Lubricating oil composition and preparation method thereof

Abstract

The invention provides a lubricating oil composition and a preparation method thereof. The lubricating oil composition of the present invention comprises: (A) an alkyl phosphonate compound; (B) a thio phenolic ester type antioxidant; (C) a polyisobutylene succinimide ashless dispersant; (D) sulfurized olefin; (E) a dialkyl dithiocarbamic acid salt and / or a dialkyl dithiocarbamic acid ester; (F) an oil-soluble organic molybdenum friction modifier; (G) a metal corrosion inhibitor; (H) a pour point depressant; (I) a major amount of a lubricating base oil. The lubricating oil composition disclosed by the invention has excellent high-temperature oxidation resistance, extreme pressure wear resistance, corrosion resistance and storage stability, and is suitable for a wind power transmission system.

Description

Technical Field

[0001] This invention relates to a lubricating oil, and more particularly to a lubricating oil composition with excellent extreme pressure anti-wear properties and its preparation method. Background Technology

[0002] With the increasing demand for renewable energy driven by low-carbon and environmental protection needs, wind power, as a clean and sustainable energy source, is rapidly emerging and being widely applied globally. In my country, wind farms are mostly concentrated in the frigid northeast, northwest, and coastal areas, where winters are extremely harsh, with strong winds, large temperature differences, and high levels of salt spray. The gears and bearings in the main gearbox of wind turbine generators share the same lubrication system, making them prone to surface wear and micropitting. Micropitting can cause surface cracking, forming micro-points with a diameter of less than 10 micrometers. Under the combined action of these micro-points, the surface cracks are further expanded. A single micro-point can range in size from 5 to 20 micrometers, with a maximum depth of 10 micrometers. Although these micro-points appear small, they can reduce the meshing of the gear teeth, and in severe cases, lead to gear breakage.

[0003] Therefore, improving the extreme pressure anti-wear properties of lubricating oil compositions for wind power transmission systems and preventing micropitting has been a hot research topic for researchers in this field. Developing lubricating oil compositions for wind power transmission systems with excellent extreme pressure anti-wear properties, corrosion resistance, thermal oxidation stability, and low-temperature fluidity is a research objective in this field. Summary of the Invention

[0004] This invention proposes a lubricating oil composition and its preparation method.

[0005] The lubricating oil composition of the present invention comprises:

[0006] (A) Alkylphosphonate compounds, comprising 0.1% to 15% (preferably 0.3% to 5%) of the total mass of the composition;

[0007] (B) Thiophenol ester type antioxidant, accounting for 0.1% to 10% (preferably 0.1% to 5%) of the total mass of the composition;

[0008] (C) Polyisobutylene succinimide ashless dispersant, accounting for 0.1% to 15% (preferably 0.5% to 10%) of the total mass of the composition;

[0009] (D) Sulfated olefins, comprising 0.2% to 10% (preferably 0.5% to 8%) of the total mass of the composition;

[0010] (E) Dialkyl dithiocarbamate and / or dialkyl dithiocarbamate, comprising 0.1% to 5% (preferably 0.2% to 3%) of the total mass of the composition;

[0011] (F) Oil-soluble organic molybdenum friction modifier, comprising 0.02% to 5% (preferably 0.05% to 3%) of the total mass of the composition;

[0012] (G) Metal corrosion inhibitor, comprising 0.01% to 3% (preferably 0.02% to 1%) of the total mass of the composition;

[0013] (H) A pour point depressant, comprising 0.02% to 5% (preferably 0.1% to 3%) of the total mass of the composition;

[0014] (I) Main component of lubricating base oil;

[0015] The structure of the alkylphosphonate compounds is shown in formula (α):

[0016]

[0017] The R1 group is selected from C1 to C1. 20 Straight-chain or branched alkyl groups, C2-C 30 The alkenyl group is preferably selected from C1 to C2. 10 The straight-chain or branched alkyl group, for example, can be selected from methyl, ethyl, or propyl; the R2 group is selected from C2 to C3. 20 Straight-chain or branched alkyl groups, with a total carbon number of C7 to C8. 30 Alkylphenyl groups, preferably C2-C3 10 Straight-chain or branched alkyl groups, with a total carbon number of C7 to C8. 20 Alkylphenyl groups, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, 1-hexyl, 1-heptyl, 1-octyl, isooctyl(2-ethylhexyl), 1-nonyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-hexylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-sec-octylphenyl, 4-nonylphenyl, 4-decylphenyl, 4-dodecylphenyl, 4-tetradecylphenyl, 4-hexadecylphenyl, 4-octadecylphenyl, and 4-eicosylphenyl.

