Ltd.), N,N,N',N'-Tetramethyl-1,10-decanediamine (95%, Shanghai Bid Pharmaceutical Technology Co., Ltd.), diisooctyl phosphate (99%, Shanghai Aladdin Biochemical Technology Co., Ltd.), 1,2- Dibromoethane (99%, Shanghai Maclean Biochemical Technology Co., Ltd.), 1,4-Dibromobutane (98%, Shanghai Maclean Biochemical Technology Co., Ltd.), 1,6-Dibromohexane (97%, THIAI Shanghai Chemical Industry Development Co., Ltd.), 1,10-Dibromodecane (95%, Shanghai Aladdin Biochemical Technology Co., Ltd.), Dimethyloctadecylamine (97%, Shanghai Maclean Biochemical Technology Co., Ltd.), NaOH (AR, Tianjin Damao Chemical Reagent Factory), Anhydrous Sodium Sulfate (99%, Beijing Inokai Technology Co., Ltd.), Petroleum Ether (AR, Beijing Inokai Technology Co., Ltd.), Acetonitrile (99.9%, Beijing Inokai Technology Co., Ltd.), Dichloromethane (99.9%, Beijing Inokai Technology Co., Ltd.), Xylene (AR, Tianjin Damao Chemical Reagent Factory), Pentaerythritol Ester Base Oil (Shandong Ruijie New Materials Co., Ltd.).

[0048] Example 1

[0049] The main raw materials include: N,N,N',N'-tetramethyl-1,2-ethylenediamine, diisooctyl phosphate, and xylene.

[0050] In a 100 ml three-necked flask, xylene (50 ml) and diisooctyl phosphate (6.4484 g, 0.02 mol) were added as solvent. The mixture was heated to 30 °C, and N,N,N',N'-tetramethyl-1,2-ethylenediamine (1.1621 g, 0.01 mol) was added dropwise. The mixture was heated to 80 °C and reacted for 12 hours. The organic solvent was removed by vacuum distillation to obtain product 1, which is a yellow transparent oily liquid.

[0051] The reaction equation for preparing the bis-tertiary amine phosphate amine salt of the present invention in Example 1 is as follows:

[0052]

[0053] Product 1 was analyzed by mass spectrometry to confirm its structure. The mass spectrometry conditions were as follows: Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), model Bruker SolariX XR, magnetic field strength 15T; experimental conditions: injection rate 120μL / h, electrospray ionization source, positive ion mode (ESI+), capillary voltage 4500V, nebulizer 1 bar, drying gas flow rate 4.0L / min, desiccator temperature 200℃, TOF 0.6ms, Q1 mass 150u, RF 800Vpp, front and rear baffle voltage 1.8V, SEP (Sweep Excitation Power) 15, mass-to-charge ratio (m / z) detection range 50~1500, and a total of 64 scans during sampling; sample preparation: a sample of approximately 0.1mg / mL was prepared using chromatographic grade pure methanol.

[0054] Mass spectrometry results are shown below Figure 1 .

[0055] Figure 1 The characteristic peak at 439.365922 indicates that compound 1 in product 1 is bound to a Na group. + The molecular ion peak; the characteristic peak at 761.593218 indicates that compound 2 in product 1 has a bound H atom. + The molecular ion peaks were obtained, and the molar ratio of compound 1 to compound 2 was calculated to be 32:1 based on the peak area. Compound 1 had a mass fraction of 94.9% in product 1, and compound 2 had a mass fraction of 3.0% in product 1.

[0056] Example 2

[0057] The main raw materials include: N,N,N',N'-tetramethyl-1,4-butanediamine, diisooctyl phosphate, and xylene.

[0058] In a 100 ml three-necked flask, xylene (50 ml) and diisooctyl phosphate (6.4484 g, 0.02 mol) were added as solvent. The mixture was heated to 30 °C, and N,N,N',N'-tetramethyl-1,4-butanediamine (1.4426 g, 0.01 mol) was added dropwise. The mixture was heated to 80 °C and reacted for 12 hours. The organic solvent was removed by vacuum distillation to obtain product 2, which is a yellow transparent oily liquid.

