Preparation method of high-performance multifunctional heavy-load diesel engine oil complexing agent

Abstract

The invention discloses a preparation method of a high-performance multifunctional heavy-load diesel engine oil complexing agent, and relates to the technical field of engine oil. The high-performance multifunctional heavy-load diesel engine oil complexing agent is prepared from the following components in parts by weight: 6-15 parts of super-alkaline synthetic calcium sulfonate, 3-11 parts of sulfur-phosphorus secondary alcohol zinc salt, 3-8 parts of modified memory alloy nano powder, 2-9 parts of low-alkaline calcium sulfonate, 1.5-4 parts of oil-soluble graphene, 60-80 parts of a macromolecular boronized ashless dispersant and 1-5 parts of dinonyl diphenylamine. The engine oil meets the performance requirements of API CK-4-grade engine oil, has excellent high-temperature detergency, oxidation and abrasion resistance and soot dispersing capacity, can meet the requirement for prolonging the oil change period and improving the energy-saving effect, and meanwhile meets the requirements for high oxidation resistance and low ash content of LNG. The lubricating oil provided by the invention can provide better lubrication protection for an engine, can inhibit viscosity increase at a high temperature only through excellent oxidation resistance, and improves economical efficiency. And CK-4 grade requirements can be met under high-power, heavy-load and poor-quality road conditions.

Description

Technical Field

[0001] The present invention relates to the technical field of engine oil, and particularly to a preparation method of a high-performance multi-functional heavy-duty diesel engine oil compound agent. Background Art

[0002] With the development of the automotive industry, more and more heavy-duty diesel engine oils are facing problems such as oil thickening caused by soot, filter clogging, and increased deposits. A series of problems caused by soot lead to wear of related machine parts, such as valve train wear, etc. Excessive ash in the oil is likely to cause an increase in soot and piston deposits. In addition, people's requirements for environmental protection, fuel economy, and the upgrading of diesel engines. In December 2016, API launched the latest generation of diesel engine oil specification - CK-4 specification. CK-4 diesel engine oil is applicable to heavy-duty high-speed four-stroke diesel engines using exhaust gas recirculation (EGR), particulate filter (DPF) and other after-treatment technologies for vehicle exhaust. It reduces the sulfate ash in the oil, improves the anti-wear performance of the engine oil, enables the oil to have excellent anti-deposit and anti-soot capabilities, and at the same time can also provide good anti-lead and anti-metal corrosion capabilities, with good oxidation stability and shear stability, thus protecting the normal operation of the engine well and extending its service life. With the increasingly strict environmental protection regulations, gaseous fuels represented by natural gas are widely used due to their excellent environmental emission performance, high thermodynamic performance, and relatively rich reserves after combustion. The design of gas engines is significantly different from that of traditional gasoline and diesel engines. Ordinary diesel engine oils and gasoline engine oils cannot meet the lubrication requirements of gas engines. In addition to the basic requirements that the oil should have excellent detergency and dispersancy performance to effectively control piston deposits, and excellent anti-wear performance to provide comprehensive protection for lubricated parts, it also requires excellent antioxidant and anti-nitrification capabilities, and appropriate oil ash. The development and research of special gas engine oils have received more and more attention. Since there is no latest standard for gas engine oils and there is no diesel-gasoline universal engine oil in the market, the present invention provides a high-performance multi-purpose compound agent that can meet both API CK-4 and LNG engine requirements. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation method of a high-performance multi-functional heavy-duty diesel engine oil compound agent, which is applicable to high-power diesel engine oils and is composed of additives such as high-molecular boronized ashless dispersants, detergents, antioxidant friction modifiers, etc. It can meet the performance requirements of API CK-4 and LNG grades under suitable Group II, III, IV, V base oils and other functional agents (such as viscosity index improvers, pour point depressants, defoamers, etc.).

