A gasoline engine oil composition and preparation method thereof

Abstract

The present invention relates to the field of gasoline engine oil production, and in particular, to a gasoline engine oil composition and a preparation method thereof. The gasoline engine oil composition comprises the following components by weight: 20 to 50 parts of a first dispersant, 15 to 30 parts of an aromatic amine type soot ashless dispersant, 3 to 10 parts of calcium sulfonate, 3 to 10 parts of magnesium sulfonate, 2 to 10 parts of zinc dialkyl dithiophosphate, 2 to 15 parts of an amine antioxidant, 0.2 to 2 parts of a molybdenum salt, 0.03 to 0.2 parts of a silicon antifoaming agent, and 2 to 5 parts of a base oil. The gasoline engine oil composition has the properties of long service life and low low-speed pre-ignition frequency.

Description

Technical Field

[0001] The invention relates to the field of gasoline engine oil production, and in particular to a gasoline engine oil composition and a preparation method thereof. Background Art

[0002] As environmental protection efforts increase, the control of recycling waste oil is becoming more and more stringent. Therefore, reducing the generation of waste oil requires extending the oil change cycle of gasoline engine oil. At present, the most commonly used antioxidants are phenols, amines, phosphorus-containing and sulfur-containing antioxidants, among which hindered phenols and amines are the two most effective antioxidants. However, due to the relatively low molecular weight of traditional antioxidants, under high temperature conditions or as the use time goes by, they can be continuously volatilized, migrated and extracted by solvents into the atmosphere, soil and waters, causing environmental pollution, thereby causing potential impacts on human health. At the same time, after the loss of antioxidants, the lubricating oil tends to thicken, greatly reducing the service life of the lubricating oil.

[0003] Compared with port injection and naturally aspirated gasoline engines, turbocharged direct injection gasoline engines are increasingly used in the market due to their advantages of low energy consumption, strong power and flexible control. However, with the continuous increase in the boost ratio, the engine power density and the thermal load in the cylinder have increased significantly, and an abnormal combustion phenomenon has occurred in turbocharged direct injection gasoline engines. This phenomenon mainly occurs under low speed (≤1750r / min) and high load (BMEP≥15bar) conditions. The spark ignition occurs first at the beginning of combustion, which is currently called low-speed pre-ignition. Studies have shown that lubricating oil is an important cause of low-speed pre-ignition in gasoline engines, and common lubricating oils cannot reduce the frequency of low-speed pre-ignition.

[0004] The antioxidants used in the existing technical solutions for gasoline engine oil compositions are generally octylbutyl diphenylamine, dioctyl diphenylamine, di-tert-butyl-p-cresol, shielded phenols, sulfur-containing compounds, etc. These antioxidants are volatile at high temperatures and do not have a good antioxidant effect. They do not have a good ability to inhibit viscosity growth, so the oil change cycle is short. The detergents used in the existing technical solutions for gasoline engine oil compositions are generally calcium salicylate, calcium alkylphenol sulfonate, calcium sulfonate, etc. Studies have shown that the calcium content in the gasoline engine oil composition will affect low-speed pre-ignition. As the calcium content increases, the frequency of low-speed pre-ignition increases significantly.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] One aspect of the present invention relates to a gasoline engine oil composition, comprising the following components in parts by weight:

[0007] 20-50 parts of the first dispersant, 15-30 parts of aromatic amine type soot ashless dispersant, 3-10 parts of calcium sulfonate, 3-10 parts of magnesium sulfonate, 2-10 parts of dialkyl dithiophosphate zinc, 2-15 parts of amine antioxidant, 0.2-2 parts of molybdenum salt, 0.03-0.2 parts of silicon antifoaming agent and 2-5 parts of base oil.

[0008] The gasoline engine oil composition is mainly composed of amine antioxidants, aromatic amine soot ashless dispersants, magnesium sulfonate and calcium sulfonate according to a certain ratio. The components work synergistically to extend the service life of the gasoline engine oil and reduce the frequency of low-speed pre-ignition problems.

