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CN117025286B - Modified high-bearing gear oil and production process thereof - Google Patents

Modified high-bearing gear oil and production process thereof Download PDF

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Publication number
CN117025286B
CN117025286B CN202311270694.6A CN202311270694A CN117025286B CN 117025286 B CN117025286 B CN 117025286B CN 202311270694 A CN202311270694 A CN 202311270694A CN 117025286 B CN117025286 B CN 117025286B
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gear oil
cystamine
oil
extreme pressure
modified high
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CN117025286A (en
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罗刚
杨乃堂
王正杰
杨闻焕
安晓非
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Shandong North Zite Special Oil Co ltd
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Shandong North Zite Special Oil Co ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/048Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/401Fatty vegetable or animal oils used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/402Castor oils
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04Siloxanes with specific structure
    • C10M2229/041Siloxanes with specific structure containing aliphatic substituents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/74Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The application relates to the technical field of gear oil, in particular to modified high-bearing gear oil and a production process thereof. The gear oil is compounded by vegetable oil, extreme pressure antiwear agent, polydimethylsiloxane, hydroquinone, sodium dodecyl benzene sulfonate and polyethylene glycol, wherein the extreme pressure antiwear agent plays a key role in bearing capacity and abrasion resistance of the gear oil. In order to obtain excellent lubricating effect under high bearing condition, the extreme pressure antiwear agent is obtained through the following steps: firstly, coating the inorganic nano particles with a fatty acid polymer, then grafting a sulfur-containing compound on the molecular chain of the fatty acid polymer, and then grafting a phosphorus-containing compound. The extreme pressure antiwear agent obtained by the method not only has good dispersion stability in base oil, but also has excellent bearing capacity and antiwear property.

Description

Modified high-bearing gear oil and production process thereof
Technical Field
The application relates to the technical field of gear oil, in particular to modified high-bearing gear oil and a production process thereof.
Background
The gear oil is an important lubricating oil prepared by taking petroleum lubricating oil, synthetic lubricating oil or natural vegetable oil as base oil and adding additives such as extreme pressure antiwear agent, antioxidant, antirust agent and the like, and is used for various gear transmission devices so as to prevent tooth surfaces from being worn, scratched, sintered and the like, prolong the service life of gears and improve the transmission efficiency of the gears.
According to the load, the gear oil can be divided into light load gear oil, medium load gear oil and heavy load gear oil, and the tooth surface abrasion and scratch are more serious with the increase of the gear tooth surface load, so that proper gear oil needs to be selected according to the actual use scene.
The gear oil is used as a gear protective agent and has the following basic performances: firstly, the viscosity is proper and the foam resistance is good, the larger the viscosity of the gear oil is, the thicker the formed oil film is, the larger the load resistance is, but the viscosity is too large, the generated foam cannot disappear quickly in the gear meshing process, the formation of the oil film can be influenced, and therefore the use effect of the gear oil is reduced, and the gear is not suitable for gears running at high speed; secondly, to have enough bearing capacity and wear resistance, the tooth surface of the gear generally bears a certain load, the load of a part of hyperbolic tooth surface is higher, the abrasion and scratch of the tooth surface under high load are reduced, and the gear oil has enough bearing capacity and wear resistance; thirdly, the gear oil has good emulsification resistance, rust resistance and dispersion stability, otherwise, the gear oil is easy to deteriorate when meeting water, oxygen, heat and the like, and the use effect of the gear oil can be reduced.
Currently, the bearing capacity and wear resistance of gear oil are required to be improved, and under the condition of high bearing capacity or heavy load, the extreme pressure antiwear agent in the gear oil determines the bearing capacity and wear resistance of the gear oil. In order to improve the bearing capacity and wear resistance of gear oil, additives such as extreme pressure agents, wear-resistant agents and the like are generally compounded, but the compounding technology mixes different types of additives together, so that compatibility problem can be caused, and different additives can react or precipitate to generate impurities or byproducts, so that the dispersion stability of the gear oil is reduced.
