CN111575096B

CN111575096B - Antirust gearbox engine oil and preparation method thereof

Info

Publication number: CN111575096B
Application number: CN202010542705.1A
Authority: CN
Inventors: 许卫明
Original assignee: Shandong Zero Mileage Lubrication Technology Co ltd
Current assignee: Shandong Zero Mileage Lubrication Technology Co ltd
Priority date: 2020-06-15
Filing date: 2020-06-15
Publication date: 2022-09-16
Anticipated expiration: 2040-06-15
Also published as: CN111575096A

Abstract

The invention discloses antirust gearbox oil and a preparation method thereof. The preparation method of the antirust gearbox oil comprises the following steps: step one, preparing materials; step two: mixing the other raw materials except the special defoaming agent for the lubricating oil in the step one, then adding the special defoaming agent for the lubricating oil, stirring and mixing, and naturally cooling to room temperature to obtain a mixture; step three: and D, performing filter pressing on the mixture obtained in the step two to obtain the antirust gearbox engine oil. The antirust gearbox oil provided by the invention has excellent corrosion resistance, thermal oxidation stability, sealing adaptability, wear resistance and durability and extreme pressure wear resistance, can simultaneously meet the requirements of lubrication of manual gearboxes of high-grade cars, manual gearboxes of vehicle drive axles, trucks and buses, and can achieve the purposes of prolonging the service cycle of the gearbox oil, reducing the maintenance frequency of equipment, saving energy, reducing consumption and reducing cost.

Description

Antirust gearbox engine oil and preparation method thereof

Technical Field

The invention relates to the technical field of gear oil, in particular to antirust gearbox oil and a preparation method thereof.

Background

An automatic transmission is a transmission device that can automatically perform an automatic shift operation in accordance with a vehicle speed and an engine speed, which occurs in contrast to a manual transmission. At present, four types of automatic transmissions for automobiles are common, namely a hydraulic automatic transmission, a mechanical stepless automatic transmission, an electric control mechanical automatic transmission and a double-clutch automatic transmission. The automatic transmission oil is called automatic transmission oil for short, and is oil liquid specially used for an automatic transmission. Early automatic transmissions did not have dedicated oil, but instead were replaced with engine oil. Because of the wide variation in operating conditions and specifications, engine oils are rapidly being eliminated as an automatic transmission fluid. The special oil liquid for the automatic transmission used at present is not only transmission oil of a hydraulic torque converter, but also lubricating oil of a planetary gear structure and hydraulic oil of a gear shifting device. The automatic transmission oil in the prior art has the defects of short service life, poor lubricating effect, easiness in foaming, no oxidation resistance, poor antirust performance and the like.

Application number 201610832394.6 relates to a powershift transmission oil composition, consisting of the following components in percentage by weight: 0.1-0.2% of alkyl diphenylamine; 0.2-0.3% of liquid phenol antioxidant; 9.0-10.0% of multifunctional composite additive; 0.5-1.0% of pour point depressant; 0.1-0.2% of a friction modifier; 0-0.04% of an antifoaming agent; the kinematic viscosity is 10.0-11.5 mm ² The balance of base oil/s. Has the advantages of extremely high viscosity index,meanwhile, the lubricating oil has excellent high oxidation resistance and a friction plate service life, and has the effect of prolonging the service life of the friction plate by more than one time compared with the common power gear shifting transmission oil.

Application number 201711270380.0 discloses an automatic transmission oil, which is composed of the following raw materials by mass percent: 0.1-0.9% of an antiwear agent, 0.3-1.4% of an antioxidant, 0.5-1.5% of molybdenum dialkyl dithiocarbamate, 0.2-0.6% of a defoaming agent, and the balance of base oil. The automatic transmission oil disclosed by the invention is reasonable in proportion, has a good lubricating effect in a low-temperature state, can improve the friction performance of an oil product, has good anti-shaking performance, and can improve the discomfort problem experienced by a driver.

Application number 201810674718.7 discloses an automatic transmission oil comprising the following components in parts by weight: 75-90 parts of base oil; 2-5 parts of viscosity index improver; 2-4 parts of a detergent dispersant; 0.5-1.5 parts of antioxidant; 0.1-0.2 part of metal deactivator; 1-2 parts of an antiwear agent; 1-1.5 parts of dialkyl dithiocarbamate; 0.1-0.5 part of defoaming agent. The lubricating grease has excellent lubricating property, oxidation stability and low-temperature fluidity, has good abrasion resistance and clean dispersing property, does not foam, and prolongs the service life.

Disclosure of Invention

The automatic transmission oil is mainly used for automatic transmission systems of cars and light trucks, along with the rapid development of the automatic transmission manufacturing industry, the requirement on the automatic transmission oil in the market is increasingly improved, the extreme pressure abrasion resistance, the low temperature flow property and the oxidation stability are all important indexes for inspecting the automatic transmission oil, but most automatic transmission oils in the current market have the defects of short service life, easiness in foaming, poor lubricating effect, no oxidation resistance, poor cleaning and dispersing performance and general friction performance, and cannot meet the market requirement.

In order to solve the problems, the invention provides a preparation method of antirust gearbox oil, which comprises the following steps:

the method comprises the following steps: preparing materials according to the following mixture ratio: 3-7 parts of a composite material of nano montmorillonite and a polymer, 0.3-0.8 part of a composite antirust antioxidant, 2.0-3.8 parts of vulcanized isobutylene, 0.1-0.5 part of a special defoaming agent for lubricating oil, 0.5-1.0 part of a bis-alkoxy monothiophosphate ester triazine derivative, 1-5 parts of polyisobutylene bis-succinimide, 0.1-0.2 part of thiophosphate amine salt, 0.5-2 parts of an antiwear agent, 1-2 parts of a fluorine-containing additive and 70-130 parts of base oil;

step two: mixing the raw materials except the special defoaming agent for the lubricating oil in the step one, stirring for 30-60 minutes at 50-80 ℃, then adding the special defoaming agent for the lubricating oil, stirring for 10-30 minutes at 50-80 ℃, and naturally cooling to room temperature to obtain a mixture;

step three: and D, performing filter pressing on the mixture obtained in the step two under the condition of 0.3-0.5 MPa to obtain the antirust gearbox engine oil.

In some technical schemes of the invention, the composite material of the nano montmorillonite and the polymer uses the nano montmorillonite as a carrier, and the nano montmorillonite is organically modified by cetyl trimethyl ammonium bromide to obtain organically modified nano montmorillonite; then polymerizing and grafting monomers of octadecyl methacrylate and acrylamide into the montmorillonite layer to synthesize the nano-montmorillonite composite viscosity reducer.

The composite antirust antioxidant comprises the following components in parts by weight: 10-40 parts of glucose derivative, 10-40 parts of benzothiazole borate, 2-8 parts of film forming agent, 0.5-2 parts of film forming additive and 0.3-0.6 part of surfactant.

The glucose derivative is 3-benzoyl-alpha-D-glucopyranose shown in the following formula (I),

the benzothiazole borate is 2- [ (2-benzothiazolyl) thio ] ethyl boric acid-2-octyl alcohol ester shown in the following formula (II),

the film forming agent is one or more of triacontyl PVP, VP/eicosene copolymer and polytrimethylsiloxane methacrylate copolymer.