[0059] The reaction equation for preparing the bis-tertiary amine phosphate amine salt of the present invention in Example 2 is shown below:

[0060]

[0061] Product 2 was subjected to mass spectrometry to confirm its structure, and the mass spectrometry conditions were the same as in Example 1.

[0062] Mass spectrometry results are shown below Figure 2 .

[0063] Figure 2 The characteristic peak at 467.397222 indicates that compound 1 in product 2 has a hydrogen atom bonded to it. + The molecular ion peak; the characteristic peak at 789.624518 indicates that compound 2 in product 2 has a bound H atom. + The molecular ion peak, and the characteristic peak at 811.60667, indicate that compound 2 in product 2 has a Na+ ion bonded to it. + The molecular ion peak was obtained, and the molar ratio of compound 1 and compound 2 was calculated to be 94:1 based on the peak area. The mass fraction of compound 1 in product 2 was 97.4%, and the mass fraction of compound 2 in product 2 was 1.1%.

[0064] Comparative Example 1

[0065] The main raw materials include: N,N-dimethylethylamine, diisooctyl phosphate, and xylene.

[0066] In a 100 mL three-necked flask, xylene (50 mL) and diisooctyl phosphate (6.4484 g, 0.02 mol) were added as solvent. The mixture was heated to 30 °C, and N,N-dimethylethylamine (1.4628 g, 0.02 mol) was added dropwise. The mixture was then heated to 80 °C and reacted for 12 hours. The organic solvent was removed by vacuum distillation to obtain product D1, which is a yellow, transparent, oily liquid.

[0067] The reaction equations in Comparative Example 1 are shown below:

[0068]

[0069] Example 3

[0070] The main raw materials include: N,N,N',N'-tetramethyl-1,6-hexanediamine, diisooctyl phosphate, and xylene.

[0071] In a 100 mL three-necked flask, xylene (50 mL) and diisooctyl phosphate (6.4484 g, 0.02 mol) were added as solvent. The temperature was raised to 30 °C, and N,N,N',N'-tetramethyl-1,6-hexanediamine (1.7231 g, 0.01 mol) was added dropwise. The temperature was raised to 80 °C and the reaction was carried out for 12 hours. The organic solvent was removed by vacuum distillation to obtain product 3, which is a yellow transparent oily liquid.

[0072] The reaction equation for preparing the bis-tertiary amine phosphate amine salt of the present invention in Example 3 is shown below:

[0073]

[0074] Product 3 was subjected to mass spectrometry to confirm its structure, and the mass spectrometry conditions were the same as in Example 1.

[0075] Mass spectrometry results are shown below Figure 3 .

[0076] Figure 3 The characteristic peak at 495.428522 indicates that compound 1 in product 3 has a bound H atom. + The molecular ion peak; the characteristic peak at 817.655818 indicates that compound 2 in product 3 has a bound H atom. + The molecular ion peak, 839.639329, is a characteristic peak indicating that compound 2 in product 3 has a Na+ ion bonded to it. + The molecular ion peak was obtained, and the molar ratio of compound 1 to compound 2 was calculated to be 1243:1 based on the peak area. Compound 1 had a mass fraction of 99.8% in product 3, and compound 2 had a mass fraction of 0.1% in product 3.

[0077] Comparative Example 2

[0078] The main raw materials include: N,N-dimethylpropylamine, diisooctyl phosphate, and xylene.

[0079] In a 100 ml three-necked flask, xylene (50 ml) and diisooctyl phosphate (6.4484 g, 0.02 mol) were added as solvent. The mixture was heated to 30 °C, and N,N-dimethylpropylamine (1.7432 g, 0.02 mol) was added dropwise. The mixture was then heated to 80 °C and reacted for 12 hours. The organic solvent was removed by vacuum distillation to obtain product D2, which is a yellow, transparent, oily liquid.