Disclosure of Invention
The application provides modified high-bearing gear oil and a production process thereof, which aim to improve the bearing capacity and wear resistance of the gear oil on the basis of improving the dispersion stability of the gear oil.
A modified high-bearing gear oil comprises the following components in percentage by weight: 8-12% of extreme pressure antiwear agent, 0.5-2% of polydimethylsiloxane, 0.5-2% of hydroquinone, 1-1.5% of sodium dodecyl benzene sulfonate, 1-1.5% of polyethylene glycol and the balance of vegetable oil; the vegetable oil is one or more of olive oil, palm oil, castor oil, cocoa butter and rapeseed oil;
the extreme pressure antiwear agent is prepared by a method comprising the following steps:
s1: taking inorganic nano material, absolute ethyl alcohol, alkali liquor, deionized water and silane coupling agent, uniformly mixing, performing ultrasonic dispersion for 1-3h, stirring at room temperature for reaction for 8-12h, and filtering, precipitating and washing after the reaction is finished to obtain an intermediate material A;
s2: dissolving the intermediate material A, unsaturated fatty acid monomers and azodiisobutyronitrile in absolute ethyl alcohol, introducing inert gas, heating to 60-80 ℃, reacting for 12-18h while stirring, filtering and washing the product to obtain an intermediate material B; the unsaturated fatty acid is one of acrylic acid, palmitoleic acid and oleic acid;
s3: taking an intermediate material B, a cystamine compound, N-hydroxysuccinimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and a phosphate buffer salt solution, uniformly mixing and stirring, then adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide once every 20-30min, repeatedly adding 4-7 times, and finally dialyzing the obtained mixed solution with deionized water to obtain an intermediate material C;
s4: dissolving the intermediate material C in ethanol, slowly dripping phosphate compound at 22-25deg.C, maintaining the reaction temperature at 30-40deg.C, stirring for reacting for 12-24 hr, and distilling under reduced pressure to remove ethanol.
In the technical scheme, the extreme pressure antiwear agent plays a key role in bearing load capacity and wear resistance of gear oil, firstly, the extreme pressure antiwear agent contains inorganic nano particles, and in the process of gear engagement, the inorganic nano particles roll between two tooth surfaces, so that friction force between the tooth surfaces is greatly reduced, and tooth surface wear is greatly reduced; secondly, as the surface of the friction pair is rough, micro-nano level grooves and micro-protrusions exist on the surface after long-time abrasion, inorganic nano particles with higher hardness in the extreme pressure antiwear agent can be filled in the grooves and also can be used as a polishing agent to consume the micro-protrusions on the surface of the friction pair, so that the surface roughness is reduced, and the abrasion between tooth surfaces is reduced; thirdly, one end of the fatty acid coated by the inorganic nano material is provided with a hydrophilic functional group carboxyl, and the other end is provided with an oleophylic functional group alkyl, so that the dispersion of the inorganic nano particles can be promoted, and the fatty acid can also form a composite boundary lubricating film on the surface of the inorganic nano particles, thereby being beneficial to improving the antifriction and antiwear properties of the gear oil; fourthly, sulfur-sulfur bonds and carbon-sulfur bonds in the extreme pressure antiwear agent are easily broken under high temperature and high pressure in the meshing process, active sulfur is released, and the active sulfur reacts with iron on the surface of the gear to generate an iron sulfide solid film, so that the extreme pressure antiwear agent plays a role in extreme pressure and can bear high-load pressure; fifth, the phosphate in the extreme pressure antiwear agent can form a wear-resistant ferric phosphate chemical reaction film on the surface of the friction pair, so that the wear resistance of the gear oil is improved.
The base oil of the gear oil is vegetable oil, the oleic acid content is high, the thermal stability is relatively high, the degradation performance is good, and the gear oil is environment-friendly; in addition, the vegetable oil contains more fatty acid, and has hydrophilicity and lipophilicity, so that the dispersibility of each additive in the vegetable oil is good, and when the vegetable oil is used in a high-humidity environment, a part of water vapor can be absorbed, and good lubricating performance can be maintained; moreover, the oil film produced by the vegetable oil has high strength and can bear larger load.
