A method for preparing a high-performance, multifunctional, heavy-load diesel engine oil compound

Abstract

The present invention discloses a method for preparing a high-performance, multifunctional, heavy-duty diesel engine oil compound, relating to the field of engine oil technology. The high-performance, multifunctional, heavy-duty diesel engine oil compound is prepared from the following components by weight: 6-15 parts of overbased synthetic calcium sulfonate, 3-11 parts of sulfur-phosphorus secondary alcohol zinc salt, 3-8 parts of modified memory alloy nanopowder, 2-9 parts of low-alkalinity calcium sulfonate, 1.5-4 parts of oil-soluble graphene, 60-80 parts of a high-molecular-weight boronized ashless dispersant, and 1-5 parts of dinonyldiphenylamine. The compound meets the performance requirements of API CK-4 grade engine oil, exhibiting excellent high-temperature detergency, antioxidant and anti-wear properties, and excellent soot dispersibility. It can meet the requirements for extending oil change intervals, improve energy conservation, and simultaneously meet the high antioxidant and low ash content requirements of LNG. The compound provides better lubrication protection for engines, and its excellent antioxidant properties suppress viscosity growth at high temperatures, improving economic efficiency. It can also meet CK-4 grade requirements under high-power, heavy-load, and poor road conditions.

Description

Technical Field

[0001] The invention relates to the technical field of engine oils, and in particular to a method for preparing a high-performance, multifunctional, heavy-load diesel engine oil composite. Background Art

[0002] With the development of the automotive industry, heavy-duty diesel engine oils are increasingly facing challenges such as oil thickening, filter clogging, and increased deposits caused by soot. Soot-induced problems lead to wear on related components, such as valve train wear. Excessive ash content in oils can easily lead to increased soot and piston deposits. Furthermore, fuel efficiency and environmental concerns are driving demand for diesel engine upgrades. In December 2016, API introduced its latest generation diesel engine oil specification, the CK-4. CK-4 diesel engine oil is suitable for heavy-duty, high-speed, four-stroke diesel engines equipped with exhaust after-treatment technologies such as exhaust gas recirculation (EGR) and particulate filters (DPF). It reduces sulfated ash content, improves engine oil anti-wear properties, and provides excellent resistance to deposits and soot. It also offers excellent resistance to lead and metal corrosion, and exhibits excellent oxidation and shear stability, ensuring optimal engine operation and extending service life. With increasingly stringent environmental regulations, gaseous fuels, represented by natural gas, are gaining increasing popularity due to their excellent post-combustion environmental emissions performance, efficient thermodynamic properties, and relatively abundant reserves. Gas engine design differs significantly from traditional gasoline and diesel engines, and conventional diesel and gasoline engine oils cannot meet the lubrication requirements of gas engines. In addition to the basic requirements of excellent detergency and dispersancy to effectively control piston deposits, and excellent anti-wear properties to provide comprehensive protection for lubricated parts, these oils also require excellent antioxidant and anti-nitrification properties, as well as an appropriate ash content. Consequently, the development and research of specialized gas engine oils is gaining increasing attention. However, due to the lack of the latest standards for gas engine oils, there are no universal diesel and gas engine oils on the market. Therefore, the present invention provides a high-performance, multi-purpose composite that simultaneously meets API CK-4 and LNG engine requirements. Summary of the Invention

[0003] The present invention aims to provide a method for preparing a high-performance, multifunctional, heavy-duty diesel engine oil compound, which is suitable for high-power diesel engine oils. The compound is composed of a high-molecular-weight boronized ashless dispersant, a detergent, an antioxidant friction modifier, and other additives. The compound can meet the performance requirements of API CK-4 and LNG grades under the conditions of suitable Class II, III, IV, and V oils and other functional agents (such as viscosity index agents, pour point depressants, and defoamers).

