Engine cleaning agent and preparation method thereof

Abstract

The invention discloses an engine cleaning agent and a preparation method thereof, and belongs to the field of cleaning oil. The lubricating oil comprises base oil, a surfactant, a purification dispersant, a neutralizer and an antioxidant, or also comprises other functional additives at the same time, the base oil comprises one or more of mineral oil, deep hydroisodewaxing base oil, synthetic hydrocarbon oil, synthetic ester oil and oil-soluble polyether; the surfactant is a sulfonic acid type zwitterionic surfactant; the purification dispersant is a polyisobutylene succinate type purification dispersant; the neutralizer is high-base-number composite calcium sulfonate; the antioxidant is substituted diphenylamine. The materials are heated, uniformly mixed, filtered and dehydrated to obtain the engine cleaning agent. The engine cleaning agent disclosed by the invention has the advantages of high cleaning strength, wear resistance of a cleaned engine, cost control and the like.

Description

Technical Field

[0001] This invention belongs to the field of cleaning oil technology, and more specifically, relates to an engine cleaning agent and its preparation method. Background Technology

[0002] During operation, automotive lubrication systems experience varying degrees of wear on different components. The resulting wear debris remains suspended in the engine oil, accumulating over time and eventually combining with other impurities to form sludge. This sludge adheres to pipes and pores, clogging oil passages, causing insufficient oil supply, and accelerating component wear. Currently, the quality of lubricating oils on the market varies greatly. Oils with high sulfur and phosphorus content can generate acidic substances in the engine, corroding it and producing large amounts of carbon deposits, gum, sludge, and harmful substances. This affects the engine oil's protective function, accelerates engine component wear, and reduces its lifespan. Therefore, when changing engine oil, the engine must be cleaned to remove internally deposited carbon deposits, sludge, and other impurities.

[0003] A search revealed Chinese patent application number 202310554284.8, published on September 29, 2023, which discloses a cleaning oil for an engine lubrication system. The composition includes 60-75% base oil and 25-40% functional additives; the base oil is a mixture of 400N, 500N, and 650N base oils in any mass ratio; the functional additives, by weight, include: 1-5 parts organic boron lubricant, 2-5 parts detergent-dispersant, 0.3-1 part antioxidant, 5-15 parts auxiliary agent, 0.1-0.5 parts rust inhibitor, 0.0001-0.0005 parts fatty amine-ethylene oxide condensate, 3-5 parts carbon deposit cleaner, and 4-8 parts dispersant. The core idea is to create a "temporary engine oil" with excellent cleaning capabilities, added before oil changes and used briefly, simultaneously providing lubrication and cleaning functions. However, on the one hand, carbon deposit cleaners contain ceramic particles, and it is questionable whether micron-sized ceramic particles can be 100% filtered by the oil filter or drained with the oil, which may pose a risk of wear in the long run; on the other hand, strong cleaning causes large pieces of sludge to fall off, clogging the oil pump filter or oil passages.

[0004] Chinese patent application No. 202110108796.2, published on June 11, 2021, discloses an anti-wear and environmentally friendly engine cleaning oil and its preparation method. The raw materials contain the following percentages by mass: 93.95-97.84% saturated synthetic ester oil, 0.15-1% anti-wear agent, 2-5% carbon deposit cleaner, and 0.01-0.05% antifoaming agent. The prepared engine cleaning oil exhibits good biodegradability and lubrication performance, and is safe and environmentally friendly. The core principle is the use of biodegradable saturated synthetic ester as the base oil, utilizing the natural polarity of ester oil to dissolve and disperse sludge. However, for severe carbon deposits and stubborn sludge, its gentle dissolution method may not be thorough enough, resulting in slow effectiveness; moreover, the price of synthetic ester base oil is much higher than that of mineral oil, leading to high product costs.

[0005] Therefore, in order to obtain an engine cleaning agent that combines cleaning strength, post-cleaning engine wear resistance, and cost control, it is urgent to develop an engine cleaning agent and its preparation method. Summary of the Invention

[0006] 1. The problem to be solved One of the objectives of this invention is to provide an engine cleaner that achieves excellent oil and dirt decomposition capabilities while reducing engine wear during cleaning.

[0007] Another objective of this invention is to provide a method for preparing an engine cleaner that is simple and easy to operate.

[0008] 2. Technical Solution To solve the above problems, the technical solution adopted by the present invention is as follows: The first aspect of the present invention provides an engine cleaner comprising a base oil, a surfactant, a detergent-dispersant, a neutralizer, and an antioxidant, or further comprising other functional additives. The base oil includes one or more of mineral oil, deeply hydrotreated isomerized dewaxed base oil, synthetic hydrocarbon oil, synthetic ester oil, and oil-soluble polyether; The surfactant is a sulfonic acid type zwitterionic surfactant; The detergent-dispersant is a polyisobutylene succinate type detergent-dispersant; The neutralizing agent is high-alkalinity compound calcium sulfonate; The antioxidant is a substituted diphenylamine, with substituents being tert-butyl and / or tert-octyl.