[0004] Therefore, the present invention provides the following technical solution: A high-performance multi-functional heavy-duty diesel engine oil compound agent, in parts by weight ratio, includes:

[0005]

[0006] The preparation method of the modified shape memory alloy nanopowder is as follows: Mix 18 - 24 g of silanized alloy micropowder, 9 - 15 g of boric acid, and 150 mL of xylene, heat up to 140 °C and keep the temperature for 3 h for reaction, add 20 - 25 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, continue the reaction at 120 °C for 3 h, after the reaction is completed, filter at room temperature, collect the solid crude product, wash it three times with petroleum ether and then dry it, and grind it to the nanometer particle size.

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

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

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

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

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

[0012] Further, the silanized alloy micropowder is prepared by grafting with 4-triethoxysilylbutanol.

[0013] Further, the particle size of the silanized alloy micropowder is 0.1 - 1 μm.

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

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

[0016] Further, for the nanometer particle size, the particles with a particle size of 30 - 50 nm account for 50 - 80 wt%, and the particles with a particle size of 50 - 100 nm account for 20 - 50 wt%.

[0017] A preparation method of a high-performance multi-functional heavy-duty engine oil compound, and the specific steps are as follows: Add raw materials according to the weight distribution ratio into a blending kettle, heat up to 60°C - 70°C, fully stir for 1.5 h - 2 h under normal pressure, and then pack into barrels after passing the inspection.

[0018] An application of a high-performance multi-functional heavy-duty engine oil compound in heavy-duty engine oil. Use the present invention to formulate diesel engine oils corresponding to SAE viscosity grades, and the formula is as follows:

[0019]

[0020] Further, the viscosity index improver LZ7067 is made into a 10% gum solution with mineral oil for use.

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

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0023] (1) The present invention adds a modified nano-alloy powder as the main anti-wear agent and antioxidant, which is composed of elements such as nickel, copper, iron, and tin, and is doped with a small amount of rare earth metals. The presence of the nickel and copper matrix endows the alloy powder with unique shape memory characteristics, making it have a certain elasticity. This elastic characteristic 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 enables the powder to easily adsorb and deposit on the friction surface at the initial stage of friction, playing a role similar to a micro-bearing. This role can transform the original sliding friction into rolling friction, thereby effectively reducing the surface friction coefficient. During the friction process, some nano-particles will penetrate into the depressions on 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, and then form a more stable and complete plane. In addition, due to the difference in the electrode potentials of various metal elements in the alloy powder, an electrostatic catalytic effect will occur between them. This electrostatic catalytic effect can effectively prevent the covalent aggregation of hydrocarbons in the engine oil and avoid the oxidation of these compounds into oxidation polymers, thus significantly improving the antioxidant performance 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 requirements of extending the oil change cycle, improve the energy-saving effect, and at the same time meet the requirements of high antioxidant performance and low ash content for LNG.

[0025] (3) The present invention can provide better lubrication protection for the engine. Excellent antioxidant performance can inhibit the viscosity increase at high temperatures and improve economy. It can also meet the CK-4 grade requirements under conditions of high power, heavy load, and poor road conditions. Detailed implementation mode

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0027] Embodiment 1

[0028] A high-performance multifunctional heavy-duty diesel engine oil compound includes the following components by weight ratio:

[0029]

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

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

[0032] (1) The shape 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 successively with absolute ethanol and distilled water, and then dried for use; the volume ratio of H2O2 to H2SO4 in the mixed solution is 1:0.5, and it is ground to a particle size of 0.1 μm to obtain activated alloy micropowder; the shape memory alloy is composed of 0.1% Ce, 15 wt% copper, 8 wt% iron, 5 wt% tin, and the rest is nickel;

[0033] (2) Weigh ethanol, deionized water, 4-triethoxysilylbutanol, and activated alloy micropowder. 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 micropowder is 10:1. Mix ethanol and deionized water, then add 4-triethoxysilylbutanol. After mixing evenly, adjust the pH value to 4 with glacial acetic acid, then add activated alloy micropowder, mix evenly, heat to 80 °C and reflux and stir for 23 hours, then filter. The obtained solid phase is washed with ethanol and then dried at 115 °C for 2 hours to obtain silanized alloy micropowder;