[0018] According to the present invention, the method for preparing the alkylphosphonate compound comprises: reacting an alkylphosphonic acid with an alkyl alcohol and / or an alkylphenol in the presence of an imine catalyst, and collecting the product.

[0019] According to the present invention, the structure of the alkylphosphonic acid can be as follows: The R1 group is selected from C1 to C1. 20 Straight-chain or branched alkyl groups, C2-C 30 The alkenyl group is preferably selected from C1 to C2. 10 The straight-chain or branched alkyl group, for example, can be selected from methyl, ethyl, or propyl.

[0020] According to the present invention, the structure of the alkyl alcohol and / or alkylphenol can be R 2 OH, wherein the R2 group can be selected from C2 to C3. 20 Straight-chain or branched alkyl groups, with a total carbon number of C7 to C8. 30 Alkylphenyl groups, preferably C2-C3 10 Straight-chain or branched alkyl groups, with a total carbon number of C7 to C8. 20 Alkylphenyl groups, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, 1-hexyl, 1-heptyl, 1-octyl, isooctyl(2-ethylhexyl), 1-nonyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-hexylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-sec-octylphenyl, 4-nonylphenyl, 4-decylphenyl, 4-dodecylphenyl, 4-tetradecylphenyl, 4-hexadecylphenyl, 4-octadecylphenyl, and 4-eicosylphenyl.

[0021] According to the present invention, optionally, the R2OH may be selected from one or more of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, 1-hexanol, 1-heptanol, 1-octanol, isooctanol, 1-nonanol, 1-decanol, 1-dodecylol, 1-tetradecylol, 1-hexadecylol, 1-octadecylol, 4-methylphenol, 4-ethylphenol, 4-propylphenol, 4-butylphenol, 4-pentylphenol, 4-hexylphenol, 4-heptylphenol, 4-octylphenol, 4-sec-octylphenol, 4-nonylphenol, 4-decylphenol, 4-dodecylphenol, 4-tetradecylphenol, 4-hexadecylphenol, 4-octadecylphenol, and 4-eicosylphenol.

[0022] According to the present invention, the imine catalyst is preferably a carbodiimine compound with the structure R'-N=C=N-R', wherein each R' group is independently selected from C5 to C6. 10 cycloalkyl, C2-C 10 The linear or branched alkyl group may be selected, for example, one or more of dicyclohexylcarbodiimide, diisopropylcarbodiimide and diisobutylcarbodiimide.

[0023] According to the present invention, the molar ratio between the alkylphosphonic acid and the alkyl alcohol and / or alkylphenol can be 1:1 to 3, preferably 1:2 to 2.2.

[0024] According to the present invention, the molar ratio between the imine catalyst and the alkylphosphonic acid can be 1 to 3:1, preferably 1.05 to 2.1:1.

[0025] According to the present invention, the reaction temperature of the alkylphosphonic acid with alkyl alcohol and / or alkylphenol can be -5 to 30°C, for example, it can be carried out at room temperature.

[0026] According to the present invention, the reaction time of the alkylphosphonic acid with alkyl alcohol and / or alkylphenol can be 10-40 h, preferably 15-30 h.

[0027] According to the present invention, the reaction between the alkylphosphonic acid and alkyl alcohols and / or alkylphenols is preferably carried out in the presence of an oxygen-containing heterocyclic solvent, which may be one or more of 1,4-dioxane, tetrahydrofuran, furan, and benzofuran, preferably 1,4-dioxane. The weight ratio of the oxygen-containing heterocyclic solvent to the alkylphosphonic acid may be 5 to 50:1. The oxygen-containing heterocyclic solvent can be removed after the reaction is complete by conventional methods in the art, such as distillation, rectification, etc.