[0004] To this end, the present invention provides the following technical solution: a high-performance, multifunctional, heavy-duty diesel engine oil compound, comprising, by weight:

[0005]

[0006] The modified memory alloy nanopowder is prepared by mixing 18 to 24 g of silanized alloy powder, 9 to 15 g of boric acid, and 150 mL of xylene, heating the mixture to 140° C. and then maintaining the temperature for reaction for 3 hours, adding 20 to 25 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, and continuing the reaction at 120° C. for 3 hours. After the reaction is completed, the mixture is filtered at room temperature to collect a solid crude product, which is then rinsed three times with petroleum ether, dried, and ground into a nanoparticle size.

[0007] The present invention modifies the surface of the memory alloy and introduces long-chain alkanes, which can achieve excellent dispersibility in engine oil. The boric acid ester and sulfur atoms on the surface can act as antioxidant and anti-wear additives, and synergize with the memory alloy and oil-soluble graphene to achieve excellent antioxidant and anti-wear properties.

[0008] Furthermore, the high molecular weight boronized ashless dispersant is high molecular weight polyisobutylene succinimide, with a nitrogen content of 1.0-1.1% and a boron content of ≥0.3%.

[0009] Furthermore, the calcium content of the superbased synthetic calcium sulfonate is ≥14%, and the total base number is ≥395 mgKOH / g.

[0010] Furthermore, the zinc content of the sulfur-phosphorus secondary alcohol zinc salt is ≥9.5%, the phosphorus content is ≥7.5%, and the sulfur content is 15-19%.

[0011] Furthermore, the low-alkalinity calcium sulfonate is T104 low-alkalinity calcium sulfonate.

[0012] Furthermore, the silanized alloy powder is prepared by grafting 4-triethoxysilylbutanol.

[0013] Furthermore, the particle size of the silanized alloy powder is 0.1 to 1 μm.

[0014] Furthermore, the alloy fine powder in the silanized alloy fine powder consists of 0.1-1 wt% rare earth, 15-24 wt% copper, 8-10 wt% iron, 5-10 wt% tin, and the rest is nickel.

[0015] Furthermore, the rare earth is one of Ce, Nd and Dy.

[0016] Furthermore, the nanoparticles have a particle size of 30-50 nm accounting for 50-80 wt %, and particles with a particle size of 50-100 nm accounting for 20-50 wt %.

[0017] A method for preparing a high-performance, multifunctional, heavy-duty engine oil compound comprises the following specific steps: adding raw materials according to a weight distribution ratio into a blending kettle, heating to 60-70°C, stirring thoroughly for 1.5-2 hours under normal pressure, inspecting and barreling the qualified materials.

[0018] A high-performance, multifunctional, heavy-duty engine oil compound is used in heavy-duty engine oil. The compound is used to prepare a diesel engine oil of the corresponding SAE viscosity grade. The formula is as follows:

[0019]

[0020] Furthermore, the viscosity index improver LZ7067 is mixed with mineral oil to form a 10% glue solution for use.

[0021] The blended finished oil of the present invention is analyzed for all quality indicators and its application performance is tested by multiple bench tests. The oil product has excellent performance and fully meets the API CK-4 grade requirements.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The present invention adds modified nano alloy powder as the main anti-wear agent and antioxidant, which is composed of elements such as nickel, copper, iron, tin, and doped with a small amount of rare earth metals. The presence of the nickel and copper matrix gives the alloy powder a unique deformation memory property, which makes it have a certain elasticity. This elastic property plays an important role in avoiding preferential damage to the surface during the friction process. In addition, due to its nano-scale structure, this alloy powder has an extremely high specific surface area, which allows the powder to be easily adsorbed and deposited on the friction surface in the initial stage of friction, playing a role similar to a micro bearing. This effect can convert the original sliding friction into rolling friction, thereby effectively reducing the surface friction coefficient. During the friction process, some nanoparticles will penetrate into the depressions of the friction surface. As the friction continues, the local gasoline engine oil temperature will rise. At this time, the metal elements in the nano alloy powder will penetrate into the metal surface or subsurface to form a solid solution, thereby forming a more stable and fully filled plane. In addition, due to the differences in the electrode potentials of the various metal elements in the alloy powder, electrostatic catalysis will occur between them. This electrostatic catalytic effect can effectively prevent the covalent aggregation of hydrocarbons in the engine oil, avoiding the oxidation of these compounds into oxidized polymers, thereby significantly improving the antioxidant properties of the engine oil.