The film-forming assistant is one or more of propylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol butyl ether and tripropylene glycol methyl ether.

The surfactant is one or more of alkylphenol polyoxyethylene 9, alkylphenol polyoxyethylene 4, sodium dodecyl sulfate, sodium oleate and dodecyl dimethyl betaine.

The antirust agent is a substance which can prevent metal corrosion or reduce the metal corrosion speed in a corrosion medium, and the mechanism is as follows; polar groups in molecules can be adsorbed on the metal surface, and hydrophobic hydrocarbon groups form a protective film on the metal surface to prevent water from corroding the metal surface, so that the antirust effect is achieved. Polar groups include; -COOH, -COONH, -SO3H, -OH, -H.

The glucose derivative has wide source and low preparation cost, and the molecular structure comprises a plurality of hydroxyl polar groups which can be substituted by different substituents, so the glucose derivative can be used as an antirust agent.

The boric acid ester is a multifunctional lubricating oil additive, has excellent antifriction and antiwear properties, has excellent oil wettability when long-chain groups are introduced, improves the strength of a protective film by introducing boron elements, and can more effectively inhibit the corrosion of active elements such as sulfur and the like.

The film forming agent can further supplement the amount of hydrophobic alkyl in the system, and strengthen the formation of a protective film on the metal surface. The film forming assistant can promote the film forming agent to disperse homogeneously in the system and improve the strength of the formed protecting film. The surfactant is used for improving the dissolving performance of each component in the composite antirust antioxidant in a system.

In some technical schemes of the invention, the raw materials of the composite antirust antioxidant adopt the technical characteristics of compounding 3-benzoyl-alpha-D-glucopyranose and 2- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octanol ester. The molecular structure of the 3-benzoyl-alpha-D-furanose contains a plurality of hydroxyl polar groups, the polar groups can be adsorbed on the metal surface, and benzoyl is introduced through substitution reaction. The molecular structure of 2- [ (2-benzothiazolyl) thio ] ethyl boric acid-2-octanol ester is introduced with introduced long-chain group to form protective film on the metal surface. The benzoyl group in 3-benzoyl-alpha-D-furanglucose and the benzothiazolyl group in 2- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octanol ester have pi-pi interaction force, and hydroxyl group, sulfur atom and nitrogen atom can form hydrogen bond. Therefore, the two become a whole through pi-pi action and hydrogen bond, the 3-benzoyl-alpha-D-glucopyranose is adsorbed on the metal surface, the 2- [ (2-benzothiazolyl) thio ] ethylborate-2-octyl alcohol ester is connected through pi-pi action and hydrogen bond, and the hydrophobic octanol alkyl forms a protective film on the metal surface, so that the synergistic effect is realized, and the antirust performance is further improved.

The preparation process of the composite material of the nano montmorillonite and the polymer comprises the following steps:

pretreatment of reactants and initiators

(1) Purification of reactant octadecyl methacrylate: washing octadecyl methacrylate with a sodium hydroxide aqueous solution with the mass fraction of 5-10% until the octadecyl methacrylate is colorless, then repeatedly washing with distilled water until the washing liquid is neutral, and performing vacuum drying to obtain purified octadecyl methacrylate, and storing in a brown reagent bottle for storage;

(2) purification of initiator azobisisobutyronitrile: adding 50-200 mL of ethanol aqueous solution with volume fraction of 95% into a three-neck flask provided with a reflux condenser tube, heating until ethanol is nearly boiled, quickly adding 5-20 g of azobisisobutyronitrile, stirring until the azobisisobutyronitrile is completely dissolved, performing suction filtration while hot, cooling to obtain white crystals, performing vacuum drying, and storing the purified azobisisobutyronitrile in a brown reagent bottle for later use.

Organic modification of II nano montmorillonite

(1) Adding 0.1-5 g of nano montmorillonite into 10-100 mL of distilled water, stirring for 2-4 hours, and standing until complete swelling to obtain a montmorillonite aqueous solution;

(2) adding 5-30 mL of distilled water into 5-10 g of intercalation agent hexadecyl trimethyl ammonium bromide, and stirring until the distilled water is completely dissolved to obtain an intercalation agent aqueous solution;

(3) placing the montmorillonite aqueous solution in a water bath at 50-70 ℃ for heat preservation for 2-3 hours, then adding an intercalator aqueous solution, performing heat preservation reaction at 50-70 ℃ for 4-8 hours, cooling to room temperature, performing centrifugal separation, and collecting bottom precipitate; and (4) drying the bottom precipitate in vacuum to obtain the organic modified montmorillonite.

Preparation of composite material of III nano montmorillonite and polymer

Taking organic modified montmorillonite according to a solid-liquid ratio of 1: (50-100) (g/mL) is added into absolute ethyl alcohol, and ultrasonic treatment is carried out for 30-60 minutes to obtain a dispersion liquid; sequentially adding acrylamide and octadecyl methacrylate into the dispersion liquid, wherein the organic modified montmorillonite accounts for 5-7% of the total mass of the acrylamide and the octadecyl methacrylate, and the molar ratio of the acrylamide to the octadecyl methacrylate is (1-3): 1, introducing nitrogen and preserving heat for 0.5-1 hour at the temperature of 60-80 ℃; then adding an initiator of azobisisobutyronitrile, wherein the initiator of azobisisobutyronitrile accounts for 0.3-0.75% of the total mass of acrylamide and octadecyl methacrylate, and reacting for 4-6 hours at the temperature of 60-80 ℃; centrifuging the reaction solution, and collecting bottom solids; and (4) drying the bottom solid in vacuum to obtain the composite material of the nano montmorillonite and the polymer.

In some technical schemes of the invention, the composite material of the nano montmorillonite and the polymer uses the nano montmorillonite as a carrier, and the nano montmorillonite is organically modified by sodium dodecyl benzene sulfonate to obtain organically modified nano montmorillonite; then polymerizing and grafting monomers of octadecyl methacrylate, N-hydroxymethyl acrylamide and maleic anhydride into the montmorillonite layer to synthesize the nano-montmorillonite composite viscosity reducer.

pretreatment of reactants and initiators

Organic modification of II nano montmorillonite

(1) Adding 0.1-5 g of nano montmorillonite into 10-100 mL of distilled water, stirring for 2-4 hours, standing until the nano montmorillonite is completely swelled, and adjusting the pH to be neutral by using 0.1-1 mol/L hydrochloric acid to obtain a montmorillonite aqueous solution;

(2) adding 5-30 mL of distilled water into 5-10 g of anionic surfactant sodium dodecyl benzene sulfonate, and stirring until the distilled water is completely dissolved to obtain an anionic surfactant aqueous solution;

(3) placing the montmorillonite aqueous solution in a water bath at 50-70 ℃ for heat preservation for 2-3 hours, then adding an anionic surfactant aqueous solution, performing heat preservation reaction at 50-70 ℃ for 4-8 hours, cooling to room temperature, performing centrifugal separation, and collecting bottom precipitate; and (4) drying the bottom precipitate in vacuum to obtain the organic modified montmorillonite.

