Highly dispersed lubricating oil composition, method for producing the same, and diesel engine oil

Abstract

This invention discloses a highly dispersible lubricating oil composition, its preparation method, and a diesel engine oil, belonging to the field of lubricating oil technology. The lubricating oil composition, by mass percentage, comprises: detergent, 1%–6%; dispersant, 1%–8%; corrosion inhibitor, 0.1%–5%; antioxidant, 0.1%–6%; viscosity index improver, 0.1%–4%; base oil, balance; wherein the dispersant is selected from succinimidyl-succinate polymers. The highly dispersible lubricating oil composition and diesel engine oil provided by this invention exhibit excellent dispersing and detergency properties.

Description

Technical Field

[0001] This invention belongs to the field of lubricating oil technology, specifically relating to highly dispersible lubricating oil compositions, their preparation methods, and diesel engine oils. Background Technology

[0002] The fourth-stage fuel consumption regulations and China's seventh-stage emission regulations are also imminent, posing higher challenges to diesel engine technology. In addition to using technologies such as delayed fuel injection, exhaust gas recirculation (EGR), particulate filters (PDF), and selective catalytic reduction (SCR), new technologies such as ultra-high pressure combustion, high-efficiency combustion, dual-zone combustion chambers, and high-efficiency coupled turbocharging are needed to improve the thermal efficiency of diesel engines. However, using these new technologies will increase combustion temperatures, piston temperatures, cylinder liner temperatures, and exhaust temperatures within the combustion chamber. Increased piston temperature correspondingly increases the temperature of the lubricating oil in the internal cooling oil passages, increasing the risk of lubricating oil coking. Simultaneously, the amount of lubricating oil coking remaining on the piston fire land will also increase. Therefore, it is necessary to optimize and reduce the degree of lubricating oil coking to the greatest extent possible while ensuring engine reliability. Thus, the detergency and dispersancy of lubricating oil is one of the important indicators of lubricating oil performance.

[0003] Ashless dispersants are one of the three major functional additives in engine oils. Their main function is to keep insoluble substances formed during oil use due to oxidation or other chemical reactions in suspension, and to prevent sludge from forming and insoluble substances from depositing. Another function is to prevent soot particles from agglomerating and to reduce the viscosity increase of lubricating oil during use. The ability to inhibit carbon deposits and sludge depends on the quality and proportion of detergent-dispersants in the lubricating oil.

[0004] Chinese invention patent application publication CN116904247A discloses a diesel engine oil compound that uses a novel ashless dispersant to give the blended diesel engine oil excellent soot dispersibility, high-temperature detergency and anti-wear properties. However, it still has problems such as insufficient dispersibility, complex synthesis of multifunctional ashless dispersants and high cost.

[0005] Chinese invention patent application publication CN111040840A discloses a diesel engine oil composition that uses a viscosity index improver with dispersing function, which gives the oil excellent high-temperature detergency, soot dispersibility, oxidation resistance, wear resistance, metal corrosion inhibition performance and low-temperature performance, but its dispersing performance is still insufficient. Summary of the Invention

[0006] The purpose of this invention is to provide a highly dispersible lubricating oil composition, its preparation method, and its application, so as to solve the technical problem that the dispersion performance of diesel engine oil in the prior art is not ideal.

[0007] The technical solution adopted in this invention is as follows: a lubricating oil composition, comprising, by mass percentage, the following components:

[0008] The detergent comprises 1% to 6% (preferably 2% to 4%) of the total mass of the composition;

[0009] The dispersant comprises 1% to 8% (preferably 4% to 7%) of the total mass of the composition;

[0010] The preservative accounts for 0.1% to 5% (preferably 0.5% to 3%) of the total mass of the composition;

[0011] Antioxidant, comprising 0.1% to 6% (preferably 0.3% to 4%) of the total mass of the composition;

[0012] A viscosity index improver, comprising 0.1% to 4% (preferably 0.2% to 2%) of the total mass of the composition;

[0013] The remaining amount of lubricating base oil;

[0014] The dispersant is selected from succinimide-succinate polymer;

[0015] As a preferred technical solution, the viscosity index improver is selected from the dispersion-type ethylene-propylene copolymer shown in Formula I;

[0016]

[0017] In Formula I, m:n = 45:55 to 55:45; R1 is a polar functional group selected from amide, imine, ester, amino, or alkyl groups; preferably C 1-10 amide group, C 1-10 ester group or C 1-10 alkyl.