[0024] (2) The present invention meets the performance requirements of API CK-4 grade engine oil, has excellent high-temperature detergency, antioxidant and anti-wear properties, and excellent soot dispersion ability, can meet the needs of extending the oil change cycle, improve energy saving, and at the same time meet the high antioxidant and low ash requirements of LNG.

[0025] (3) The present invention can provide better lubrication protection for the engine. Its excellent anti-oxidation performance can inhibit viscosity growth at high temperatures and improve economy. It can also meet CK-4 grade requirements under high power, heavy load and poor road conditions. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0027] Example 1

[0028] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0029]

[0030] The oil-soluble graphene is prepared with reference to patent CN201911313129.7;

[0031] The preparation method of the modified memory alloy nanopowder is:

[0032] (1) The memory alloy is immersed in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 1-5 hours, and the activated alloy is taken out and rinsed with anhydrous ethanol and distilled water in sequence, and dried for use; wherein the volume ratio of H2O2 to H2SO4 in the mixed solution is 1:0.5, and the alloy is ground to a particle size of 0.1 μm to obtain an activated alloy powder; the memory alloy is composed of 0.1% Ce, 15wt% copper, 8wt% iron, 5wt% tin, and the rest is nickel;

[0033] (2) Weighing ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy powder, wherein the mass ratio of ethanol to deionized water is 80:1, the mass ratio of 4-triethoxysilylbutanol to ethanol is 1:50, and the mass ratio of ethanol to activated alloy powder is 10:1, mixing ethanol and deionized water, and then adding 4-triethoxysilylbutanol, mixing evenly, adjusting the pH value to 4 with glacial acetic acid, and then adding activated alloy powder, mixing evenly, heating to 80°C and reflux stirring for 23 hours, and then filtering, washing the obtained solid phase with ethanol, and then drying at 115°C for 2 hours to obtain silanized alloy powder;

[0034] (3) 18 g of silanized alloy powder, 9 g of boric acid, and 150 mL of xylene were mixed, heated to 140 ° C and kept warm for 3 h, 20 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine was added, and the reaction was continued at 120 ° C for 3 h. After the reaction was completed, the solid crude product was filtered at room temperature and washed three times with petroleum ether, dried, and ground. The nanoparticle size was 50 wt% of the particles with a particle size of 30 nm and 50 wt% of the particles with a particle size of 50 nm;

[0035] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.0%, a boron content of 0.3%, a calcium content of 14% of superbased synthetic calcium sulfonate, a total base number of 395 mgKOH / g, a zinc content of 9.5% in sulfur-phosphorus secondary alcohol zinc salt, a phosphorus content of 7.5%, and a sulfur content of 15%.

[0036] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 60℃, stir thoroughly for 1.5 hours under normal pressure, and then pack them into barrels after inspection.

[0037] Example 2

[0038] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0039]

[0040] The oil-soluble graphene is prepared with reference to patent CN201911313129.7;

[0041] The preparation method of the modified memory alloy nanopowder is:

[0042] (1) The memory alloy was immersed in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 2 h, and the activated alloy was taken out and rinsed with anhydrous ethanol and distilled water in sequence, and dried for use; wherein the volume ratio of H2O2 to H2SO4 in the mixed solution was 1:1.6, and the alloy was ground to a particle size of 0.3 μm to obtain an activated alloy powder; the memory alloy was composed of 0.3% Nd, 16.8wt% copper, 8.5wt% iron, 6.2wt% tin, and the rest was nickel;