[0034] (3) Mix 18 g of silanized alloy micropowder, 9 g of boric acid, and 150 mL of xylene, heat up to 140 °C, keep the temperature for reaction for 3 h, add 20 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, and continue the reaction at 120 °C for 3 h. After the reaction is completed, filter at room temperature, collect the solid crude product, rinse it three times with petroleum ether, dry it, grind it, and the nano-particle size has 50 wt% of particles with a particle size of 30 nm and 50 wt% of particles with a particle size of 50 nm;

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

[0036] Add the raw materials according to the weight distribution ratio into a blending kettle, heat up to 60 °C, fully stir for 1.5 h under normal pressure, and then fill the qualified product into barrels after inspection.

[0037] Example 2

[0038] A high-performance multifunctional heavy-duty diesel engine oil compound includes, according to the weight portion ratio:

[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 as follows:

[0042] (1) Immerse the memory alloy in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 2 h, take out the activated alloy, rinse it successively with absolute ethanol and distilled water, and dry it for use; the volume ratio of H2O2 to H2SO4 in the mixed solution is 1:1.6, grind it to a particle size of 0.3 μm to obtain activated alloy micropowder; the memory alloy is composed of 0.3% Nd, 16.8 wt% copper, 8.5 wt% iron, 6.2 wt% tin, and the rest is nickel;

[0043] (2) Weigh ethanol, deionized water, 4-triethoxysilylbutanol, and activated alloy micropowder. 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 micropowder is 8:1. Mix ethanol and deionized water, then add 4-triethoxysilylbutanol. After mixing evenly, adjust the pH value to 4 with glacial acetic acid, then add the activated alloy micropowder, mix evenly, heat to 80 °C and reflux and stir for 23 h, then filter. Wash the obtained solid phase with ethanol, and then dry it at 115 °C for 2 h to obtain silanized alloy micropowder;

[0044] (3) Mix 19.5 g of silanized alloy micropowder, 10.5 g of boric acid, and 150 mL of xylene, heat to 140 °C and hold for 3 h, add 21 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, and continue to react at 120 °C for 3 h. After the reaction is completed, filter at room temperature, collect the solid crude product, wash it three times with petroleum ether, dry it, grind it, and the nano-particle size is such that the particles with a particle size of 35 nm account for 57 wt%, and the particles with a particle size of 60 nm account for 43 wt%.

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

[0046] Add the raw materials according to the weight distribution ratio to a blending kettle, heat to 60 °C, fully stir at normal pressure for 1.5 h - 2 h, and then fill into barrels after passing the inspection.

[0047] Example 3

[0048] A high-performance multifunctional heavy-duty diesel engine oil compound, according to the weight portion ratio, includes:

[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 shape memory alloy is immersed in a mixed solution of 30% H2O2 and 98% H2SO4 for 3 h of activation, and after taking out the activated alloy, it is rinsed successively with absolute ethanol and distilled water and dried for use; the volume ratio of H2O2 to H2SO4 in the mixed solution is 1:2.7, and it is ground to a particle size of 0.5 μm to obtain activated alloy micropowder; the shape memory alloy is composed of 0.5% Dy, 19.5 wt% copper, 9 wt% iron, 7.5 wt% tin, and the rest is nickel;

[0053] (2) Weigh ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy micropowder, where 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 micropowder is 10:1. Mix ethanol and deionized water, then add 4-triethoxysilylbutanol. After mixing evenly, adjust the pH value to 4.5 with glacial acetic acid, then add the activated alloy micropowder, mix evenly, heat to 90 °C and reflux and stir for 24 h, then filter. Wash the obtained solid phase with ethanol, and then dry it at 120 °C for 2 h to obtain silanized alloy micropowder;

[0054] (3) Mix 21 g of silanized alloy micropowder, 12 g of boric acid, and 150 mL of xylene, heat up to 140 °C and keep the temperature for 3 h of reaction, add 23 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, and continue the reaction at 120 °C for 3 h. After the reaction is completed, filter at room temperature, collect the solid crude product, wash it three times with petroleum ether and then dry it, grind it, and the nano-particle size is composed of particles with a particle size of 40 nm accounting for 65 wt% and particles with a particle size of 75 nm accounting for 35 wt%.