[0080] The reaction equations in Comparative Example 2 are shown below:

[0081]

[0082] Comparative Example 3

[0083] Main raw materials: N,N-dimethyl-n-octylamine, diisooctyl phosphate, xylene.

[0084] Add xylene (50 ml) as solvent and diisooctyl phosphate (6.4484 g, 0.02 mol) to 100 ml of the solution. Heat to 30 °C and add N,N-dimethyl-n-octylamine (3.2667 g, 0.02 mol) dropwise to the flask. Heat to 80 °C and react for 12 hours. Remove the organic solvent by vacuum distillation to obtain product D3, which is a yellow transparent oily liquid.

[0085] The reaction equations in Comparative Example 3 are shown below:

[0086]

[0087] Example 4

[0088] The main raw materials include: N,N,N',N'-tetramethyl-1,10-decanediamine, diisooctyl phosphate, and xylene.

[0089] In a 100 mL three-necked flask, xylene (50 mL) and diisooctyl phosphate (6.4484 g, 0.02 mol) were added as solvent. The temperature was raised to 30 °C, and N,N,N',N'-tetramethyl-1,10-decanediamine (2.2842 g, 0.01 mol) was added dropwise. The temperature was raised to 80 °C and the reaction was carried out for 12 hours. The organic solvent was removed by vacuum distillation to obtain product 4, which is a yellow transparent oily liquid.

[0090] The reaction equation for preparing the bis-tertiary amine phosphate amine salt of the present invention in Example 4 is shown below:

[0091]

[0092] Product 4 was subjected to mass spectrometry to confirm its structure, and the mass spectrometry conditions were the same as in Example 1.

[0093] Mass spectrometry results are shown below Figure 4 .

[0094] Figure 4 The characteristic peak at 551.491122 indicates that compound 1 in product 4 has a hydrogen atom bonded to it. + The molecular ion peak; the characteristic peak at 895.700363 indicates that compound 2 in product 4 is bound to a Na+ ion. + The molecular ion peak was obtained, and the molar ratio of compound 1 to compound 2 was calculated to be 1117:1 based on the peak area. Compound 1 had a mass fraction of 98.9% in product 4, and compound 2 had a mass fraction of 0.1% in product 4.

[0095] Comparative Example 4

[0096] The main raw materials include: 1,2-dibromoethane, dimethyloctadecylamine, diisooctyl phosphate, petroleum ether, acetonitrile, NaOH, dichloromethane, and anhydrous sodium sulfate.

[0097] 1,2-Dibromoethane (1.8786 g, 0.01 mol) and dimethyloctadecylamine (5.9512 g, 0.02 mol) were added to a 500 ml three-necked flask, with 150 ml acetonitrile as solvent. The mixture was reacted at 80 °C for 24 h. After cooling to room temperature, a white powder precipitated. The powder was filtered under reduced pressure, washed with petroleum ether, and dried to obtain 1,2-bis-N,N-dimethyl-octadecylammonium bromide. 0.01 mol (7.8306 g) of 1,2-bis-N,N-dimethyl-octadecylammonium bromide was added to a 250 ml three-necked flask. This bromide was mixed with twice the molar amount of diisooctyl phosphate in 100 ml of acetonitrile. 0.8 g (0.02 mol) of NaOH was dissolved in 20 ml of deionized water and added to the three-necked flask. The mixture was reacted at 80 °C for 24 h. The acetonitrile was distilled off under reduced pressure, dissolved in 50 ml of dichloromethane, washed three times with deionized water, and dried overnight with anhydrous sodium sulfate. The sodium sulfate was filtered off, and the dichloromethane was distilled off under reduced pressure to obtain product D4.

[0098] The reaction equations in Comparative Example 4 are shown below:

[0099]

[0100] Comparative Example 5

[0101] The main raw materials include: 1,4-dibromobutane, dimethyloctadecylamine, diisooctyl phosphate, petroleum ether, acetonitrile, NaOH, dichloromethane, and anhydrous sodium sulfate.