[0043] (2) Weighing ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy powder, wherein the mass ratio of ethanol to deionized water is 80:1, the mass ratio of 4-triethoxysilylbutanol to ethanol is 1:70, and the mass ratio of ethanol to activated alloy powder is 8:1, mixing ethanol and deionized water, and then adding 4-triethoxysilylbutanol, mixing evenly, adjusting the pH value to 4 with glacial acetic acid, and then adding activated alloy powder, mixing evenly, heating to 80°C and reflux stirring for 23 hours, and then filtering, washing the obtained solid phase with ethanol, and then drying at 115°C for 2 hours to obtain silanized alloy powder;

[0044] (3) 19.5 g of silanized alloy powder, 10.5 g of boric acid, and 150 mL of xylene were mixed, heated to 140 ° C and kept warm for 3 h, 21 g of [3-(ethylthio)-1,2,4-thiadiazole-5-yl]amine was added, and the reaction was continued at 120 ° C for 3 h. After the reaction was completed, it was filtered at room temperature to collect the solid crude product, rinsed three times with petroleum ether, dried, and ground. The nanoparticle size was 57 wt% for particles with a particle size of 35 nm and 43 wt% for particles with a particle size of 60 nm.

[0045] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.0%, a boron content of 0.4%, a calcium content of 14% of superbased synthetic calcium sulfonate, a total base number of 405 mgKOH / g, a zinc content of 9.5% in sulfur-phosphorus secondary alcohol zinc salt, a phosphorus content of 8.5%, and a sulfur content of 15%.

[0046] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 60℃, stir thoroughly for 1.5h-2h under normal pressure, and then pack them into barrels after inspection.

[0047] Example 3

[0048] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0049]

[0050] The oil-soluble graphene is prepared with reference to patent CN201911313129.7;

[0051] The preparation method of the modified memory alloy nanopowder is:

[0052] (1) The memory alloy was immersed in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 3 hours, and the activated alloy was taken out and rinsed with anhydrous ethanol and distilled water in sequence, and dried for use; wherein the volume ratio of H2O2 to H2SO4 in the mixed solution was 1:2.7, and the alloy was ground to a particle size of 0.5 μm to obtain an activated alloy powder; the memory alloy was composed of 0.5% Dy, 19.5wt% copper, 9wt% iron, 7.5wt% tin, and the rest was nickel;

[0053] (2) Weighing ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy powder, wherein the mass ratio of ethanol to deionized water is 80:1, the mass ratio of 4-triethoxysilylbutanol to ethanol is 1:50, and the mass ratio of ethanol to activated alloy powder is 10:1, mixing ethanol and deionized water, and then adding 4-triethoxysilylbutanol, mixing evenly, adjusting the pH value to 4.5 with glacial acetic acid, and then adding activated alloy powder, mixing evenly, heating to 90 ° C and reflux stirring for 24 hours, and then filtering, washing the obtained solid phase with ethanol, and then drying at 120 ° C for 2 hours to obtain silanized alloy powder;

[0054] (3) 21 g of silanized alloy powder, 12 g of boric acid, and 150 mL of xylene were mixed, heated to 140 ° C and kept warm for 3 h, 23 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine was added, and the reaction was continued at 120 ° C for 3 h. After the reaction was completed, it was filtered at room temperature to collect the solid crude product, rinsed three times with petroleum ether, dried, and ground. The nanoparticle size was 40 nm, accounting for 65 wt%, and the particle size of 75 nm accounted for 35 wt%.

[0055] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.0 and a boron content of 0.3%; the calcium content of the superbased synthetic calcium sulfonate is 14% and the total base number is 405 mgKOH / g; the zinc content of the sulfur-phosphorus secondary alcohol zinc salt is 9.5%, the phosphorus content is 7.5%, and the sulfur content is 15%.

[0056] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 70℃, stir thoroughly for 2 hours under normal pressure, and then pack them into barrels after inspection.

