Quenching oil composition as well as preparation method and application thereof

Abstract

The invention provides a quenching oil composition as well as a preparation method and application thereof, and belongs to the technical field of quenching oil. Comprising the following raw materials in parts by weight: 80-100 parts of vegetable oil, 1-2 parts of petroleum sodium sulfonate, 0.5-1 part of a nano antioxidant and antirust agent, 0.05-0.15 part of alkylene hindered phenol and 0.05-0.2 part of imidazoline oleate. The nano anti-oxidation and anti-rust agent is prepared by coating magnetic ferroferric oxide nanoparticles with porous silicon dioxide, coating the surfaces with polydopamine for modification, coupling with salicylic acid and thionyl chloride for chlorination, and reacting with 2, 4-dihydroxybenzophenone and 2, 2, 6, 6-tetramethyl piperidylamine. The quenching oil composition prepared by the invention has excellent biodegradability and environmental protection property, good stability in cooling speed, good thermal and photo-oxidation stability, good anti-rust property and high repeated utilization rate, and meets the requirements of application occasions in quenching processing of automobile fasteners.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of quenching oil, in particular to a quenching oil composition, a preparation method and application thereof. BACKGROUND

[0002] Quenching is a heat treatment process in which a casting is heated to above the critical temperature at an appropriate speed, and then cooled at a speed greater than the critical cooling speed to obtain a non-equilibrium structure. Different components and specifications of grinding balls have different hardenability and structure transformation temperature, so quenching oil is required to have the ability to adjust the cooling curve. However, the existing ordinary quenching oil is usually used at a temperature of 80-100℃, and the adjustment space is limited, which is difficult to meet the heat treatment needs of multiple types of grinding balls; and its anti-oxidation performance is poor, and oxidation products are easy to deposit, which shortens the service life and affects the subsequent machining process of the workpiece. If the quenching oil cannot fully prevent oxidation, oxidation products will form deposits on the quenched workpiece, which will cause serious coking, not only shortening the service life of the quenching oil, but also seriously affecting the subsequent machining process. At the same time, the thermal oxidation stability of the traditional quenching oil is insufficient when used at high temperature, and the rust prevention performance also needs to be improved. These problems limit its application in the fields of mechanical manufacturing, aerospace, etc.

[0003] It has been the goal of those skilled in the art to seek more effective anti-oxidation additives and develop new high-performance graded quenching oil.

[0004] US Patent No. 5304314 discloses a phenolic compound containing sulfur and aromatic amine suitable for use as an antioxidant. US Patent No. 2006 / 0189824A1 discloses a shielded phenolic compound containing secondary aromatic amine suitable for use as an antioxidant.

[0005] Chinese Patent No. CN1078489 discloses a graded quenching oil composition, which comprises a high-temperature antioxidant, a cooling catalyst, a rust inhibitor, a brightener and a base oil. The high-temperature antioxidant is 4,4-methylene-2,6-di-tert-butyl phenol.

[0006] However, when these prior art compounds are used in quenching oil, there is still room for improvement in the high-temperature oxidation resistance and the detergency and dispersion performance of the oil product. In addition, in addition to the adverse effects of deposits, rust will also seriously affect the subsequent machining of the workpiece. The existing technology still pays insufficient attention to the rust prevention performance.

[0007] Therefore, there is still a need in the prior art for a quenching oil composition that not only meets the increasingly stringent requirements for high-temperature oxidation resistance of today's higher-specification products, but also exhibits excellent detergency and dispersion performance and rust prevention performance. SUMMARY

[0008] The present application aims to provide a quenching oil composition, a preparation method and application thereof, which has excellent biodegradability and environmental protection, good stability of cooling speed, good thermal and photo-oxidation stability, good rust prevention, and high reusability, and meets the requirements of application occasions in quenching processing of automobile fasteners.

[0009] The technical scheme of the present application is implemented as follows:

[0010] The present application provides a quenching oil composition, which comprises the following raw materials in parts by weight: 80-100 parts of vegetable oil, 1-2 parts of sodium petroleum sulfonate, 0.5-1 part of nano antioxidant and rust inhibitor, 0.05-0.15 part of silyl hindered phenol, and 0.05-0.2 part of imidazoline oleate.

[0011] As a further improvement of the present application, the preparation method of the nano antioxidant and rust inhibitor is as follows:

[0012] S1. Preparation of porous silica-coated magnetic ferroferric oxide nanoparticles: magnetic ferroferric oxide nanoparticles are added to ethanol, a silane coupling agent is added, heating and stirring are performed, water and a porogen are added, the pH value of the solution is adjusted, stirring and hydrolysis are performed, a magnet is used for separation, washing, drying, and calcination are performed, and porous silica-coated magnetic ferroferric oxide nanoparticles are prepared.

[0013] S2. Preparation of polydopamine-modified nanoparticles: the porous silica-coated magnetic ferroferric oxide nanoparticles are added to a Tris-HCl solution, hydrochloric acid dopamine is added, heating and stirring are performed, a magnet is used for separation, washing, and drying are performed, and polydopamine-modified nanoparticles are prepared.