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

[0056] Add the raw materials according to the weight distribution ratio to a blending kettle, heat up to 70 °C, and fully stir for 2 h under normal pressure, and then fill the barrels after passing the inspection.

[0057] Example 4

[0058] A high-performance multifunctional heavy-duty diesel engine oil compound includes, according to the weight part ratio:

[0059]

[0060]

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

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

[0063] (1) The memory alloy is soaked in a mixed solution of 30% H2O2 and 98% H2SO4 for activation for 4 h, and the activated alloy is taken out and rinsed successively with absolute ethanol and distilled water, and dried for use; the volume ratio of H2O2 to H2SO4 in the mixed solution is 1:3.8, and it is ground to a particle size of 0.7 μm to obtain activated alloy micropowder; the memory alloy is composed of 0.7% Ce, 21.7 wt% copper, 9.5 wt% iron, 8.7 wt% tin, and the rest is nickel;

[0064] (2) Weigh ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy micropowder, where 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 micropowder is 8:1. Mix ethanol and deionized water, then add 4-triethoxysilylbutanol. After mixing evenly, adjust the pH value to 5 with glacial acetic acid, then add activated alloy micropowder, mix evenly, heat to 100 °C and reflux and stir for 25 h, then filter. The obtained solid phase is washed with ethanol, and then dried at 125 °C for 4 h to obtain silanized alloy micropowder;

[0065] (3) Mix 22.5 g of silanized alloy micropowder, 17.2 g of boric acid, and 150 mL of xylene, heat up to 140 °C and keep the temperature for reaction for 3 h, add 24 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, and continue the reaction at 120 °C for 3 h. After the reaction is completed, filter at room temperature, collect the solid crude product, wash it three times with petroleum ether and then dry it, grind it, and the nanoparticle size is composed of particles with a particle size of 45 nm accounting for 72 wt% and particles with a particle size of 85 nm accounting for 28 wt%.

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

[0067] Add the raw materials according to the weight distribution ratio to a blending kettle, heat up to 70 °C, and fully stir at normal pressure for 2 h, and then fill the barrels after passing the inspection.

[0068] Example 5

[0069] A high-performance multifunctional heavy-duty diesel engine oil compound includes, according to the weight portion ratio:

[0070]

[0071]

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

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

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

[0075] (2) Weigh ethanol, deionized water, 4-triethoxysilylbutanol and activated alloy micropowder, where 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 micropowder is 10:1. Mix ethanol and deionized water, then add 4-triethoxysilylbutanol. After mixing evenly, adjust the pH value to 4 with glacial acetic acid, then add activated alloy micropowder, mix evenly, heat to 100 °C and reflux and stir for 25 h, then filter. The obtained solid phase is washed with ethanol, and then dried at 125 °C for 4 h to obtain silanized alloy micropowder;

[0076] (3) Mix 24 g of silanized alloy micropowder, 15 g of boric acid, and 150 mL of xylene, heat to 140 °C and hold for 3 h for reaction, add 25 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, and continue the reaction at 120 °C for 3 h. After the reaction is completed, filter at room temperature, collect the solid crude product, wash it three times with petroleum ether, then dry, grind, and the nanoparticle size has 80 wt% of particles with a particle size of 50 nm and 20 wt% of particles with a particle size of 100 nm.

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

[0078] Add the raw materials according to the weight distribution ratio to a blending kettle, heat to 70 °C, and fully stir at normal pressure for 2 h, and then fill into barrels after passing the inspection.

[0079] Comparative Example 1 (No surface modification of the shape memory alloy)

[0080] A high-performance multi-functional heavy-duty diesel engine oil compound includes the following components by weight ratio:

[0081]

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

[0083] The shape memory alloy nanopowder consists of 0.5% Dy, 19.5 wt% copper, 9 wt% iron, 7.5 wt% tin, and the balance nickel; the nanoparticle size is composed of 65 wt% of particles with a particle size of 40 nm and 35 wt% of particles with a particle size of 75 nm.