[0018] As a preferred technical solution, the molecular weight of the succinimide-succinate polymer is 500 to 5000.

[0019] As a preferred technical solution, in the succinimide-succinate polymer, the molar ratio of succinimide to succinate is 6 to 10:1, preferably 9:1.

[0020] As a preferred technical solution, the nitrogen molar content in the succinimide-succinate polymer is 0.3-0.4%.

[0021] As a preferred technical solution, the succinimide is selected from polyisobutylene succinimide.

[0022] As a preferred technical solution, the number-average molecular weight of the polyisobutylene portion in the polyisobutylene succinimide is preferably 500 to 5000, and common commercial products include T161.

[0023] As a preferred technical solution, the lubricating oil composition comprises, by weight percentage:

[0024] The detergent, preferably comprising 2% to 4% of the total mass of the composition;

[0025] The dispersant preferably accounts for 4% to 7% of the total mass of the composition;

[0026] The preservative preferably accounts for 0.5% to 3% of the total mass of the composition;

[0027] Antioxidant, preferably 0.3% to 4% of the total mass of the composition;

[0028] A viscosity index improver, preferably comprising 0.2% to 2% of the total mass of the composition;

[0029] The remaining amount of lubricating base oil.

[0030] In the above technical solution, preferably, the succinate is selected from one or more of pentaerythritol succinate, diester of pentaerythritol succinate, half-ester of pentaerythritol succinate, cyclic ester of pentaerythritol succinate, or polyester of pentaerythritol succinate, with common commercial products including T171.

[0031] In the above technical solution, preferably, the preservative is an alkyl thiophosphate or an alkyl thiocarbamate; the alkyl group in the preservative is C2-C. 10 Straight-chain or branched alkyl groups, common products include T202, T203, and T205.

[0032] In the above technical solution, preferably, the antioxidant is selected from at least one of amine antioxidants, phenolic antioxidants, thiadiazole antioxidants, or carbamate antioxidants.

[0033] In the above technical solution, preferably, the detergent is selected from at least one of sulfonates and phenolates.

[0034] In the above technical solution, preferably, the viscosity index improver is selected from dispersible ethylene propylene copolymer, and can be at least one of commercially available T612, T621, T622, ECA8358, ECA8586, H5777, LZ7075, LZ7077, LZ7067, SV200, SV250, and SV253.

[0035] In the above technical solution, preferably, the base oil is selected from one or more of HVI 150, HVI 500, 150BS, II4, II6, II10 or 150SN, PAO.

[0036] In a second aspect, the present invention provides a method for preparing a lubricating oil composition, wherein the components are mixed at a temperature of 50-65°C to obtain the lubricating oil composition.

[0037] In the above technical solution, preferably, the viscosity index improver, pour point depressant and base oil are mixed first.

[0038] The above technical solution preferably includes the following steps:

[0039] Each component is added to the base oil at 50-60°C and stirred for 1-4 hours until completely dissolved to obtain a highly dispersible diesel engine oil composition.

[0040] Thirdly, the present invention provides a method for using the prepared diesel engine oil composition in a diesel engine, providing a diesel engine oil containing any of the above-mentioned lubricating oil compositions.

[0041] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0042] The highly dispersible lubricating oil composition and diesel engine oil provided by this invention have excellent dispersing and detergency properties. Detailed Implementation

[0043] The present invention will be further illustrated below through examples, but not in a way that limits the invention.

[0044] The specific information regarding the reagents used in the embodiments and comparative examples of this invention is as follows:

[0045] Alkylphenol calcium sulfide S206C, Wuxi Southern Petroleum Additives Co., Ltd.

[0046] Synthetic calcium sulfonate T104, Jiangsu Aorun New Materials Co., Ltd.