[0009] Another aspect of the present invention also relates to a method for preparing the gasoline engine oil composition, comprising the following steps:

[0010] Mix all components well.

[0011] The method for preparing the gasoline engine oil composition is simple and does not require complicated process methods. The obtained gasoline engine oil has a long service life, is not prone to the problem of low-speed pre-ignition, and has excellent performance.

[0012] Compared with the prior art, the present invention has the following beneficial effects:

[0013] (1) The gasoline engine oil composition provided by the present invention is mainly composed of components such as amine antioxidants, aromatic amine soot ashless dispersants, magnesium sulfonate and calcium sulfonate in a certain ratio. The components act synergistically to extend the service life of the gasoline engine oil and reduce the frequency of low-speed pre-ignition problems.

[0014] (2) The method for preparing the gasoline engine oil composition provided by the present invention is simple and does not require complicated process methods. The obtained gasoline engine oil has a long service life, is not prone to the problem of low-speed pre-ignition, and has excellent performance. DETAILED DESCRIPTION

[0015] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be appreciated by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work, all belong to the scope of protection of the present invention. If specific conditions are not indicated in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0016] One aspect of the present invention relates to a gasoline engine oil composition, comprising the following components in parts by weight:

[0017] 20-50 parts of the first dispersant (e.g., 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts), 15-30 parts of the aromatic amine type soot ashless dispersant (e.g., 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 28 parts or 30 parts), 3-10 parts of calcium sulfonate (e.g., 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts), 3-10 parts of magnesium sulfonate (e.g., 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts), 2-10 parts of zinc dialkyl dithiophosphate (e.g., 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts), The invention relates to a composition comprising the following: the composition comprises: a) 2-15 parts (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14 or 15 parts) of an amine antioxidant; b) 0.2-2 parts (for example, 0.2, 0.5, 0.8, 1.1, 1.4, 1.7 or 2 parts) of a molybdenum salt; c) 0.03-0.2 parts (for example, 0.03, 0.05, 0.08, 0.1, 0.13, 0.15, 0.18 or 0.2 parts) of a silicon antifoaming agent; and 2-5 parts (for example, 2, 3, 4 or 5 parts) of a base oil.

[0018] The gasoline engine oil composition is mainly composed of amine antioxidants, aromatic amine soot ashless dispersants, magnesium sulfonate and calcium sulfonate according to a certain ratio. The components work synergistically to extend the service life of the gasoline engine oil and reduce the frequency of low-speed pre-ignition problems.

[0019] The main functions of sulfonates in gasoline engine oil are: acid neutralization. Sulfonates have a large alkali reserve and can continuously neutralize the oxygen-containing acids generated by the oxidation of lubricating oil and fuel oil during use, preventing them from further oxidation and condensation, thereby reducing varnish; washing effect: sulfonates have a strong adsorption capacity for produced varnish and carbon deposits. They can wash off the varnish and carbon deposits adsorbed on the piston and disperse them in the oil; dispersing effect: sulfonates can adsorb small solid particles such as colloids and carbon particles that have been generated and disperse them in the oil. When placed together, they can gather together to form large particles and adhere to the cylinder or settle as sludge; solubilization effect: sulfonate itself is a surfactant that can dissolve liquid solutes that are originally insoluble in oil.

