Long-life SN-grade gasoline engine oil composition as well as preparation method and application thereof

Abstract

The invention provides a long-life SN-grade gasoline engine oil composition and a preparation method and application thereof.The gasoline engine oil composition comprises a metal clearing agent, a dispersing agent, dialkyl dithiophosphate, an anti-wear agent, an antioxidant, a pour point depressant and base oil, the metal clearing agent contains alkyl phenate with the base number being 290-310 mgKOH / g and sulfonate with the base number being 395-420 mgKOH / g; the antioxidant is selected from at least two of an amine type antioxidant, a phenol type antioxidant, a thiadiazole type antioxidant or a carbamate antioxidant. The gasoline engine oil composition disclosed by the invention has excellent lasting antioxidation and detergency, can provide more lasting detergency for gasoline engine oil, reduces the generation of acidic substances and paint films, and prolongs the service life of oil products.

Description

Technical Field

[0001] The invention relates to the field of gasoline engine oil, in particular to a long-life SN-grade gasoline engine oil composition and a preparation method and application thereof. Background Art

[0002] Nowadays, people attach increasing importance to efficiency, energy conservation and environmental protection. The government has formulated relevant regulations to put forward higher requirements for lubricants. At the same time, internal combustion engine technology is changing with each passing day. Engines are developing in the direction of miniaturization, high power and high speed. Their operating conditions are becoming increasingly harsh, but users' demand for extending the oil change cycle is also increasing. Therefore, the demand for improving the performance of engine oil is becoming increasingly urgent.

[0003] Gasoline engine oil is an important component of lubricating oil products. SN-grade gasoline engine oil has excellent performance in anti-oxidation, carbon black dispersion and acid neutralization, so it is widely used. However, in the actual driving process, due to the high and low speed cross-driving of vehicles, high-temperature carbon deposits and low-temperature sludge will be caused at the same time. These oxidizing substances will cause problems such as oil line blockage and piston ring wear, resulting in a short service life of the engine oil and the normal operation of the equipment. Therefore, in order to make SN-grade gasoline engine oil have a longer service life, its anti-oxidation and cleanliness properties need to be improved urgently.

[0004] The Chinese invention patent application publication CN116083149A discloses a low-carbon SN-grade gasoline engine oil composition, which includes the following components: 1% to 30% plant-based synthetic fat; 70% to 99% base oil; 6.0% to 12.0% compounding agent; 3.0% to 12.0% viscosity index improver; 0.1% to 0.7% pour point depressant; 0.001% to 0.01% antifoaming agent. The lubricating oil composition has significant carbon emission reduction effect, low-temperature starting performance and antioxidant performance, but it still has the problem of insufficient antioxidant performance and cleaning performance under long-term operation.

[0005] The Chinese invention patent application publication CN112011387A discloses an SN-grade gasoline engine oil, comprising: zinc dialkyl dithiophosphate; antioxidant; rust inhibitor; calcium sulfonate; calcium alkyl phenol sulfide; succinimide ashless dispersant; friction modifier. The prepared SN-grade gasoline engine oil can provide the engine with certain anti-low-temperature deposit performance, anti-wear and friction reduction performance, and anti-oxidation performance, but it still has the problem of insufficient anti-oxidation performance and detergency performance under long-term operation.

[0006] Therefore, it is of great practical significance to develop a long-life SN-grade gasoline engine oil composition with good antioxidant and detergency properties. Summary of the invention

[0007] One of the technical problems to be solved by the present invention is that the SN-grade gasoline engine oil composition in the prior art has insufficient antioxidant performance and cleaning performance under long-term operation, and provides a new SN-grade gasoline engine oil composition that can still have good antioxidant performance and cleaning performance under long-term operation.

[0008] The second technical problem to be solved by the present invention is to provide a preparation method corresponding to the first technical problem to be solved.

[0009] The third technical problem to be solved by the present invention is to provide a use corresponding to solving the first technical problem.