[0047] Synthetic calcium sulfonate T106D, Wuxi Southern Petroleum Additives Co., Ltd.

[0048] Synthetic calcium sulfonate T106A, Jiangsu Aorun New Materials Co., Ltd.

[0049] Succinimide-succinate LZ6401 (molecular weight 500-5000, succinimide:succinate = 9:1), Lubrizol Corporation.

[0050] Monoalkenyl succinimide T151, Yangzi Petrochemical.

[0051] High molecular weight succinimide T161, Yangzi Petrochemical.

[0052] T202, a monooctyl zinc salt of thiophosphoric acid, manufactured by Wuxi Southern Petroleum Additives Co., Ltd.

[0053] Zinc thiophosphate dioctyl zinc salt T203, Wuxi Southern Petroleum Additives Co., Ltd.

[0054] Phenolic antioxidant T512, Shanghai Qike Fluorosilicon Materials Co., Ltd.

[0055] Phenolic antioxidant T535, Shanghai Qike Fluorosilicone Materials Co., Ltd.

[0056] Amine-type antioxidant T557, Changsha Wangcheng Petrochemical Co., Ltd.

[0057] II4, Maoming Petrochemical.

[0058] II6, Maoming Petrochemical.

[0059] 150BS, Gaoqiao Petrochemical.

[0060] Ethylene-propylene copolymer LZ7067, Lubrizol Corporation;

[0061]

[0062] M:n = ≥60 / 40.

[0063] Ethylene-propylene copolymer H5777, Afton Laboratories;

[0064]

[0065] R1 = Polar functional group, including amide, imine, ester, amino, alkyl, etc. m:n = 45 / 55 to 55 / 45.

[0066] Ethylene-propylene copolymer ECA8358, ExxonMobil;

[0067]

[0068] R1 = Polar functional group, including amide, imine, ester, amino, alkyl, etc. m:n = 45 / 55 to 55 / 45.

[0069] Ethylene-propylene copolymer T612, Wuxi Southern Petroleum Additives Co., Ltd.;

[0070]

[0071] m:n = 45 / 55 ~ 55 / 45.

[0072] Example 1

[0073] A highly dispersible diesel engine oil composition is prepared from the following components in parts by weight:

[0074] (1) Detergent: Alkylphenol calcium sulfide S206C, 1.8%;

[0075] Synthetic calcium sulfonate T104, 0.4%;

[0076] Synthetic calcium sulfonate T106D, 1.5%;

[0077] Synthetic calcium sulfonate T106A, 0.3%;

[0078] (2) Dispersant: Succinimidyl-succinate LZ6401, 1.5%;

[0079] Monoalkenyl succinimide T151, 2.5%;

[0080] High molecular weight succinimide, 3.0%;

[0081] (3) Anti-corrosion agent: zinc thiophosphate dioctyl salt T203, 0.2%;

[0082] Zinc thiophosphate monooctyl salt T202, 0.3%;

[0083] (4) Antioxidant: Phenolic type T535, 0.5%;

[0084] Phenolic form T512, 0.6%;

[0085] Amine form T557, 0.4%;

[0086] (5) Viscosity index improver: ethylene-propylene copolymer H5777, 10%;

[0087] (6) Base oil: II4, 35%;

[0088] 150BS, 10%;

[0089] II6, 41.7%.

[0090] Preparation method: Add each component to the base oil at 50-60℃ and stir for 1-4 hours until completely dissolved to obtain a highly dispersible diesel engine oil composition 1#.