[0057] Example 4

[0058] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0059]

[0060]

[0061] The oil-soluble graphene is prepared with reference to patent CN201911313129.7;

[0062] The preparation method of the modified memory alloy nanopowder is:

[0063] (1) The memory alloy was immersed in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 4 hours, and the activated alloy was taken out and rinsed with anhydrous ethanol and distilled water in sequence, and dried for use; wherein the volume ratio of H2O2 to H2SO4 in the mixed solution was 1:3.8, and the alloy was ground to a particle size of 0.7 μm to obtain an activated alloy powder; the memory alloy was composed of 0.7% Ce, 21.7wt% copper, 9.5wt% iron, 8.7wt% tin, and the rest was nickel;

[0064] (2) Weighing ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy powder, wherein the mass ratio of ethanol to deionized water is 80:1, the mass ratio of 4-triethoxysilylbutanol to ethanol is 1:100, and the mass ratio of ethanol to activated alloy powder is 8:1, mixing ethanol and deionized water, and then adding 4-triethoxysilylbutanol, mixing evenly, adjusting the pH value to 5 with glacial acetic acid, and then adding activated alloy powder, mixing evenly, heating to 100 ° C and reflux stirring for 25 hours, and then filtering, washing the obtained solid phase with ethanol, and then drying at 125 ° C for 4 hours to obtain silanized alloy powder;

[0065] (3) 22.5 g of silanized alloy powder, 17.2 g of boric acid, and 150 mL of xylene were mixed, heated to 140 ° C and kept warm for 3 h, 24 g of [3-(ethylthio)-1,2,4-thiadiazole-5-yl]amine was added, and the reaction was continued at 120 ° C for 3 h. After the reaction was completed, it was filtered at room temperature to collect the solid crude product, rinsed three times with petroleum ether, dried, and ground. The nanoparticle size was 45 nm, accounting for 72 wt%, and the particle size of 85 nm accounted for 28 wt%.

[0066] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.1%, a boron content of 0.5%, a calcium content of 15% of superbased synthetic calcium sulfonate, a total base number of 410 mgKOH / g, a zinc content of 9.5% in sulfur-phosphorus secondary alcohol zinc salt, a phosphorus content of 7.5%, and a sulfur content of 17%.

[0067] Add the raw materials into the blending kettle according to the weight distribution ratio, heat to 70℃, stir thoroughly for 2 hours under normal pressure, and then pack into barrels after inspection.

[0068] Example 5

[0069] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0070]

[0071]

[0072] The oil-soluble graphene is prepared with reference to patent CN201911313129.7;

[0073] The preparation method of the modified memory alloy nanopowder is:

[0074] (1) The memory alloy is immersed in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 1-5 hours, and the activated alloy is taken out and rinsed with anhydrous ethanol and distilled water in sequence, and dried for use; wherein the volume ratio of H2O2 to H2SO4 in the mixed solution is 1:2.5, and the alloy is ground to a particle size of 1 μm to obtain an activated alloy powder; the memory alloy is composed of 1% Ce, 24wt% copper, 10wt% iron, 10wt% tin, and the rest is nickel;

[0075] (2) Weighing ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy powder, wherein the mass ratio of ethanol to deionized water is 80:1, the mass ratio of 4-triethoxysilylbutanol to ethanol is 1:100, and the mass ratio of ethanol to activated alloy powder is 10:1, mixing ethanol and deionized water, and then adding 4-triethoxysilylbutanol, mixing evenly, adjusting the pH value to 4 with glacial acetic acid, and then adding activated alloy powder, mixing evenly, heating to 100 ° C and reflux stirring for 25 hours, and then filtering, washing the obtained solid phase with ethanol, and then drying at 125 ° C for 4 hours to obtain silanized alloy powder;

[0076] (3) 24 g of silanized alloy powder, 15 g of boric acid, and 150 mL of xylene were mixed, heated to 140 ° C and kept warm for 3 h, 25 g of [3-(ethylthio)-1,2,4-thiadiazole-5-yl]amine was added, and the reaction was continued at 120 ° C for 3 h. After the reaction was completed, it was filtered at room temperature to collect the solid crude product, rinsed three times with petroleum ether, dried, and ground. The nanoparticle size was 50 nm, accounting for 80 wt%, and the particle size of 100 nm accounted for 20 wt%.

