阅读说明：本技术 一种抗磨防锈润滑油的改性方法 (Modification method of anti-wear and anti-rust lubricating oil ) 是由 李孙德 于 2019-09-29 设计创作，主要内容包括：本发明公开了一种抗磨防锈润滑油的改性方法,将六水合三氯化铁、四水合氯化亚铁分散到去离子水中,加入氧化石墨烯分散液,在氮气保护下超声反应,滴加水合肼搅拌反应,将黑色固体产物析出、清洗、干燥得到四氧化三铁负载石墨烯；向羟基磷酸钙中加磷酸水溶液、KH560,磁力搅拌回流反应,离心分离、水洗、干燥得改性羟基磷酸钙,将其与三聚磷酸二氢铝混合研磨,过滤、烘干得改性羟基磷酸钙-三聚磷酸二氢铝；将蓖麻油甲酯、甲酸、催化剂浓硫酸混合,滴加双氧水,搅拌冷凝回流反应,分离、水洗至中性,蒸出水分,得到环氧脂肪酸甲酯；将其与改性纳米二氧化硅、纳米四氧化三铁负载石墨烯、改性羟基磷酸钙-三聚磷酸二氢铝混匀得抗磨防锈润滑油。(The invention discloses a method for modifying wear-resistant antirust lubricating oil, which comprises the steps of dispersing ferric trichloride hexahydrate and ferrous chloride tetrahydrate into deionized water, adding graphene oxide dispersion liquid, carrying out ultrasonic reaction under the protection of nitrogen, dropwise adding hydrazine hydrate, stirring for reaction, separating out a black solid product, cleaning and drying to obtain ferroferric oxide-loaded graphene; adding phosphoric acid aqueous solution and KH560 into calcium hydroxy phosphate, performing magnetic stirring reflux reaction, performing centrifugal separation, washing with water, drying to obtain modified calcium hydroxy phosphate, mixing with aluminium dihydrogen tripolyphosphate, grinding, filtering, and oven drying to obtain modified calcium hydroxy phosphate-aluminium dihydrogen tripolyphosphate; mixing castor oil methyl ester, formic acid and catalyst concentrated sulfuric acid, dropwise adding hydrogen peroxide, stirring, condensing, refluxing, reacting, separating, washing with water to neutrality, and evaporating water to obtain epoxy fatty acid methyl ester; and uniformly mixing the modified nano silicon dioxide, nano ferroferric oxide loaded graphene and modified calcium hydroxy phosphate-aluminium dihydrogen tripolyphosphate to obtain the anti-wear and anti-rust lubricating oil.)

1. The modification method of the anti-wear and anti-rust lubricating oil is characterized by comprising the following steps of:

(1) preparing nano ferroferric oxide loaded graphene:

dispersing 2-4 parts of ferric trichloride hexahydrate and 1-2 parts of ferrous chloride tetrahydrate into 100-200 parts of deionized water, adding 25-50 parts of graphene oxide dispersion liquid, adjusting the pH to 11 by using concentrated ammonia water, carrying out ultrasonic reaction for 1-2 hours at 55-60 ℃ under the protection of nitrogen, dropwise adding 1-2 parts of hydrazine hydrate, stirring and reacting for 4-6 hours at 90-95 ℃, separating out a black solid product, respectively cleaning for 3-5 times by using absolute ethyl alcohol and deionized water, and carrying out vacuum drying for 4-6 hours at 60-65 ℃ to obtain nano ferroferric oxide loaded graphene;

preparing modified calcium hydroxy phosphate-aluminium dihydrogen tripolyphosphate:

adding a phosphoric acid aqueous solution with the pH value of 4 into 5-10 parts of calcium hydroxy phosphate at the ratio of 1:200, adding 0.05-0.1 part of silane coupling agent KH560, magnetically stirring for 30-40min, carrying out reflux reaction at the temperature of 80-85 ℃ for 3-5h, adjusting the pH value to be neutral, carrying out centrifugal separation and water washing for 3-5 times, carrying out vacuum drying for 2-4h to obtain modified calcium hydroxy phosphate, mixing the modified calcium hydroxy phosphate with 2.5-5 parts of aluminium dihydrogen tripolyphosphate, grinding, filtering and drying to obtain modified calcium hydroxy phosphate-aluminium dihydrogen tripolyphosphate;

preparing the anti-wear and anti-rust lubricating oil:

mixing 8-11 parts of castor oil methyl ester, 8-11 parts of formic acid and 1-2 parts of catalyst concentrated sulfuric acid, placing in a water bath at 50-55 ℃, dropwise adding 40-53 parts of hydrogen peroxide, stirring, condensing, refluxing for reaction for 7-10h, separating, adjusting acidity and alkalinity with a saturated sodium carbonate solution, washing with water to neutrality, and distilling off water at 80-85 ℃ and 0.01MPa to obtain epoxy fatty acid methyl ester; and (3) uniformly mixing the wear-resistant and rust-proof lubricating oil with 3-6 parts of modified nano silicon dioxide, the materials obtained in the step (1) and the step (2) to prepare the wear-resistant and rust-proof lubricating oil.