[0009] When using the above technical solution, the synergistic effect of sulfonic acid-type zwitterionic surfactant, polyisobutylene succinate-type detergent dispersant, and high-alkalinity complex calcium sulfonate not only enables joint cleaning of the engine, but also creates a protective environment during the cleaning process. Initial stage: Sulfonic acid amphoteric surfactants adsorb and penetrate into the sludge-metal interface, while high-alkalinity complex calcium sulfonate provides basic lubrication and begins to neutralize acidic substances; Stripping stage: Sulfonic acid amphoteric surfactants reduce interfacial tension, enabling the oil sludge to curl and peel off; polyisobutylene succinate dispersant begins to adsorb onto newly generated sludge particles; and high-alkalinity composite calcium sulfonate forms a lubricating protective film on the exposed metal surface after stripping. Dispersion and stabilization stage: Polyisobutylene succinate dispersant stabilizes sludge particles through steric hindrance, preventing deposition; at the same time, high-alkalinity compound calcium sulfonate continuously neutralizes the acidic contaminants washed off. Emission stage: Sulfonic acid amphoteric surfactants and polyisobutylene succinate dispersants carry pollutants and are completely discharged with the old oil; high-alkalinity complex calcium sulfonate ensures that the engine interior is in a neutral or weakly alkaline environment with no acid residue.

[0010] As one possible implementation, the method for preparing the sulfonic acid type zwitterionic surfactant is as follows: dodecyl dimethyl tertiary amine reacts with epichlorohydrin in a quaternization reaction to generate a quaternary ammonium salt cationic intermediate containing an epoxy group; then, sodium p-aminobenzenesulfonate ring-opens the epoxy group of the quaternary ammonium salt cationic intermediate; and after washing, the sulfonic acid type zwitterionic surfactant is obtained.

[0011] Specifically as follows: Step 1: Dissolve dodecyl dimethyl tertiary amine in isopropanol, stir and mix evenly, then add epichlorohydrin and 10% hydrochloric acid. The ratio of the number of moles of dodecyl dimethyl tertiary amine, the volume of isopropanol, the number of moles of epichlorohydrin, and the volume of 10% hydrochloric acid is 10:5:5:2. Step 2: Heat to 70~90℃, reflux for about 5 hours, cool to 50~65℃ to remove excess isopropanol and epichlorohydrin, and obtain a pale yellow intermediate product - a quaternary ammonium salt cationic intermediate containing epoxy groups. Step 3: Dissolve the pale yellow intermediate obtained in Step 2 and sodium p-aminobenzenesulfonate in an appropriate amount of deionized water at a molar ratio of 2:1, heat to 80~90℃, stir for about 24 h, and then remove the solvent by rotary evaporation to obtain the crude product. Step 4: Wash the crude product from Step 3 three times with ethyl acetate, and dry it to obtain a sulfonic acid type zwitterionic surfactant.

[0012] When using the above technical solution, the sulfonic acid-type zwitterionic surfactant has a hydrophilic sulfonic acid group (negatively charged) at one end and a lipophilic long-chain alkyl group at the other end, along with a quaternary ammonium salt group (positively charged). During engine cleaning, its lipophilic end adsorbs onto oil particles, while its hydrophilic end extends into the surrounding oil, penetrating into the tiny gaps at the oil-metal interface. On the one hand, this reduces the interfacial tension between the oil and the cleaning oil, weakening the adhesion of the oil to the metal surface; on the other hand, it forms a double electric layer between the oil particles and the metal surface, generating electrostatic repulsion and further promoting peeling. Simultaneously, due to the excellent wetting properties of zwitterionic surfactants, they can more effectively change the metal surface from hydrophobic to hydrophilic. When the contact angle of the surface changes, the robust oil film curls and contracts from the edges, eventually peeling off completely from the metal surface and breaking into tiny particles.

[0013] As one possible implementation, the preparation method of the polyisobutylene succinate type detergent dispersant is as follows: polyisobutylene succinic anhydride undergoes an esterification reaction with polyglycerol, and the polar polyglycerol head group is attached to the non-polar polyisobutylene long chain. The product is purified and washed to obtain the polyisobutylene succinate type detergent dispersant.

[0014] Specifically: (1) Take polyisobutylene succinic anhydride and polyglycerol in a molar ratio of 1:1 and add them to the reaction vessel. Add xylene as a solvent and dehydrating agent, and stir until the raw materials are fully dissolved. (2) Heat to 80~100℃, stir and react for 16~20 h, cool to 50℃, remove solvent by rotary evaporation to obtain the desired crude product; (3) Wash the crude product obtained in step (2) three times with n-octane and dry it to obtain a polyisobutylene succinate type detergent dispersant.