[0091] Example 2

[0092] A highly dispersible diesel engine oil composition is prepared from the following components in parts by weight:

[0093] (1) Detergent: Alkylphenol calcium sulfide S206C, 1.8%;

[0094] Synthetic calcium sulfonate T104, 0.4%;

[0095] Synthetic calcium sulfonate T106D, 1.5%;

[0096] Synthetic calcium sulfonate T106A, 0.3%;

[0097] (2) Dispersant: Succinimidyl-succinate LZ6401, 2.0%;

[0098] Monoalkenyl succinimide T151, 2.0%;

[0099] High molecular weight succinimide, 3.0%;

[0100] (3) Anti-corrosion agent: zinc thiophosphate dioctyl salt T203, 0.2%;

[0101] Zinc thiophosphate monooctyl salt T202, 0.3%;

[0102] (4) Antioxidant: Phenolic type T535, 0.5%;

[0103] Phenolic form T512, 0.6%;

[0104] Amine form T557, 0.4%;

[0105] (5) Viscosity index improver: Ethylene-propylene copolymer ECA8358, 10%;

[0106] (6) Base oil: II4, 35%;

[0107] 150BS, 10%;

[0108] II6, 41.7%.

[0109] Preparation method: Add each component to the base oil at 50-60℃ and stir for 1-4 hours until completely dissolved to obtain a highly dispersible diesel engine oil composition 2#.

[0110] Example 3

[0111] A highly dispersible diesel engine oil composition is prepared from the following components in parts by weight:

[0112] (1) Detergent: Alkylphenol calcium sulfide S206C, 1.8%;

[0113] Synthetic calcium sulfonate T104, 0.4%;

[0114] Synthetic calcium sulfonate T106D, 1.5%;

[0115] Synthetic calcium sulfonate T106A, 0.3%;

[0116] (2) Dispersant: Succinimidyl-succinate LZ6401, 2.5%;

[0117] Monoalkenyl succinimide T151, 1.5%;

[0118] High molecular weight succinimide, 3.0%;

[0119] (3) Anti-corrosion agent: zinc thiophosphate dioctyl salt T203, 0.2%;

[0120] Zinc thiophosphate monooctyl salt T202, 0.3%;

[0121] (4) Antioxidant: Phenolic type T535, 0.5%;

[0122] Phenolic form T512, 0.6%;

[0123] Amine form T557, 0.4%;

[0124] (5) Viscosity index improver: 10% of ethylene-propylene copolymer T612;

[0125] (6) Base oil: II4, 35%;

[0126] 150BS, 10%;

[0127] II6, 41.7%.

[0128] Preparation method: Add each component to the base oil at 50-60℃ and stir for 1-4 hours until completely dissolved to obtain a highly dispersible diesel engine oil composition 3#.

[0129] Example 4

[0130] A highly dispersible diesel engine oil composition is prepared from the following components in parts by weight:

[0131] (1) Detergent: Alkylphenol calcium sulfide S206C, 1.8%;

[0132] Synthetic calcium sulfonate T104, 0.4%;

[0133] Synthetic calcium sulfonate T106D, 1.5%;

[0134] Synthetic calcium sulfonate T106A, 0.3%;

[0135] (2) Dispersant: Succinimidyl-succinate LZ6401, 3.0%;

[0136] Monoalkenyl succinimide T151, 1.0%;

[0137] High molecular weight succinimide, 3.0%;

[0138] (3) Anti-corrosion agent: zinc thiophosphate dioctyl salt T203, 0.2%;

[0139] Zinc thiophosphate monooctyl salt T202, 0.3%;

[0140] (4) Antioxidant: Phenolic type T535, 0.5%;

[0141] Phenolic form T512, 0.6%;

[0142] Amine form T557, 0.4%;

[0143] (5) Viscosity index improver: ethylene-propylene copolymer H5777, 10%;

[0144] (6) Base oil: II4, 35%;

[0145] 150BS, 10%;

[0146] II6, 41.7%.

[0147] Preparation method: Add each component to the base oil at 50-60℃ and stir for 1-4 hours until completely dissolved to obtain a highly dispersible diesel engine oil composition 4#.

