Gas engine lubricating oil composition and preparation method thereof

Abstract

The invention provides a gas engine lubricating oil composition and a preparation method thereof. The gas engine lubricating oil composition of the present invention comprises: (A) an alkyl phosphate compound; (B) alkylated diphenylamine; (C) a polyisobutylene succinic acid pentaerythritol ester dispersing agent; (D) a salicylate and / or sulfonate; (E) zinc dialkyl dithiophosphate; (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 gas engine lubricating oil composition disclosed by the invention has excellent high-temperature oxidation resistance, cleaning performance, extreme pressure anti-wear performance and anti-corrosion performance.

Description

Technical Field

[0001] This invention relates to a lubricating oil composition, and more particularly to a gas engine lubricating oil composition and its preparation method that have excellent high-temperature oxidation resistance, detergency, extreme pressure anti-wear properties and rust prevention properties. Background Technology

[0002] Compressed natural gas (CNG) is gaining increasing international attention due to its low emissions, low cost, and efficient fuel resource allocation, driving the development of CNG and CNG vehicles, and its technology is maturing. CNG / diesel dual-fuel vehicles converted from gasoline and diesel vehicles are widely welcomed in large and medium-sized cities, with a bright future. However, these vehicles have experienced problems such as excessive carbon buildup, sludge buildup, shortened oil change intervals, premature engine wear, and reduced overhaul mileage after using the original diesel engine oil. Developing CNG / diesel engine lubricants that reduce wear and improve anti-wear performance has become a hot research topic in the industry. CNG / diesel engines operate at high combustion chamber and exhaust temperatures, requiring lubricants with strong high-temperature oxidation resistance. Furthermore, high-ash additives easily form hard deposits on engine component surfaces, leading to increased carbon buildup and engine damage. Therefore, developing CNG / diesel engine oils with outstanding anti-wear properties, strong oxidation resistance, and low ash content is the future trend. Summary of the Invention

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

[0004] The gas engine lubricating oil composition of the present invention comprises:

[0005] (A) Alkyl phosphate compounds, comprising 0.1% to 15% (preferably 0.5% to 5%) of the total mass of the composition;

[0006] (B) Alkylated diphenylamine, comprising 0.1% to 10% (preferably 0.5% to 5%) of the total mass of the composition;

[0007] (C) Polyisobutylene succinate pentaerythritol dispersant, accounting for 1% to 15% (preferably 3% to 10%) of the total mass of the composition;

[0008] (D) Salicylate and / or sulfonate, comprising 0.2% to 10% (preferably 0.5% to 8%) of the total mass of the composition;

[0009] (E) Zinc dialkyl dithiophosphate, comprising 0.1% to 5% (preferably 0.2% to 3%) of the total mass of the composition;

[0010] (F) Oil-soluble organic molybdenum friction modifier, comprising 0.02% to 5% (preferably 0.1% to 3%) of the total mass of the composition;

[0011] (G) Metal corrosion inhibitor, comprising 0.01% to 3% (preferably 0.02% to 1%) of the total mass of the composition;

[0012] (H) A pour point depressant, comprising 0.02% to 5% (preferably 0.1% to 3%) of the total mass of the composition;

[0013] (I) Main component of lubricating base oil;

[0014] The structure of the alkyl phosphate compound is shown in formula (α):

[0015]

[0016] 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.

[0017] 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.

[0018] 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.

[0019] According to the present invention, the alkyl alcohol and / or alkylphenol may have the structure R2OH, wherein the R2 group may 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.

[0020] 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.

[0021] According to the present invention, the imine catalyst is preferably 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 The straight-chain or branched alkyl group may be selected, for example, one or more of dicyclohexylcarbodiimide, diisopropylcarbodiimide and diisobutylcarbodiimide.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] The reaction equation for the preparation of the alkylphosphonate compounds of the present invention is shown below:

[0030]

[0031] 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.

[0032] 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 oils.

[0033] According to the present invention, the alkyl group in the alkylated diphenylamine can be C2 to C3. 12Straight-chain or branched alkyl groups, preferably C4-C8 straight-chain or branched alkyl groups, can be selected from IRGANOX L-01 and IRGANOX L-57 produced by BASF, T534 produced by Beijing Xingpu Company, LZ5150A produced by Lubrizol Lanzhou Refinery Additives Co., Ltd., VANLUBE NA, VANLUBE 961 and dioctyl diphenylamine VANLUBE 81 produced by Vanderbilt, USA, and p,p' diisooctyl diphenylamine RC7001 produced by Rheinland Chemical Company, Germany, etc.