[0015] When using the above technical solution, the polyisobutylene succinate-type detergent dispersant comprises a polar succinate "head" and a non-polar polyisobutylene long-chain "tail": after the surfactant peels off and breaks down large oil sludge particles into tiny particles, the polar head of the dispersant firmly "anchors" to the surface of these particles through acid-base action or polar adsorption. The non-polar polyisobutylene long chain extends outward from the particle surface, forming a three-dimensional barrier around the particles. When two particles carrying dispersant molecules approach each other, their polyisobutylene long chains compress against each other, generating a strong physical repulsive force (steric hindrance effect), thereby effectively preventing particle re-aggregation (flocculation) and deposition. It should be noted that while avoiding sludge formation, this also ensures the normal flow of cleaning oil in the narrow oil passages of the engine, preventing blockages.

[0016] As one possible implementation, the preparation method of the high-alkalinity complex calcium sulfonate is as follows: Specifically: Step a): Add heavy alkylbenzene sulfonic acid and base oil to the reaction vessel, followed by calcium hydroxide, xylene, and methanol. React at 50-70°C for 1-2 hours. The mass percentage of heavy alkylbenzene sulfonic acid is 30%-55%, the mass percentage of base oil is approximately 20%-40%, the molar ratio of heavy alkylbenzene sulfonic acid to calcium hydroxide is 2:1, and the remainder is xylene and methanol, until the reaction system is dissolved. Step b): Add sec-butanol, calcium hydroxide and calcium oxide in a mass ratio of 2:1 to the above reaction product, introduce carbon dioxide, and react at 40~60℃ until the reaction is complete; wherein, the mass of calcium hydroxide and calcium oxide mixture accounts for 0.5%~2.5% of the total feed amount, and the carbon dioxide introduction rate is 400 mL / min; Step c): After the reaction reaches the target, filter to remove residue, remove excess solvent by rotary evaporation, and dry to obtain the desired high-alkalinity complex calcium sulfonate.

[0017] When using the above technical solution, the core of high-alkalinity calcium sulfonate is calcium carbonate microcrystals, which are encapsulated by calcium sulfonate molecules. On one hand, during the cleaning process, when the cleaning oil flows through heavy-duty components such as camshafts and tappets, localized high temperatures and pressures are generated. The alkaline components in the high-alkalinity calcium sulfonate undergo a brief decomposition under high pressure, reacting chemically on the metal surface to form an extremely thin protective film with extreme pressure anti-wear properties. This film fills the lubrication gap caused by the dilution or draining of old engine oil, providing crucial temporary protection for the engine in a "dry cleaning" state and greatly reducing the risk of wear during the cleaning process. On the other hand, acidic oxides (such as sulfuric acid and nitric acid) generated during engine operation are the source of sludge formation and metal corrosion. High-alkalinity calcium sulfonate stores a large amount of alkaline substances, which can continuously neutralize these acidic substances, maintaining a "clean" cleaning oil environment. This not only helps remove existing deposits but also prevents corrosion of metal parts, thereby "improving service life." It should be noted that calcium sulfonate itself also has a certain degree of detergency, helping to prevent the formation of high-temperature deposits.

[0018] As one possible implementation, the tert-butyl / octyl-substituted diphenylamine is prepared by: obtaining tert-butyl / octyl-substituted diphenylamine by Friedel-Crafts alkylation reaction. Specifically: Step 1: Add diphenylamine, diisobutylene, and copper wire catalyst sequentially to the reactor, heat to 180-200℃ under nitrogen atmosphere, and stir for about 12 hours; wherein, the molar ratio of diphenylamine to diisobutylene is controlled between 1:1.1 and 1:1.9, and diisobutylene is in excess. Step 2: Cool the reaction vessel to room temperature, filter to remove impurities, and distill to remove excess diisobutylene to obtain tert-butyl / octyl-substituted diphenylamine.

[0019] When the above technical solution is adopted, the antioxidant is tert-butyl / octyl-substituted diphenylamine. Diphenylamine itself has certain antioxidant properties, and the introduction of long-chain alkyl chains can significantly improve its oil solubility, thereby broadening its application range. Combined with other functional additives, it can provide good protection for engine parts while cleaning.

[0020] As one possible implementation, the other functional additives include, but are not limited to, rust inhibitors.

[0021] As one possible implementation, the mass fractions of each reagent are: 2-10 parts of surfactant; 0.3-1.5 parts of detergent-dispersant; Neutralizing agent 0.03~0.15 parts; Antioxidant 0.5~1.5 parts; Other functional additives: 0.05~0.2 parts; Base oil 85-98 parts.

[0022] As one possible implementation, the base oil is preferably a mixture of synthetic hydrocarbon oil and synthetic ester oil, wherein the synthetic hydrocarbon oil is selected as polyalphaolefin, and the polyalphaolefin and synthetic ester base oil are blended and used in a mass ratio of 10:(1~2).