2. The method for modifying anti-wear and anti-rust lubricating oil according to claim 1, wherein deionized water is added to 1:50 parts of graphene oxide in the step (1), and the graphene oxide dispersion liquid is obtained by performing ultrasonic treatment for 30-50min to disperse the mixture uniformly.

3. The method for modifying anti-wear and anti-rust lubricating oil according to claim 1, wherein the mass fraction of formic acid in step (3) is 85-90%, and the mass fraction of concentrated sulfuric acid is 90-95%.

4. The method for modifying anti-wear and anti-rust lubricating oil according to claim 1, wherein the modification of the nano silica particles in step (3): mixing 3-6 parts of nano silicon dioxide, a modifier silane coupling agent KH560 and a modifying solvent ethylene glycol, uniformly stirring, heating at a constant temperature of 105-.

Technical Field

The invention belongs to the field of lubricating oil, and particularly relates to a method for modifying anti-wear and anti-rust lubricating oil.

Background

The lubricant is made by mixing a base oil and an additive, about 95% of the base oil being a mineral oil derived from petroleum. The mineral lubricant has poor biodegradability, soil can be directly polluted when the mineral lubricant runs off in the environment, 1kg of petroleum-based lubricant can pollute 1000000L of water, and meanwhile, due to the gradual reduction and non-regenerability of the mineral oil, the development of environment-friendly lubricants is imperative. Vegetable oil-based lubricants, known as "biolubricants," are biodegradable, renewable, non-toxic, and, in addition, have a variety of performance advantages, such as good lubricity, high viscosity index, high flash point, and the like. However, vegetable oil base oils have poor oxidative stability due to the presence of C = C bonds as unsaturated bonds in the fatty acid chains of vegetable oils, and this problem can be solved by reducing the unsaturation of vegetable oils by chemical modification, the hydrogenation of vegetable oils being a common modification method.

As a novel nano reinforcing material, the unique structure of graphene determines that graphene has more excellent friction reducing and wear resisting properties compared with graphite. The lubricating oil is used as a filling material to be added into lubricating oil, and is expected to improve the antifriction and wear resistance of the lubricating oil. However, graphene sheets do not contain other active functional groups, and strong van der waals force exists between the sheets, so that the graphene sheets are easily stacked, and thus it is difficult to exert excellent performance.

The nano silicon dioxide is nano particles with excellent performance, has remarkable wear resistance and wear reduction performance, and shows good dispersibility in lubricating oil. Therefore, the search for a good nano silicon dioxide surface modifier to improve the wear resistance and the antifriction performance is of great significance. The nano particles are used as a lubricating oil additive, have obvious effect on improving the tribological performance of lubricating oil, show the excellent performance of the lubricating oil, and the nano silicon dioxide is widely applied to nano materials. The modified nano silicon dioxide is used as an additive, and the change from hydrophilicity to lipophilicity improves the dispersibility and stability of the modified nano silicon dioxide in base oil. Therefore, the nano silicon dioxide as an additive is added into the lubricating base oil, and has important economic value and application value for reducing abrasion and prolonging the service life of parts.

Most of commercially available lubricating oil has the defects of poor friction-reducing and wear-resisting properties and poor salt spray-resistant and rust-proof properties, the invention provides a modification method of the wear-resisting and rust-proof lubricating oil, and the lubricating oil prepared by the method provided by the invention has excellent friction-reducing and wear-resisting properties and salt spray-resistant and rust-proof properties.

Disclosure of Invention

The invention aims to solve the existing problems and provides a method for modifying anti-wear and anti-rust lubricating oil, and the modified lubricating oil prepared by the method has excellent anti-friction and anti-wear performance and salt spray resistance and anti-rust performance.