[0034] According to the present invention, the number average molecular weight of the polyisobutylene fraction in the polyisobutylene pentaerythritol succinate dispersant is 500-4000, preferably 700-2500, and Lubrizol's LZ936 can be selected.

[0035] According to the present invention, the salicylate and / or sulfonate can be selected from calcium salicylate and / or magnesium sulfonate, preferably a mixture of calcium salicylate with an alkalinity of (200-450) mgKOH / g and magnesium sulfonate with an alkalinity of (100-400) mgKOH / g, and the mass ratio between the two is preferably between 1:0.1 and 1. The calcium salicylate can be selected from T109 produced by Xinxiang Ruifeng New Materials Co., Ltd., or T109A, T109B, T109C, etc., produced by Wuxi Nanfang Additives Co., Ltd. The magnesium sulfonate can be selected from T107Mg produced by Wuxi Nanfang Additives Co., Ltd., or T107Mg produced by Xinxiang Ruifeng New Materials Co., Ltd.

[0036] According to the present invention, the alkyl group in the zinc dialkyl dithiophosphate is an alkyl group containing 2 to 12 carbon atoms, preferably an alkyl group containing 2 to 8 carbon atoms, and may be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, or 2-ethylhexyl. The zinc dialkyl dithiophosphate may be selected from T202 and T203 produced by Wuxi Southern Petroleum Additives Co., Ltd., primary alkyl group T202, primary alkyl group T203, primary and secondary alkyl group T204, and secondary alkyl group T205 produced by Jinzhou Petrochemical Branch Additives Plant, LZ1371 and LZ1375 produced by Lubrizol, C9417, C9425, and C9426 produced by Infineum, and Hitec7169 and Hitec1656 produced by Afton.

[0037] 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 oxydialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum xanthate, molybdenum thioxanthate, trinuclear molybdenum-sulfur complex, molybdenum amine complex, and molybdate oil-soluble organic molybdenum friction modifier. For example, it may be selected from MolyVan L, 822, 855, and 3000 produced by Vanderbilt Corporation of the United States; 515, 525, and 710 produced by Asahi Denka Co., Ltd. of Japan; and POUPC 1001, 1002, and 1003 produced by Pacific United (Beijing) Petrochemical Co., Ltd.

[0038] According to the present invention, the metal corrosion inhibitor may be selected from one or more of triazole derivatives, thiazole derivatives, and thiadiazole derivatives, including 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.

[0039] 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 Chemical Co., Ltd.'s T803, and Runyinglian's VX385, etc.

[0040] According to the present invention, the lubricating base oil can be selected from mineral oil and / or synthetic lubricating oil. The mineral oil can be one or more of API Group I, II, and III base oils, with common commercial brands including II-4 and II-6. The synthetic lubricating oil includes polymerized hydrocarbon oils, alkylbenzenes and their derivatives, ester oils, and Fischer-Tropsch synthetic hydrocarbon oils. Preferably, the lubricating base oil has a viscosity index greater than 80, a saturated hydrocarbon mass fraction greater than 90%, and a sulfur content mass fraction less than 0.03%.

[0041] The method for preparing the gas engine 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 hour and 6 hours.

[0042] The gas engine lubricating oil composition of the present invention has excellent high-temperature oxidation resistance, detergency, extreme pressure anti-wear properties and anti-rust properties. Attached Figure Description

[0043] Figure 1 The GCMS chromatogram of product 1 in Example 1;

[0044] Figure 2 The GCMS mass spectrum of product 1 in Example 1;

[0045] Figure 3 The GCMS chromatogram of product 2 in Example 2;

[0046] Figure 4 The GCMS mass spectrum of product 2 in Example 2;

[0047] Figure 5 The GCMS chromatogram of the comparative product D1 in Comparative Example 1;

[0048] Figure 6 The GCMS chromatogram of the comparative product D2 in Comparative Example 2;

[0049] Figure 7 The image shows the GCMS chromatogram of the comparative product D3 in Comparative Example 3. Detailed Implementation

[0050] The present invention will be explained and described below through specific embodiments, but these do not constitute a limitation on the present invention.