In the preparation process of the extreme pressure antiwear agent, firstly, the surface of the inorganic nano particles is coated with the fatty acid polymer, and the rigid inorganic nano particles can serve as micro balls and roll between two tooth surfaces, so that the friction force between the tooth surfaces is greatly reduced, and the tooth surface abrasion is greatly reduced; in addition, the rigid inorganic nano particles have repairing and polishing effects, and in the gear meshing friction process, the inorganic nano particles can be filled in pits on the surface of the friction pair or micro-protrusions on the surface of the friction pair, so that the surface roughness is reduced, the friction stability is improved, the abrasion is reduced, and the abrasion resistance of gear oil is improved. However, the surface hardness of the rigid inorganic nanoparticles is high, abrasion of tooth surface is caused to a certain extent, and the rigid inorganic nanoparticles are easy to agglomerate in vegetable oil and difficult to disperse in vegetable oil stably, so that the surface of the rigid inorganic nanoparticles is coated with fatty acid polymer for modification, on one hand, the rigid inorganic nanoparticles and the flexible fatty acid polymer are matched, so that the hardness of the surface of the rigid inorganic nanoparticles can be reduced, abrasion of the abrasive particles in the friction process can be reduced, the flexibility of the fatty acid polymer can be utilized, and the abrasive particle abrasion caused by the boundary and mixed lubrication state is reduced in the friction process of gear engagement, so that the friction surface is protected well, the abrasion of the tooth surface is reduced, and the abrasion resistance of the gear oil is improved. On the other hand, the inorganic nano particles are easier to uniformly disperse in the vegetable oil, and the dispersion stability of the inorganic nano particles in the vegetable oil is improved.
Secondly, after the surface of the inorganic nano particle is coated with the fatty acid polymer, more carboxyl functional groups exist on the surface and can react with amino groups to generate amide groups, so that sulfur-containing compounds are introduced into the fatty acid polymer, the bond energy of carbon-sulfur bonds and sulfur-sulfur bonds of the sulfur-containing compounds is weaker, the temperature between tooth surfaces is instantaneously increased along with the increase of load when gears are meshed, at the moment, part of sulfur-sulfur bonds are broken and react with metal to form an iron mercaptide covering film, and the antiwear effect is realized; when the load continues to increase, part of carbon-sulfur bonds are broken, active sulfur is released, the active sulfur reacts with metal to generate an iron sulfide solid film, and the two tooth surfaces are separated, so that the abrasion and sintering of the metal are avoided, and the abrasion resistance and bearing capacity of the gear oil are improved.
Finally, phosphate or phosphite ester is grafted on the sulfur-containing compound, and hydrolysis is carried out under the high bearing condition to generate an inorganic ferric phosphate film or an inorganic ferrous phosphate film, so that the bearing capacity of the gear oil is improved, and meanwhile, the abrasion or sintering abrasion is reduced.
Preferably, in step S1, the inorganic nanoparticle is one of carbon powder, nano silica and nano titania; the silane coupling agent is one of vinyl trimethoxy silane, propenyl trimethoxy silane, methyl vinyl dimethoxy silane, methyl propenyl diethoxy silane and gamma-methacryloxypropyl trimethoxy silane.
In the technical scheme, the activated surface of the inorganic nano particles is provided with active groups, which is beneficial to modifying the inorganic nano particles. Besides containing silicon oxygen radical, the silane coupling agent also contains carbon-carbon double bond, which is beneficial to the polymerization of unsaturated fatty acid on inorganic nano particles.
Preferably, in step S3, the cystamine compound is one or more of cystamine, D-cystine, cystamine sulfate, cystamine hydrochloride, tert-Ding Yangtan-yl-cystamine hydrochloride, N-bis (acryl) cystamine and di-tert-butoxycarbonyl-cystamine.