[0020] The amount of calcium sulfonate added will affect the problem of low-speed pre-ignition. As the calcium content in the oil increases, the frequency of low-speed pre-ignition will gradually increase. The calcium content in the oil has a certain corresponding relationship with the alkalinity. The higher the calcium content, the greater the alkalinity of the oil. The alkalinity is mainly used to neutralize the acidic substances produced during the use of the oil, so a certain alkalinity is required in the oil to achieve the effect of neutralizing the acidic substances. In the patent of the present invention, a certain amount of magnesium sulfonate is added to cooperate with a certain amount of magnesium sulfonate. Under the premise of maintaining the same alkalinity, the frequency of low-speed pre-ignition can be reduced. At the same time, it can inhibit the oxidation and deterioration of lubricating oil under high temperature conditions, reduce the formation of high-temperature deposits on the surface of the piston ring area (piston, piston ring, cylinder liner, ring groove), and under the same working conditions, the oil change cycle can be extended.

[0021] The dispersant and the high base sulfonate are combined to have a good synergistic effect, which can significantly enhance the solubilization effect while maintaining a good stabilization effect. In particular, due to the strong neutralization ability of the high base metal detergent, the acidic oxides that serve as the sludge matrix can be neutralized in time, thereby protecting the solubilization ability of succinimide from being quickly consumed by these products, so that succinimide can fully maintain and play its role as a dispersant, while maintaining the strong dispersibility of succinimide.

[0022] The aromatic amine type soot ashless dispersant has not only better anti-oxidation performance and sludge dispersibility, but also excellent soot dispersibility compared with conventional dispersants. It has better soot dispersibility. In the conventional scheme, the usual method to improve the soot dispersibility of oil products is to increase the amount of dispersant, but using too much dispersant will affect the low temperature fluidity and wear resistance of the oil products.

[0023] The dialkyl zinc dithiosulfate can decompose the peroxides generated during the use of oil products, capture free radicals and free radical decomposition, reduce the generation of oil sludge, and inhibit the viscosity growth of oil products, have a certain anti-wear effect, and reduce some harm caused by large metal wear.

[0024] The amine antioxidant is a free radical terminator, which can react with the chain carrier to make it inactive, thus terminating the oxidation reaction. Common antioxidants have relatively low molecular weights. Under high temperature conditions or over time, they can be continuously volatilized, migrated, and extracted by solvents into the atmosphere, soil, and waters, causing environmental pollution, thereby causing potential impacts on human health. At the same time, after the loss of the antioxidant, the lubricating oil tends to thicken, greatly reducing the service life of the lubricating oil. There is a potential risk of precipitation. The amine antioxidant used in the present invention is a polymeric antioxidant, which is characterized by being resistant to high temperatures, not volatile, and having good anti-oxidation and viscosity growth inhibition effects at high temperatures.

[0025] The molybdenum salt has good anti-wear and anti-oxidation properties. When added to lubricating oil, it can form a complex protective film or even a friction polymer, which can reduce the friction coefficient of the oil and make the sliding of the parts smoother. While enhancing the anti-wear and load-bearing capacity of the oil, it can also save fuel. When used in combination with an antioxidant, it can extend the oxidation induction period of the lubricating oil.

[0026] The silicon antifoaming agent can reduce the amount of foam generated by the lubricating oil, improve the fluidity of the oil film on the foam surface, make the foaming oil film thinner, and accelerate the speed of the bubbles rising to the oil surface and breaking.

[0027] The base oil serves to improve the solubility of the composition, and includes at least one of Hengli 150N, Formosa 150N or Huizhou 150N.

[0028] Preferably, the engine oil composition comprises the following components by weight:

[0029] 25-45 parts of the first dispersant, 18-25 parts of aromatic amine type soot ashless dispersant, 5-8 parts of calcium sulfonate, 5-8 parts of magnesium sulfonate, 4-7 parts of dialkyl zinc dithiophosphate, 4-12 parts of amine antioxidant, 0.05-0.15 parts of molybdenum salt and silicon antifoaming agent and 3-4 parts of base oil.

[0030] Preferably, the molecular weight of the amine antioxidant is 1000-1500 (e.g., 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450 or 1500).

[0031] Preferably, the amine antioxidant can be purchased from Vanderbilt under the model number VANLUBE9317.