[0010] In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a gasoline engine oil composition, in terms of mass percentage, comprises the following components:

[0011] Metal detergent, accounting for 1% to 6% (preferably 2% to 4%) of the total mass of the composition;

[0012] Dispersant, accounting for 1% to 8% (preferably 4% to 7%) of the total mass of the composition;

[0013] Dialkyl dithiophosphate, accounting for 0.1% to 5% (preferably 0.5% to 3%) of the total weight of the composition;

[0014] Antiwear agent, accounting for 0.05% to 3% (preferably 0.1% to 2%) of the total mass of the composition;

[0015] Antioxidant, accounting for 0.1% to 8% (preferably 0.3% to 5%) of the total mass of the composition;

[0016] Pour point depressant, accounting for 0.1% to 3% (preferably 0.2% to 1%) of the total mass of the composition;

[0017] A major amount of lubricating base oil;

[0018] The metal cleaner comprises: an ultra-high base alkylphenol salt with a base value of 290 to 310 mgKOH / g and an ultra-high base sulfonate salt with a base value of 395 to 420 mgKOH / g; and the antioxidant is selected from at least two of an amine antioxidant, a phenolic antioxidant, a thiadiazole antioxidant or a carbamate antioxidant.

[0019] In the above technical solution, preferably, the antioxidant is selected from at least two of T501, T512, T534, T535, T552, T536, T545, and T561.

[0020] In the above technical solution, preferably, the mass ratio of the super overbased alkyl phenol salt to the super overbased sulfonate salt in the metal detergent is 1:(0.1-10), preferably 1:(0.5-5).

[0021] In the above technical scheme, the dispersant is selected from pentaerythritol succinate and / or polyisobutylene succinimide; pentaerythritol succinate is preferably one or more of its diester, half ester, cyclic ester or polyester, and common commercial products include T171; the number average molecular weight of the polyisobutylene part in the polyisobutylene succinimide is preferably 500-5000, and common commercial products include T161.

[0022] In the above technical solution, preferably, the alkyl group in the dialkyl dithiophosphate is C 2 ~C 10 Straight chain or branched chain alkyl, common commercial products include T202, T203, T205.

[0023] In the above technical solution, preferably, the anti-wear agent is selected from one or more of polysulfides, phosphates, and thiocarbamates, and the main commercial products include T304 and T323.

[0024] In the above technical solution, preferably, the pour point depressant is selected from one or more of polymethacrylate, alkyl naphthalene or poly-α-olefin, and the main commercial products include T866.

[0025] In the above technical solution, preferably, the gasoline engine oil composition further includes the following components, calculated by mass percentage: friction modifier, 0.1% to 5%; preferably 0.2% to 3%; the friction modifier is a mixture of ashless friction modifier and oil-soluble organic molybdenum friction modifier, and the mass ratio of ashless friction modifier to oil-soluble organic molybdenum friction modifier is 1:(0.1 to 5).

[0026] In the above technical solution, preferably, the gasoline engine oil composition further includes components in terms of mass percentage: a viscosity index improver, 3% to 15%; preferably 5% to 12%; the viscosity index improver is selected from at least one of polymethacrylate, ethylene-propylene copolymer or polyisobutylene; the main products include T612.

[0027] In the above technical solution, preferably, the base oil is selected from one or more of HVI 150, HVI 500, II4, II6, II10 or 150SN, PAO.

[0028] To solve the second technical problem mentioned above, the technical solution adopted by the present invention is: a method for preparing a gasoline engine oil composition, mixing the components at a temperature of 50 to 65° C. to obtain the gasoline engine oil composition.

[0029] In the above technical solution, preferably, the viscosity index improver, the pour point depressant and the base oil are mixed first.

[0030] In the above technical solution, preferably, the following steps are included:

[0031] (1) stirring the base oil at a temperature of 50 to 65° C. to obtain material I;

[0032] (2) Add viscosity index improver and pour point depressant to material I in sequence, maintain stirring at 50-65° C. for 0.1-1 h, and obtain material II;

[0033] (3) Maintaining the temperature at 50-65° C., add metal detergent, pentaerythritol succinate and / or polyisobutylene succinimide dispersant, dialkyl dithiophosphate, antiwear agent, antioxidant, and friction modifier to material II in sequence while stirring, and continue stirring at 50-65° C. for 0.5-5 h to obtain a gasoline engine oil composition.