[0077] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.1%, a boron content of 0.3%, a calcium content of 14% of superbased synthetic calcium sulfonate, and a total base number of 405 mgKOH / g; the zinc content of the sulfur-phosphorus secondary alcohol zinc salt is 9.5%, the phosphorus content is 7.5%, and the sulfur content is 19%.

[0078] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 70℃, stir thoroughly for 2 hours under normal pressure, and then pack them into barrels after inspection.

[0079] Comparative Example 1 (no surface modification of memory alloy)

[0080] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0081]

[0082] The oil-soluble graphene is prepared with reference to patent CN201911313129.7;

[0083] The memory alloy nanopowder consists of 0.5% Dy, 19.5wt% copper, 9wt% iron, 7.5wt% tin, and the rest is nickel; the nanoparticle size is 40nm, accounting for 65wt%, and the particle size of 75nm accounts for 35wt%.

[0084] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.0 and a boron content of 0.3%; the calcium content of the superbased synthetic calcium sulfonate is 14% and the total base number is 405 mgKOH / g; the zinc content of the sulfur-phosphorus secondary alcohol zinc salt is 9.5%, the phosphorus content is 7.5%, and the sulfur content is 15%.

[0085] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 70℃, stir thoroughly for 2 hours under normal pressure, and then pack them into barrels after inspection.

[0086] Comparative Example 2 (alloy nanopowder without modifier)

[0087] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0088]

[0089] The oil-soluble graphene is prepared with reference to patent CN201911313129.7;

[0090] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.0 and a boron content of 0.3%; the calcium content of the superbased synthetic calcium sulfonate is 14% and the total base number is 405 mgKOH / g; the zinc content of the sulfur-phosphorus secondary alcohol zinc salt is 9.5%, the phosphorus content is 7.5%, and the sulfur content is 15%.

[0091] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 70℃, stir thoroughly for 2 hours under normal pressure, and then pack them into barrels after inspection.

[0092] Comparative Example 3 (Modified memory alloy nanopowder replaced with conventional memory alloy)

[0093] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0094]

[0095] The oil-soluble graphene is prepared with reference to patent CN201911313129.7, and the memory alloy nanopowder is titanium-nickel alloy (Ni56Ti44) with a particle size of 45 nm.

[0096] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.0 and a boron content of 0.3%; the calcium content of the superbased synthetic calcium sulfonate is 14% and the total base number is 405 mgKOH / g; the zinc content of the sulfur-phosphorus secondary alcohol zinc salt is 9.5%, the phosphorus content is 7.5%, and the sulfur content is 15%.

[0097] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 70℃, stir thoroughly for 2 hours under normal pressure, and then pack them into barrels after inspection.

[0098] Comparative Example 4 (modified memory alloy is micron structure)

[0099] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0100]

[0101]

[0102] The oil-soluble graphene is prepared with reference to patent CN201911313129.7;

[0103] The preparation method of the modified memory alloy nanopowder is:

[0104] (1) The memory alloy was immersed in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 3 hours, and the activated alloy was taken out and rinsed with anhydrous ethanol and distilled water in sequence, and dried for use; wherein the volume ratio of H2O2 to H2SO4 in the mixed solution was 1:2.7, and the alloy was ground to a particle size of 0.5 μm to obtain an activated alloy powder; the memory alloy was composed of 0.5% Dy, 19.5wt% copper, 9wt% iron, 7.5wt% tin, and the rest was nickel;

[0105] (2) Weighing ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy powder, wherein the mass ratio of ethanol to deionized water is 80:1, the mass ratio of 4-triethoxysilylbutanol to ethanol is 1:50, and the mass ratio of ethanol to activated alloy powder is 10:1, mixing ethanol and deionized water, and then adding 4-triethoxysilylbutanol, mixing evenly, adjusting the pH value to 4.5 with glacial acetic acid, and then adding activated alloy powder, mixing evenly, heating to 90 ° C and reflux stirring for 24 hours, and then filtering, washing the obtained solid phase with ethanol, and then drying at 120 ° C for 2 hours to obtain silanized alloy powder;

[0106] (3) 21 g of silanized alloy powder, 12 g of boric acid, and 150 mL of xylene were mixed, heated to 140 °C, and kept warm for 3 h. 23 g of [3-(ethylthio)-1,2,4-thiadiazole-5-yl]amine was added and the reaction was continued at 120 °C for 3 h. After the reaction was completed, the crude solid product was collected by filtration at room temperature, rinsed three times with petroleum ether, and then dried.