[0014] S3. Coupling of salicylic acid: salicylic acid is added to a MES buffer solution, N-hydroxysuccinimide and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide are added, stirring is performed to activate, an activated solution is obtained, the polydopamine-modified nanoparticles are added to a PBS buffer solution, the activated solution is added, stirring is performed, a magnet is used for separation, washing is performed, and drying is performed, and salicylic acid-coupled polydopamine-modified nanoparticles are prepared.

[0015] S4. Chlorination reaction: the salicylic acid-coupled polydopamine-modified nanoparticles are added to dichloromethane, dichlorosulfoxide is added, stirring is performed, a magnet is used for separation, washing is performed, and drying is performed, and chlorinated salicylic acid-coupled polydopamine-modified nanoparticles are prepared.

[0016] S5. Preparation of nano-antioxidant and anti-rust agent: add chlorinated salicylic acid coupled polydopamine modified nanoparticles into acetonitrile, add 2,4-dihydroxybenzophenone and 2,2,6,6-tetramethylpiperidinamine, add acid binding agent, heat reflux stirring reaction, magnetic separation, washing, drying, to prepare nano-antioxidant and anti-rust agent.

[0017] As a further improvement of the present application, the mass ratio of the magnetic ferroferric oxide nanoparticles, silane coupling agent, pore forming agent in step S1 is 10:8-12:1-2, the silane coupling agent is selected from at least one of KH550, KH602, KH792, the pore forming agent is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride, the temperature of the heating stirring reaction is 50-60℃, the time is 2-4h, the pH value of the solution is adjusted to 9-10, the time of the stirring hydrolysis is 8-12h, the temperature of the calcination is 500-600℃, the time is 1-2h.

[0018] As a further improvement of the present application, the pH value of the Tris-HCl solution in step S2 is 8-9, the mass ratio of the porous silica coated magnetic ferroferric oxide nanoparticles and dopamine hydrochloride is 10:3-4, the temperature of the heating stirring reaction is 55-65℃, the time is 3-5h.

[0019] As a further improvement of the present application, the pH value of the MES buffer in step S3 is 5.5-6, the mass ratio of the salicylic acid, N-hydroxysuccinimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide, polydopamine modified nanoparticles is 1.2-1.4:1.1-1.2:1.8-2:7-10, the pH value of the PBS buffer is 7-7.5.

[0020] As a further improvement of the present application, the mass ratio of the salicylic acid coupled polydopamine modified nanoparticles and thionyl chloride in step S4 is 10:1-2, the time of the stirring reaction is 1-3h.

[0021] As a further improvement of the present application, the mass ratio of the chlorinated salicylic acid coupled polydopamine modified nanoparticles, 2,4-dihydroxybenzophenone, 2,2,6,6-tetramethylpiperidinamine, acid binding agent in step S5 is 10:4-5:3-3.4:8-10, the acid binding agent is selected from at least one of triethylamine, NaOH, KOH, diethylamine, the time of the heating reflux stirring reaction is 4-6h.

[0022] As a further improvement of the present application, the vegetable oil is selected from at least one of rapeseed oil, corn oil, sunflower seed oil, olive oil, soybean oil.

[0023] The application further protects a preparation method of the quenching oil composition, comprising the following steps:

[0024] (1) 40-50% of the total mass of the vegetable oil is added into a reactor, and stirred to be heated to 80-100 DEG C;

[0025] (2) the sodium petroleum sulfonate, the azylene hindered phenol and the nano antioxidant and rust-proof agent are added into the system of step (1) and stirred to be uniformly dispersed;

[0026] (3) the temperature is reduced to 50-60 DEG C, the imidazoline oleate is added, and the remaining vegetable oil is added and stirred to be uniformly mixed, so that the quenching oil composition is prepared.

[0027] The application further protects an application of the quenching oil composition in quenching processing of automobile fasteners.

[0028] The application has the following beneficial effects:

[0029] Compared with mineral oil, the vegetable oil has excellent biodegradability and environmental protection, and the pour point thereof is usually more than 450 DEG C, and no steam film, and the kinematic viscosity thereof at 40 DEG C is obviously better than that of the mineral oil with 30-40 mm 2 / s, and the pour point thereof is usually below 370 DEG C, but the oxidation stability of the vegetable oil still cannot meet the requirement of industrial application, and has limitations.

[0030] The antioxidant principle of the nano antioxidant and rust-proof agent prepared by the application not only includes the traditional phenolic or amine antioxidant which blocks the oxidation reaction by capturing free radicals, but also the porous structure of the nano particles which can selectively capture small molecular oxidation products such as water, aldehyde, ketone and carboxylic acid generated in the oxidation process. These oxidation products are considered to be catalysts for accelerating the oxidation polymerization reaction, and the existence of these substances in the system can effectively reduce the occurrence of the oxidation polymerization reaction, so as to achieve the purpose of prolonging the service life of the lubricating oil. The phenolic hydroxyl structure of salicylic acid preferentially donates hydrogen, and the generated phenoxy free radical is re-reduced by the internal electron transfer of the polydopamine quinone-catechol network, so that the regenerative antioxidant cycle is realized. The antioxidants of different mechanisms are coupled to form a complex for compounding, and the toxicity of the phenolic or amine antioxidant is greatly reduced, and the environment is more friendly.