Preparation of composite material of III nano montmorillonite and polymer

Taking organic modified montmorillonite according to a solid-liquid ratio of 1: (50-100) (g/mL) is added into absolute ethyl alcohol, and ultrasonic treatment is carried out for 30-60 minutes to obtain a dispersion liquid; adding octadecyl methacrylate, N-hydroxymethyl acrylamide and maleic anhydride into the dispersion liquid in sequence, wherein the organic modified montmorillonite accounts for 5-7% of the total mass of the octadecyl methacrylate, the N-hydroxymethyl acrylamide and the maleic anhydride, and the molar ratio of the N-hydroxymethyl acrylamide to the octadecyl methacrylate to the maleic anhydride is (1-3): 1: (0.2-0.7), introducing nitrogen and preserving heat for 0.5-1 hour at the temperature of 60-80 ℃; then adding an initiator azobisisobutyronitrile, wherein the initiator azobisisobutyronitrile accounts for 0.3-0.75% of the total mass of the octadecyl methacrylate, the N-hydroxymethyl acrylamide and the maleic anhydride, and reacting for 4-6 hours at the temperature of 60-80 ℃; centrifuging the reaction solution, and collecting bottom solids; and drying the solid at the bottom in vacuum to obtain the composite material of the nano montmorillonite and the polymer.

The preparation principle of the composite material viscosity reducer of the nano montmorillonite and the polymer is as follows: firstly, adding water to swell dry montmorillonite, and then organically modifying the montmorillonite by using an auxiliary agent at a certain temperature to ensure that auxiliary agent molecules enter montmorillonite layers through the ion exchange effect, thereby enlarging the interlayer spacing of the montmorillonite. The organic ions generally contain long-chain alkyl groups, and the long-chain alkyl groups can be filled in the montmorillonite layers, so that the original hydrophilicity of the inner and outer montmorillonite layers is changed into hydrophobicity, the montmorillonite layers can be fused with organic substances, the specific surface area of the montmorillonite layers is increased due to the enlarged interlayer spacing, and the organic substances can be introduced into the interlayers, so that the nano-montmorillonite and polymer composite viscosity reduction material is synthesized.

The viscosity reducer of the composite material of the nano montmorillonite and the polymer obtained by the two technical schemes has the following characteristics:

(1) the viscosity reducer of the nano montmorillonite composite material can be used as a nucleation point of paraffin wax crystallization due to the small size effect and the special nucleation effect of the nano material, so as to prevent the crystallization of the paraffin wax to form a larger wax block; meanwhile, the strong polar groups introduced between the montmorillonite layers can form hydrogen bonds through the action of colloid and asphaltene of the thick oil to prevent the colloid asphalt from forming a three-dimensional network structure, and the two groups act together to reduce the condensation point and viscosity of the thick oil and improve the low-temperature fluidity of the thick oil.

(2) The second technical scheme introduces a new monomer on the basis of using acrylamide and octadecyl methacrylate as polymerization monomers, so that the polymer molecular chain of the viscosity reducer molecule is lengthened, the montmorillonite layer is filled with organic polymers as much as possible, the diversity of organic viscosity reducing components and polar groups is increased, and the grafting rate and the viscosity reducing effect are improved.

(3) In natural montmorillonite layers, a large amount of inorganic metal ions exist, the cations can be replaced, when hexadecyl trimethyl ammonium bromide is used for modifying the montmorillonite layers, strong van der Waals force can be formed in the organic cation time, and the organic cation has certain hydrophobicity, so the organic cation can replace the inorganic metal cations among the montmorillonite layers to further generate organic montmorillonite, but anionic surfactants can be adsorbed among other layers. The second technical scheme is different from the method that cetyl trimethyl ammonium bromide is used for carrying out organic modification on montmorillonite, an anionic surfactant dodecyl benzene sulfonate is used for carrying out organic modification on the montmorillonite, negative ions in water can adsorb particles with negative charges among montmorillonite layers, meanwhile, C-H bonds in surfactant branched chains can form hydrogen bonds with molecules with stronger non-polarity among montmorillonite layers to be attached together, when a certain amount of negative ions are adsorbed among the montmorillonite layers, the density of the negative charges among the montmorillonite layers is increased, the repulsive force is increased, and therefore the interlayer spacing of the montmorillonite is increased.

Further, the fluorine-containing additive is a surface-modified nano lanthanum fluoride solid additive, and in the preparation process: dissolving 8-12 g of lanthanum chloride solid in 300-600 mL of distilled water, heating to 50-70 ℃, adding 30-50 mL of ammonia fluoride solution with the molar concentration of 1-5 mmol/L into the solution, and reacting at 50-70 ℃ for 2-4 hours; after the reaction is completed, adding 0.1-1 g of surface modifier into the reaction solution, reacting at 50-70 ℃ for 1-2 hours, stopping heating and stirring, and collecting the reaction solution; and naturally cooling the reaction solution to room temperature, and carrying out vacuum freeze drying to finally obtain the surface modified nano lanthanum fluoride solid additive.

Further, the fluorine-containing additive is a surface-modified nano lanthanum fluoride liquid additive, and the preparation process comprises the following steps: placing 15-30 g of oleic acid and 5-8 g of methanol in a three-neck flask with a reflux condenser tube, sequentially adding 0.1-0.3 g of toluenesulfonic acid as a catalyst and 2-5 mL of petroleum ether as a water-carrying agent, heating to 80-90 ℃, and stopping reaction at 80-90 ℃ until no water is generated, thus obtaining a methyl oleate modifier; dissolving 8-12 g of lanthanum chloride solid in 300-600 mL of distilled water, heating to 50-70 ℃, adding 30-50 mL of ammonia fluoride solution with the molar concentration of 1-5 mmol/L into the solution, and reacting at 50-70 ℃ for 2-4 hours; after the reaction is completed, adding 0.1-1 g of surface modifier into the reaction solution, and reacting at 50-70 ℃ for 1-2 hours to obtain surface modified lanthanum fluoride colloid; adding the surface modified lanthanum fluoride colloid into a methyl oleate modifier at 50-60 ℃, then sequentially adding 0.06-0.1 g of tetrabutylammonium bromide serving as a phase transfer catalyst and 4-10 mL of petroleum ether serving as a water-carrying agent, reacting at 50-60 ℃ for 4-10 hours while keeping the temperature, stopping stirring and heating, and drying in vacuum to obtain the surface modified nano lanthanum fluoride liquid additive.

In the above preparation scheme of the fluorine-containing additive, the surface modifier is one of KH560, oleic acid, cetyl trimethyl ammonium bromide, citric acid and stearic acid. The surface modifier is preferably KH 560.