[0051] The main raw materials used and their sources:

[0052] 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 Inokay Technology Co., Ltd.), 1,4-Dioxane (99%, Beijing Inokay Technology Co., Ltd.), Ethyl acetate (99%, Beijing Inokay 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.), PAO 10 base oil (industrial grade, ExxonMobil).

[0053] Taking p-cresol as an example, the following is an example reaction equation for preparing the alkylphosphonate of the present invention:

[0054]

[0055] The alkyl phosphonates prepared by the above reaction can be used as lubricant additives.

[0056] Example 1

[0057] The main raw materials include: methylphosphonic acid, p-methylphenol, dicyclohexylcarbodiimide, 1,4-dioxane, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0058] The reaction steps for preparing the alkylphosphonate compounds of the present invention are as follows:

[0059] 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.

[0060] Characterization of Product 1

[0061] Product 1 was determined by gas chromatography-mass spectrometry (GC-MS), see [see details]. Figure 1 , 2 .

[0062] The GCMS measurement conditions are as follows:

[0063] Experimental instruments: Gas chromatography-mass spectrometry system, Agilent 7890-5975, chromatographic column HP-5MS (30m×250μm×0.25μm).

[0064] 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).

[0065] 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.

[0066] 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%.

[0067]

[0068] Example 2

[0069] The main raw materials include: methylphosphonic acid, 2-ethylhexanol, dicyclohexylcarbodiimide, 1,4-dioxane, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0070] The reaction steps for preparing the alkylphosphonate compounds of the present invention are as follows:

[0071] 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.

[0072] Characterization of Product 2

[0073] Product 2 was determined by gas chromatography-mass spectrometry (GC-MS), see [see details]. Figure 3 , 4 .

[0074] The GCMS measurement conditions were the same as in Example 1.

[0075] 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.

[0076] 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.

[0077]

[0078] Comparative Example 1

[0079] The main raw materials include: methylphosphonodichloro, p-methylphenol, triethylamine, acetonitrile, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0080] The comparative reaction steps for preparing phosphonate compounds are as follows:

[0081] 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.

[0082] Characterization of product D1

[0083] The comparative product D1 was determined by gas chromatography-mass spectrometry (GC-MS), see attached figure. Figure 5 .

[0084] The GCMS measurement conditions were the same as in Example 1.

[0085] 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.

[0086] 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.

[0087]

[0088] Comparative Example 2

[0089] The main raw materials include: methylphosphonodichloro, p-methylphenol, acetonitrile, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0090] The comparative reaction steps for preparing phosphonate compounds are as follows:

[0091] 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.

[0092] Characterization of product D2

[0093] The comparative product D2 was determined by gas chromatography-mass spectrometry (GC-MS), see [see details]. Figure 6 .

[0094] The GCMS measurement conditions were the same as in Example 1.

[0095] 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.

[0096] 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.

[0097]

[0098] Comparative Example 3

[0099] The main raw materials include: methylphosphonodichloro, p-methylphenol, acetonitrile, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0100] The comparative reaction steps for preparing phosphonate compounds are as follows:

[0101] 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.

[0102] Characterization of product D3

[0103] The comparative product D3 was determined by gas chromatography-mass spectrometry (GC-MS), see [see details]. Figure 7 .

[0104] The GCMS measurement conditions were the same as in Example 1.

[0105] 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.

[0106] 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.

[0107]

[0108] 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.

[0109] Examples and comparative examples of gas engine lubricating oil compositions

[0110] According to the formulation composition in Table 1, the gas engine lubricating oil compositions were prepared by stirring at 40°C for 2 hours to obtain Examples I-1 to I-6 and Comparative Examples DI-1 to DI-5. TCP (Tianmen Hengchang Chemical Co., Ltd.) and T304 (Zibo Huihua Chemical Co., Ltd.) were used as comparative agents.

[0111] The high-temperature oxidation resistance of the gas turbine engine lubricating oil compositions in the examples and comparative cases was tested using pressure differential scanning calorimetry (PDSC). The test results are expressed as the oxidation induction period (in minutes) of the test samples. The test conditions were: pressure 3.5 MPa and oxygen flow rate 100 mL / min. A longer oxidation induction period indicates better high-temperature oxidation resistance of the test sample.