[0023] When using the above technical solution, the base oil is a blend of polyalphaolefin (PAO) and synthetic ester-type base oil. This addresses two issues: firstly, PAO can cause some rubbers to shrink or harden, affecting sealing performance; secondly, it can solve the problem of poor solubility of PAO for certain additives. Furthermore, since synthetic ester-type base oils are expensive, adding a small amount in a blend with PAO can control costs while achieving excellent performance.

[0024] As one possible implementation, the selection criteria for the synthetic ester oil are: kinematic viscosity at 40°C between 30 and 150 mmHg. 2 The kinematic viscosity at 100℃ is between 6 and 20 mm / s. 2 Between / s, the pour point is not higher than -40℃.

[0025] When the above technical solution is adopted, the use of this synthetic ester base oil can effectively meet the formulation requirements of the present invention, work synergistically with another base oil, and extend the service life of the oil.

[0026] The second aspect of the present invention provides a method for preparing an engine cleaner, comprising the following steps: adding base oil to a reactor, stirring and heating to 50-70°C, adding surfactant, detergent-dispersant, neutralizer, antioxidant and other functional additives, stirring for 2-3 hours, filtering, and then dehydrating to obtain the above-mentioned engine cleaner.

[0027] By adopting the above technical solution, and through research on the selection and compatibility of base oils and additives, and with the assistance of appropriate preparation process parameters, a high-performance engine cleaner is prepared that not only has strong cleaning ability, but also has good comprehensive performance, which can ensure the long-term stable operation of the engine.

[0028] As one possible implementation scheme, the preparation method includes the following steps: S1. Preparation of surfactants, detergents, dispersants, neutralizers, antioxidants and other functional additives; S2. Add the base oil to the reactor, stir and heat to 50~70℃; S3. Continue adding surfactants, detergents, dispersants, neutralizers, antioxidants and other functional additives, and continue stirring for 2-3 hours until the mixture is homogeneous and a mixture is obtained. S4. Filter and dehydrate the mixture from step S3 to obtain a high-performance engine cleaner.

[0029] 3. Beneficial effects Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The cleaning agent of the present invention, through the selection of base oils, additives and other raw materials, and the study of the compatibility and synergistic effect between components, not only improves the cleaning ability of the product, but also effectively lubricates the internal parts of the engine, prevents wear and corrosion, alleviates the production of carbon deposits and sludge, and ensures the cleanliness of the machine's interior. At the same time, the lubricating oil of the present invention also has good biodegradability, thus effectively meeting the environmentally friendly concept. Furthermore, it has low manufacturing costs and high economic benefits compared to using imported oils.

[0030] (2) Excellent sludge and carbon deposit decomposition ability is essential for engine cleaners. The cleaner of this invention, on the one hand, selects a sulfonic acid-type zwitterionic surfactant. The molecular structure of this surfactant contains both hydrophilic and lipophilic groups, which can form a stable film at the oil-water interface, reduce the interfacial tension between oil and water, and weaken the adsorption of sludge and carbon deposits on the surface of parts, so that the oil stains can be peeled off, effectively improving the cleaning ability of the oil. This agent is a gemini surfactant. Compared with traditional single-chain surfactants, the critical micelle concentration of gemini surfactants is one or more orders of magnitude lower. Therefore, the amount of gemini surfactant used is less and it is more environmentally friendly. At the same time, gemini surfactants have both anionic and cationic groups, which greatly improves the salt resistance. The rigid groups in its molecular structure also greatly improve its temperature resistance. Therefore, this agent is more stable and has a longer lifespan. Secondly, excellent detergency and dispersancy are also essential for engine cleaners. Engine oil produces acidic gums and acidic oxides during operation, and over time, it accumulates a large amount of sludge and carbon deposits. These deposits can clump together and clog oil passages during cleaning, thus requiring the cleaner to possess excellent detergency and dispersancy. This invention uses a polyisobutylene succinate-type detergency and dispersant. The polar 'head' of this molecule is a polyamine substance that can adsorb deposits. Then, the lipophilic 'tail' of the polyisobutylene chain, with its good solubility in fuel, transforms oxidized gums and other deposits into a suspended state. Simultaneously, the polar groups at the head of the detergency and dispersant adsorb onto small particles formed by oxidation, and its long tail acts as a steric hindrance, preventing these small particles from agglomerating and keeping them in suspension. Furthermore, when the concentration of the detergency and dispersant molecules in the oil is high, they aggregate to form micelles with polar groups facing inward and lipophilic groups facing outward. These micelles can surround the generated oil-insoluble polar substances within themselves, dispersing them in the oil as if the insoluble substances had been dissolved. These combined capabilities enable more thorough cleaning of oil stains and prevent clogging of oil passages.

[0031] Based on this, the neutralizing agent uses high-alkalinity compound calcium sulfonate, which has excellent acid-base neutralization ability and thermal stability, further improving the cleaning ability of the cleaning agent and extending the service life of the new oil.