[0102] (2.1591 g, 0.01 mol) of 1,4-dibromobutane and (4.3183 g, 0.02 mol) of dimethyloctadecylamine were added to a 500 ml three-necked flask, with 150 ml of acetonitrile as solvent. The mixture was reacted at 80 °C for 24 h. After cooling to room temperature, a white powder precipitated. The powder was filtered under reduced pressure, washed with petroleum ether, and dried to obtain 1,4-bis-N,N-dimethyl-octadecylammonium bromide. 0.01 mol (8.1106 g) of 1,4-bis-N,N-dimethyl-octadecylammonium bromide was added to a 250 ml three-necked flask. This bromide was mixed with twice the molar amount of diisooctyl phosphate in 100 ml of acetonitrile. 0.8 g (0.02 mol) of NaOH was dissolved in 20 ml of deionized water and added to the three-necked flask. The mixture was reacted at 80 °C for 24 h. The acetonitrile was distilled off under reduced pressure, dissolved in 50 ml of dichloromethane, washed three times with deionized water, and dried overnight with anhydrous sodium sulfate. The sodium sulfate was filtered off, and the dichloromethane was distilled off under reduced pressure to obtain product D5.

[0103] The reaction equation in Comparative Example 5 is shown below:

[0104]

[0105] Comparative Example 6

[0106] The main raw materials include: 1,6-dibromohexane, dimethyloctadecylamine, diisooctyl phosphate, petroleum ether, acetonitrile, NaOH, dichloromethane, and anhydrous sodium sulfate.

[0107] In a 500 ml three-necked flask, 2.4397 g (0.01 mol) of 1,6-dibromohexane and 4.3183 g (0.02 mol) of dimethyloctadecylamine were added, with 150 ml of acetonitrile as solvent. The mixture was reacted at 80 °C for 24 h. After cooling to room temperature, a white powder precipitated. The powder was filtered under reduced pressure, washed with petroleum ether, and dried to obtain 1,6-bis-N,N-dimethyl-octadecylammonium bromide. 0.01 mol (8.3911 g) of 1,6-bis-N,N-dimethyl-octadecylammonium bromide was added to a 250 ml three-necked flask. This bromide was mixed with twice the molar amount of diisooctyl phosphate in 100 ml of acetonitrile. 0.8 g (0.02 mol) of NaOH was dissolved in 20 ml of deionized water and added to the three-necked flask. The mixture was reacted at 80 °C for 24 h. The acetonitrile was distilled off under reduced pressure, dissolved in 50 ml of dichloromethane, washed three times with deionized water, and dried overnight with anhydrous sodium sulfate. The sodium sulfate was filtered off, and the dichloromethane was distilled off under reduced pressure to obtain product D6.

[0108] The reaction equations in Comparative Example 6 are shown below:

[0109]

[0110] Comparative Example 7

[0111] The main raw materials include: 1,10-dibromodecane, dimethyloctadecylamine, diisooctyl phosphate, petroleum ether, acetonitrile, NaOH, dichloromethane, and anhydrous sodium sulfate.

[0112] In a 500 ml three-necked flask, add (3.0008 g, 0.01 mol) 1,10-dibromodecane and (4.3183 g, 0.02 mol) dimethyloctadecylamine, and use 150 ml acetonitrile as solvent. React at 80 °C for 24 h. After cooling to room temperature, a white powder precipitates. Filter under reduced pressure, wash the white powder with petroleum ether, and dry to obtain 1,10-bis-N,N-dimethyl-octadecylammonium bromide. 0.01 mol (9.0311 g) of 1,10-bis-N,N-dimethyl-octadecylammonium bromide was added to a 250 ml three-necked flask. This bromide was mixed with twice the molar amount of diisooctyl phosphate in 100 ml of acetonitrile. 0.8 g (0.02 mol) of NaOH was dissolved in 20 ml of deionized water and added to the three-necked flask. The mixture was reacted at 80 °C for 24 h. The acetonitrile was distilled off under reduced pressure, dissolved in 50 ml of dichloromethane, washed three times with deionized water, and dried overnight with anhydrous sodium sulfate. The sodium sulfate was filtered off, and the dichloromethane was distilled off under reduced pressure to obtain product D7.