[0032] Preferably, the calcium sulfonate includes at least one of a first calcium sulfonate, a second calcium sulfonate or a third calcium sulfonate.

[0033] Preferably, the alkalinity value of the first calcium sulfonate is 20-30 mgKOH / g (eg, 20 mgKOH / g, 23 mgKOH / g, 25 mgKOH / g, 28 mgKOH / g or 30 mgKOH / g).

[0034] Preferably, the base value of the second calcium sulfonate is 285-315 mgKOH / g (e.g., 285 mgKOH / g, 290 mgKOH / g, 295 mgKOH / g, 300 mgKOH / g, 305 mgKOH / g, 310 mgKOH / g or 315 mgKOH / g).

[0035] Preferably, the alkalinity value of the third calcium sulfonate is 385-415 mgKOH / g (e.g., 385 mgKOH / g, 390 mgKOH / g, 395 mgKOH / g, 400 mgKOH / g, 405 mgKOH / g, 410 mgKOH / g or 415 mgKOH / g).

[0036] Preferably, the magnesium sulfonate has a base value of 385 to 415 mgKOH / g (e.g., 385 mgKOH / g, 390 mgKOH / g, 395 mgKOH / g, 400 mgKOH / g, 405 mgKOH / g, 410 mgKOH / g or 415 mgKOH / g).

[0037] Preferably, the molecular weight of the silicon antifoaming agent is 100 to 12500 (eg, 100, 200, 300, 500 or 12500), and can be purchased from Dow Corning.

[0038] Preferably, the aromatic amine type soot ashless dispersant includes at least one of an aromatic amine type, a heteroatom ring type or a grafted type.

[0039] Preferably, the first dispersant comprises at least one of monoisobutylene succinimide, diisobutylene succinimide, polyisobutylene succinimide, boronated polyisobutylene succinimide or high molecular weight polyisobutylene succinimide.

[0040] Preferably, the molecular weight of the polymer polyisobutylene succinimide is 2100-2400.

[0041] Preferably, the dialkyl zinc dithiophosphate includes at least one of a primary alkyl zinc salt of bis-zinc thiophosphate, a primary alkyl zinc salt of butyl octyl thiophosphate, a primary alkyl zinc salt of propyl octyl thiophosphate or a basic bis-octyl zinc salt of bis-zinc thiophosphate.

[0042] Preferably, the molybdenum salt comprises at least one of dialkyl dithiocarbamate molybdenum, non-sulfur phosphorus organic molybdenum or dialkyl dithiophosphate molybdenum.

[0043] Another aspect of the present invention also relates to a method for preparing the gasoline engine oil composition, comprising the following steps:

[0044] Mix all components.

[0045] The preparation method is simple and does not require complicated process methods. The obtained gasoline engine oil has a long service life, is not prone to the problem of low-speed pre-ignition, and has excellent use performance.

[0046] Preferably, the mixing specifically includes:

[0047] The first dispersant, the aromatic amine soot ashless dispersant and the base oil are first mixed to obtain a first mixed system; an amine antioxidant, a molybdenum salt, a zinc dialkyl dithiophosphate and a silicon antifoaming agent are added to the first mixed system and then a second mixed system is obtained; and calcium sulfonate and magnesium sulfonate are added to the second mixed system and then a third mixed system is performed.

[0048] Preferably, the temperature of the first mixing is 75-85° C., and the time of the first mixing is 25-35 min.

[0049] Preferably, the temperature of the second mixing is 70-75° C., and the time of the second mixing is 25-35 min.

[0050] Preferably, the temperature of the third mixing is 70-75° C., and the time of the third mixing is 50-60 min.

[0051] The embodiments of the present invention will be described in detail below with reference to specific examples and comparative examples.

[0052] Embodiments 1 to 5

[0053] The engine oil compositions provided in Examples 1 to 5 include the following components, measured in parts by weight, as shown in Table 1.