The invention is realized by the following technical scheme:

a modification method of anti-wear and anti-rust lubricating oil comprises the following steps of:

(1) preparing nano ferroferric oxide loaded graphene:

dispersing 2-4 parts of ferric trichloride hexahydrate and 1-2 parts of ferrous chloride tetrahydrate into 100-200 parts of deionized water, adding 25-50 parts of graphene oxide dispersion liquid, adjusting the pH to 11 by using concentrated ammonia water, carrying out ultrasonic reaction for 1-2 hours at 55-60 ℃ under the protection of nitrogen, dropwise adding 1-2 parts of hydrazine hydrate, stirring and reacting for 4-6 hours at 90-95 ℃, separating out a black solid product, respectively cleaning for 3-5 times by using absolute ethyl alcohol and deionized water, and carrying out vacuum drying for 4-6 hours at 60-65 ℃ to obtain nano ferroferric oxide loaded graphene;

the ferroferric oxide loaded graphene is prepared by a chemical coprecipitation method, has obvious antifriction and antiwear effects on lubricating oil, and shows lower friction coefficient and self-lubricity in a paraffin oil system; because the ferroferric oxide loaded graphene has high strength and self-lubricating property, a layer of protective film with the self-lubricating property can be formed on the surface of the friction ball in the friction process, and the protective film serves as a gasket, so that the direct contact of the metal friction ball is effectively prevented; meanwhile, the existence of the lubricating film reduces the shearing force between the friction ball and the lubricating oil, thereby effectively improving the lubricating performance of the paraffin oil;

(2) preparing modified calcium hydroxy phosphate-aluminium dihydrogen tripolyphosphate:

adding a phosphoric acid aqueous solution with the pH value of 4 into 5-10 parts of calcium hydroxy phosphate at the ratio of 1:200, adding 0.05-0.1 part of silane coupling agent KH560, magnetically stirring for 30-40min, carrying out reflux reaction at the temperature of 80-85 ℃ for 3-5h, adjusting the pH value to be neutral, carrying out centrifugal separation and water washing for 3-5 times, carrying out vacuum drying for 2-4h to obtain modified calcium hydroxy phosphate, mixing the modified calcium hydroxy phosphate with 2.5-5 parts of aluminium dihydrogen tripolyphosphate, grinding, filtering and drying to obtain modified calcium hydroxy phosphate-aluminium dihydrogen tripolyphosphate;

the silane coupling agent KH560 is grafted on the surface of the hydroxyl calcium phosphate, so that the dispersibility of the hydroxyl calcium phosphate in lubricating oil is improved, the compactness and the corrosion resistance of the lubricating oil are enhanced, the dispersibility of modified calcium phosphate in the lubricating oil is obviously improved, the compactness of the lubricating oil is enhanced, and the corrosion resistance of the lubricating oil is obviously improved; grinding and modifying the aluminum dihydrogen tripolyphosphate by using the modified calcium hydroxy phosphate to obtain a modified calcium hydroxy phosphate-aluminum dihydrogen tripolyphosphate antirust pigment, wherein the modified calcium hydroxy phosphate-aluminum dihydrogen tripolyphosphate antirust pigment has excellent salt spray resistance in lubricating oil due to the synergistic antirust effect of the modified calcium hydroxy phosphate and the aluminum dihydrogen tripolyphosphate;

(3) preparing the anti-wear and anti-rust lubricating oil:

mixing 8-11 parts of castor oil methyl ester, 8-11 parts of formic acid and 1-2 parts of catalyst concentrated sulfuric acid, placing in a water bath at 50-55 ℃, dropwise adding 40-53 parts of hydrogen peroxide, stirring, condensing, refluxing for reaction for 7-10h, separating, adjusting acidity and alkalinity with a saturated sodium carbonate solution, washing with water to neutrality, and distilling off water at 80-85 ℃ and 0.01MPa to obtain epoxy fatty acid methyl ester; uniformly mixing the modified nano silicon dioxide with 3-6 parts of the materials obtained in the steps (1) and (2) to prepare the anti-wear and anti-rust lubricating oil;

the method comprises the following steps of (1) carrying out epoxidation reaction on castor oil methyl ester, formic acid and hydrogen peroxide under the action of a catalyst concentrated sulfuric acid to generate epoxy fatty acid methyl ester; the nano-silica is used as a raw material, ethylene glycol is used as a modification solvent, a silane coupling agent KH560 is used as a modifier, and the modified nano-silica shows good dispersibility in lubricating oil; obtaining epoxy fatty acid methyl ester; and uniformly mixing the epoxy fatty acid methyl ester, the modified nano silicon dioxide, the nano ferroferric oxide-loaded graphene and the modified calcium hydroxy phosphate-aluminum dihydrogen tripolyphosphate to obtain the wear-resistant and rust-proof lubricating oil.