[0031] In addition, the surface polydopamine and salicylic acid structure can be well complexed with iron ions, the orthoquinone / hemiquinone of the polydopamine can be complexed with the d-orbital of iron to produce charge transfer, reduce the surface electron work function, positively move the corrosion potential, realize passivation, and have good rust-proof performance. At the same time, the nano particles form a dense film at the metal-oil interface, block the diffusion of water-oxygen to the matrix, and greatly improve the rust-proof effect.

[0032] This invention uses magnetic iron oxide (Fe3O4) as a core, exhibiting superparamagnetism, to achieve clean separation of nanoparticles, which can be reused multiple times after regeneration. Furthermore, the surface-covalently grafted 2,4-dihydroxybenzophenone can shield against photo-oxidation of oils; its phenolic hydroxyl group forms intramolecular hydrogen bonds with the ortho-carbonyl group, preventing photo-thermal synergistic oxidation. The resulting nano-antioxidant and rust inhibitor possesses comprehensive properties including long lifespan, low deposition, low acid value, and high rust prevention, without adversely affecting cooling characteristics. Simultaneously, the charge load of the nanoparticles forms an electrostatic shield, and polydopamine modification enhances interfacial compatibility and steric hindrance, making it difficult for nanoparticles to aggregate.

[0033] Sodium petroleum sulfonate is an emulsifier. When added to quenching oil, it can indeed reduce the surface tension and dynamic contact angle of the oil, thus improving its wettability. Adding sodium petroleum sulfonate to quenching oil can improve its cooling performance; however, it also has a certain emulsifying effect, which can affect the water-separating properties (anti-emulsification) of the quenching oil. In addition, sodium petroleum sulfonate can neutralize oxidizing acids, disperse sludge, and form a protective film on the metal surface, thus providing both rust prevention and cleaning effects.

[0034] The quenching oil composition prepared by this invention has excellent biodegradability and environmental friendliness. It has good stability in cooling rate, good thermal and photo-oxidation stability, good rust prevention, and high reusability, meeting the requirements of applications in automotive fastener quenching. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 SEM image of the nano-antioxidant and rust inhibitor prepared in Example 1. Detailed Implementation

[0037] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0038] Magnetic iron oxide nanoparticles, Xianfeng Nano, 10-30nm.

[0039] Preparation Example 1: Nano Antioxidant and Rust Inhibitor

[0040] The preparation method is as follows:

[0041] S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: 1g of magnetic iron oxide nanoparticles were added to 100mL of ethanol, 0.8g of silane coupling agent KH550 was added, the mixture was heated to 50℃ and stirred for 2h, 100mL of deionized water and 0.1g of cetyltrimethylammonium bromide were added, the pH of the solution was adjusted to 9, the mixture was stirred and hydrolyzed for 8h, separated by magnets, washed, dried, and calcined at 500℃ for 1h to obtain porous silica-coated magnetic iron oxide nanoparticles;

[0042] S2. Preparation of polydopamine-modified nanoparticles: 1g of porous silica-coated magnetic iron oxide nanoparticles were added to 100mL of Tris-HCl solution with a pH of 8, 0.3g of dopamine hydrochloride was added, the mixture was heated to 55℃, stirred for 3h, separated by magnets, washed, and dried to obtain polydopamine-modified nanoparticles.

[0043] S3. Salicylic acid coupling: 0.12 g of salicylic acid was added to 100 mL of MES buffer with a pH of 5.5, along with 0.11 g of N-hydroxysuccinimide and 0.18 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The mixture was stirred and activated for 30 min to obtain the activation solution. 0.7 g of polydopamine-modified nanoparticles were added to 100 mL of PBS buffer with a pH of 7, along with the activation solution. The mixture was stirred and reacted for 10 h. The nanoparticles were separated by magnet, washed, and dried to obtain salicylic acid-coupled polydopamine-modified nanoparticles.

[0044] S4. Chlorination reaction: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of dichloromethane, and 20mL of dichloromethane solution containing 0.1g of sulfoxide was added. The mixture was stirred and reacted for 1h. The nanoparticles were separated by magnet, washed, and dried to obtain chlorinated salicylic acid-coupled polydopamine modified nanoparticles.

[0045] S5. Preparation of nano-antioxidant and rust inhibitor: 1g of salicylic acid-coupled polydopamine-modified nanoparticles were added to 100mL of acetonitrile, along with 0.4g of 2,4-dihydroxybenzophenone and 0.3g of 2,2,6,6-tetramethylpiperidinamine, and 0.8g of NaOH. The mixture was heated under reflux and stirred for 4h. The mixture was then separated by magnetism, washed, and dried to obtain the nano-antioxidant and rust inhibitor. Figure 1 The image shows the SEM image of the prepared nano-antioxidant and rust inhibitor. As can be seen from the image, the particle size is between 200-400 nm.