In the technical scheme, the cystamine compound not only has amino groups, but also has sulfur-sulfur bonds, the amino groups react with carboxyl groups to generate amide groups, and meanwhile, the sulfur-sulfur bonds are introduced to the fatty acid polymer.
Preferably, in step S4, the phosphate is one of tributyl phosphate, dibutyl phosphate, triethyl phosphite, dibutyl phosphite, tributyl phosphite, dioctyl phosphite and dodecyl octyl phosphite.
In the technical scheme, the phosphate can react with the amino group, so that the phosphate is grafted in a molecular chain of the sulfur-containing compound, and the phosphate and the sulfur-containing compound act synergistically to improve the extreme pressure and the wear resistance of the gear oil.
Preferably, in the step S3, the mass ratio of the intermediate B, the cystamine compound, the N-hydroxysuccinimide and the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is 1 (5-10): 0.15-0.3.
In the above technical scheme, in order to make the cystamine compound react with the carboxyl of the intermediate material B as much as possible, so that more sulfur-sulfur bonds are introduced into the molecular chain, the cystamine compound should be properly excessive, and after the reaction is finished, unreacted cystamine compound is removed by dialysis.
In addition, the N-hydroxysuccinimide is used together with 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, so that amidation modification of the cystamine compound can be promoted, and grafting of the cystamine compound on other polymer molecules is facilitated.
The production process of the modified high-bearing gear oil is characterized by comprising the following steps of:
respectively weighing vegetable oil, extreme pressure antiwear agent, polydimethylsiloxane, hydroquinone, sodium dodecyl benzene sulfonate and polyethylene glycol according to a formula, and uniformly mixing and stirring.
In the technical scheme, the vegetable oil contains carboxyl, ester group, long-chain alkyl and other groups, and has hydrophilicity and lipophilicity, so that the additive is easy to disperse in the vegetable oil to form a stable mixture.
The technical scheme of the application at least comprises the following beneficial effects:
1. load bearing capacity and wear resistance are improved: the extreme pressure antiwear agent contains inorganic nano particles modified by fatty acid polymer, a compound containing sulfur-sulfur bonds and a compound containing phosphorus, which are mutually cooperated, so that the bearing capacity and the wear resistance of gear oil are greatly improved.
2. Improving the dispersion stability of the additive in the vegetable oil: according to the application, the fatty acid polymer is coated outside the inorganic nano particles, so that the dispersion stability of the inorganic nano particles in the vegetable oil is improved; simultaneously, the sulfur-containing compound and the phosphorus-containing compound are grafted on the surface of the inorganic nano-particles in sequence, so that the stability of the compounding of the sulfur-containing compound and the phosphorus-containing compound with the inorganic nano-particles is improved.
Drawings
FIG. 1 is a graph showing the change in the wear scar diameter of the gear oils of examples 1 to 9 and comparative examples 1 to 5.
FIG. 2 is a graph showing the change in PB value of gear oils of examples 1 to 9 and comparative examples 1 to 5.
Fig. 3 is a graph showing the trend of PD values of gear oils of examples 1 to 9 and comparative examples 1 to 5.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials of the examples and comparative examples of the present application are commercially available in general except for the specific descriptions.