[0113] The reaction equations in Comparative Example 7 are shown below:

[0114]

[0115] According to the formulations in Tables 1 and 2, engine lubricating oil compositions were prepared in Examples 5 to 12 and Comparative Examples 8 to 14, respectively.

[0116] Table 1

[0117]

[0118]

[0119] The thermal decomposition temperature of the above-mentioned lubricating oil composition was tested using a TA5000-DSC2910 differential thermal analyzer. A higher thermal decomposition temperature indicates better thermal stability of the oil sample.

[0120] The oxidation induction period of the above-mentioned lubricating oil composition was tested using high-pressure differential scanning calorimetry (PDSC). A longer oxidation induction period indicates better oxidation resistance of the oil sample.

[0121] The above-mentioned lubricating oil composition was tested for inhibiting piston deposit formation using a crankcase coking plate test method. This method involves adding 300 ml of oil sample to a coking plate tester, heating it to 160°C, splashing the oil onto an aluminum plate at 330°C, and weighing the amount of coke formed on the aluminum plate after a 5-hour test to simulate piston deposits. Higher coke levels indicate poorer performance in inhibiting high-temperature deposits.

[0122] Table 2

[0123]

[0124] The detergency of the above-mentioned lubricating oil composition was tested using a heat pipe coking simulation test. This method involves circulating the test sample in a heat pipe while simultaneously injecting oxygen to accelerate oil aging. The sample is heated to 310°C, and the glass tube wall is scored after 6 hours. The maximum score is 10; a lower score indicates poorer detergency of the test sample.

[0125] The high-temperature wear resistance test of the above-mentioned lubricating oil composition was carried out using a high-frequency reciprocating friction tester. The test load was 1000g, the reciprocating frequency was 20Hz, the oil temperature was 100℃, and the test time was 1h.

[0126] The extreme pressure bearing capacity of the above-mentioned lubricating oil composition was evaluated using a four-ball friction testing machine. The evaluation tests were conducted in accordance with GB / T3142-2019 standard.

[0127] The results of the above experiments are shown in Table 3.

[0128] As shown in Table 3, the lubricating oil composition of the present invention has excellent antioxidant properties, detergency properties and extreme pressure carrying properties.

[0129] Table 3

[0130]

[0131] The above embodiments are only used to illustrate the technical solutions of the embodiments of this disclosure, and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features.

Claims

1. A lubricating oil composition comprising the following components: (A) a bis-tertiary amine phosphate amine salt; (B) a dispersant; (C) Detergent; (D) Zinc dialkyl dithiophosphate; (E) Antioxidant; (F) Friction modifier; (G) Metal deactivator; (H) Pour point depressant; (I) Viscosity index improver; (J) Lubricating oil base oil; wherein the structure of the bis-tertiary amine phosphate amine salt is as shown in formula (α) and / or formula (β): Each R group is independently selected from C1 to C4 straight-chain or branched alkyl groups, and the R0 group is selected from C2 to C4 straight-chain or branched alkyl groups. 10 Straight-chain or branched alkylene groups, with R' groups at C1-C1. 12 Straight-chain or branched alkyl groups.

2. The lubricating oil composition according to claim 1, characterized in that, Each R group is independently selected from methyl or ethyl groups, and the R0 group is selected from C4 to C5. 10 Straight-chain or branched alkylene groups, with R' group at C4-C5. 10 Straight-chain or branched alkyl groups (preferably 2-ethylhexyl).

3. The lubricating oil composition according to claim 1, characterized in that, In the bistertiary amine phosphate amine salt, the molar ratio between the compound shown in formula (α) and the compound shown in formula (β) is 10 to 2000:

1.