The fluorine-containing additive used in the invention has excellent wear resistance by virtue of the special electronic structure of the rare earth element and the unique crystal structure of the rare earth compound, but solid particles have large specific surface area due to extremely fine crystal grains, so that large surface energy is formed, and in addition, attractive force exists among the particles, so that the particles have the tendency of self-aggregation. The engine oil is generally in a high-temperature, high-pressure and high-load working environment, suspended nano particles are easy to agglomerate under the conditions, so that the suspended nano particles are settled to damage the stable state of the suspended nano particles, and finally the abrasion resistance of the nano particles is lost. Meanwhile, the rare earth compound nano per se is insoluble in base oil, so that the surface modification of rare earth particles is required to enable the rare earth compound nano per se to be stably dispersed in the base oil. The invention simultaneously adopts silane coupling agent and methyl oleate to jointly modify and prepare the liquid additive, prepares colloid primarily modified by the silane coupling agent, then transfers the prepared colloid into the methyl oleate by a phase transfer method, rotationally evaporates redundant petroleum ether after complete reaction to finally obtain the nano rare earth particle liquid additive, and compared with nano LaF in base oil ₃ The powder additive has better dispersion stability and high-temperature stability.

Further, the base oil is one of Lanzhou petrochemical intermediate base oil MVIS600, Dalian petrochemical paraffin base oil HVI650, Daqing hydro-isodewaxing base oil HVIW H350 and poly alpha-olefin synthetic oil PAO-10.

Further, the antiwear agent is an ionic liquid functionalized carbon quantum dot, and the preparation process is as follows: adding 3-5 g of ionic liquid into a reaction device, and heating to 230-260 ℃ under the protection of nitrogen; adding 0.5-2 g of citric acid monohydrate under the stirring condition, and reacting for 4-10 hours at 230-260 ℃; then naturally cooling to room temperature, adding 20-30 mL of distilled water, and stirring for 2-3 hours to obtain an aqueous dispersion; dialyzing the dispersion liquid for 3-4 days by using a dialysis bag with the cut-off molecular weight of 1000-2000 Da, and changing water once every half day in the period; and finally, removing water in the dialysate, and drying in vacuum at 50-60 ℃ to obtain the carbon quantum dots functionalized by the ionic liquid.

In the preparation of the ionic liquid functionalized carbon quantum dot, the ionic liquid is 1-N-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and/or N-butylpyridinium tetrafluoroborate ionic liquid. Preferably, the ionic liquid is a mixture of 1-N-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and N-butylpyridinium tetrafluoroborate ionic liquid in a mass ratio of 1: 1.

In the prior art, traditional carbon nano-based additives such as fullerene, carbon tube and graphene are often used as antiwear components, but because of surface inertness, relatively complicated surface pretreatments are usually required before the carbon nano-based additives are prepared and used, and the pretreatments not only take time but also greatly increase the cost. In addition, fullerene is difficult to realize monodispersion in base liquid due to strong agglomeration capacity, and exists in a cluster form; the carbon tubes and graphene are not uniform in size; this makes the traditional nano carbon material still have a great promotion space for the embedding stability between the surface asperities of the friction interface. The invention forms a boundary lubricating film in the friction process by means of the synergistic lubricating effect between the carbon quantum dots and the ionic liquid, thereby greatly reducing the friction and the abrasion of a friction interface.

The second technical problem to be solved by the invention is to provide an antirust gearbox oil.

The antirust gearbox oil is processed by using any one of the preparation methods of the antirust gearbox oil.

The antirust gearbox oil provided by the invention has excellent corrosion resistance, thermal oxidation stability, sealing adaptability, wear resistance and durability and extreme pressure wear resistance, can meet the lubricating requirements of manual gearboxes of high-grade cars, and can simultaneously meet the lubricating requirements of manual gearboxes of vehicles such as drive axles, trucks and buses, and can achieve the purposes of prolonging the service cycle of the gearbox oil, reducing the maintenance frequency of equipment, saving energy, reducing consumption and reducing cost.

Detailed Description

The raw materials in the examples are as follows:

octadecyl methacrylate, CAS No.: 32360-05-7.

Azobisisobutyronitrile, CAS number: 78-67-1.

Nanometer montmorillonite, Autai mineral processing factory of Lingshou county, with 1250 mesh.

Cetyl trimethylammonium bromide, CAS number: 57-09-0.

Acrylamide, CAS No.: 79-06-1.

Sodium dodecylbenzenesulfonate, CAS No.: 25155-30-0.

N-methylolacrylamide, CAS No.: 924-42-5.

Maleic anhydride, CAS No.: 108-31-6.

Lanthanum chloride, CAS No.: 10099-58-8, 1000 mesh, Jinan Wanduoxin chemical Co., Ltd.

Oleic acid, CAS number: 112-80-1.

Toluenesulfonic acid, CAS number: 104-15-4.

Tetrabutylammonium bromide, CAS No.: 1643-19-2.

Citric acid monohydrate, CAS No.: 77-92-9.

3-benzoyl- α -D-glucofuranose, chapter 3 in the synthesis method reference (liu laugh, preparation and performance characterization of polyhydroxy glucose derivative water-based rust inhibitor [ D ]. china geological university (beijing), 2010.), 3.33-benzoyl- α -D-glucofuranose 2- [ (2-benzothiazolyl) thio ] ethyl boronic acid-2-octanol ester.

2- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octyl alcohol ester, synthesis method referring to (Ewing Jianwei. Synthesis of novel boron-containing benzothiazole ester derivative lubricating additive and tribological performance research [ D ]. Zhongnan university, 2010.) Chapter 2 2.2.4.42- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octyl alcohol ester

Triacontyl PVP, CAS: 136445-69-7, available from Shih Shu Biotech, Inc.

Dipropylene glycol methyl ether, CAS: 34590-94-8% pure, available from Shanghai Aladdin Biotechnology Ltd.

Alkylphenol ethoxylates 40, available from south-jensen australia chemical ltd.

The basic criteria for the four base oils used in the examples are as follows:

embodiments 1-5 a method of making a rust inhibiting transmission oil, comprising the steps of:

the method comprises the following steps: preparing materials according to the following mixture ratio: 4 parts by weight of a composite material of nano montmorillonite and polymer, 0.3 part by weight of a composite antirust antioxidant (obtained by uniformly mixing an antirust agent (the product number ALOX2188, the company Limited chemical industry, Inc. of Kunshan Tada, the main component of which is sodium petroleum sulfonate), a phosphite type antioxidant (the product number Qingdajie good new material science and technology Inc. of the company Ltd.) and a phenol type antioxidant 1010 (the company Limited chemical industry, the company Toguan, the company Ltd.) in a mass ratio of 3: 2: 2), 3.5 parts by weight of sulfurized isobutylene (the product number T321, the company Limited chemical industry, the company Limited, the main component of polyether modified organosilicon) special for lubricating oil, 0.19 part by weight of a dialkoxy monothiophosphate ester triazine derivative (refer to the synthesis of the dialkoxy monothiophosphate ester triazine derivative and the tribology research (loyalty of the rapeseed oil additive, scientific bulletin 2005, 10) 0.5 part by weight, polyisobutylene bissuccinimide (prepared from high-activity polyisobutylene (Mn ═ 1000), CAS No.: 9003-27-4, cat # RF1154, manufactured by Shaoxing chemical technology, Inc., Shaoxing, Guangzhou, 2 parts by weight, 0.1 part by weight of thiophosphate amine salt (also known as T307, cat # 004, manufactured by Santa chemical Co., Ltd., cat #), 0.5 part by weight of an antiwear agent, 2 parts by weight of a fluorine-containing additive, and 120 parts by weight of paraffin-based base oil HVI650 (supplied by Dalian chemical);

step two: mixing the paraffin-based base oil HVI650, the composite material of the nano montmorillonite and the polymer, the composite antirust antioxidant, the sulfurized isobutylene, the bis-alkoxy monosulfur phosphate ester-based triazine derivative, the dispersing agent, the thiophosphate amine salt, the antiwear agent and the fluorine-containing additive in a stirrer, stirring for 40 minutes at 70 ℃, then adding the lubricating oil antifoaming agent, stirring for 20 minutes at 70 ℃, and naturally cooling to room temperature to obtain a mixture;

step three: and D, filtering the mixture obtained in the step two under the pressure of 0.3MPa to obtain the antirust gearbox oil.