[0028] According to the present invention, the reaction between the alkylphosphonic acid and alkyl alcohol and / or alkylphenol is preferably carried out under the protection of an inert gas, such as nitrogen or argon.

[0029] According to the present invention, after the reaction between the alkylphosphonic acid and the alkyl alcohol and / or alkylphenol is completed, a purification process can be performed. The purification process includes one or more of the following methods: filtration, alkaline washing, extraction, salt washing, water washing, drying, and distillation. In the alkaline washing operation, sodium bicarbonate solution, sodium hydroxide solution, potassium hydroxide solution, etc., can be used. In the extraction operation, ester or ether solvents can be used for extraction and separation, such as ethyl acetate, petroleum ether, etc. In the salt washing operation, sodium chloride solution, potassium chloride solution, etc., can be used.

[0030] The reaction equation for the preparation of the alkylphosphonate compounds of the present invention is shown below:

[0031]

[0032] The preparation method of the alkylphosphonate compounds described in this invention has advantages over traditional synthesis methods, such as mild reaction conditions, low toxicity, few by-products, high conversion rate, strong reaction selectivity, high product purity, environmental friendliness, and energy saving.

[0033] The alkylphosphonate compounds prepared according to the method of the present invention have excellent extreme pressure, anti-wear, and friction-reducing properties, and can be used as extreme pressure anti-wear agents for lubricating greases.

[0034] According to the present invention, the thiophenol ester type antioxidant can be one or more of 2,2'-thiobis[methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thiobis[ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 2,2'-thiobis[propyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], preferably 2,2'-thiobis[ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Common commercial brands include T535 from Xinxiang Ruifeng New Materials Co., Ltd., IRGANOX L115 from BASF AG, Germany, and antioxidant 1035 from Sichuan Yongye Chemical Co., Ltd.

[0035] According to the present invention, the number average molecular weight of the polyisobutylene (PIB) portion in the polyisobutylene succinimide ashless dispersant is 800-4000, preferably 900-3000. Suitable materials include T151 and T161 from Wuxi Southern Additives Company, T161 from Suzhou Special Oil Products Factory, T161A and T161B from Jinzhou Petrochemical Branch Additives Plant, LZL157 from Lubrizol Lanzhou Refinery Additives Co., Ltd., LZ6418 and LZ6420 from Lubrizol, and Hitec646 from Afton.

[0036] According to the present invention, the sulfurized olefin may be selected from isobutylene sulfide and / or diisobutylene sulfide, with isobutylene sulfide being preferred. The commercial brands of the sulfurized olefin include isobutylene sulfide T321 and diisobutylene sulfide T321D from Shenyang Guangda Chemical Co., Ltd.

[0037] According to the present invention, the dialkyl dithiocarbamate and / or dialkyl dithiocarbamate can be selected from Vanlube AZ and Vanlube 7723 of Vanderbilt, dialkyl dithiocarbamate T323 of Changsha Wangcheng Additives Co., Ltd., etc., preferably a mixture of dialkyl dithiocarbamate and dialkyl dithiocarbamate, and the mass ratio between the two is preferably 1:0.5 to 2.

[0038] According to the present invention, the oil-soluble organic molybdenum friction modifier may be selected from one or more of the following: molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithiophosphate oxydiphosphite, molybdenum dialkyl dithiocarbamate, molybdenum xanthate, molybdenum thioxanthate, trinuclear molybdenum-sulfur complex, molybdenum amine complex, and molybdate ester. Common commercial brands include POUPC 1001, 1002, and 1003 produced by Pacific United (Beijing) Petrochemical Co., Ltd.; MolyVan L, 822, 855, and 3000 produced by Vanderbilt Corporation of the United States; and 515, 525, and 710 produced by Asahi Denka Co., Ltd. of Japan.

[0039] According to the present invention, the metal corrosion inhibitor can be selected from one or more of triazole derivatives, thiazole derivatives, and thiadiazole derivatives. For example, it can be selected from one or more of benzotriazole, 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. Common commercial brands include T551, T561, and T706 produced by Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.