4. The lubricating oil composition according to claim 1, characterized in that, The bis-tertiary amine phosphate amine salt is selected from any one of the following single compounds or a composition obtained by mixing these single compounds in any proportion:

5. The lubricating oil composition according to claim 1, characterized in that, The preparation method of the bis-tertiary amine phosphate amine salt includes: React the compound shown in formula (X) with the compound shown in formula (Y) and collect the products; Each R group is independently selected from C1 to C4 straight-chain or branched alkyl groups, and the R0 group is selected from C2 to C4 straight-chain or branched alkyl groups. 10 Straight-chain or branched alkylene groups, with R' groups at C1-C1. 12 Straight-chain or branched alkyl groups.

6. The lubricating oil composition according to claim 5, characterized in that, Each R group is independently selected from methyl or ethyl groups, and the R0 group is selected from C4 to C5. 10 Straight-chain or branched alkylene groups, with R' group at C4-C5. 10 Straight-chain or branched alkyl groups (preferably 2-ethylhexyl).

7. The lubricating oil composition according to claim 5, characterized in that, The molar ratio between the compound shown in formula (X) and the compound shown in formula (Y) is 1:0.5 to 5; the reaction temperature between the compound shown in formula (X) and the compound shown in formula (Y) is 60 to 120°C; and the reaction time between the compound shown in formula (X) and the compound shown in formula (Y) is 5 to 20 hours.

8. The lubricating oil composition according to claim 5, characterized in that, The bis-tertiary amine phosphate amine salt accounts for 0.1% to 10% of the total mass of the lubricating oil composition; the dispersant accounts for 1% to 15% of the total mass of the lubricating oil composition; the detergent accounts for 0.5% to 10% of the total mass of the lubricating oil composition; the dialkyl dithiophosphate zinc accounts for 0.05% to 3% of the total mass of the lubricating oil composition; the antioxidant accounts for 0.1% to 6% of the total mass of the lubricating oil composition; the friction modifier accounts for 0.02% to 3% of the total mass of the lubricating oil composition; the metal deactivator accounts for 0.02% to 3% of the total mass of the lubricating oil composition; the pour point depressant accounts for 0.1% to 3% of the total mass of the lubricating oil composition; the viscosity index improver accounts for 1% to 15% of the total mass of the lubricating oil composition; and the lubricating oil base oil constitutes the main component of the lubricating oil composition.

9. The lubricating oil composition according to any one of claims 1 to 8, characterized in that, The dispersant is selected from one or more of monoisobutylene succinimide, diisobutylene succinimide, polyisobutylene succinimide, high molecular weight polyisobutylene succinimide, boronized polyisobutylene succinimide, and polyisobutylene succinate; the detergent is selected from one or more of sulfonates, alkyl salicylates, and sulfurized alkylphenol salts; the alkyl group in the dialkyl dithiophosphate zinc is C2-C6. 12 The alkyl group; the antioxidant is selected from one or more of phenolic ester antioxidants, amine antioxidants, phenolic antioxidants, and thiophenolic ester antioxidants; the friction modifier is selected from oil-soluble organic molybdenum friction modifiers and / or ashless friction modifiers; the metal deactivator is selected from one or more of triazole derivatives, thiazole derivatives, and thiadiazole derivatives; the pour point depressant is selected from polyα-olefins, vinyl acetate copolymers, and alkyl groups with C8 to C96 alkyl groups. 18 The viscosity index improver is selected from one or more of the following: dialkyl fumarate, polyalkyl methacrylate, and alkyl naphthalene; the viscosity index improver is selected from one or more of the following: ethylene propylene copolymer, polymethyl methacrylate, polyalkyl methacrylate, styrene-acrylate copolymer, hydrogenated or partially hydrogenated styrene / isoprene copolymer, hydrogenated or partially hydrogenated styrene / butadiene copolymer, and hydrogenated or partially hydrogenated isoprene / butadiene copolymer; the lubricating oil base oil is selected from one or more of the following: API Group I, Group II, Group III, Group IV, and Group V base oils.

10. A method for preparing a lubricating oil composition according to any one of claims 1 to 9, comprising the step of mixing the components therein.

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