pretreatment of reactants and initiators

(1) Purification of reactant octadecyl methacrylate: washing octadecyl methacrylate with a sodium hydroxide aqueous solution with the mass fraction of 5% until the octadecyl methacrylate is colorless, then repeatedly washing with distilled water until the washing liquid is neutral, and performing vacuum drying at 50 ℃ for 24 hours to obtain purified octadecyl methacrylate, and storing in a brown reagent bottle for cooling for later use;

(2) purification of initiator azobisisobutyronitrile: adding 100mL of ethanol aqueous solution with volume fraction of 95% into a three-neck flask provided with a reflux condenser, heating until the ethanol is nearly boiled, quickly adding 10g of azobisisobutyronitrile, stirring at 100 revolutions per minute until the azobisisobutyronitrile is completely dissolved, carrying out suction filtration while the solution is hot, cooling to obtain white crystals, carrying out vacuum drying at 50 ℃ for 12 hours, and storing the purified azobisisobutyronitrile in a brown reagent bottle for later use.

Organic modification of II nano montmorillonite

(1) Adding 1g of nano montmorillonite into 20mL of distilled water, stirring for 2 hours at 100 revolutions per minute, and standing for 24 hours until complete swelling to obtain montmorillonite aqueous solution;

(2) adding 10mL of distilled water into 7g of intercalation agent hexadecyl trimethyl ammonium bromide, and stirring at 100 revolutions per minute until the solution is completely dissolved to obtain an intercalation agent aqueous solution;

(3) placing montmorillonite aqueous solution in water bath at 60 ℃ for heat preservation for 2 hours, then adding intercalation agent aqueous solution, simultaneously carrying out heat preservation reaction at 60 ℃ for 6 hours, cooling to room temperature, centrifuging for 30 minutes at 5000 revolutions per minute, and collecting bottom precipitate; and (3) drying the bottom precipitate at 50 ℃ for 6 hours in vacuum to obtain the organic modified montmorillonite.

Preparation of composite material of III nano montmorillonite and polymer

Taking organic modified montmorillonite according to a solid-liquid ratio of 1: 60(g/mL) is added into absolute ethyl alcohol, and ultrasonic treatment is carried out for 40 minutes under the conditions of ultrasonic power of 300W and ultrasonic frequency of 25kHz to obtain dispersion liquid; sequentially adding acrylamide and octadecyl methacrylate into the dispersion, wherein the organic modified montmorillonite accounts for 7 percent of the total mass of the acrylamide and the octadecyl methacrylate, and the molar ratio of the acrylamide to the octadecyl methacrylate is 2: 1, introducing nitrogen and preserving heat for 0.5 hour at 60 ℃; then adding an initiator of azobisisobutyronitrile, wherein the initiator of azobisisobutyronitrile accounts for 0.75 percent of the total mass of acrylamide and octadecyl methacrylate, and reacting for 4 hours at 60 ℃; centrifuging the reaction solution at 5000 rpm for 30 minutes, and collecting a bottom solid; and (3) drying the bottom solid at 50 ℃ for 12 hours in vacuum to obtain the composite material of the nano montmorillonite and the polymer.

The antiwear agent is an ionic liquid functionalized carbon quantum dot, and the preparation process comprises the following steps: adding 4g of ionic liquid (specifically, 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid is used, and the ionic liquid is prepared according to the synthesis research of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (Liuhongxia, chemical world, 11 th 2006), wherein the reaction temperature is 80 ℃, the reaction time is 18 hours, the microwave power is 240W, the molar ratio of reactants is 1: 1: 1), and heating to 260 ℃ at 5 ℃/min under the protection of nitrogen; adding 1g of citric acid monohydrate under the stirring condition of 100 revolutions per minute, and reacting for 6 hours at 260 ℃; then naturally cooling to room temperature, adding 25mL of distilled water, and stirring at 100 revolutions per minute for 2 hours to obtain an aqueous dispersion; dialyzing the dispersion with dialysis bag with cut-off molecular weight of 1000Da for 3 days, and changing water once every half day; finally, water in the dialysate was removed and vacuum dried at 60 ℃ for 12 hours to obtain ionic liquid functionalized carbon quantum dots.

The fluorine-containing additive is a surface-modified nano lanthanum fluoride solid additive, and the preparation process comprises the following steps: dissolving 10g lanthanum chloride solid in 500mL distilled water, heating to 60 ℃ at 2 ℃/min, dripping 40mL ammonia fluoride solution with the molar concentration of 1mmol/L into the solution at the speed of 0.3mL/min, and reacting for 2 hours at 60 ℃; after the reaction is completed, adding 0.1g of surface modifier into the reaction solution, reacting for 1 hour at 60 ℃, stopping heating and stirring, and collecting the reaction solution; and naturally cooling the reaction solution to room temperature, and carrying out vacuum freeze drying to finally obtain the surface modified nano lanthanum fluoride solid additive.

Examples 1 to 5 differ in that: the surface modifying agents used in the fluorine-containing additives of examples 1 to 5 were different. The surface modifiers used in examples 1 to 5 were oleic acid, stearic acid, cetyltrimethylammonium bromide, citric acid, and KH560, respectively.

The dispersion stabilizer of the fluorine-containing additive in the paraffin-based base oil HVI650 was tested: adding a fluorine-containing additive accounting for 1.6 percent of the weight of the paraffin base oil HVI650 into the paraffin base oil HVI650, carrying out ultrasonic treatment for 30 minutes, heating to 35 ℃, and stirring for 2 hours to prepare lubricating oil; adding the lubricating oil into a centrifuge tube, centrifuging for 10 minutes at four rotating speeds of 500 revolutions per minute, 1000 revolutions per minute, 2000 revolutions per minute and 3000 revolutions per minute by adopting a desktop centrifuge, and observing the precipitation condition of the lubricating oil in the centrifuge tube.

The specific test results are shown in table 1.

TABLE 1 Dispersion stability of fluorine-containing additives in paraffinic base oil HVI650

Example 6

The preparation method of the antirust gearbox oil is the same as that in the embodiment 5, and the difference is that:

i, pretreatment of reactants and an initiator: the pretreatment process was the same as in examples 1 to 5.