[0040] According to the present invention, the pour point depressant may be selected from one or more of fumarate, vinyl acetate copolymer, polymethyl methacrylate and polyalphaolefin, with fumarate being preferred. Common commercial brands include Evonik's 1-248, Jinzhou Shengda Lubricating Additives' T803, and Infineum's VX385, etc.

[0041] According to the present invention, the lubricating base oil is preferably a synthetic lubricating oil. The synthetic lubricating oil may be selected from one or more of polyalphaolefin synthetic oil, alkylbenzene and its derivatives, ester oil and Fischer-Tropsch synthetic hydrocarbon oil, with polyalphaolefin synthetic oil being preferred. Common commercial brands include PAO-4, PAO-6, PAO-8, PAO-10, PAO-40, etc.

[0042] 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 preferably between 40°C and 90°C, and the mixing time is preferably between 1 and 6 hours.

[0043] The lubricating oil composition of the present invention is suitable for wind power transmission systems.

[0044] The lubricating oil composition of the present invention has excellent high-temperature oxidation resistance, extreme pressure anti-wear properties, corrosion resistance and storage stability. Attached Figure Description

[0045] Figure 1 The GCMS chromatogram of product 1 in Example 1;

[0046] Figure 2 The GCMS mass spectrum of product 1 in Example 1;

[0047] Figure 3 The GCMS chromatogram of product 2 in Example 2;

[0048] Figure 4 The GCMS mass spectrum of product 2 in Example 2;

[0049] Figure 5The GCMS chromatogram of the comparative product D1 in Comparative Example 1;

[0050] Figure 6 The GCMS chromatogram of the comparative product D2 in Comparative Example 2;

[0051] Figure 7 The image shows the GCMS chromatogram of the comparative product D3 in Comparative Example 3. Detailed Implementation

[0052] The present invention will be explained and described below through specific embodiments, but these do not constitute a limitation on the present invention.

[0053] The main raw materials used and their sources:

[0054] Methylphosphonic acid (98%, Chongqing Zhangbang Pharmaceutical Technology Co., Ltd.), 2-ethylhexanol (99%, Aladdin Industrial Corporation), 4-dimethylaminopyridine (99%, TCI (Shanghai) Chemical Industry Development Co., Ltd.), triethylamine (99%, Thermo Scientific), dicyclohexylcarbodiimide (98%, Beijing Inokai Technology Co., Ltd.), 1,4-dioxane (99%, Beijing Inokai Technology Co., Ltd.), ethyl acetate (99%, Beijing Inokai Technology Co., Ltd.), anhydrous sodium sulfate (98%, Shanghai Maclean Biochemical Technology Co., Ltd.), sodium bicarbonate (98%, Shanghai Maclean Biochemical Technology Co., Ltd.), sodium chloride (98%, Shanghai Maclean Biochemical Technology Co., Ltd.).

[0055] Example 1

[0056] The main raw materials include: methylphosphonic acid, p-methylphenol, dicyclohexylcarbodiimide, 1,4-dioxane, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0057] The reaction steps for preparing the alkylphosphonate compounds of the present invention are as follows:

[0058] Methylphosphonic acid (2 g, 20.83 mmol) was dispersed in 40 mL of 1,4-dioxane and added to a reaction flask. Under N2 protection, the mixture was stirred, and dicyclohexylcarbodiimide (9.4553 g, 45.83 mmol) was added. The mixture was stirred for 30 min, and then p-methylphenol (4.51 g, 41.66 mmol) was added. The mixture was then stirred at room temperature for 24 h. During the reaction, a white solid (dicyclohexylurea) continuously precipitated from the clear reaction solution. After the reaction was complete, the white solid was removed by filtration. The reaction solution was washed with saturated sodium bicarbonate solution, extracted with ethyl acetate, and the organic phase was collected. The organic phase was washed with saturated brine and dried with anhydrous sodium sulfate. The solvent and residual p-methylphenol were removed by filtration and rotary evaporation to obtain product 1, a pale yellow liquid.