[0032] (3) The selection of base oil in the cleaning agent of this invention is directly related to whether the final lubricating oil can meet all performance requirements. Considering the lubrication characteristics of the engine and its operating conditions, a suitable synthetic oil is selected as the base oil for the oil being developed. Synthetic oils include synthetic hydrocarbon oils, polyether oils, ester oils, silicone oils, etc. Through extensive experimental research, the applicant has found that polyalphaolefin (PAO) among synthetic hydrocarbons is particularly suitable for lubricating oils used at high temperatures or over a wide temperature range, as well as for applications in cold regions and outdoor machinery where general mineral oils cannot meet the requirements. Therefore, a high-oxygen synthetic hydrocarbon base oil is selected as the main component of the blending oil, and polyalphaolefin is further preferred. This type of base oil has the characteristics of high viscosity index and low volatility, as well as excellent low temperature performance and excellent oxidation stability, which can ensure the basic performance of gear oil.

[0033] (4) The cleaning agent of the present invention has excellent comprehensive performance, mainly in that: ① Excellent cleaning ability: Utilizing novel surfactants and detergent-dispersants, it effectively removes oil stains from inside the engine while dispersing them in the oil, preventing oil passage blockage during cleaning. Simultaneously, the neutralizing agent added in this invention effectively neutralizes acidic oil stains, improving the internal engine environment and reducing the formation of new sludge.

[0034] ② Excellent oil compatibility: By selecting synthetic base oils as solvents, the product is better compatible with mainstream engine oils on the market.

[0035] ③ Excellent engine protection capability: This invention uses a new type of antioxidant that can solve the oxidation problem from the mechanism. When used in conjunction with a rust inhibitor, it can prevent engine rust and prevent the engine from being corroded by oxides, thus extending the engine's service life. Detailed Implementation

[0036] The present invention will be further described below with reference to specific embodiments.

[0037] First, surfactants, detergent-dispersants, neutralizing agents, and antioxidants were prepared separately for use in each example and comparative example: I. Preparation of sulfonic acid type zwitterionic surfactants Step 1: Dissolve dodecyl dimethyl tertiary amine in isopropanol, stir and mix evenly, then add epichlorohydrin and 10% hydrochloric acid. The ratio of the number of moles of dodecyl dimethyl tertiary amine, the volume of isopropanol, the number of moles of epichlorohydrin, and the volume of 10% hydrochloric acid is 10:5:5:2. Step 2: Heat to 70~90℃, reflux for about 5 hours, cool to 50~65℃ to remove excess isopropanol and epichlorohydrin, and obtain a pale yellow intermediate product. Step 3: Dissolve the pale yellow intermediate obtained in Step 2 and sodium p-aminobenzenesulfonate in an appropriate amount of deionized water at a molar ratio of 2:1, heat to 80~90℃, stir for about 24 h, and then remove the solvent by rotary evaporation to obtain the crude product. Step 4: Wash the crude product from Step 3 three times with ethyl acetate, and dry it to obtain a sulfonic acid type zwitterionic surfactant for later use.

[0038] II. Preparation of Polyisobutylene Succinate Type Detergent Dispersant (1) Take polyisobutylene succinic anhydride and polyglycerol in a molar ratio of 1:1 and add them to the reaction vessel. Add a certain amount of xylene as a solvent and dehydrating agent, and stir until the raw materials are fully dissolved. (2) Heat to 80~100℃, stir and react for 16~20 h, cool to 50℃, remove solvent by rotary evaporation to obtain the desired crude product; (3) Wash the crude product obtained in step (2) three times with n-octane, and dry it to obtain polyisobutylene succinate type detergent dispersant for later use.

[0039] III. Preparation of High-Alkalinity Compound Calcium Sulfonate Neutralizing Agent Step a): Add an appropriate amount of heavy alkylbenzene sulfonic acid and base oil to the reaction vessel, followed by calcium hydroxide, xylene, and methanol. React at 50-70℃ for 1-2 hours. The mass percentage of heavy alkylbenzene sulfonic acid is 30%-55%, the mass percentage of base oil is about 20%-40%, the molar ratio of heavy alkylbenzene sulfonic acid to calcium hydroxide is 2:1, and the remainder is xylene and methanol, until the reaction system is dissolved. Step b): Add sec-butanol, calcium hydroxide and calcium oxide in a mass ratio of 2:1 to the above reaction product, introduce carbon dioxide, and react at 40-60℃ until the reaction is complete; wherein, the mass of calcium hydroxide and calcium oxide mixture accounts for 0.5%~2.5% of the total feed amount, and the carbon dioxide introduction rate is 400 mL / min; Step c): After the reaction reaches the target, filter to remove slag, remove excess solvent by rotary evaporation, and dry to obtain the required high-alkalinity complex calcium sulfonate as a neutralizing agent for later use.