Organic modification of II nano montmorillonite

(1) Adding 1g of montmorillonite into 40mL of distilled water, stirring for 2 hours at 100 revolutions per minute, standing for 24 hours until complete swelling is achieved, and adjusting the pH to be neutral by using 0.1mol/L hydrochloric acid to obtain a montmorillonite aqueous solution;

(2) adding 10mL of distilled water into 7g of anionic surfactant sodium dodecyl benzene sulfonate, and stirring at 100 revolutions per minute until the distilled water is completely dissolved to obtain an anionic surfactant aqueous solution;

(3) putting the montmorillonite aqueous solution into a water bath at 60 ℃ for heat preservation for 2 hours, then adding an anionic surfactant aqueous solution into the montmorillonite aqueous solution, simultaneously carrying out heat preservation reaction at 60 ℃ for 6 hours, cooling to room temperature, centrifuging for 30 minutes at 5000 revolutions per minute, and collecting bottom sediment; and (3) drying the bottom precipitate at 50 ℃ for 6 hours in vacuum to obtain the organic modified montmorillonite.

Preparation of composite material of III nano montmorillonite and polymer

Taking organic modified montmorillonite according to a solid-liquid ratio of 1: 60(g/mL) is added into absolute ethyl alcohol, and ultrasonic treatment is carried out for 40 minutes under the conditions of ultrasonic power of 300W and ultrasonic frequency of 25kHz to obtain dispersion liquid; adding octadecyl methacrylate, N-hydroxymethyl acrylamide and maleic anhydride into the dispersion liquid in sequence, wherein the organic modified montmorillonite accounts for 7 percent of the total mass of the octadecyl methacrylate, the N-hydroxymethyl acrylamide and the maleic anhydride, and the molar ratio of the N-hydroxymethyl acrylamide to the octadecyl methacrylate to the maleic anhydride is 2: 1: 0.5, introducing nitrogen and keeping the temperature at 80 ℃ for 0.5 hour; then adding an initiator of azobisisobutyronitrile, wherein the initiator of azobisisobutyronitrile accounts for 0.75 percent of the total mass of the octadecyl methacrylate, the N-hydroxymethyl acrylamide and the maleic anhydride, and reacting for 5 hours at 60 ℃; centrifuging the reaction solution at 5000 rpm for 30 minutes, and collecting a bottom solid; and (3) drying the bottom solid at 50 ℃ for 12 hours in vacuum to obtain the composite material of the nano montmorillonite and the polymer.

Example 7

The preparation method of the antirust gearbox oil is the same as that of the embodiment 5.

The preparation process of the composite material of the nano montmorillonite and the polymer is the same as that of the example 6.

The fluorine-containing additive is a surface-modified nano lanthanum fluoride liquid additive, and the preparation process comprises the following steps: placing 20g of oleic acid and 5.5g of methanol in a three-neck flask provided with a reflux condenser tube, sequentially adding 0.1g of toluenesulfonic acid as a catalyst and 2mL of petroleum ether as a water-carrying agent, heating to 80 ℃ at the speed of 2 ℃/min, and stopping reaction at the temperature of 80 ℃ until no water is generated to obtain a methyl oleate modifier; dissolving 10g lanthanum chloride solid in 500mL distilled water, heating to 60 ℃ at the speed of 2 ℃/min, dripping 40mL ammonia fluoride solution with the molar concentration of 1mmol/L into the solution at the speed of 0.3mL/min, and reacting for 2 hours at 60 ℃; after the reaction is completed, adding 0.1g KH560 into the reaction solution, and reacting at 60 ℃ for 1 hour to obtain surface-modified lanthanum fluoride colloid; adding the surface-modified lanthanum fluoride colloid into a methyl oleate modifier at 60 ℃, then sequentially adding 0.09g of tetrabutylammonium bromide serving as a phase transfer catalyst and 5mL of petroleum ether serving as a water-carrying agent, reacting at 60 ℃ for 5 hours, stopping stirring and heating, and drying at 50 ℃ for 8 hours in vacuum to obtain the surface-modified nano lanthanum fluoride liquid additive.

Examples 8 to 10

The formulation and preparation method of the rust-proof transmission engine oil are the same as those of example 7.

The difference is that: the base oils used in the formulation of the rustproof transmission motor oil were different, and the base oil used in example 7 was a major petrochemical paraffin base oil HVI650, the base oil used in example 8 was a lanzhou petrochemical intermediate base oil MVIS600, the base oil used in example 9 was a major hydro-isodewaxing base oil HVIW H350, and the base oil used in example 10 was a poly a-olefin synthetic oil PAO-10.

Example 11

Essentially the same as example 7, except that: the antiwear agent is an ionic liquid functionalized carbon quantum dot, and the preparation process is as follows: adding 4g of ionic liquid (specifically N-butylpyridinium tetrafluoroborate ionic liquid, prepared according to research on synthesis of ionic liquid N-butylpyridinium tetrafluoroborate (Sun sea, chemical reagent, 6 months 2009)) into a reaction device, wherein the molar ratio of pyridine to N-bromobutane is 1: 1.2, the reaction temperature is 75 ℃, the reaction time is 12 hours, and the solvent is 20mL of acetonitrile, and heating to 260 ℃ at the temperature of 5 ℃/min under the protection of nitrogen; adding 1g of citric acid monohydrate under the stirring condition of 100 revolutions per minute, and reacting for 6 hours at 260 ℃; then naturally cooling to room temperature, adding 25mL of distilled water, and stirring at 100 revolutions per minute for 2 hours to obtain an aqueous dispersion; dialyzing the dispersion with dialysis bag with cut-off molecular weight of 1000Da for 3 days, and changing water every half day; finally, water in the dialysate was removed and vacuum dried at 60 ℃ for 12 hours to obtain ionic liquid functionalized carbon quantum dots.

Example 12

Essentially the same as example 7, except that: the antiwear agent is an ionic liquid functionalized carbon quantum dot, and the preparation process is as follows: adding 4g of ionic liquid into a reaction device, and heating to 260 ℃ at 5 ℃/min under the protection of nitrogen; adding 1g of citric acid monohydrate under the stirring condition of 100 revolutions per minute, and reacting for 6 hours at 260 ℃; then naturally cooling to room temperature, adding 25mL of distilled water, and stirring at 100 revolutions per minute for 2 hours to obtain an aqueous dispersion; dialyzing the dispersion with dialysis bag with cut-off molecular weight of 1000Da for 3 days, and changing water every half day; finally, water in the dialysate was removed and vacuum dried at 60 ℃ for 12 hours to obtain ionic liquid functionalized carbon quantum dots.

The ionic liquid is a mixture of 1-N-butyl-3-methylimidazole tetrafluoroborate ionic liquid and N-butylpyridine tetrafluoroborate ionic liquid in a mass ratio of 1: 1.