Examples
Example 1
The modified high-bearing gear oil of the embodiment comprises the following components in percentage by weight: 8% of extreme pressure antiwear agent, 2% of polydimethylsiloxane, 2% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 86% of rapeseed oil;
the extreme pressure antiwear agent in the embodiment is prepared by a method comprising the following steps:
s1: weighing 5g of nano titanium dioxide, 150mL of absolute ethyl alcohol, 5mL of ammonia water with the concentration of 20%, 10mL of deionized water and 3.0g of vinyltrimethoxysilane, placing into a flask, performing ultrasonic dispersion for 1h, stirring for 12h at room temperature, filtering to precipitate after the reaction is finished, and washing with absolute ethyl alcohol to obtain an intermediate A;
s2: weighing 5g of intermediate A, 20mL of absolute ethyl alcohol, 2g of acrylic acid monomer and 0.05g of azodiisobutyronitrile, placing the mixture into a three-neck flask provided with a condenser tube and a nitrogen-introducing pipe, introducing nitrogen for 10min, heating to 60 ℃, stirring and reacting for 18h, filtering the product, and washing with acetone to obtain an intermediate B;
s3: weighing 3g of intermediate B, D-cystine 15g, N-hydroxysuccinimide 0.45g, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide 0.1g and phosphate buffer solution 1.5L, placing into a flask, mixing and stirring uniformly, then adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide 0.05g once every 20min, repeating the adding for 7 times, and finally dialyzing the obtained mixed solution with deionized water to obtain an intermediate C;
s4: taking 24g of intermediate C and 500mL of ethanol, placing the mixture into a three-neck flask, slowly dropwise adding 20mL of triethyl phosphite at 25 ℃, keeping the reaction temperature in the three-neck flask below 40 ℃, stirring and reacting for 12h, and distilling under reduced pressure to remove the ethanol;
the production process of the modified high-bearing gear oil in the embodiment comprises the following steps:
according to the formula, 860g of rapeseed oil, 80g of extreme pressure antiwear agent, 20g of polydimethylsiloxane, 20g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, and uniformly mixed and stirred to obtain the lubricating oil.
Example 2
The modified high-bearing gear oil of the embodiment comprises the following components in percentage by weight: 8% of extreme pressure antiwear agent, 0.5% of polydimethylsiloxane, 0.5% of hydroquinone, 1.5% of sodium dodecyl benzene sulfonate, 1.5% of polyethylene glycol and 88% of olive oil;
the extreme pressure antiwear agent in the embodiment is prepared by a method comprising the following steps:
s1: weighing 5g of nano silicon dioxide, 150mL of absolute ethyl alcohol, 5mL of ammonia water with the concentration of 20%, 10mL of deionized water and 3.0g of methylpropenyl dimethoxy silane, placing in a flask, performing ultrasonic dispersion for 3h, stirring for 8h at room temperature, filtering precipitate after the reaction is finished, and washing with absolute ethyl alcohol to obtain an intermediate A;
s2: weighing 5g of intermediate A, 20mL of absolute ethyl alcohol, 2g of palmitoleic acid monomer and 0.05g of azodiisobutyronitrile, placing the mixture in a three-neck flask provided with a condenser tube and a nitrogen-introducing pipe, introducing nitrogen for 10min, heating to 80 ℃, stirring and reacting for 12h, filtering the product, and washing with acetone to obtain an intermediate B;
s3: weighing 3g of intermediate B, N, 15g of N-bis (acryloyl) cystamine, 0.45g of N-hydroxysuccinimide, 0.25g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and 300mL of phosphate buffer solution, placing the mixture in a flask, uniformly mixing and stirring, then adding 0.5g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide once every 30min, repeatedly adding 4 times, and finally dialyzing the obtained mixed solution with deionized water to obtain an intermediate C;
s4: taking 24g of intermediate C and 500mL of ethanol, placing the mixture into a three-neck flask, slowly dropwise adding 20mL of dioctyl phosphite at 22 ℃, keeping the reaction temperature in the three-neck flask below 30 ℃, stirring the mixture for reaction for 24 hours, and distilling the mixture under reduced pressure to remove the ethanol;
the production process of the modified high-bearing gear oil in the embodiment comprises the following steps:
according to the formula, 880g of rapeseed oil, 80g of extreme pressure antiwear agent, 5g of polydimethylsiloxane, 5g of hydroquinone, 15g of sodium dodecyl benzene sulfonate and 15g of polyethylene glycol are respectively weighed, and uniformly mixed and stirred to obtain the lubricating oil.