[0148] Comparative Example 1

[0149] The diesel engine oil composition is prepared from the following components in parts by weight:

[0150] (1) Detergent: Alkylphenol calcium sulfide S206C, 1.8%;

[0151] Synthetic calcium sulfonate T104, 0.4%;

[0152] Synthetic calcium sulfonate T106D, 1.5%;

[0153] Synthetic calcium sulfonate T106A, 0.3%;

[0154] (2) Dispersant: Mono-alkenyl succinimide T151, 1.0%;

[0155] High molecular weight succinimide, 6.0%;

[0156] Succinimide-succinate LZ6401, 1%;

[0157] (3) Anti-corrosion agent: zinc thiophosphate dioctyl salt T203, 0.2%;

[0158] Zinc thiophosphate monooctyl salt T202, 0.3%;

[0159] (4) Antioxidant: Phenolic type T535, 0.5%;

[0160] Phenolic form T512, 0.6%;

[0161] Amine form T557, 0.4%;

[0162] (5) Base oil: II4, 35%;

[0163] 150BS, 10%;

[0164] II6, 42%.

[0165] Preparation method: Add each component to the base oil at 50-60℃ and stir for 1-4 hours until completely dissolved to obtain diesel engine oil composition A.

[0166] Comparative Example 2

[0167] The diesel engine oil composition is prepared from the following components in parts by weight:

[0168] (1) Detergent: Alkylphenol calcium sulfide S206C, 1.8%;

[0169] Synthetic calcium sulfonate T104, 0.4%;

[0170] Synthetic calcium sulfonate T106D, 1.5%;

[0171] Synthetic calcium sulfonate T106A, 0.3%;

[0172] (2) Dispersant: Mono-alkenyl succinimide T151, 3.0%;

[0173] High molecular weight succinimide, 4.0%;

[0174] (3) Anti-corrosion agent: zinc thiophosphate dioctyl salt T203, 0.2%;

[0175] Zinc thiophosphate monooctyl salt T202, 0.3%;

[0176] (4) Antioxidant: Phenolic type T535, 0.5%;

[0177] Phenolic form T512, 0.6%;

[0178] Amine form T557, 0.4%;

[0179] (5) Base oil: II4, 35%;

[0180] 150BS, 10%;

[0181] II6, 42%.

[0182] Preparation method: Add each component to the base oil at 50-60℃ and stir for 1-4 hours until completely dissolved to obtain diesel engine oil composition B.

[0183] Comparative Example 3

[0184] The diesel engine oil composition is prepared from the following components in parts by weight:

[0185] (1) Detergent: Alkylphenol calcium sulfide S206C, 1.8%;

[0186] Synthetic calcium sulfonate T104, 0.4%;

[0187] Synthetic calcium sulfonate T106D, 1.5%;

[0188] Synthetic calcium sulfonate T106A, 0.3%;

[0189] (2) Dispersant: Succinimidyl-succinate LZ6401, 1.0%;

[0190] Monoalkenyl succinimide T151, 3.0%;

[0191] High molecular weight succinimide, 3.0%;

[0192] (3) Anti-corrosion agent: zinc thiophosphate dioctyl salt T203, 0.2%;

[0193] Zinc thiophosphate monooctyl salt T202, 0.3%;

[0194] (4) Antioxidant: Phenolic type T535, 0.5%;

[0195] Phenolic form T512, 0.6%;

[0196] Amine form T557, 0.4%;

[0197] (5) Viscosity index improver: 10% of ethylene-propylene copolymer LZ7067;

[0198] (6) Base oil: II4, 35%;

[0199] 150BS, 10%;

[0200] II6, 41.7%.

[0201] Preparation method: Add each component to the base oil at 50-60℃ and stir for 1-4 hours until completely dissolved to obtain diesel engine oil composition C.

[0202] Comparative Example 4

[0203] Kunlun engine oil CI 15W-40, purchased from JD.com.

[0204] Table 1 Component Raw Material Formulation

[0205]

[0206] Test case

[0207] The performance indicators of the diesel engine oil compositions prepared in the examples and comparative examples were tested, and the specific methods are as follows:

[0208] Dispersion performance test: The dispersion performance of the dispersant was determined according to Appendix A of SH / T 0623, using the sludge spot dispersibility test method. During the test, the oven temperature was 80℃. Different types of reference oil were mixed with the sample. 20 μL of the mixed oil sample was dropped onto filter paper, and the filter paper was placed in the oven and allowed to stand for 1 hour. The diffusion of the oil sample on the filter paper was observed. Based on the diffusion of the sludge ring and the oil ring, the sludge spot dispersion values ​​SDT and SDT' were measured. Generally, the larger the SDT and SDT' results and the lighter the color of the intermediate layer, the better the dispersion performance of the dispersant.