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

[0085] Add the raw materials according to the weight distribution ratio into a blending kettle, heat up to 70°C, and fully stir for 2 h under normal pressure, and then fill the barrels after passing the inspection.

[0086] Comparative Example 2 (No modifier alloy nanopowder)

[0087] A high-performance multi-functional heavy-duty diesel engine oil compound includes the following components by weight ratio:

[0088]

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

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

[0091] Add the raw materials according to the weight distribution ratio into a blending kettle, heat up to 70°C, and fully stir for 2 h under normal pressure, and then fill the barrels after passing the inspection.

[0092] Comparative Example 3 (Replace the modified shape memory alloy nanopowder with a conventional shape memory alloy)

[0093] A high-performance multi-functional heavy-duty diesel engine oil compound includes the following components by weight ratio:

[0094]

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

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

[0097] The raw materials are added to a blending kettle according to the weight distribution ratio, heated to 70 °C, and fully stirred under normal pressure for 2 h, and then filled into barrels after passing the inspection.

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

[0099] A high-performance multifunctional heavy-duty diesel engine oil compound includes, according to the weight ratio:

[0100]

[0101]

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

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

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

[0105] (2) Weigh ethanol, deionized water, 4-triethoxysilyl butanol, and activated alloy micropowder, where the mass ratio of ethanol to deionized water is 80:1, the mass ratio of 4-triethoxysilyl butanol to ethanol is 1:50, and the mass ratio of ethanol to activated alloy micropowder is 10:1. Mix ethanol and deionized water, then add 4-triethoxysilyl butanol. After mixing evenly, adjust the pH value to 4.5 with glacial acetic acid, then add activated alloy micropowder, mix evenly, heat to 90 °C and reflux and stir for 24 h, then filter. The obtained solid phase is washed with ethanol, and then dried at 120 °C for 2 h to obtain silanized alloy micropowder;

[0106] (3) Mix 21 g of silanized alloy micropowder, 12 g of boric acid, and 150 mL of xylene, heat up to 140 °C, keep the temperature for 3 h for reaction, add 23 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, continue the reaction at 120 °C for 3 h, after the reaction is completed, filter at room temperature, collect the solid crude product, wash it three times with petroleum ether and then dry it.

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

[0108] Add the raw materials according to the weight distribution ratio to a blending kettle, heat up to 70 °C, stir fully for 2 h under normal pressure, and then fill the barrels after passing the inspection.

[0109] Comparative Example 5 (without oil-soluble graphene)

[0110] A high-performance multifunctional heavy-duty diesel engine oil compound includes, according to the weight portion ratio:

[0111]

[0112]

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

[0114] (1) Immerse the memory alloy in a mixed solution of 30% H2O2 and 98% H2SO4 for 3 h for activation, take out the activated alloy, rinse it successively with absolute ethanol and distilled water, and dry it for standby; the volume ratio of H2O2 to H2SO4 in the mixed solution is 1:2.7, grind it to a particle size of 0.5 μm to obtain activated alloy micropowder; the memory alloy is composed of 0.5% Dy, 19.5 wt% copper, 9 wt% iron, 7.5 wt% tin, and the rest is nickel;

[0115] (2) Weigh ethanol, deionized water, 4-triethoxysilylbutanol, and activated alloy micropowder, where 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 micropowder is 10:1. Mix ethanol and deionized water, then add 4-triethoxysilylbutanol, mix evenly, adjust the pH value to 4.5 with glacial acetic acid, then add the activated alloy micropowder, mix evenly, heat to 90 °C and reflux and stir for 24 h, then filter, wash the obtained solid phase with ethanol, and then dry it at 120 °C for 2 h to obtain silanized alloy micropowder;

[0116] (3) Mix 21 g of silanized alloy micropowder, 12 g of boric acid, and 150 mL of xylene, heat up to 140 °C, keep the temperature for reaction for 3 h, add 23 g of [3-(ethylthio)-1,2,4-thiadiazol-5-yl]amine, and continue the reaction at 120 °C for 3 h. After the reaction is completed, filter at room temperature, collect the solid crude product, wash it three times with petroleum ether, dry it, grind it, and the nano-particle size has 65 wt% of particles with a particle size of 40 nm and 35 wt% of particles with a particle size of 75 nm.