[0040] IV. Preparation of tert-butyl / octyl-substituted diphenylamine antioxidants Alkylation of diphenylamine yields tert-butyl / octyl-substituted diphenylamines. Specifically: Step 1: Add diphenylamine, diisobutylene, and copper wire catalyst sequentially to the reactor, heat to 180-200℃ under nitrogen atmosphere, and stir for about 12 hours; wherein, the molar ratio of diphenylamine to diisobutylene is controlled between 1:1.1 and 1:1.9, and diisobutylene is in excess. Step 2: Cool the reaction vessel to room temperature, filter to remove impurities, and distill to remove excess diisobutylene to obtain tert-butyl / octyl-substituted diphenylamine as an antioxidant for later use.

[0041] In addition, to enhance the engine's rust prevention capabilities, a rust inhibitor (T711 from Wuhan Jiyesheng Chemical Co., Ltd.) is added in the specific implementation. Simultaneously, the synthetic ester base oil uses Mobil's Esterex synthetic ester, with a kinematic viscosity of 30~150 mmHg at 40°C. 2 The kinematic viscosity at 100℃ is between 6 and 20 mm / s. 2 Between / s, the pour point is not higher than -40℃.

[0042] Example 1 This embodiment describes a method for preparing an engine cleaning agent, comprising the following steps: S1. Prepare surfactants, detergents, dispersants, antioxidants, and neutralizers, and select rust inhibitors as other additives; S2. Blend 93.35 parts of base oil, mix polyalphaolefin and synthetic ester base oil in a mass ratio of 10:1 until uniform, stir and heat to 50~70℃; S3. Add 5 parts surfactant, 1 part detergent-dispersant, 0.5 parts antioxidant, 0.1 parts rust inhibitor, and 0.05 parts neutralizer. Continue stirring for 2-3 hours until evenly mixed. Note that... S4. The product obtained in step S3 is filtered and dehydrated to obtain the engine cleaning agent of this embodiment.

[0043] The obtained engine cleaner was tested, and the test results are shown in Table 1.

[0044] Example 2 This embodiment describes a method for preparing an engine cleaner, comprising the following steps: S1. Prepare surfactants, detergents, dispersants, antioxidants, and neutralizers, and select rust inhibitors as other additives; S2. Blend 97.12 parts of base oil, mix polyalphaolefin and synthetic ester base oil in a mass ratio of 10:1.3, stir and heat to 50~70℃; S3. Add 2 parts surfactant, 0.3 parts detergent dispersant, 0.5 parts antioxidant, 0.05 parts rust inhibitor, and 0.03 parts neutralizer. Continue stirring for 2-3 hours until the mixture is homogeneous. S4. The product obtained in step S3 is filtered and dehydrated to obtain the engine cleaning agent of this embodiment.

[0045] The obtained engine cleaner was tested, and the test results are shown in Table 1.

[0046] Example 3 This embodiment describes a method for preparing an engine cleaner, comprising the following steps: S1. Prepare surfactants, detergents, dispersants, antioxidants, and neutralizers, and select rust inhibitors as other additives; S2. Blend 89.95 parts of base oil, mix polyalphaolefin and synthetic ester base oil in a mass ratio of 10:1.6, stir and heat to 50~70℃; S3. Add 8 parts surfactant, 0.8 parts detergent-dispersant, 1 part antioxidant, 0.15 parts rust inhibitor, and 0.1 parts neutralizer. Continue stirring for 2-3 hours until the mixture is homogeneous. S4. The product obtained in step S3 is filtered and dehydrated to obtain the engine cleaning agent of this embodiment.

[0047] The obtained engine cleaner was tested, and the test results are shown in Table 1.

[0048] Example 4 This embodiment describes a method for preparing an engine cleaning agent, comprising the following steps: S1. Prepare surfactants, detergents, dispersants, antioxidants, and neutralizers, and select rust inhibitors as other additives; S2. Blend 86.65 parts of base oil, mix polyalphaolefin and synthetic ester base oil in a mass ratio of 10:2, stir and heat to 50~70℃; S3. Add 10 parts surfactant, 1.5 parts detergent-dispersant, 1.5 parts antioxidant, 0.2 parts rust inhibitor, and 0.15 parts neutralizer. Continue stirring for 2-3 hours until the mixture is homogeneous. S4. The product obtained in step S3 is filtered and dehydrated to obtain the engine cleaning agent of this embodiment.

[0049] The obtained engine cleaner was tested, and the test results are shown in Table 1.

[0050] Example 5 The preparation method of the engine cleaner in this embodiment is basically the same as that in Embodiment 1, except that the base oil is only polyalphaolefin.

[0051] The obtained engine cleaner was tested, and the test results are shown in Table 2.

[0052] Example 6 The preparation method of the engine cleaner in this embodiment is basically the same as that in Embodiment 1, except that the base oil is mineral oil (ExxonMobil).

[0053] The obtained engine cleaner was tested, and the test results are shown in Table 2.

[0054] Example 7 The preparation method of the high-performance engine cleaner in this embodiment is basically the same as that in Example 1, except that the base oil used is a deeply hydrotreated isomerized dewaxed base oil (YUBASE® base oil from SK Korea).