[0209] Anti-wear performance test: The anti-wear performance of the sample was evaluated according to SH / T 0189—Determination of anti-wear performance of lubricating oil (four-ball machine method). The test conditions were: 392N, 75℃, 1200r / min, 60min. The test result was the wear scar diameter. According to GB / T3142—Determination of load-carrying capacity of lubricant (four-ball machine method), the maximum non-seize load of the oil sample was determined, and the result was PB (N).

[0210] Detergent performance test: The diesel engine oil composition was tested for 2-3 hours at a plate temperature of 200-400℃ and an oil temperature of 100-200℃ according to SH / T 0300-06 "Crankcase Simulation Test Method"; the smaller the mass increase of coking plate, the better the detergency performance of the diesel engine oil composition.

[0211] Table 2 Performance data of diesel engine oil compositions

[0212]

[0213] As can be seen from the above results, the highly dispersible diesel engine oil composition provided by the present invention can have excellent dispersibility and high-temperature detergency by adding succinimide-succinate dispersant and viscosity index improver of ethylene propylene copolymer to the formulation.

[0214] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50–90, in this specification it means specifically listing values ​​such as 51–89, 52–88, ..., 69–71, and 70–71. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0215] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A lubricating oil composition, comprising, by weight percentage: Detergent, 1%–6%; Dispersant, 1%–8%; Preservatives, 0.1%–5%; Antioxidant, 0.1%–6%; Viscosity index improver, 0.1%–4%; Base oil, balance; The dispersant is selected from succinimide-succinate polymer; The viscosity index improver is selected from the dispersion-type ethylene-propylene copolymer shown in Formula I; In formula I, m:n = 45:55 to 55:45; R1 is a polar functional group selected from amide, imine, ester, amino, or alkyl groups.

2. The lubricating oil composition according to claim 1, characterized in that, The molecular weight of the succinimide-succinate polymer is 500 to 5000; In the succinimide-succinate polymer, the molar ratio of succinimide to succinate is 6 to 10:

1. The succinimide-succinate polymer contains 0.3-0.4% nitrogen in molar amounts. The succinimide is selected from polyisobutylene succinimide; And / or, the number-average molecular weight of the polyisobutylene portion in the polyisobutylene succinimide is 500 to 5000.

3. The lubricating oil composition according to claim 1 or 2, characterized in that, R1is selected from C 1-10 amide, C 1-10 ester or C 1-10 alkyl.

4. The lubricating oil composition according to claim 1, 2, or 3, characterized in that, By weight percentage, including components: Cleaning agent, 2%–4%; Dispersant, 4%–7%; Antiseptic, 0.5%–3%; Antioxidant, 0.3%–4%; Viscosity index improver, 0.2%–2%; Base oil, balance.

5. The lubricating oil composition according to any one of claims 1-4, characterized in that, The succinate is selected from one or more of pentaerythritol succinate, diester of pentaerythritol succinate, half-ester of pentaerythritol succinate, cyclic ester of pentaerythritol succinate, or polyester of pentaerythritol succinate.

6. The lubricating oil composition according to any one of claims 1-5, characterized in that, The antiseptic is an alkyl thiophosphate or an alkyl thio carbamate; the alkyl group is a C2-C 10 linear or branched alkyl group.

7. The lubricating oil composition according to any one of claims 1-6, characterized in that, The antioxidant is selected from at least one of amine antioxidants, phenolic antioxidants, thiadiazole antioxidants, or carbamate antioxidants.

8. The lubricating oil composition according to any one of claims 1-7, characterized in that, The detergent is selected from at least one of sulfonate detergents and phenolic detergents.

9. A method for preparing the lubricating oil composition according to any one of claims 1-8, characterized in that, The raw materials containing the aforementioned components are mixed at a temperature of 50–65°C to obtain the lubricating oil composition.

10. A diesel engine oil comprising the lubricating oil composition according to any one of claims 1-8.

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