[0107] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.0 and a boron content of 0.3%; the calcium content of the superbased synthetic calcium sulfonate is 14% and the total base number is 405 mgKOH / g; the zinc content of the sulfur-phosphorus secondary alcohol zinc salt is 9.5%, the phosphorus content is 7.5%, and the sulfur content is 15%.

[0108] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 70℃, stir thoroughly for 2 hours under normal pressure, and then pack them into barrels after inspection.

[0109] Comparative Example 5 (no oil-soluble graphene)

[0110] A high-performance, multifunctional, heavy-duty diesel engine oil compound comprising, by weight:

[0111]

[0112]

[0113] The preparation method of the modified memory alloy nanopowder is:

[0114] (1) The memory alloy was immersed in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 3 hours, and the activated alloy was taken out and rinsed with anhydrous ethanol and distilled water in sequence, and dried for use; wherein the volume ratio of H2O2 to H2SO4 in the mixed solution was 1:2.7, and the alloy was ground to a particle size of 0.5 μm to obtain an activated alloy powder; the memory alloy was composed of 0.5% Dy, 19.5wt% copper, 9wt% iron, 7.5wt% tin, and the rest was nickel;

[0115] (2) Weighing ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy powder, wherein the mass ratio of ethanol to deionized water is 80:1, the mass ratio of 4-triethoxysilylbutanol to ethanol is 1:50, and the mass ratio of ethanol to activated alloy powder is 10:1, mixing ethanol and deionized water, and then adding 4-triethoxysilylbutanol, mixing evenly, adjusting the pH value to 4.5 with glacial acetic acid, and then adding activated alloy powder, mixing evenly, heating to 90 ° C and reflux stirring for 24 hours, and then filtering, washing the obtained solid phase with ethanol, and then drying at 120 ° C for 2 hours to obtain silanized alloy powder;

[0116] (3) 21 g of silanized alloy powder, 12 g of boric acid, and 150 mL of xylene were mixed, heated to 140 ° C and kept warm for 3 h, 23 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine was added, and the reaction was continued at 120 ° C for 3 h. After the reaction was completed, it was filtered at room temperature to collect the solid crude product, rinsed three times with petroleum ether, dried, and ground. The nanoparticle size was 40 nm, accounting for 65 wt%, and the particle size of 75 nm accounted for 35 wt%.

[0117] The high molecular boronized ashless dispersant is a high molecular weight polyisobutylene succinimide with a nitrogen content of 1.0 and a boron content of 0.3%; the calcium content of the superbased synthetic calcium sulfonate is 14% and the total base number is 405 mgKOH / g; the zinc content of the sulfur-phosphorus secondary alcohol zinc salt is 9.5%, the phosphorus content is 7.5%, and the sulfur content is 15%.

[0118] Add the raw materials into the blending kettle according to the weight distribution ratio, raise the temperature to 70℃, stir thoroughly for 2 hours under normal pressure, and then pack them into barrels after inspection.

[0119] Performance testing

[0120] 1. Oil blending example:

[0121]

[0122] The viscosity index improver LZ7067 is mixed with mineral oil to form a 10% glue solution for use.