[0055] The obtained high-performance engine cleaner was tested, and the test results are shown in Table 2.

[0056] Example 8 The preparation method of this comparative example of a high-performance engine cleaner is basically the same as that of Example 1, except that the base oil used is an oil-soluble polyether (Dow: UCON™ 50-HB series).

[0057] The obtained engine cleaner was tested, and the test results are shown in Table 2.

[0058] Comparative Example 1 The preparation method of the engine cleaner in this comparative example is basically the same as that in Example 1, except that the neutralizing agent used is Petro 22N LIQUID alkyl naphthalene sulfonate.

[0059] The obtained engine cleaner was tested, and the test results are shown in Table 3.

[0060] Comparative Example 2 The preparation method of the engine cleaner in this comparative example is basically the same as that in Example 1, except that the cleaning and dispersing agent used is alkyl salicylate (China Petroleum Lanzhou: T109).

[0061] The obtained engine cleaner was tested, and the test results are shown in Table 4.

[0062] Comparative Example 3 The preparation method of the engine cleaner in this comparative example is basically the same as that in Example 1, except that the antioxidant is a single amine alkylation agent (Tianjin Zhengda T531).

[0063] The obtained engine cleaner was tested, and the test results are shown in Table 5.

[0064] Comparative Example 4 The preparation method of the engine cleaner in this comparative example is basically the same as that in Example 1, except that the surfactant used is polyisobutylene succinimide.

[0065] The obtained engine cleaner was tested, and the test results are shown in Table 6.

[0066] Performance testing (1) Cleaning test The cleaning test includes the following steps: 1. Preparation of oil sludge: Add 200g of Shell Helix Super 10W-40 engine oil to a 1000ml beaker and heat to 300℃ with stirring at 800rpm. While stirring, add 10g of 10% H2SO4 solution, maintaining stirring, and then add 10g of #1 carnauba wax. Heat for 72 hours, then cool to room temperature to obtain the test oil sludge.

[0067] 2. Sample preparation: Prepare a 76×25×4mm glass plate, and record the weight of the blank plate as m0. Heat the oil sludge to 100℃, drop it onto the glass plate, cool it to room temperature, and weigh it, recording the weight as m1.

[0068] 3. Cleaning: Place the test plate into a beaker containing 450ml of cleaning agent and start the stirring device. Test for 60 seconds, keeping the temperature at room temperature and the stirring speed at 400rpm.

[0069] 4. Weighing: After cleaning, place the test plate in a beaker containing petroleum ether for 1 minute, then remove the test plate, dry it at 50°C for 1 hour, cool it to room temperature, and weigh it. The weight is recorded as m2.

[0070] 5. Calculation: Cleaning rate = (m1 - m2) ÷ (m1 - m0) × 100% The cleaning rate rating is as follows:

[0071] (2) Conduct copper strip corrosion test according to GB / T 5096. Table 1. Test results of the high-performance engine cleaners obtained in Examples 1-4

[0072] As can be seen from the test results of Examples 1 to 4 in Table 1, the engine cleaning agents prepared in Examples 1 to 4 have strong cleaning ability, low corrosiveness, and excellent performance.

[0073] Table 2 Test results of the high-performance engine cleaners obtained in Examples 5-8

[0074] As can be seen from the data in Table 2, replacing the base oil with a single polyalphaolefin, mineral oil, deeply hydrotreated isomerized dewaxed base oil, oil-soluble polyether, etc. in Examples 5-8 respectively resulted in slight deficiencies in overall performance.

[0075] Table 3. Performance comparison results of the engine cleaners obtained in Comparative Example 1 and Example 1

[0076] As shown in Table 3, after the neutralizer was replaced in Comparative Example 1, the cleaning ability and corrosion resistance of the cleaning agent decreased.

[0077] Table 4. Performance comparison results of the high-performance engine cleaners obtained in Comparative Example 2 and Example 1

[0078] As shown in Table 4, the cleaning ability of the cleaning agent decreased after the detergent-dispersant was replaced in Comparative Example 2.

[0079] Table 5. Performance comparison results of the high-performance engine cleaners obtained in Comparative Example 3 and Example 1

[0080] As shown in Table 5, the corrosion resistance of Comparative Example 3 decreased after the antioxidant was replaced, proving that the performance of the replaced antioxidant was not as good as the original.

[0081] Table 6. Performance comparison results of the high-performance engine cleaners obtained in Comparative Example 4 and Example 1

[0082] As shown in Table 6, the cleaning ability decreased after the surfactant was replaced in Comparative Example 4, proving that the performance of the replaced surfactant was not as good as the original.

[0083] In summary, the engine cleaning agents prepared in Examples 1-8 of this invention have the characteristics of strong cleaning ability and excellent overall performance.

[0084] More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, such as combinations between various embodiments, adaptive changes, and / or substitutions, as would be apparent to those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly as used in the language of the claims and are not limited to the examples described in the foregoing detailed description or during the implementation of this application, which should be considered non-exclusive. Any step listed in any method or process claim may be performed in any order and is not limited to the order set forth in the claims. Therefore, the scope of the invention should be determined solely by the appended claims and their legal equivalents, and not by the description and examples given above.