[0059] Characterization of Product 1

[0060] Product 1 was determined by gas chromatography-mass spectrometry (GC-MS), see [see details]. Figure 1 , 2 .

[0061] The GCMS measurement conditions are as follows:

[0062] Experimental instruments: Gas chromatography-mass spectrometry system, Agilent 7890-5975, chromatographic column HP-5MS (30m×250μm×0.25μm).

[0063] Experimental conditions: injection volume 0.5 μL, pressure 126.44 kPa, total flow rate 79.5 mL / min, split ratio 50:1, split flow rate 75 mL / min, column 1 (pressure 126.44 kPa, flow rate 1.5 mL / min, average flow rate 30.794 cm / s), column 2 (pressure 26.20 kPa, flow rate 5.0454 mL / min, average flow rate 255.78 cm / s).

[0064] Figure 1 The GCMS chromatogram of product 1 shows that the chromatographic absorption peak with a retention time of 36.520 min is the chromatographic absorption peak of xylenol methylphosphonate. Figure 2 The image shows the GCMS mass spectrum of product 1. The spectrum displays the fragment ion characteristic peaks of xylenol methylphosphonate, with the absorption peak at 276.1 being the absorption peak of xylenol methylphosphonate.

[0065] According to the chromatographic peak area normalization method, the structure of product 1 is methylphosphonic acid xylenol ester as shown in the following formula, with a purity of 99.215%.

[0066]

[0067] Example 2

[0068] The main raw materials include: methylphosphonic acid, 2-ethylhexanol, dicyclohexylcarbodiimide, 1,4-dioxane, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0069] The reaction steps for preparing the alkylphosphonate compounds of the present invention are as follows:

[0070] Methylphosphonic acid (2 g, 20.83 mmol) was dispersed in 30 mL of 1,4-dioxane and added to a reaction flask. Under N2 protection, the mixture was stirred, and dicyclohexylcarbodiimide (9.4553 g, 45.83 mmol) was added. The mixture was stirred for 30 min, and then 2-ethylhexanol (5.6963 g, 43.74 mmol) was added. The reaction was continued at room temperature with stirring for 24 h. During the reaction, a white solid (dicyclohexylurea) continuously precipitated from the clear reaction solution. After the reaction was complete, the white solid was removed by filtration. The reaction solution was washed with saturated sodium bicarbonate solution, extracted with ethyl acetate, and the organic phase was collected. The organic phase was washed with saturated brine and dried with anhydrous sodium sulfate. The solvent and residual 2-ethylhexanol were removed by filtration and rotary evaporation to obtain product 2, a pale yellow liquid.

[0071] Characterization of Product 2

[0072] Product 2 was determined by gas chromatography-mass spectrometry (GC-MS), see [see details]. Figure 3 , 4 .

[0073] The GCMS measurement conditions were the same as in Example 1.

[0074] Figure 3 The GCMS chromatogram of product 2 shows the following peaks: retention time 35.034 min for di(2-ethylhexyl) methylphosphonic acid; retention time 35.807 min for dicyclohexylurea; retention time 29.432 min for dicyclohexylcarbodiimide; and retention time 12.070 min for 2-ethylhexanol. Figure 4 The image shows the GCMS mass spectrum of product 2, where the absorption peak at 321.2 is the characteristic peak of the fragment ion of di(2-ethylhexyl) methylphosphonic acid ester.

[0075] According to the chromatographic peak area normalization method, the structural composition of product 2 is as shown in the following formula, which includes: 87.530% di(2-ethylhexyl) methylphosphonic acid, 3.069% dicyclohexylurea, 5.842% dicyclohexylcarbodiimide, and 3.559% 2-ethylhexanol.