[0046] Preparation Example 2: Nano Antioxidant and Rust Inhibitor

[0047] The preparation method is as follows:

[0048] S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: 1g of magnetic iron oxide nanoparticles were added to 100mL of ethanol, 1.2g of silane coupling agent KH602 was added, the mixture was heated to 60℃ and stirred for 4h, 100mL of deionized water and 0.2g of hexadecyltrimethylammonium chloride were added, the pH of the solution was adjusted to 10, and the mixture was stirred and hydrolyzed for 12h. The mixture was separated by magnets, washed, dried, and calcined at 600℃ for 2h to obtain porous silica-coated magnetic iron oxide nanoparticles.

[0049] S2. Preparation of polydopamine-modified nanoparticles: 1g of porous silica-coated magnetic iron oxide nanoparticles were added to 100mL of Tris-HCl solution with a pH of 9, and 0.4g of dopamine hydrochloride was added. The mixture was heated to 65℃ and stirred for 5h. The nanoparticles were separated by magnets, washed, and dried to obtain polydopamine-modified nanoparticles.

[0050] S3. Salicylic acid coupling: 0.14 g of salicylic acid was added to 100 mL of MES buffer with a pH of 6, along with 0.12 g of N-hydroxysuccinimide and 0.2 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The mixture was stirred and activated for 30 min to obtain the activation solution. 1 g of polydopamine-modified nanoparticles were added to 100 mL of PBS buffer with a pH of 7.5, along with the activation solution. The mixture was stirred and reacted for 12 h. The nanoparticles were separated by magnet, washed, and dried to obtain salicylic acid-coupled polydopamine-modified nanoparticles.

[0051] S4. Chlorination reaction: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of dichloromethane, and 20mL of dichloromethane solution containing 0.2g of sulfoxide was added. The mixture was stirred and reacted for 3h. The nanoparticles were separated by magnet, washed, and dried to obtain chlorinated salicylic acid-coupled polydopamine modified nanoparticles.

[0052] S5. Preparation of nano-antioxidant and rust inhibitor: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of acetonitrile, along with 0.5g of 2,4-dihydroxybenzophenone and 0.34g of 2,2,6,6-tetramethylpiperidineamine, and 1g of KOH. The mixture was heated under reflux and stirred for 6h. The mixture was then separated by magnetism, washed, and dried to obtain the nano-antioxidant and rust inhibitor.

[0053] Preparation Example 3: Nano Antioxidant and Rust Inhibitor

[0054] The preparation method is as follows:

[0055] S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: 1g of magnetic iron oxide nanoparticles were added to 100mL of ethanol, 1g of silane coupling agent KH792 was added, the mixture was heated to 55℃ and stirred for 3h, 100mL of deionized water and 0.15g of cetyltrimethylammonium bromide were added, the pH of the solution was adjusted to 9.5, the mixture was stirred and hydrolyzed for 10h, separated by magnets, washed, dried, and calcined at 550℃ for 1.5h to obtain porous silica-coated magnetic iron oxide nanoparticles;

[0056] S2. Preparation of polydopamine-modified nanoparticles: 1g of porous silica-coated magnetic iron oxide nanoparticles were added to 100mL of Tris-HCl solution with a pH of 8.5, and 0.35g of dopamine hydrochloride was added. The mixture was heated to 60℃ and stirred for 4h. The nanoparticles were separated by magnets, washed, and dried to obtain polydopamine-modified nanoparticles.

[0057] S3. Salicylic acid coupling: 0.13 g of salicylic acid was added to 100 mL of MES buffer with a pH of 5.7, along with 0.115 g of N-hydroxysuccinimide and 0.19 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The mixture was stirred and activated for 30 min to obtain the activation solution. 0.8 g of polydopamine-modified nanoparticles were added to 100 mL of PBS buffer with a pH of 7.4, along with the activation solution. The mixture was stirred and reacted for 11 h. The nanoparticles were separated by magnet, washed, and dried to obtain salicylic acid-coupled polydopamine-modified nanoparticles.

[0058] S4. Chlorination reaction: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of dichloromethane, and 20mL of dichloromethane solution containing 0.15g of sulfoxide was added. The mixture was stirred and reacted for 2h. The nanoparticles were separated by magnet, washed, and dried to obtain chlorinated salicylic acid-coupled polydopamine modified nanoparticles.

[0059] S5. Preparation of nano-antioxidant and rust inhibitor: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of acetonitrile, along with 0.45g of 2,4-dihydroxybenzophenone and 0.32g of 2,2,6,6-tetramethylpiperidineamine, and 0.9g of triethylamine. The mixture was heated under reflux and stirred for 5h. The mixture was then separated by magnetism, washed, and dried to obtain the nano-antioxidant and rust inhibitor.

[0060] Comparative Preparation Example 1

[0061] The difference from preparation example 3 is that step S2 was not performed.