[0085] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In case of conflict, the definitions in this specification shall prevail. When a rate, pressure, temperature, time, or other value or parameter is expressed as a range, preferred range, or a range defined by a series of upper and lower preferred values, this shall be understood to specifically disclose all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether such range is disclosed individually. For example, the range 1-50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, as well as all decimal values ​​between the integers mentioned above, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. Regarding subranges, specifically consider "nested subranges" extending from any endpoint of the range. For example, nested sub-ranges of the exemplary range 1-50 may include 1-10, 1-20, 1-30 and 1-40 in one direction, or 50-40, 50-30, 50-20 and 50-10 in another direction.

Claims

1. An engine cleaner, characterized in that: It includes base oils, surfactants, detergents and dispersants, neutralizers and antioxidants, and may also contain other functional additives; The base oil includes one or more of mineral oil, deeply hydrotreated isomerized dewaxed base oil, synthetic hydrocarbon oil, synthetic ester oil, and oil-soluble polyether; The surfactant is a sulfonic acid type zwitterionic surfactant; The detergent-dispersant is a polyisobutylene succinate type detergent-dispersant; The neutralizing agent is high-alkalinity compound calcium sulfonate; The antioxidant is a substituted diphenylamine.

2. The engine cleaner according to claim 1, characterized in that: The method for preparing the sulfonic acid type zwitterionic surfactant is as follows: dodecyl dimethyl tertiary amine reacts with epichlorohydrin in a quaternization reaction to generate a quaternary ammonium salt cationic intermediate containing an epoxy group. Subsequently, sodium p-aminobenzenesulfonate ring-opens the epoxy group of the quaternary ammonium salt cationic intermediate containing an epoxy group. After washing, the sulfonic acid type zwitterionic surfactant is obtained.

3. The engine cleaner according to claim 2, characterized in that: The molar ratio of dodecyl dimethyl tertiary amine to epichlorohydrin is 2:1; the molar ratio of monosodium p-aminobenzenesulfonate to the quaternary ammonium salt cationic intermediate containing epoxy groups is 1:

2.

4. The engine cleaner according to claim 1, characterized in that: The preparation method of the polyisobutylene succinate type detergent dispersant is as follows: polyisobutylene succinic anhydride undergoes an esterification reaction with polyglycerol, and the polar polyglycerol head group is attached to the non-polar polyisobutylene long chain. The product is purified and washed to obtain the polyisobutylene succinate type detergent dispersant.

5. An engine cleaner according to claim 4, characterized in that: The molar ratio of polyisobutylene succinic anhydride to polyglycerol is 1:

1.

6. The engine cleaner according to claim 1, characterized in that: The preparation method of the high-alkalinity complex calcium sulfonate is as follows: heavy alkylbenzene sulfonic acid and calcium hydroxide undergo a neutralization reaction to obtain heavy alkylbenzene sulfonate calcium, then calcium hydroxide and calcium oxide are added, and carbon dioxide is introduced to carry out a carbonation reaction. Finally, the mixture is purified and dried to obtain the desired high-alkalinity complex calcium sulfonate.

7. The engine cleaner according to claim 1, characterized in that: The method for preparing the substituted diphenylamine is as follows: diphenylamine is obtained by Friedel-Crafts alkylation reaction.

8. An engine cleaner according to claim 1, characterized in that: The mass fractions of each reagent are as follows: 2-10 parts of surfactant; 0.3-1.5 parts of detergent-dispersant; Neutralizing agent 0.03~0.15 parts; Antioxidant 0.5~1.5 parts; Other functional additives: 0.05~0.2 parts; Base oil 85-98 parts.

9. An engine cleaner according to any one of claims 1 to 8, characterized in that: The base oil is a blend of synthetic hydrocarbon oil and synthetic ester oil. The synthetic hydrocarbon oil is selected from polyalphaolefins, and the selection criteria for the synthetic ester oil are: kinematic viscosity at 40°C of 30~150 mmHg. 2 The kinematic viscosity at 100℃ is between 6 and 20 mm / s. 2 Between / s, the pour point is not higher than -40℃; among them, polyalphaolefin and synthetic ester base oil are in a mass ratio of 10:(1~2).

10. A method for preparing an engine cleaner according to any one of claims 1 to 9, characterized in that: The steps are as follows: S1. Preparation of surfactants, detergents, dispersants, neutralizers, antioxidants and other functional additives; S2. Add the base oil to the reactor, stir and heat to 50~70℃; S3. Continue adding surfactants, detergents, dispersants, neutralizers, antioxidants and other functional additives, and continue stirring for 2-3 hours until the mixture is homogeneous and a mixture is obtained. S4. Filter and dehydrate the mixture from step S3 to obtain the engine cleaner.

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