[0076]

[0077] Comparative Example 1

[0078] The main raw materials include: methylphosphonodichloro, p-methylphenol, triethylamine, acetonitrile, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0079] The comparative reaction steps for preparing phosphonate compounds are as follows:

[0080] Phenol (4.7 g, 0.025 mol) and triethylamine (5.06 g, 0.025 mol) were dissolved in anhydrous acetonitrile (60 ml). Then, 10 ml of acetonitrile solution containing dissolved methylphosphonodichloro (2.66 g, 0.02 mol) was added. The mixture was stirred at 80 °C for 2 hours. The reaction was stopped, and the reaction solution was washed with saturated sodium bicarbonate solution. The mixture was extracted with ethyl acetate, and the organic phase was collected. The organic phase was washed with saturated brine and dried with anhydrous sodium sulfate. The solvent and residual p-methylphenol were removed by filtration and rotary evaporation to obtain the comparative product D1, a deep yellow liquid.

[0081] Characterization of product D1

[0082] The comparative product D1 was determined by gas chromatography-mass spectrometry (GC-MS), see attached figure. Figure 5 .

[0083] The GCMS measurement conditions were the same as in Example 1.

[0084] Figure 5 To compare the GCMS chromatograms of product D1, the chromatographic absorption peak with a retention time of 36.446 min is the chromatographic absorption peak of xylenol methylphosphonate; the chromatographic absorption peak with a retention time of 23.706 min is the chromatographic absorption peak of methylphosphonamide; and the chromatographic absorption peak with a retention time of 14.238 min is the chromatographic absorption peak of p-cresol.

[0085] According to the chromatographic peak area normalization method, the composition of the comparative product D1 is as follows: 70.958% xylenol methylphosphonate, 10.535% methylphosphonamide, and 18.507% p-cresol.

[0086]

[0087] Comparative Example 2

[0088] The main raw materials include: methylphosphonodichloro, p-methylphenol, acetonitrile, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0089] The comparative reaction steps for preparing phosphonate compounds are as follows:

[0090] Phenol (4.7 g, 0.025 mol) was dissolved in anhydrous acetonitrile (60 ml), and then added to 10 ml of acetonitrile solution containing dissolved methylphosphonodichloro (2.66 g, 0.02 mol). The mixture was stirred at 80 °C for 2 hours, and the reaction was stopped. The reaction solution was washed with saturated sodium bicarbonate solution, extracted with ethyl acetate, and the organic phase was collected. The organic phase was washed with saturated brine and dried with anhydrous sodium sulfate. The solvent and residual p-methylphenol were removed by filtration and rotary evaporation to obtain the comparative product D2, which is a deep yellow liquid.

[0091] Characterization of product D2

[0092] The comparative product D2 was determined by gas chromatography-mass spectrometry (GC-MS), see [see figure]. Figure 6 .

[0093] The GCMS measurement conditions were the same as in Example 1.

[0094] Figure 6 To compare the GCMS chromatograms of product D2, the chromatographic absorption peak with a retention time of 36.558 min is the chromatographic absorption peak of xylenol methylphosphonate; the chromatographic absorption peak with a retention time of 11.299 min is the chromatographic absorption peak of p-methylchlorobenzene; and the chromatographic absorption peak with a retention time of 13.941 min is the chromatographic absorption peak of p-cresol.

[0095] According to the chromatographic peak area normalization method, the composition of the comparative product D2 is as follows: 42.307% xylenol methylphosphonate, 48.694% p-cresol, and 8.999% p-methylchlorobenzene.

[0096]

[0097] Comparative Example 3

[0098] The main raw materials include: methylphosphonodichloro, p-methylphenol, acetonitrile, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0099] The comparative reaction steps for preparing phosphonate compounds are as follows:

[0100] Phenol (4.7 g, 0.025 mol) was dissolved in anhydrous acetonitrile (60 ml), and then added to 10 ml of acetonitrile solution containing dissolved methylphosphonodichloro (2.66 g, 0.02 mol). The mixture was stirred at room temperature for 24 hours, and the reaction was stopped. The reaction solution was washed with saturated sodium bicarbonate solution, extracted with ethyl acetate, and the organic phase was collected. The organic phase was washed with saturated brine and dried with anhydrous sodium sulfate. The solvent and residual p-methylphenol were removed by filtration and rotary evaporation to obtain the comparative product D3, which is a deep yellow liquid.

[0101] Characterization of product D3

[0102] The comparative product D3 was determined by gas chromatography-mass spectrometry (GC-MS), see [see details]. Figure 7 .