[0062] The preparation method is as follows:

[0063] S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: 1g of magnetic iron oxide nanoparticles were added to 100mL of ethanol, 1g of silane coupling agent KH792 was added, the mixture was heated to 55℃ and stirred for 3h, 100mL of deionized water and 0.15g of cetyltrimethylammonium bromide were added, the pH of the solution was adjusted to 9.5, the mixture was stirred and hydrolyzed for 10h, separated by magnets, washed, dried, and calcined at 550℃ for 1.5h to obtain porous silica-coated magnetic iron oxide nanoparticles;

[0064] S2. Salicylic acid coupling: 0.13 g of salicylic acid was added to 100 mL of MES buffer with a pH of 5.7, along with 0.115 g of N-hydroxysuccinimide and 0.19 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The mixture was stirred and activated for 30 min to obtain the activation solution. 0.8 g of porous silica-coated magnetic iron oxide nanoparticles were added to 100 mL of PBS buffer with a pH of 7.4, along with the activation solution. The mixture was stirred and reacted for 11 h. The nanoparticles were separated by magnets, washed, and dried to obtain salicylic acid-coupled porous silica-coated magnetic iron oxide nanoparticles.

[0065] S3. Chlorination reaction: 1g of salicylic acid coupled porous silica-coated magnetic iron oxide nanoparticles were added to 100mL of dichloromethane, and 20mL of dichloromethane solution containing 0.15g of sulfoxide was added. The mixture was stirred and reacted for 2h. The nanoparticles were separated by magnets, washed, and dried to obtain chlorinated salicylic acid coupled porous silica-coated magnetic iron oxide nanoparticles.

[0066] S4. Preparation of nano-antioxidant and rust inhibitor: 1g of magnetic iron oxide nanoparticles coated with porous silica coupled with salicylic acid were added to 100mL of acetonitrile, along with 0.45g of 2,4-dihydroxybenzophenone and 0.32g of 2,2,6,6-tetramethylpiperidineamine, and 0.9g of triethylamine. The mixture was heated under reflux and stirred for 5h. The mixture was then separated by magnetization, washed, and dried to obtain the nano-antioxidant and rust inhibitor.

[0067] Comparative Preparation Example 2

[0068] The difference from preparation example 3 is that step S3 was not performed.

[0069] The preparation method is as follows:

[0070] S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: 1g of magnetic iron oxide nanoparticles were added to 100mL of ethanol, 1g of silane coupling agent KH792 was added, the mixture was heated to 55℃ and stirred for 3h, 100mL of deionized water and 0.15g of cetyltrimethylammonium bromide were added, the pH of the solution was adjusted to 9.5, the mixture was stirred and hydrolyzed for 10h, separated by magnets, washed, dried, and calcined at 550℃ for 1.5h to obtain porous silica-coated magnetic iron oxide nanoparticles;

[0071] S2. Preparation of polydopamine-modified nanoparticles: 1g of porous silica-coated magnetic iron oxide nanoparticles were added to 100mL of Tris-HCl solution with a pH of 8.5, and 0.35g of dopamine hydrochloride was added. The mixture was heated to 60℃ and stirred for 4h. The nanoparticles were separated by magnets, washed, and dried to obtain polydopamine-modified nanoparticles.

[0072] S3. Chlorination reaction: 1g of polydopamine-modified nanoparticles were added to 100mL of dichloromethane, and 20mL of dichloromethane solution containing 0.15g of sulfoxide was added. The mixture was stirred and reacted for 2h. The nanoparticles were separated by magnet, washed, and dried to obtain chlorinated polydopamine-modified nanoparticles.

[0073] S4. Preparation of nano-antioxidant and rust inhibitor: 1g of chlorinated polydopamine modified nanoparticles were added to 100mL of acetonitrile, along with 0.45g of 2,4-dihydroxybenzophenone and 0.32g of 2,2,6,6-tetramethylpiperidineamine, and 0.9g of triethylamine. The mixture was heated under reflux and stirred for 5h. The mixture was then separated by magnetism, washed, and dried to obtain the nano-antioxidant and rust inhibitor.

[0074] Comparative preparation example 3

[0075] The difference from Preparation Example 3 is that 2,4-dihydroxybenzophenone was not added in step S5.

[0076] The preparation method is as follows:

[0077] S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: 1g of magnetic iron oxide nanoparticles were added to 100mL of ethanol, 1g of silane coupling agent KH792 was added, the mixture was heated to 55℃ and stirred for 3h, 100mL of deionized water and 0.15g of cetyltrimethylammonium bromide were added, the pH of the solution was adjusted to 9.5, the mixture was stirred and hydrolyzed for 10h, separated by magnets, washed, dried, and calcined at 550℃ for 1.5h to obtain porous silica-coated magnetic iron oxide nanoparticles;

[0078] S2. Preparation of polydopamine-modified nanoparticles: 1g of porous silica-coated magnetic iron oxide nanoparticles were added to 100mL of Tris-HCl solution with a pH of 8.5, and 0.35g of dopamine hydrochloride was added. The mixture was heated to 60℃ and stirred for 4h. The nanoparticles were separated by magnets, washed, and dried to obtain polydopamine-modified nanoparticles.

[0079] S3. Salicylic acid coupling: 0.13 g of salicylic acid was added to 100 mL of MES buffer with a pH of 5.7, along with 0.115 g of N-hydroxysuccinimide and 0.19 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The mixture was stirred and activated for 30 min to obtain the activation solution. 0.8 g of polydopamine-modified nanoparticles were added to 100 mL of PBS buffer with a pH of 7.4, along with the activation solution. The mixture was stirred and reacted for 11 h. The nanoparticles were separated by magnet, washed, and dried to obtain salicylic acid-coupled polydopamine-modified nanoparticles.