The 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid is prepared by referring to the synthesis research of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (Liuhongxia, chemical world, 11 th 2006), the reaction temperature is 80 ℃, the reaction time is 18 hours, the microwave power is 240W, and the molar ratio of reactants is 1: 1: 1.

the N-butylpyridinium tetrafluoroborate ionic liquid is prepared by referring to the research on synthesis of ionic liquid N-butylpyridinium tetrafluoroborate (Sun sea, chemical reagent, 6 months 2009), wherein the molar ratio of pyridine to N-bromobutane is 1: 1.2, reaction temperature of 75 ℃, reaction time of 12 hours and solvent of 20mL of acetonitrile.

Example 13

The composite antirust antioxidant comprises the following components in parts by weight: 20 parts of 3-benzoyl-alpha-D-glucopyranose, 20 parts of 2- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octanol ester, 5 parts of triacontyl PVP, 1 part of dipropylene glycol methyl ether and 405 parts of alkylphenol polyoxyethylene ether.

The preparation method of the antirust gearbox oil comprises the following steps:

the method comprises the following steps: preparing materials according to the following mixture ratio: 4 parts of composite material of nano montmorillonite and polymer, 0.3 part of composite antirust antioxidant, 3.5 parts of sulfurized isobutylene (T321, Shang Sheng research chemical technology Co., Ltd., manufacturer), 0.19 part of special defoaming agent for lubricating oil (DF-668, Defeng defoaming agent Co., Ltd., manufactured Dongguan city, polyether modified organic silicon as main component), 0.5 part of bis-alkoxy monothiophosphate triazine derivative (obtained by synthesis of bis-alkoxy monothiophosphate triazine derivative and tribology research (which is the loyalty of 10 th year in 2005) and 2 parts of polyisobutylene bis-succinimide (prepared by high-activity polyisobutylene (Mn 1000), CAS number: 9003-27-4, product number RF1154, Guangzhou Shai research chemical technology Co., Ltd., manufacturer), 0.1 part by weight of thiophosphate amine salt (also known as T307, Cat. No. 004, St. major chemical Co., Ltd., Inc. of manufacturer), 0.5 part by weight of antiwear agent, 2 parts by weight of fluorine-containing additive, and 120 parts by weight of paraffin-based base oil HVI650 (supplied by Dalian chemical);

step two: mixing the paraffin-based base oil HVI650, the composite material of the nano montmorillonite and the polymer, the composite antirust antioxidant, the sulfurized isobutylene, the bis-alkoxy monothiophosphate triazine derivative, the dispersant, the thiophosphate amine salt, the antiwear agent and the fluorine-containing additive in the step one in a stirrer, stirring for 40 minutes at 70 ℃, then adding the lubricating oil antifoaming agent, stirring for 20 minutes at 70 ℃, and naturally cooling to room temperature to obtain a mixture;

The preparation process of the carbon quantum dot with the antiwear agent being ionic liquid functionalized is the same as that of example 12.

The preparation process of the fluorine-containing additive which is a surface-modified nano lanthanum fluoride liquid additive is the same as that in example 7.

Comparative example 1

Essentially the same as in example 13, except that:

the composite antirust antioxidant comprises the following components in parts by weight: 40 parts of 3-benzoyl-alpha-D-glucopyranose, 5 parts of triacontyl PVP, 1 part of dipropylene glycol methyl ether and 405 parts of alkylphenol polyoxyethylene.

Comparative example 2

Essentially the same as in example 13, except that:

the composite antirust antioxidant comprises the following components in parts by weight: 40 parts of 2- [ (2-benzothiazolyl) thio ] ethyl boric acid-2-octyl alcohol ester, 5 parts of triacontyl PVP, 1 part of dipropylene glycol methyl ether and 405 parts of alkylphenol polyoxyethylene ether.

Comparative example 3

Essentially the same as in example 13, except that:

the method comprises the following steps: preparing materials according to the following mixture ratio: 4 parts by weight of a composite material of nano-montmorillonite and polymer, 3.5 parts by weight of sulfurized isobutylene (also known as T321, manufactured by Shaoge Sanyo chemical science and technology Co., Ltd.), 0.19 part by weight of a defoaming agent special for lubricating oil (product No. DF-668, manufactured by Defeng defoaming agent Co., Ltd. of Dongguan city, main component polyether modified organosilicon), 0.5 part by weight of a bis-alkoxy monothiophosphate triazine derivative (prepared by referring to the synthesis of a bis-alkoxy monothiophosphate triazine derivative and the tribology research thereof as a rapeseed oil additive (loyal, science bulletin 2005, 10 th)) 0.5 part by weight of a polyisobutylene bis-succinimide (prepared by high-activity polyisobutylene (Mn ═ 1000), No. CAS 3-27-4, product No. RF1154, manufactured by Guangzhou Sha Sanyo chemical science and technology Co., Ltd.), 2 parts by weight of a thiophosphate amine salt (also known as T307, cat No. 004, manufactured by saint chemicals ltd, mallow) 0.1 part by weight, an antiwear agent 0.5 part by weight, a fluorine-containing additive 2 parts by weight, and paraffin-based base oil HVI650 (supplied by macrochemical);

step two: mixing the paraffin-based base oil HVI650, the composite material of the nano montmorillonite and the polymer, the sulfurized isobutylene, the bis-alkoxy monothiophosphate-based triazine derivative, the dispersing agent, the thiophosphate amine salt, the antiwear agent and the fluorine-containing additive in a stirrer, stirring for 40 minutes at 70 ℃, then adding the lubricating oil defoaming agent, stirring for 20 minutes at 70 ℃, and naturally cooling to room temperature to obtain a mixture;

Test example 1

Four-ball friction wear test experiments were carried out on the rust-proof transmission machine oil of examples 5 to 11: the testing device of the four-ball testing machine is provided with 4 small balls, one steel ball at the upper part is connected with the main rotating shaft through a fixing device, and three steel balls at the lower part are tightly clamped in the oil cup. The upper steel ball is respectively in point contact with the lower three balls (called lower test balls for short), the upper main rotating shaft rotates under certain extrusion force to drive the upper ball to perform sliding friction with the fixed lower test balls, and a grinding spot is left after the lower test steel ball is rubbed.

The steel ball for the test is a special steel ball with the diameter of 12.7mm for a four-ball machine, and is made of the following materials: GCr15 bearing steel, hardness: 60-63 HRC.

The characteristics of tribological properties mainly include coefficient of friction, Wear Scar Diameter (WSD), maximum non-seizing load (P) _B ). Wherein the maximum non-seizing load (P) is predominant _B ) The measurement of (1) is that under the experimental condition, the maximum load added by the steel ball without clamping is represented by the load intensity which can be born by the oil film. At low load, the diameter of the wear scar of the steel ball is in direct proportion to the load, and the steel ball rubs in a low load rangeThe surface has a relatively complete oil film; when the load reaches P _B At this time, the wear scar diameter rises sharply. P of lubricating oil _B The larger the value, the stronger the load-bearing capacity of the oil film formed on the friction surface.