Further, deionized water is added into 1:50 parts of graphene oxide in the step (1), and the graphene oxide dispersion liquid is obtained after uniform dispersion for 30-50min by ultrasonic treatment.

Further, in the step (3), the mass fraction of the formic acid is 85-90%, and the mass fraction of the concentrated sulfuric acid is 90-95%.

Further, modification of the nano silicon dioxide particles in the step (3): mixing 3-6 parts of nano silicon dioxide, a modifier silane coupling agent KH560 and a modifying solvent ethylene glycol, uniformly stirring, heating at a constant temperature of 105-.

Compared with the prior art, the invention has the following advantages:

(1) the ferroferric oxide loaded graphene is prepared by a chemical coprecipitation method, has obvious antifriction and antiwear effects on lubricating oil, and shows lower friction coefficient and self-lubricity in a paraffin oil system; because the ferroferric oxide loaded graphene has high strength and self-lubricating property, a layer of protective film with the self-lubricating property can be formed on the surface of the friction ball in the friction process, and the protective film serves as a gasket, so that the direct contact of the metal friction ball is effectively prevented; meanwhile, the existence of the lubricating film reduces the shearing force between the friction ball and the lubricating oil, thereby effectively improving the lubricating performance of the paraffin oil;

the graphene and ferroferric oxide nanoparticles on the surface of the graphene have a synergistic effect in the aspect of improving the tribological performance of the lubricating oil, the problems of superposition of reduced graphene sheet layers and aggregation of the ferroferric oxide nanoparticles can be solved by depositing the ferroferric oxide nanoparticles on the surface of the graphene, and the ferroferric oxide-loaded graphene can occupy a larger volume in a lubricating oil matrix; the nano particles are deposited on the surface of graphene, so that the thermodynamic stability of the graphene can be effectively improved, because the ferroferric oxide nano particles on the surface of the graphene can form more boundaries, the ferroferric oxide loaded graphene nano particles near a wear surface can be separated out in the friction process, and a firm and self-lubricating 'transfer film' is formed on the surfaces of a counter-grinding ring and a composite material, meanwhile, in the friction process, the ferroferric oxide loaded graphene nano particles can fall off from the surface of the graphene and are distributed in a discontinuous area of the 'transfer film' with the self-lubricating property, along with the formation of the 'transfer film', the friction between the rough surface of the composite material and the metal counter-grinding ring is converted into the friction between the self-lubricating 'transfer film', and the friction reduction and wear resistance of the composite material are effectively improved.

(2) The silane coupling agent KH560 is grafted on the surface of the hydroxyl calcium phosphate, so that the dispersibility of the hydroxyl calcium phosphate in lubricating oil is improved, the compactness and the corrosion resistance of the lubricating oil are enhanced, the dispersibility of modified calcium phosphate in the lubricating oil is obviously improved, the compactness of the lubricating oil is enhanced, and the corrosion resistance of the lubricating oil is obviously improved; and grinding and modifying the aluminum dihydrogen tripolyphosphate by using the modified calcium hydroxy phosphate to obtain the modified calcium hydroxy phosphate-aluminum dihydrogen tripolyphosphate anti-rust pigment, wherein the modified calcium hydroxy phosphate-aluminum dihydrogen tripolyphosphate anti-rust pigment has excellent salt spray resistance in lubricating oil due to the synergistic anti-rust effect of the modified calcium hydroxy phosphate and the aluminum dihydrogen tripolyphosphate.

(3) The method comprises the following steps of (1) carrying out epoxidation reaction on castor oil methyl ester, formic acid and hydrogen peroxide under the action of a catalyst concentrated sulfuric acid to generate epoxy fatty acid methyl ester; the nano-silica is used as a raw material, ethylene glycol is used as a modification solvent, a silane coupling agent KH560 is used as a modifier, and the modified nano-silica shows good dispersibility in lubricating oil; obtaining epoxy fatty acid methyl ester; and uniformly mixing the epoxy fatty acid methyl ester, the modified nano silicon dioxide, the nano ferroferric oxide-loaded graphene and the modified calcium hydroxy phosphate-aluminum dihydrogen tripolyphosphate to obtain the wear-resistant and rust-proof lubricating oil.

Detailed Description