[0080] S4. Chlorination reaction: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of dichloromethane, and 20mL of dichloromethane solution containing 0.15g of sulfoxide was added. The mixture was stirred and reacted for 2h. The nanoparticles were separated by magnet, washed, and dried to obtain chlorinated salicylic acid-coupled polydopamine modified nanoparticles.

[0081] S5. Preparation of nano-antioxidant and rust inhibitor: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of acetonitrile, 0.77g of 2,2,6,6-tetramethylpiperidineamine was added, and 0.9g of triethylamine was added. The mixture was heated under reflux and stirred for 5h. The mixture was separated by magnetism, washed, and dried to obtain the nano-antioxidant and rust inhibitor.

[0082] Comparative preparation example 4

[0083] The difference from Preparation Example 3 is that 2,2,6,6-tetramethylpiperidineamine was not added in step S5.

[0084] The preparation method is as follows:

[0085] S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: 1g of magnetic iron oxide nanoparticles were added to 100mL of ethanol, 1g of silane coupling agent KH792 was added, the mixture was heated to 55℃ and stirred for 3h, 100mL of deionized water and 0.15g of cetyltrimethylammonium bromide were added, the pH of the solution was adjusted to 9.5, the mixture was stirred and hydrolyzed for 10h, separated by magnets, washed, dried, and calcined at 550℃ for 1.5h to obtain porous silica-coated magnetic iron oxide nanoparticles;

[0086] S2. Preparation of polydopamine-modified nanoparticles: 1g of porous silica-coated magnetic iron oxide nanoparticles were added to 100mL of Tris-HCl solution with a pH of 8.5, and 0.35g of dopamine hydrochloride was added. The mixture was heated to 60℃ and stirred for 4h. The nanoparticles were separated by magnets, washed, and dried to obtain polydopamine-modified nanoparticles.

[0087] S3. Salicylic acid coupling: 0.13 g of salicylic acid was added to 100 mL of MES buffer with a pH of 5.7, along with 0.115 g of N-hydroxysuccinimide and 0.19 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The mixture was stirred and activated for 30 min to obtain the activation solution. 0.8 g of polydopamine-modified nanoparticles were added to 100 mL of PBS buffer with a pH of 7.4, along with the activation solution. The mixture was stirred and reacted for 11 h. The nanoparticles were separated by magnet, washed, and dried to obtain salicylic acid-coupled polydopamine-modified nanoparticles.

[0088] S4. Chlorination reaction: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of dichloromethane, and 20mL of dichloromethane solution containing 0.15g of sulfoxide was added. The mixture was stirred and reacted for 2h. The nanoparticles were separated by magnet, washed, and dried to obtain chlorinated salicylic acid-coupled polydopamine modified nanoparticles.

[0089] S5. Preparation of nano-antioxidant and rust inhibitor: 1g of salicylic acid-coupled polydopamine modified nanoparticles were added to 100mL of acetonitrile, 0.77g of 2,4-dihydroxybenzophenone was added, and 0.9g of triethylamine was added. The mixture was heated under reflux and stirred for 5h. The mixture was separated by magnetism, washed, and dried to obtain the nano-antioxidant and rust inhibitor.

[0090] Comparative preparation example 5

[0091] The difference compared to preparation example 3 is that steps S4 and S5 were not performed.

[0092] The preparation method is as follows:

[0093] S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: 1g of magnetic iron oxide nanoparticles were added to 100mL of ethanol, 1g of silane coupling agent KH792 was added, the mixture was heated to 55℃ and stirred for 3h, 100mL of deionized water and 0.15g of cetyltrimethylammonium bromide were added, the pH of the solution was adjusted to 9.5, the mixture was stirred and hydrolyzed for 10h, separated by magnets, washed, dried, and calcined at 550℃ for 1.5h to obtain porous silica-coated magnetic iron oxide nanoparticles;

[0094] S2. Preparation of polydopamine-modified nanoparticles: 1g of porous silica-coated magnetic iron oxide nanoparticles were added to 100mL of Tris-HCl solution with a pH of 8.5, and 0.35g of dopamine hydrochloride was added. The mixture was heated to 60℃ and stirred for 4h. The nanoparticles were separated by magnets, washed, and dried to obtain polydopamine-modified nanoparticles.

[0095] S3. Coupling with salicylic acid: Add 0.13g of salicylic acid to 100mL of MES buffer with pH 5.7, add 0.115g of N-hydroxysuccinimide and 0.19g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, stir and activate for 30min to obtain the activation solution; add 0.8g of polydopamine-modified nanoparticles to 100mL of PBS buffer with pH 7.4, add the activation solution, stir and react for 11h, separate with a magnet, wash, and dry to obtain salicylic acid coupled with polydopamine-modified nanoparticles, which are nano-antioxidant and rust inhibitors.

[0096] Example 1

[0097] This embodiment provides a quenching oil composition.

[0098] Raw material composition (parts by weight): 80 parts sunflower seed oil, 1 part sodium petroleum sulfonate, 0.5 parts nano antioxidant rust inhibitor prepared in Preparation Example 1, 0.05 parts ethylene-dependent hindered phenol, and 0.05 parts imidazoline oleate.