[0112] The oxidation resistance of the gas turbine engine lubricant compositions in the examples and comparative cases was tested using the thin-layer oxygen absorption oxidation test (TFOUT). The test results are expressed as the oxidation induction period (in minutes) of the test samples. The TFOUT test conditions were: 160°C, IIIE catalyst, and oxygen pressure of 620 kPa. A longer oxidation induction period indicates better oxidation resistance of the test sample.

[0113] The detergency performance of gas turbine engine lubricating oil compositions was tested using an engine crankcase coking simulation test. This method involves adding 300 ml of the test sample to a coking plate simulator, heating it to 160°C, and continuously splashing the oil onto an aluminum plate. After 6 hours, the amount of coke formed on the aluminum plate was weighed and expressed as deposits (mg), simulating deposits on a piston. Higher coke levels indicate poorer detergency of the test sample.

[0114] Table 1

[0115]

[0116] The detergency performance of the gas turbine engine lubricating oil compositions in the examples and comparative cases was tested using a heat pipe coking simulation test. This method involves circulating 15 ml of the test sample in a heat pipe while simultaneously injecting oxygen to accelerate oil aging. The sample is heated to 330°C, and the glass tube wall is scored after 8 hours. The maximum score is 10; a lower score indicates poorer detergency of the test sample.

[0117] The load-bearing and anti-wear properties of the gas engine lubricating oil compositions in the examples and comparative examples were evaluated using a four-ball testing machine. The load-bearing performance evaluation test was carried out in accordance with GB / T3142-2019 standard, and the high-temperature anti-wear test of the oil was conducted at a load of 40 kg, a time of 1 h, and an oil temperature of 75 °C.

[0118] Examples and comparative examples of gas engine lubricating oil compositions were subjected to BRT ball corrosion tests. During the entire 18-hour bench test, the metal balls protected by the test samples were continuously exposed to acidic liquid and air. After the test, the reflective surface intensity of the metal balls was measured to obtain grayscale test values, which were used to determine the corrosion area and thus evaluate the rust resistance of the test samples. The test conditions were: an injection rate of acetic acid / hydrobromic acid / hydrochloric acid / deionized water of 0.19 mL / h, an air flow rate of 40 mL / min, and an oil temperature of 48°C. A higher score indicates better rust prevention performance of the test sample.

[0119] The test results of PDSC test, TFOUT test, coking simulation test, four-ball test machine test and BRT ball corrosion test are shown in Table 2.

[0120] As can be seen from Table 2, the gas engine lubricating oil composition of the present invention has excellent high-temperature oxidation resistance, detergency, extreme pressure anti-wear performance and anti-rust performance.

[0121] Table 2

[0122]

Claims

1. A gas engine lubricating oil composition, comprising: (A) Alkyl phosphate compounds, comprising 0.1% to 15% (preferably 0.5% to 5%) of the total mass of the composition; (B) Alkylated diphenylamine, comprising 0.1% to 10% (preferably 0.5% to 5%) of the total mass of the composition; (C) Polyisobutylene succinate pentaerythritol dispersant, accounting for 1% to 15% (preferably 3% to 10%) of the total mass of the composition; (D) Salicylate and / or sulfonate, comprising 0.2% to 10% (preferably 0.5% to 8%) of the total mass of the composition; (E) Zinc dialkyl dithiophosphate, 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 0.1% 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 alkyl phosphate compound 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 method for preparing the alkylphosphonate compounds 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 alkyl group in the alkylated diphenylamine is C2-C6. 12 The polyisobutylene succinate dispersant contains straight-chain or branched alkyl groups; the polyisobutylene fraction of the polyisobutylene succinate dispersant has a number-average molecular weight of 500-4000; the salicylate and / or sulfonate are calcium salicylate and / or magnesium sulfonate; the alkyl group in the zinc dialkyl dithiophosphate is an alkyl group containing 2 to 12 carbon atoms; the oil-soluble organic molybdenum friction modifier is selected from one or more of molybdenum dialkyl dithiophosphate, molybdenum oxydialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum xanthate, molybdenum thioxanthate, trinuclear molybdenum-sulfur complex, molybdenum amine complex, and molybdate oil-soluble organic molybdenum friction modifier; 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 mineral oil and / or synthetic lubricating oil.

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

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