[0034] In order to solve the third of the above technical problems, the technical solution adopted by the present invention is: using the prepared gasoline engine oil composition in a vehicle gasoline engine system.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The SN-grade gasoline engine oil composition of the present invention is a metal detergent prepared by compounding an ultra-high base alkylphenol salt having a base value of 290 to 310 mgKOH / g and an ultra-high base sulfonate salt having a base value of 395 to 420 mgKOH / g, which can provide a more durable cleaning ability for gasoline engine oil and reduce the formation of acidic substances and paint film.

[0037] (2) The SN-grade gasoline engine oil composition of the present invention utilizes the synergistic effect of different types of antioxidants and adopts a combination of multiple antioxidants to form a composite antioxidant, thereby providing gasoline engine oil with a more durable antioxidant capacity and reducing the formation of oxides.

[0038] (3) The SN-grade gasoline engine oil composition of the present invention has good antioxidant and detergency properties, effectively prolongs the service life of the oil product, and achieves good technical effects. DETAILED DESCRIPTION

[0039] The following are only preferred implementations of the present invention and are not intended to limit the scope of protection of the present invention. All technical solutions within the scope of the present invention should fall within the scope of protection of the present invention. For professional and technical personnel in this technical field, minor improvements to the present invention without departing from the principles of the present invention should also fall within the scope of protection of the present invention.

[0040] Preparation steps of gasoline engine oil composition:

[0041] (1) Add the base oil into a stirring kettle and stir at a temperature of 50 to 65° C. to obtain material I;

[0042] (2) Add viscosity index improver and pour point depressant to material I in sequence, maintain stirring at 50-65° C. for 0.1-1 h, and obtain material II;

[0043] (3) Add metal detergent, pentaerythritol succinate and / or polyisobutylene succinimide dispersant, dialkyl dithiophosphate, antiwear agent, antioxidant and friction modifier to material II in sequence while maintaining the temperature at 50-65° C. and stirring, and continue to maintain the temperature at 50-65° C. and stir for 0.5-5 h to completely dissolve them, thereby obtaining an SN grade gasoline engine oil composition.

[0044] In each embodiment and comparative example of the present invention, the specific information of the reagents used is as follows:

[0045] S206C, Wuxi Nanfang Petroleum Additives Co., Ltd.; T122, Xinxiang Ruifeng New Materials Co., Ltd.; T106D, Wuxi Nanfang Petroleum Additives Co., Ltd.; T106A, Jiangsu Aorun New Materials Co., Ltd.; T154A, Yangzi Petrochemical; T151, Yangzi Petrochemical; T161, Yangzi Petrochemical; T152, Wuxi Nanfang Petroleum Additives Co., Ltd.; T202, Wuxi Nanfang Petroleum Additives Co., Ltd.; T203, Wuxi Nanfang Petroleum Additives Co., Ltd.; T323, Shenyang Hualun Lubricant Additives Co., Ltd.; T501 Shanghai Qike Fluorosilicone Materials Co., Ltd.; T 512, Shanghai Qike Fluorosilicone Materials Co., Ltd.; T534, Shanghai Qike Fluorosilicone Materials Co., Ltd.; T535, Shanghai Qike Fluorosilicone Materials Co., Ltd.; T536, Beijing Xingpu Fine Chemical Technology Development Co., Ltd.; T552, Changsha Wangcheng Petrochemical Co., Ltd.; T561, Changsha Wangcheng Petrochemical Co., Ltd.; T462, Jinzhou Better Chemical Co., Ltd.; Ⅱ4, Maoming Petrochemical; Ⅱ6, Maoming Petrochemical; 150SN, Gaoqiao Petrochemical; PAO, Maoming Petrochemical; T614, Hongze Zhongpeng Petroleum Additives Co., Ltd.; T866, Beijing Xingpu Fine Chemical Technology Development Co., Ltd.