[0099] The preparation method includes the following steps:

[0100] (1) Add 40% of the total mass of sunflower seed oil into the reactor and stir to raise the temperature to 80°C;

[0101] (2) Add sodium petroleum sulfonate, styrene-based hindered phenol, and nano-antioxidant rust inhibitor to the system in step (1), and stir to disperse evenly;

[0102] (3) Reduce the temperature to 50°C, add imidazoline oleate and the remaining sunflower seed oil, stir and mix evenly to obtain the quenching oil composition.

[0103] Example 2

[0104] This embodiment provides a quenching oil composition.

[0105] Raw material composition (parts by weight): 100 parts rapeseed oil, 2 parts sodium petroleum sulfonate, 1 part nano antioxidant rust inhibitor prepared in Preparation Example 2, 0.15 parts ethylene-dependent hindered phenol, and 0.2 parts imidazoline oleate.

[0106] The preparation method includes the following steps:

[0107] (1) Add 50% of the total mass of rapeseed oil into the reactor and stir to raise the temperature to 100°C;

[0108] (2) Add sodium petroleum sulfonate, styrene-based hindered phenol, and nano-antioxidant rust inhibitor to the system in step (1), and stir to disperse evenly;

[0109] (3) Reduce the temperature to 60°C, add imidazoline oleate and the remaining rapeseed oil, stir and mix evenly to obtain the quenching oil composition.

[0110] Example 3

[0111] This embodiment provides a quenching oil composition.

[0112] Raw material composition (parts by weight): 90 parts soybean oil, 1.5 parts sodium petroleum sulfonate, 0.7 parts nano antioxidant rust inhibitor prepared in Preparation Example 3, 0.1 parts ethylene-hindered phenol, and 0.12 parts imidazoline oleate.

[0113] The preparation method includes the following steps:

[0114] (1) Add 45% of the total mass of soybean oil into the reactor and stir to raise the temperature to 90°C;

[0115] (2) Add sodium petroleum sulfonate, styrene-based hindered phenol, and nano-antioxidant rust inhibitor to the system in step (1), and stir to disperse evenly;

[0116] (3) Reduce the temperature to 55°C, add imidazoline oleate and the remaining soybean oil, stir and mix evenly to obtain the quenching oil composition.

[0117] Comparative Example 1

[0118] The difference from Example 3 is that the nano-antioxidant and rust inhibitor was prepared by Comparative Preparation Example 1.

[0119] Comparative Example 2

[0120] The difference from Example 3 is that the nano-antioxidant and rust inhibitor was prepared by Comparative Preparation Example 2.

[0121] Comparative Example 3

[0122] The difference from Example 3 is that the nano-antioxidant and rust inhibitor was prepared by Comparative Preparation Example 3.

[0123] Comparative Example 4

[0124] The difference from Example 3 is that the nano-antioxidant and rust inhibitor was prepared by Comparative Preparation Example 4.

[0125] Comparative Example 5

[0126] The difference from Example 3 is that the nano-antioxidant and rust inhibitor was prepared by Comparative Preparation Example 5.

[0127] Comparative Example 6

[0128] The difference from Example 3 is that soybean oil was replaced with mineral oil (KR323).

[0129] Comparative Example 7

[0130] The difference compared to Example 3 is that sodium petroleum sulfonate was not added.

[0131] Test Example 1

[0132] The quenching oil compositions prepared in Examples 1-3 and Comparative Examples 1-7 were subjected to performance tests, and the results are shown in Table 1.

[0133] Table 1

[0134] Group Kinematic viscosity (40°C), mm 2 / s]] Oxidation induction period of PDSC test, min T vp , °C Oil-water separation time, min Copper strip corrosion test, level Rust test result Cooling rate, °C / s Test method GB / T 265 ASTM D6186-19 GB / T 30823-2014 ASTM D1401 GB / T 5096-2017 GB / T 11143-2013 ISO 9950 Example 1 33.28 44.5 849 15 1a No rust 107.72 Example 2 35.29 44.9 822 14 1a No rust 104.23 Example 3 33.09 45.2 855 12 1a No rust 115.56 Comparative Example 1 42.02 37.8 844 17 2a Medium rust 102.15 Comparative Example 2 44.57 34.7 842 16 1b Light rust 99.73 Comparative Example 3 43.75 35.8 837 18 1b Light rust 102.35 Comparative Example 4 42.24 33.2 840 19 1b Light rust 100.57 Comparative Example 5 45.24 27.2 832 21 2b Medium rust 94.22 Comparative Example 6 34.67 42.3 747 26 1a No rust 98.21 Comparative Example 7 45.31 40.1 807 12 2a Medium rust 101.34

[0135] As can be seen from the table above, the quenching oil compositions prepared in Examples 1-3 of this invention have good comprehensive properties.