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

[0118] Add the raw materials according to the weight distribution ratio to a blending kettle, heat up to 70 °C, stir fully for 2 h under normal pressure, and then fill the barrels after passing the inspection.

[0119] Performance testing

[0120] 1. Example of oil blending:

[0121]

[0122] The viscosity index improver LZ7067 is used as a 10% gum solution prepared with mineral oil.

[0123] Table 1 Test results of CK-4 SAE10W-30 oil products prepared with the compound agent in Example 3 of the present invention

[0124]

[0125] Table 2 Partial bench test data of CK-4 oil products prepared with the compound agent in Example 3 of the present invention

[0126]

[0127] 2. High-temperature oxidation detergency

[0128] According to NB / SH / T0834—Determination of Moderate High-Temperature Piston Deposits in Engine Oils (Thermal Oxidation Simulation Test Method MHT), the test conditions are 285 °C and 24 h. Test the high-temperature oxidation detergency of the test sample. The smaller the sediment mass, the better the antioxidant detergency of the oil product. The experimental results are shown in the following table:

[0129] Table 3 Test data of high-temperature oxidation detergency

[0130]

[0131]

[0132] The oxidation detergency of the present invention was evaluated in the laboratory using a TEOSTM HT-4 experimental device. From the experimental data in the table, it can be concluded that the compounding agent of the present invention not only contains overbased synthetic calcium sulfonate and T104 low-base calcium sulfonate, but also contains modified shape memory alloy nanopowder and oil-soluble graphene. The compounding of these two substances can improve the high-temperature antioxidant performance of engine oil and, in synergistic action with overbased synthetic calcium sulfonate and T104 low-base calcium sulfonate, improve the high-temperature oxidation detergency of the compounding agent.

[0133] 3. Comparison of anti-wear properties

[0134] The anti-wear properties of the samples were evaluated according to SH / T 0189 Determination Method for Anti-wear Properties of Lubricating Oils (Four-ball Machine Method) (experimental conditions: 392 N, 75 °C, 1200 r / min, 60 min). The experimental result was the wear scar diameter. The smaller the wear scar diameter, the better the anti-wear performance of the sample. The specific results are shown in the following table:

[0135] Table 4 Experimental data of anti-wear property test

[0136] Wear scar 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] From the wear data in the table, it can be concluded that the composition and surface modification of the shape memory alloy nanopowder, and its compounding with oil-soluble graphene, all exhibit good anti-wear properties.

[0138] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, in any aspect, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be embraced within the present invention. Any reference signs in the claims should not be construed as limiting the claimed rights.

Claims

1. A high-performance, multifunctional, heavy-duty diesel engine oil compound, characterized in that: The proportions by weight include: The preparation method of the modified memory alloy nanopowder is as follows: silanized alloy powder, boric acid and xylene are mixed, the temperature is raised to 140° C. and then kept warm for reaction for 3 hours, [3-(ethylthio)-1,2,4-thiadiazole-5-yl]amine is added, and the reaction is continued at 120° C. for 3 hours, and after the reaction is completed, the solid crude product is filtered at room temperature to be collected, washed with petroleum ether three times, dried, and ground into nanoparticle size.

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. A high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 1, characterized in that: The alloy micropowder in the silanized alloy micropowder consists of 0.1-1% rare earth, 15-24wt% copper, 8-10wt% iron, 5-10wt% tin, and the rest is nickel.

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

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

8. 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.

9. The high-performance, multifunctional, heavy-duty diesel engine oil compound according to claim 6, characterized in that: 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 %.

10. Use of the high-performance multifunctional heavy-duty diesel engine oil compound as claimed in any one of claims 1 to 9 in an engine.

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