[0046] The SN-grade gasoline engine oil compositions prepared in the examples and comparative examples were tested for performance indicators, and the specific method is as follows:

[0047] TEOST test: According to ASTM D7097-06a "Thermal Oxidation Simulation Test Method for Determination of Moderately High Temperature Piston Deposits in Engine Oils", an SN-grade gasoline engine oil composition is subjected to an oxidation test for 18 to 24 hours at a test temperature of 200 to 400°C; the smaller the mass of the generated deposits, the better the antioxidant performance of the SN-grade gasoline engine oil composition.

[0048] Crankcase simulation test: According to SH / T 0300-06 "Crankcase simulation test method", the SN-grade gasoline engine oil composition is tested at a plate temperature of 200-400°C and an oil temperature of 100-200°C for 2-3 hours; the smaller the mass increase of the coke plate, the better the cleaning performance of the SN-grade gasoline engine oil composition.

[0049] Example 1

[0050] The preparation of the gasoline engine oil composition comprises the following steps:

[0051] Step 1, in terms of mass percentage, prepare raw materials according to Table 1, wherein the alkalinity of S206C is 300 mgKOH / g; the alkalinity of T106D is 400 mgKOH / g;

[0052] Step 2, add II4 and II6 into a stirring blending kettle in sequence, and stir for the first time until the temperature rises to 60°C, and obtain material I at 60°C;

[0053] Step 3, add T614 and T866 to material I in sequence, maintain 60°C, stir for a second time, stir for 0.5h, and obtain material II;

[0054] Step 4, in material II, maintain 60°C, add S206C, T106D, T154A (the number average molecular weight of polyisobutylene is 500-2000), T202, T203, T512, T535, T462 in sequence while stirring (third stirring), continue to maintain 60°C, stir for the fourth time, stir for 1.5 hours, so that all components are completely dissolved, and obtain gasoline engine oil composition 1#. By testing and analyzing gasoline engine oil composition 1#, various physical and chemical properties meet the standard requirements of SN grade 5W-30 gasoline engine oil, among which the detergency and antioxidant performance index data are shown in Table 2.

[0055] Step 5: applying the prepared SN grade gasoline engine oil composition to a vehicle gasoline engine system.

[0056] Example 2

[0057] The steps in Example 1 were followed, with the only differences being the stirring temperature (the stirring temperatures of Step 2, Step 3 and Step 4 were the same), the stirring time, the raw materials and the raw material ratios, as shown in Table 1. The gasoline engine oil composition 2# was obtained. By testing and analyzing the gasoline engine oil composition 2#, various physical and chemical properties met the standard requirements of SN-grade 5W-30 gasoline engine oil, and the detergency and antioxidant performance index data were shown in Table 2.

[0058] Example 3

[0059] The steps in Example 1 were followed, with the only differences being the stirring temperature (the stirring temperatures of Step 2, Step 3 and Step 4 were the same), the stirring time, the raw materials and the raw material ratios, as shown in Table 1. The gasoline engine oil composition 3# was obtained. By testing and analyzing the gasoline engine oil composition 3#, various physical and chemical properties met the standard requirements of SN-grade 5W-30 gasoline engine oil, and the detergency and antioxidant performance index data were shown in Table 2.

[0060] Example 4

[0061] The steps in Example 1 were followed, with the only differences being the stirring temperature (the stirring temperatures of Step 2, Step 3 and Step 4 were the same), the stirring time, the raw materials and the raw material ratios, as shown in Table 1. The gasoline engine oil composition 4# was prepared. By testing and analyzing the gasoline engine oil composition 4#, various physical and chemical properties met the standard requirements of SN-grade 5W-30 gasoline engine oil, and the detergency and antioxidant performance index data were shown in Table 2.