[0123] Table 1 Test results of CK-4SAE10W-30 oil prepared by compounding agent of Example 3 of the present invention

[0124]

[0125] Table 2 Partial bench test data of CK-4 oil prepared by compounding agent of Example 3 of the present invention

[0126]

[0127] 2. High temperature oxidation cleanliness

[0128] According to NB / SH / T0834—Determination of Moderately High-Temperature Piston Deposits in Engine Oils (Thermal Oxidation Simulation Test Method MHT), the test conditions are 285°C for 24 hours. The high-temperature oxidation detergency of the test sample is tested. The smaller the deposit mass, the better the oil's anti-oxidation detergency. The test results are shown in the table below:

[0129] Table 3 High temperature oxidation detergency test data

[0130]

[0131]

[0132] The present invention uses a TEOSTMHT-4 experimental device to conduct oxidation detergency evaluation in the laboratory. From the experimental data in the table, it can be concluded that the compounding agent of the present invention not only contains superbased synthetic calcium sulfonate and T104 low-alkalinity calcium sulfonate, but also contains modified memory alloy nanopowder and oil-soluble graphene. The combination of these two substances can improve the high-temperature oxidation resistance of engine oil, and synergize with the superbased synthetic calcium sulfonate and T104 low-alkalinity calcium sulfonate to improve the high-temperature oxidation detergency of the compounding agent.

[0133] 3. Wear resistance comparison

[0134] The anti-wear properties of the samples were evaluated according to the SH / T0189 lubricating oil anti-wear performance test method (four-ball test method) (experimental conditions: 392N, 75°C, 1200r / min, 60min). The experimental results are the wear spot diameter. The smaller the wear spot diameter, the better the anti-wear performance of the sample. The specific results are shown in the table below:

[0135] Table 4 Anti-wear test experimental data

[0136] Wear spot diameter, mm Example 1 0.415 Example 2 0.419 Example 3 0.410 Example 4 0.425 Example 5 0.428 Comparative Example 1 0.430 Comparative Example 2 0.441 Comparative Example 3 0.427 Comparative Example 4 0.429 Comparative Example 5 0.425

[0137] It can be concluded from the wear data in the table that the composition and surface modification of the memory alloy nanopowder, as well as its compounding with oil-soluble graphene, all exhibit good anti-wear properties.

[0138] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A high-performance, multifunctional, heavy-duty diesel engine oil compound, characterized in that: The proportions by weight include: 6-15 parts of overbased synthetic calcium sulfonate; 3-11 parts of zinc salt of phosphorus secondary alcohol; 3-8 parts of modified memory alloy nanopowder; 2-9 parts of low-alkalinity calcium sulfonate; 1.5-4 parts of oil-soluble graphene; 60-80 parts of high molecular weight boronized ashless dispersant; 1-5 parts of dinonyldiphenylamine; The modified memory alloy nanopowder is prepared by mixing silanized alloy powder, boric acid, and xylene, heating the mixture to 140° C. and then maintaining the temperature for reaction for 3 hours, adding [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, and continuing the reaction at 120° C. for 3 hours. After the reaction is completed, the mixture is filtered at room temperature to collect a solid crude product, which is then rinsed three times with petroleum ether, dried, and ground into a nanoparticle size. The alloy fine powder in the silanized alloy fine powder consists of 0.1-1% rare earth, 15-24wt% copper, 8-10wt% iron, 5-10wt% tin, and the rest is nickel.

2. A high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 1, characterized in that: The low-alkalinity calcium sulfonate is T104 low-alkalinity calcium sulfonate.

3. A high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 1, characterized in that: The silanized alloy powder is prepared by grafting 4-triethoxysilylbutanol.

4. A high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 1, characterized in that: The particle size of the silanized alloy powder is 0.1-1 μm.

5. The high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 1, characterized in that: The rare earth is one of Ce, Nd and Dy.

6. A high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 1, characterized in that: The amount of the silanized alloy powder used is 18-24 g, the amount of boric acid used is 9-15 g, and the amount of [3-(ethylthio)-1,2,4-thiadiazole-5-yl]amine used is 20-25 g.

7. The high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 1, characterized in that: The amount of xylene used is 150 mL.

8. The high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 1, characterized in that: Among the nanoparticles, particles with a diameter of 30-50 nm account for 50-80 wt %, and particles with a diameter of 50-100 nm account for 20-50 wt %.

9. Use of the high-performance, multifunctional, heavy-duty diesel engine oil compound according to any one of claims 1 to 8 in an engine.

Images