[0054] Table 1

[0055]

[0056] Example 6

[0057] The method for preparing the gasoline engine oil composition provided in this embodiment comprises the following steps:

[0058] Add high molecular weight polyisobutylene succinimide, boronated polyisobutylene succinimide, aromatic amine type soot ashless dispersant and base oil into the production kettle in proportion, stir while heating, and stir at 80°C for 30 minutes. Then add amine antioxidant, molybdenum salt, zinc dialkyl dithiophosphate and silicon antifoaming agent, keep the temperature constant at 73°C and stir for 30 minutes. Finally, add calcium sulfonate and magnesium sulfonate, and stir at 73°C for 1 hour.

[0059] Example 7

[0060] The method for preparing the gasoline engine oil composition provided in this embodiment comprises the following steps:

[0061] Add high molecular weight polyisobutylene succinimide, boronated polyisobutylene succinimide, aromatic amine type soot ashless dispersant and base oil into the production kettle in proportion, stir while heating, and stir at 75°C for 35 minutes. Then add amine antioxidant, molybdenum salt, zinc dialkyl dithiophosphate and silicon antifoaming agent, keep the temperature constant at 70°C and stir for 35 minutes. Finally, add calcium sulfonate and magnesium sulfonate, and stir at 75°C for hours.

[0062] Example 8

[0063] The method for preparing the gasoline engine oil composition provided in this embodiment comprises the following steps:

[0064] Add high molecular weight polyisobutylene succinimide, boronated polyisobutylene succinimide, aromatic amine type soot ashless dispersant and base oil into the production kettle in proportion, stir while heating, and stir at 85°C for 25 minutes. Then add amine antioxidant, molybdenum salt, zinc dialkyl dithiophosphate and silicon antifoaming agent, keep the temperature constant at 75°C and stir for 25 minutes. Finally, add calcium sulfonate and magnesium sulfonate, and stir at 70°C for 50 minutes.

[0065] Comparative Examples 1 to 5

[0066] The engine oil compositions provided in Comparative Examples 1 to 5 include the following components, measured in parts by weight, as shown in Table 2.

[0067] Table 2

[0068]

[0069] Comparative Example 6

[0070] The only difference between this comparative example and Example 1 is that the molecular weight of the amine antioxidant is 350.

[0071] Comparative Example 7

[0072] The only difference between this comparative example and Example 1 is that the aromatic amine type soot ashless dispersant is replaced by high molecular weight polyisobutylene succinimide.

[0073] Experimental example

[0074] The gasoline engine oil compositions of Examples 1 to 5 and the gasoline engine oil compositions of Comparative Examples 1 to 7 were prepared using the preparation method provided in Example 6 to obtain the gasoline engine oil compositions.

[0075] Performance test oil solution: 59.5 parts of Dalian Hengli 150N Class II base oil, 20 parts of PAO6 Class IV base oil, 14 parts of engine oil composition, 0.5 parts of G826P pour point depressant, and 6 parts of LZ7067 viscosity index agent. Dalian Hengli 150N and PAO6 are added into a stirring kettle and stirred while heating. The mixture is heated to 70°C and stirred for 30 minutes. Then, the engine oil composition, G826P and LZ7067 prepared in the examples and comparative examples are added and stirred at 70°C for 1.5 hours to obtain ACEA C3 5W30 finished oil. The viscosity change rate after Daimler oxidation test, oxidation value test, KHT and PDSC test are performed, and the test results are shown in Table 3.

[0076] Table 3

[0077]

[0078]

[0079] Note: The lower the viscosity change rate and oxidation value, the better; the longer the PDSC time, the better; the higher the KHT grade, the better.