[0103] The GCMS measurement conditions were the same as in Example 1.

[0104] Figure 7 To compare the GCMS chromatograms of product D3, the chromatographic absorption peak with a retention time of 36.397 min is the chromatographic absorption peak of xylenol methylphosphonate; the chromatographic absorption peak with a retention time of 13.648 min is the chromatographic absorption peak of p-cresol.

[0105] According to the chromatographic peak area normalization method, the composition of the comparative product D3 is as follows: 35.421% xylenol methylphosphonate and 64.579% p-cresol.

[0106]

[0107] Comparative Examples 1, 2, and 3 represent existing methods for synthesizing alkyl phosphonates. The methylphosphonyl dichloride used in these methods is a precursor chemical for toxic substances and is highly toxic. Compared to the alkyl phosphonates used in Examples 1 and 2, these methods require stricter control measures and also pose adverse effects on human health and the environment. Comparative Example 1 involved the addition of triethylamine, resulting in the formation of the byproduct methylphosphonamide, which affected the reaction yield. Comparative Example 2 generated HCl waste gas, causing corrosion of the reaction pipeline, and also produced the byproduct 4-methoxytoluene, further impacting the yield. Comparative Example 3 also generated HCl waste gas, causing corrosion of the reaction pipeline, and exhibited a very low conversion rate at room temperature. The method for preparing alkyl phosphonates proposed in this invention can be carried out at room temperature, and the required raw material, alkyl phosphonates, is simple and readily available. Furthermore, it offers advantages such as high conversion rate, strong reaction selectivity, high product purity, and a green, environmentally friendly, and energy-saving process.

[0108] Examples and comparative examples of lubricating oil compositions

[0109] According to the formulation composition in Table 1, the lubricating oil compositions in Examples I-1 to I-6 and Comparative Examples DI-1 to DI-5 were prepared by stirring at 50°C for 4 hours. TCP (Tianmen Hengchang Chemical Co., Ltd.) and T304 (Zibo Huihua Chemical Co., Ltd.) were used as comparative agents.

[0110] Table 1

[0111]

[0112] Storage stability test, PDSC test, four-ball extreme pressure bearing test, four-ball friction test and copper strip corrosion test were conducted on the examples and comparative examples of the lubricating oil compositions, respectively.

[0113] The PDSC test is a differential scanning calorimetry test performed under pressure. The testing instrument is a TA5000 DSC instrument from TA Instruments, USA. The test conditions are: oxygen pressure 3.5 MPa and oxygen flow rate 100 mL / min.

[0114] The load-bearing and anti-wear properties were evaluated using a four-ball testing machine. The load-bearing performance test was conducted in accordance with the GB / T3142-2019 standard. The oil was subjected to a four-ball friction test at a load of 40 kg, a time of 1 h, and an oil temperature of 75 °C.

[0115] The copper sheet corrosion test involves immersing a polished copper sheet in oil at 100°C for 6 hours. After the test, the copper sheet is removed, and the corrosion level is determined based on its color. The best level is 1a, and the worst level is 4C.

[0116] The test results of the above experiment are shown in Table 2.

[0117] Table 2

[0118]

Claims

1. A lubricating oil composition, comprising: (A) Alkylphosphonate compounds, comprising 0.1% to 15% (preferably 0.3% to 5%) of the total mass of the composition; (B) Thiophenol ester type antioxidant, accounting for 0.1% to 10% (preferably 0.1% to 5%) of the total mass of the composition; (C) Polyisobutylene succinimide ashless dispersant, accounting for 0.1% to 15% (preferably 0.5% to 10%) of the total mass of the composition; (D) Sulfated olefins, comprising 0.2% to 10% (preferably 0.5% to 8%) of the total mass of the composition; (E) Dialkyl dithiocarbamate and / or dialkyl dithiocarbamate, comprising 0.1% to 5% (preferably 0.2% to 3%) of the total mass of the composition; (F) Oil-soluble organic molybdenum friction modifier, comprising 0.02% to 5% (preferably 0.05% to 3%) of the total mass of the composition; (G) Metal corrosion inhibitor, comprising 0.01% to 3% (preferably 0.02% to 1%) of the total mass of the composition; (H) A pour point depressant, comprising 0.02% to 5% (preferably 0.1% to 3%) of the total mass of the composition; (I) Main component of lubricating base oil; The structure of the alkylphosphonate compounds is shown in formula (α): The R1 group is selected from C1 to C1. 20 Straight-chain or branched alkyl groups, C2-C 30 alkenyl groups (preferably selected from C1 to C2) 10 (straight-chain or branched alkyl groups); R2 group is selected from C2 to C3. 20 Straight-chain or branched alkyl groups, with a total carbon number of C7 to C8. 30 Alkylphenyl (preferably C2-C4) 10 Straight-chain or branched alkyl groups, with a total carbon number of C7 to C8. 20 Alkylphenyl).