[0062] Example 5

[0063] The steps in Example 1 were followed, with the only differences being the stirring temperature (the stirring temperatures of Step 2, Step 3 and Step 4 were the same), the stirring time, the raw materials and the raw material ratios, as shown in Table 1. The gasoline engine oil composition 5# was prepared. By testing and analyzing the gasoline engine oil composition 5#, various physical and chemical properties met the standard requirements of SN-grade 5W-30 gasoline engine oil, and the detergency and antioxidant performance index data were shown in Table 2.

[0064] Example 6

[0065] The steps in Example 1 were followed, with the only differences being the stirring temperature (the stirring temperatures of Step 2, Step 3 and Step 4 were the same), the stirring time, the raw materials and the raw material ratios, as shown in Table 1. The gasoline engine oil composition 6# was prepared. By testing and analyzing the gasoline engine oil composition 6#, various physical and chemical properties met the standard requirements of SN-grade 5W-30 gasoline engine oil, and the detergency and antioxidant performance index data were shown in Table 2.

[0066] Example 7

[0067] The steps in Example 1 were followed, with the only differences being the stirring temperature (the stirring temperatures of Step 2, Step 3 and Step 4 were the same), the stirring time, the raw materials and the raw material ratios, as shown in Table 1. The gasoline engine oil composition 7# was prepared. By testing and analyzing the gasoline engine oil composition 7#, various physical and chemical properties met the standard requirements of SN-grade 5W-30 gasoline engine oil, and the detergency and antioxidant performance index data were shown in Table 2.

[0068] Example 8

[0069] The steps in Example 1 were followed, with the only differences being the stirring temperature (the stirring temperatures of Step 2, Step 3 and Step 4 were the same), the stirring time, the raw materials and the raw material ratios, as shown in Table 1. The gasoline engine oil composition 8# was prepared. By testing and analyzing the gasoline engine oil composition 8#, various physical and chemical properties met the standard requirements of SN-grade 5W-30 gasoline engine oil, and the detergency and antioxidant performance index data were shown in Table 2.

[0070] Comparative Example 1

[0071] The steps in Example 1 were followed, except that an equal amount of super-high base value sulfurized alkyl phenol calcium in the formula was replaced by high base value sulfurized alkyl phenol calcium, whose base value was 250 mgKOH / g, as shown in Table 1, to prepare a gasoline engine oil composition A. By testing and analyzing the gasoline engine oil composition A, various physical and chemical properties met the standard requirements of SN grade 5W-30 gasoline engine oil, wherein the detergency and antioxidant performance index data are shown in Table 2.

[0072] Comparative Example 2

[0073] The steps in Example 1 were followed, except that an equal amount of super overbased calcium sulfonate in the formula was replaced by overbased calcium sulfonate, whose base number was 300 mgKOH / g, as shown in Table 1. The gasoline engine oil composition B was prepared. By testing and analyzing the gasoline engine oil composition B, various physical and chemical properties met the standard requirements of SN grade 5W-30 gasoline engine oil, and the detergency and antioxidant performance index data were shown in Table 2.

[0074] Comparative Example 3

[0075] Kunlun Motor Oil 5W-30SN, purchased from JD.com.

[0076] Comparative Example 4

[0077] Uni-President motor oil 5W30 SN grade, purchased from JD.com.

[0078] Table 1 Raw material formula and preparation parameters of each component in the examples and comparative examples

[0079]

[0080]

[0081] The base value of the metal detergent in Table 1 is determined according to SH / T 0251-1993 “Determination of base value of petroleum products - perchloric acid potentiometric titration method”.

[0082] Table 2 Performance index data of SN grade gasoline engine oil compositions prepared in Examples and Comparative Examples

[0083]

[0084] By comparison in Table 2, it can be seen that the SN-grade gasoline engine oil composition prepared by the present invention has both good antioxidant performance and detergency performance, and can effectively solve the technical problem of insufficient antioxidant performance and detergency performance of the existing SN-grade gasoline engine oil composition in the industrial application of vehicle gasoline engine systems under long-term operation.