[0136] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A quenching oil composition, characterized in that, The raw materials include the following parts by weight: 80-100 parts vegetable oil, 1-2 parts sodium petroleum sulfonate, 0.5-1 parts nano antioxidant rust inhibitor, 0.05-0.15 parts ethylene-dependent hindered phenol, and 0.05-0.2 parts imidazoline oleate; the nano antioxidant rust inhibitor is prepared by coating porous silica with magnetic iron oxide nanoparticles, then coating the surface with polydopamine for modification, coupling with salicylic acid, chlorinating with thionyl chloride, and reacting with 2,4-dihydroxybenzophenone and 2,2,6,6-tetramethylpiperidineamine.

2. The quenching oil composition according to claim 1, characterized in that, The preparation method of the nano-antioxidant and rust inhibitor is as follows: S1. Preparation of porous silica-coated magnetic iron oxide nanoparticles: Magnetic iron oxide nanoparticles were added to ethanol, silane coupling agent was added, the mixture was heated and stirred to react, water and pore-forming agent were added, the pH value of the solution was adjusted, the mixture was stirred and hydrolyzed, separated by magnets, washed, dried and calcined to obtain porous silica-coated magnetic iron oxide nanoparticles. S2. Preparation of polydopamine-modified nanoparticles: Porous silica-coated magnetic iron oxide nanoparticles were added to Tris-HCl solution, dopamine hydrochloride was added, the mixture was heated and stirred to react, separated by magnets, washed, and dried to obtain polydopamine-modified nanoparticles. S3. Salicylic acid coupling: Salicylic acid was added to MES buffer, along with N-hydroxysuccinimide and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The mixture was stirred and activated to obtain an activated solution. Polydopamine-modified nanoparticles were added to PBS buffer, followed by the activated solution. The mixture was stirred and reacted, separated by a magnet, washed, and dried to obtain salicylic acid-coupled polydopamine-modified nanoparticles. S4. Chlorination reaction: Salicylic acid-coupled polydopamine modified nanoparticles were added to dichloromethane, thionyl chloride was added, the mixture was stirred and reacted, separated by a magnet, washed, and dried to obtain chlorinated salicylic acid-coupled polydopamine modified nanoparticles. S5. Preparation of nano-antioxidant and rust inhibitor: Chlorinated salicylic acid coupled with polydopamine modified nanoparticles was added to acetonitrile, 2,4-dihydroxybenzophenone and 2,2,6,6-tetramethylpiperidineamine were added, an acid-binding agent was added, the mixture was heated and stirred under reflux, separated by magnet, washed, and dried to obtain nano-antioxidant and rust inhibitor.

3. The quenching oil composition according to claim 2, characterized in that, In step S1, the mass ratio of magnetic iron oxide nanoparticles, silane coupling agent, and pore-forming agent is 10:8-12:1-2. The silane coupling agent is selected from at least one of KH550, KH602, and KH792. The pore-forming agent is hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride. The heating and stirring reaction temperature is 50-60℃, and the time is 2-4 hours. The pH of the solution is adjusted to 9-10. The stirring and hydrolysis time is 8-12 hours. The calcination temperature is 500-600℃, and the time is 1-2 hours.

4. The quenching oil composition according to claim 2, characterized in that, In step S2, the pH value of the Tris-HCl solution is 8-9, the mass ratio of the porous silica-coated magnetic iron oxide nanoparticles to dopamine hydrochloride is 10:3-4, and the heating and stirring reaction temperature is 55-65℃ for 3-5 hours.

5. The quenching oil composition according to claim 2, characterized in that, In step S3, the pH of the MES buffer is 5.5-6, the mass ratio of salicylic acid, N-hydroxysuccinimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and polydopamine-modified nanoparticles is 1.2-1.4:1.1-1.2:1.8-2:7-10, and the pH of the PBS buffer is 7-7.

5.

6. The quenching oil composition according to claim 2, characterized in that, In step S4, the mass ratio of salicylic acid-coupled polydopamine-modified nanoparticles to sulfoxide is 10:1-2, and the stirring reaction time is 1-3 hours.

7. The quenching oil composition according to claim 2, characterized in that, In step S5, the mass ratio of salicylic acid-coupled polydopamine-modified nanoparticles, 2,4-dihydroxybenzophenone, 2,2,6,6-tetramethylpiperidinamine, and the acid-binding agent is 10:4-5:3-3.4:8-10. The acid-binding agent is selected from at least one of triethylamine, NaOH, KOH, and diethylamine. The heating, reflux, and stirring reaction time is 4-6 hours.

8. The quenching oil composition according to claim 1, characterized in that, The vegetable oil is selected from at least one of rapeseed oil, corn oil, sunflower oil, olive oil, and soybean oil.

9. A method for preparing a quenching oil composition according to any one of claims 1-8, characterized in that, Includes the following steps: (1) Add 40-50% of the total mass of vegetable oil into the reactor and stir to raise the temperature to 80-100℃; (2) Add sodium petroleum sulfonate, propylene-based hindered phenol, and nano-antioxidant rust inhibitor to the system in step (1), and stir to disperse evenly; (3) Cool to 50-60℃, add imidazoline oleate and the remaining vegetable oil, stir and mix evenly to obtain the quenching oil composition.

10. The application of a quenching oil composition as described in any one of claims 1-8 in the quenching process of automotive fasteners.

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