2. The lubricating oil composition according to claim 1, characterized in that, The alkylphosphonate compounds The preparation method of the product includes: reacting alkylphosphonic acid with alkyl alcohol and / or alkylphenol in the presence of an imine catalyst, and collecting the product.

3. The lubricating oil composition according to claim 2, characterized in that, The structure of the alkylphosphonic acid is as follows: The R1 group is selected from C1 to C1. 20 Straight-chain or branched alkyl groups, C2-C 30 alkenyl groups (preferably selected from C1 to C2) 10 (linear or branched alkyl groups).

4. The lubricating oil composition according to claim 2, characterized in that, The alkyl alcohols and / or alkylphenols described herein have the structure R2OH, wherein the R2 group is selected from C2 to C3. 20 Straight-chain or branched alkyl groups, with a total carbon number of C7 to C8. 30 Alkylphenyl.

5. The lubricating oil composition according to claim 2, characterized in that, The imine catalyst is a carbodiimide compound with the structure R'-N=C=N-R', wherein each R' group is independently selected from C5 to C6. 10 cycloalkyl, C2-C 10 Straight-chain or branched alkyl groups (the carbodiimide compounds are preferably selected from one or more of dicyclohexylcarbodiimide, diisopropylcarbodiimide and diisobutylcarbodiimide).

6. The lubricating oil composition according to claim 2, characterized in that, The molar ratio between the alkylphosphonic acid and the alkyl alcohol and / or alkylphenol is 1:1 to 3 (preferably 1:2 to 2.2); the molar ratio between the imine catalyst and the alkylphosphonic acid is 1 to 3:1 (preferably 1.05 to 2.1:1).

7. The lubricating oil composition according to claim 2, characterized in that, The reaction temperature between the alkylphosphonic acid and alkyl alcohol and / or alkylphenol is -5 to 30°C; the reaction time between the alkylphosphonic acid and alkyl alcohol and / or alkylphenol is 10 to 40 hours.

8. The lubricating oil composition according to claim 2, characterized in that, The reaction between the alkylphosphonic acid and alkyl alcohol and / or alkylphenol is carried out in the presence of an oxygen-containing heterocyclic solvent (preferably selected from one or more of 1,4-dioxane, tetrahydrofuran, furan and benzofuran).

9. The lubricating oil composition according to any one of claims 1 to 8, characterized in that, The thiophenol ester type antioxidant is selected from one or more of 2,2'-thiobis[methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thiobis[ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2,2'-thiobis[propyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The polyisobutylene succinimide ashless dispersant has a number average molecular weight of 800-4000 for the polyisobutylene (PIB) portion. The sulfurized olefin is selected from sulfurized isobutylene and / or sulfurized diisobutylene. The dialkyl dithiocarbamate and / or dialkyl dithiocarbamate are selected from dialkyl... The mixture of dithiocarbamate and dialkyl dithiocarbamate, wherein the mass ratio of the two is 1:0.5-2; the oil-soluble organic molybdenum friction modifier is 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; the metal corrosion inhibitor is selected from one or more of triazole derivatives, thiazole derivatives and thiadiazole derivatives; the pour point depressant is selected from one or more of fumarate, vinyl acetate copolymer, polymethyl methacrylate and polyα-olefin; the lubricating base oil is selected from synthetic lubricating oil.

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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