Claims

1. A gasoline engine oil composition, comprising the following components, measured by mass percentage: Metal detergent, 1% to 6%; Dispersant, 1% to 8%; Dialkyl dithiophosphates, 0.1% to 5%; Antiwear agent, 0.05% to 3%; Antioxidant, 0.1% to 8%; Pour point depressant, 0.1% to 3%; The balance is base oil; The metal detergent comprises an alkylphenol salt having a base value of 290 to 310 mgKOH / g and a sulfonate salt having a base value of 395 to 420 mgKOH / g; The antioxidant is selected from at least two of amine antioxidants, phenol antioxidants, thiadiazole antioxidants and carbamate antioxidants.

2. The gasoline engine oil composition according to claim 1, characterized in that In terms of mass percentage, it includes the following components: Metal detergent, 2% to 4%; Dispersant, 4% to 7%; Dialkyl dithiophosphates, 0.5% to 3%; Antiwear agent, 0.1% to 2%; Antioxidant, 0.3% to 5%; Pour point depressant, 0.2% to 1%.

3. The gasoline engine oil composition according to claim 1, characterized in that In the metal detergent, the mass ratio of alkylphenol salt to sulfonate salt is 1:(0.1-10), preferably 1:(0.5-5).

4. The gasoline engine oil composition according to claim 1 or 2, characterized in that: The dispersant is selected from pentaerythritol succinate and / or polyisobutylene succinimide; Preferably, the pentaerythritol succinate is one or more of diester, half ester, cyclic ester or polyester; Preferably, the number average molecular weight of the polyisobutylene in the polyisobutylene succinimide is 500-5000.

5. The gasoline engine oil composition according to claim 1, characterized in that: The alkyl group in the dialkyl dithiophosphate is C2 to C 10 Straight chain alkyl or branched chain alkyl; And / or, the anti-wear agent is selected from at least one of polysulfide, phosphate, and thiocarbamate; and / or, the pour point depressant is selected from at least one of polymethacrylate, alkylnaphthalene or poly-α-olefin; And / or, the base oil is selected from at least one of API Group II, Group III and Group IV lubricating base oils.

6. The gasoline engine oil composition according to claim 1, characterized in that: The gasoline engine oil composition further comprises the following components in terms of mass percentage: Friction modifier, 0.1% to 5%; preferably 0.2% to 3%; The friction modifier is a mixture of an ashless friction modifier and an oil-soluble organic molybdenum friction modifier, and the mass ratio of the ashless friction modifier to the oil-soluble organic molybdenum friction modifier is 1:(0.1-5).

7. The gasoline engine oil composition according to claim 1, characterized in that: The gasoline engine oil composition further comprises the following components in terms of mass percentage: Viscosity index improver, 3% to 15%; preferably 5% to 12%; The viscosity index improver is selected from at least one of polymethacrylate, ethylene-propylene copolymer or polyisobutylene.

8. The method for preparing the gasoline engine oil composition according to any one of claims 1 to 7, characterized in that: Mixing the components at a temperature of 50 to 65° C. to obtain the gasoline engine oil composition; Preferably, the viscosity index improver, pour point depressant and base oil are mixed first.

9. The preparation method according to claim 8, characterized in that: Includes steps: (1) stirring the base oil at a temperature of 50 to 65° C. to obtain material I; (2) Add viscosity index improver and pour point depressant to material I in sequence, maintain stirring at 50-65° C. for 0.1-1 h, and obtain material II; (3) Maintaining the temperature at 50-65° C., add metal detergent, pentaerythritol succinate and / or polyisobutylene succinimide dispersant, dialkyl dithiophosphate, antiwear agent, antioxidant, and friction modifier to material II in sequence while stirring, and continue stirring at 50-65° C. for 0.5-5 h to obtain a gasoline engine oil composition.

10. Use of the gasoline engine oil composition according to any one of claims 1 to 7 or the gasoline engine oil composition obtained by the preparation method according to claim 8 or 9 in a vehicle gasoline engine system process.

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