[0080] It can be seen from the data in Table 3 that the Daimler viscosity change rate and oxidation value of the gasoline engine oil composition of the present invention are relatively small after oxidation, indicating that the degree of oxidation is small. Under the same working conditions, the smaller the degree of oxidation, the longer the mileage. The PDSC result of the gasoline engine oil composition of the present invention represents the oxidation induction period. The longer the time, the better the antioxidant effect and the longer the mileage. KHT represents the high-temperature detergency of the oil product. The higher the grade, the better the detergency. Under the same working conditions, the better the detergency performance, the longer the oil change mileage.

[0081] Low-speed pre-ignition problem: Relevant papers have shown that calcium will increase the frequency of low-speed pre-ignition, and calcium comes from calcium sulfonate. Calcium sulfonate mainly provides the base value of the product. The base value is used to neutralize the acid in the oil during use, so the base value in the oil is very important. Using magnesium salt instead of calcium salt can reduce the frequency of low-speed pre-ignition while maintaining the same base value.

[0082] In summary, the gasoline engine oil composition provided by the present invention has the characteristics of long service life and low frequency of low-speed pre-ignition.

[0083] Although the present invention has been illustrated and described with specific embodiments, it should be appreciated that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Those skilled in the art should understand that the technical solutions described in the above embodiments may be modified, or some or all of the technical features thereof may be replaced by equivalents without departing from the spirit and scope of the present invention. However, these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention. Therefore, this means that all such replacements and modifications within the scope of the present invention are included in the appended claims.

Claims

1. A gasoline engine oil composition, characterized in that: By weight, it is composed of the following components: 20-50 parts of the first dispersant, 15-30 parts of aromatic amine type soot ashless dispersant, 3-10 parts of calcium sulfonate, 3-10 parts of magnesium sulfonate, 2-10 parts of zinc dialkyl dithiophosphate, 2-15 parts of amine antioxidant, 0.2-2 parts of molybdenum salt, 0.03-0.2 parts of silicon antifoaming agent and 2-5 parts of base oil; The molecular weight of the amine antioxidant is 1000-1500; The molecular weight of the silicon antifoaming agent is 100-500; The first dispersant comprises: at least one of monopolyisobutylene succinimide, dipolyisobutylene succinimide, polyisobutylene succinimide or boronated polyisobutylene succinimide; The molybdenum salt includes non-sulfur phosphorus organic molybdenum and / or dialkyl dithiophosphate molybdenum; The method for preparing the gasoline engine oil composition comprises the following steps: The first dispersant, the aromatic amine type soot ashless dispersant and the base oil are first mixed to obtain a first mixed system; an amine antioxidant, a molybdenum salt, a zinc dialkyl dithiophosphate and a silicon antifoaming agent are added to the first mixed system and then mixed to obtain a second mixed system; calcium sulfonate and magnesium sulfonate are added to the second mixed system and then mixed for a third time; The temperature of the first mixing is 75-85° C., and the time of the first mixing is 25-35 min; The temperature of the second mixing is 70-75° C., and the time of the second mixing is 25-35 min; The temperature of the third mixing is 70-75° C., and the time of the third mixing is 50-60 min.

2. The engine oil composition according to claim 1, characterized in that The calcium sulfonate includes at least one of a first calcium sulfonate, a second calcium sulfonate or a third calcium sulfonate.

3. The engine oil composition according to claim 2, characterized in that: The alkalinity of the first calcium sulfonate is 20-30 mgKOH / g.

4. The engine oil composition according to claim 2, characterized in that: The base value of the second calcium sulfonate is 285-315 mgKOH / g.

5. The engine oil composition according to claim 2, characterized in that: The alkalinity value of the third calcium sulfonate is 385-415 mgKOH / g.

6. The engine oil composition according to claim 1, characterized in that: The base value of the magnesium sulfonate is 385-415 mgKOH / g.

7. The engine oil composition according to claim 1, characterized in that: The dialkyl zinc dithiophosphate includes at least one of bis-octyl primary alkyl zinc thionate, butyl-octyl primary alkyl zinc thionate, propyl-octyl zinc thionate or basic bis-octyl zinc thionate.

Images