Maximum no-seize load (P) _B ) The test method (2): according to GB/T12583-1998, under a certain load, the rotating speed is 1350 revolutions per minute, the time is 10s, and the temperature is normal temperature. Measurement of P _B During the test, after each test, the grinding marks of the three lower test balls need to be observed by using a microscope, whether the grinding marks are circular or not is observed, the diameter of the grinding marks is read, and the measurement requirements are met only by judging that the grinding marks of the steel balls are circular and do not exceed the maximum grinding mark diameter under the load, so that the load can be continuously increased for testing until the grinding marks of the steel balls do not meet the measurement requirements, and the loaded load is the final P _B The value is obtained.

The friction coefficient and the abrasion spot diameter are measured by the following method: referring to SH/T0762-2005 method, the rotation speed is 1200 r/min, the load is 392N, the temperature is normal temperature, the test time is60 min, the friction coefficient value of each second is obtained after the experiment, and the final friction coefficient is obtained by averaging the values; the wear scar diameters of 3 test balls were measured simultaneously, and the average value was taken as the final measured wear scar diameter in mm.

The specific test results are shown in table 2.

TABLE 2 four-ball wear test table

As can be seen from Table 2, the four ball sintering loads (PD) for the solvent refined oils (MVIS600 and HVIS650) are significantly higher than for the hydroisomerized dewaxed base oil (HVIWH350) and the synthetic base oil (PAO-10). This is because the solvent refined base oils contain natural sulfur-containing extreme pressure components, whereas the hydroisomerized dewaxed base oils are substantially freed from natural sulfur-containing extreme pressure components, and synthetic oils do not contain natural sulfur-containing extreme pressure components. Furthermore, the four-ball speck values (D392N60min) for the solvent refined oils (MVIS600 and HVIS650) were significantly lower than for the hydroisomerized dewaxed base oil (HVIWH350) and the synthetic base oil (PAO-10) because the solvent refined base oils contained natural nitrogen-containing antiwear components.

After the composite antirust antioxidant is added, the friction and wear resistance is improved, and the reason is that the composite antirust antioxidant contains boron compounds, so that the strength of the protective film is improved, and the corrosion of active elements such as sulfur can be more effectively inhibited.

Test example 2

The manual aging test is carried out on the antirust gearbox engine oil of the embodiments 5 to 7 and 11 to 12: 100g of rust-proof gearbox engine oil test oil is added into a beaker, the beaker is placed in a constant-temperature oven to be kept at the constant temperature of 150 ℃ for 192 hours, and the viscosity change rate (%) and the phosphorus consumption rate (%) of the oil are measured.

The phosphorus consumption rate is (before phosphorus test-after phosphorus test)/before phosphorus test × 100%.

The specific test results are shown in table 3.

TABLE 3 test table for artificial aging test

Test example 3

For examples 12 to 13, comparative examples 1 to 3, rust inhibitive performance tests were carried out in accordance with GB/T11143-2008 [ test method for rust inhibitive performance of mineral oil with an inhibitor in the presence of water ].

The specific procedure was to mix 300mL of the lubricant oil sample with 30mL of distilled water, immerse the cylindrical test steel bar in it completely, stir at 60 ℃ for a test period of 24 h.

TABLE 4 test results of rust inhibitive performance test

	Degree of rust
		Example 12	Moderate rust
Example 13	No corrosion
		Comparative example 1	Slight rust
Comparative example 2	Slight rusting
		Comparative example 3	Severe rust

From table 4, it can be seen that example 13 utilizes the technical feature of compounding specific contents of 3-benzoyl- α -D-furanose and 2- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octanol ester, and utilizes the characteristic that a plurality of hydroxyl polar groups contained in the molecular structure of 3-benzoyl- α -D-furanose can be adsorbed on a metal surface and a protective film can be formed on the metal surface of 2- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octanol ester. The two become a whole through pi-pi action and hydrogen bond, 3-benzoyl-alpha-D-glucopyranose is adsorbed on the metal surface, 2- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octyl alcohol ester is connected through pi-pi action and hydrogen bond, and a protective film is formed on the metal surface by hydrophobic octanol alkyl, so that the synergistic effect is realized, and the antirust performance is further improved.

It should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments may be appropriately combined to form other embodiments as will be appreciated by those skilled in the art.

Claims

1. The composite antirust antioxidant is characterized by comprising the following components in parts by weight: 10-40 parts of 3-benzoyl-alpha-D-glucopyranose, 10-40 parts of 2- [ (2-benzothiazolyl) thio ] ethylboronic acid-2-octanol ester, 2-8 parts of film forming agent, 0.5-2 parts of film forming additive and 0.3-0.6 part of surfactant;

the structural formula of the 3-benzoyl-alpha-D-glucopyranose is shown as the following formula (I),

the structural formula of the 2- [ (2-benzothiazolyl) thio ] ethyl boric acid-2-octyl alcohol ester is shown as the following formula (II),

2. the composite antirust antioxidant according to claim 1, wherein the film forming agent is one or more of triacontyl PVP, a VP/eicosene copolymer and a polytrimethylsiloxane methacrylate copolymer.

3. The composite antirust antioxidant according to claim 1, wherein the film forming aid is one or more of propylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol butyl ether and tripropylene glycol methyl ether.

4. The compound antirust antioxidant according to claim 1, wherein the surfactant is one or more of alkylphenol ethoxylate 9, alkylphenol ethoxylate 4, sodium dodecyl sulfate, sodium oleate, and dodecyl dimethyl betaine.

5. An antirust transmission oil, characterized by comprising a base oil and the composite antirust antioxidant according to any one of claims 1 to 4.

6. The rust-proof gearbox oil as recited in claim 5, characterized by comprising 70-130 parts by weight of base oil and 0.3-0.8 part by weight of the composite rust-proof antioxidant as recited in any one of claims 1-4.

7. The rust-inhibiting transmission oil according to claim 6, characterized by consisting of the following raw materials: 3-7 parts of a composite material of nano montmorillonite and polymer, 0.3-0.8 part of a composite antirust antioxidant as described in any one of claims 1-6, 2.0-3.8 parts of vulcanized isobutylene, 0.1-0.5 part of a special defoaming agent for lubricating oil, 0.5-1.0 part of a bis-alkoxy monothiophosphate-based triazine derivative, 1-5 parts of polyisobutylene bis-succinimide, 0.1-0.2 part of thiophosphate amine salt, 0.5-2 parts of an antiwear agent, 1-2 parts of a fluorine-containing additive and 70-130 parts of base oil.

8. The rust inhibitive transmission machine oil according to claim 7, characterized in that the preparation method comprises the steps of:

the method comprises the following steps: preparing materials according to the following mixture ratio: 3-7 parts of a composite material of nano montmorillonite and polymer, 0.3-0.8 part of the composite antirust antioxidant as described in any one of claims 1-6, 2.0-3.8 parts of vulcanized isobutylene, 0.1-0.5 part of a special defoaming agent for lubricating oil, 0.5-1.0 part of bis-alkoxy monothiophosphate-based triazine derivative, 1-5 parts of polyisobutylene bis-succinimide, 0.1-0.2 part of thiophosphate amine salt, 0.5-2 parts of an antiwear agent, 1-2 parts of a fluorine-containing additive and 70-130 parts of base oil;