Example 3
The modified high-bearing gear oil of the embodiment comprises the following components in percentage by weight: 8% of extreme pressure antiwear agent, 1% of polydimethylsiloxane, 1% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 88% of cocoa butter;
the extreme pressure antiwear agent in the embodiment is prepared by a method comprising the following steps:
s1: weighing 5g of carbon powder, 150mL of absolute ethyl alcohol, 5mL of ammonia water with the concentration of 20%, 10mL of deionized water and 3.0g of gamma-methacryloxypropyl trimethoxysilane, placing in a flask, performing ultrasonic dispersion for 2h, stirring at room temperature for 10h, filtering to precipitate after the reaction is finished, and washing with absolute ethyl alcohol to obtain an intermediate A;
s2: weighing 5g of intermediate A, 20mL of absolute ethyl alcohol, 2g of oleic acid monomer and 0.05g of azodiisobutyronitrile, placing the mixture into a three-neck flask provided with a condenser pipe and a nitrogen-introducing pipe, introducing nitrogen for 10min, heating to 70 ℃, reacting for 15h while stirring, filtering the product, and washing with acetone to obtain intermediate B;
s3: weighing 3g of intermediate B, 15g of cystamine, 0.45g of N-hydroxysuccinimide, 0.2g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and 300mL of phosphate buffer solution, placing the mixture in a flask, mixing and stirring uniformly, adding 0.05g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide once every 20min, repeating the addition for 5 times, and finally dialyzing the obtained mixed solution by using deionized water to obtain an intermediate C;
s4: taking 24g of intermediate C and 500mL of ethanol, placing the mixture into a three-neck flask, slowly dropwise adding 20mL of dodecyl octyl phosphite at 25 ℃, keeping the reaction temperature in the three-neck flask below 40 ℃, stirring the mixture for 18h, and distilling the mixture under reduced pressure to remove the ethanol;
the production process of the modified high-bearing gear oil in the embodiment comprises the following steps:
according to the formula, 880g of cocoa butter, 80g of extreme pressure antiwear agent, 10g of polydimethylsiloxane, 10g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, and uniformly mixed and stirred to obtain the compound.
Example 4
The weight percentage of the components of the modified high-load gear oil of this example was the same as that of example 3;
the extreme pressure antiwear agent in this example differs from that in example 3 in that:
s3: weighing 3g of intermediate B, 15g of cystamine, 0.9g of N-hydroxysuccinimide, 0.4g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and 300mL of phosphate buffer solution, placing the mixture in a flask, mixing and stirring uniformly, adding 0.1g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide once every 20min, repeating the addition for 5 times, and finally dialyzing the obtained mixed solution by using deionized water to obtain an intermediate C;
the rest of the procedure is the same as in example 3;
the production process of the modified high-load gear oil in this example was the same as in example 3.
Example 5
The weight percentage of the components of the modified high-load gear oil of this example was the same as that of example 3;
the extreme pressure antiwear agent in this example differs from that in example 3 in that:
s3: weighing 3g of intermediate B, 15g of cystamine, 0.7g of N-hydroxysuccinimide, 0.2g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and 300mL of phosphate buffer solution, placing the mixture in a flask, mixing and stirring uniformly, adding 0.1g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide once every 20min, repeating the addition for 5 times, and finally dialyzing the obtained mixed solution by using deionized water to obtain an intermediate C;
the rest of the procedure is the same as in example 3;
the production process of the modified high-load gear oil in this example was the same as in example 3.
Example 6
The weight percentage of the components of the modified high-load gear oil of this example was the same as that of example 5;
the extreme pressure antiwear agent in this example differs from that of example 5 in that:
s3: 3g of intermediate B, 30g of cystamine, 0.7g of N-hydroxysuccinimide, 0.2g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and 300mL of phosphate buffer solution are weighed, placed in a flask, mixed and stirred uniformly, then 0.1g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is added every 20min, repeated addition is carried out for 5 times, and finally the obtained mixed solution is dialyzed by deionized water to obtain intermediate C;
the rest of the procedure is the same as in example 5;
the production process of the modified high-load gear oil in this example was the same as in example 5.
Example 7
The weight percentage of the components of the modified high-load gear oil of this example was the same as that of example 5;
the extreme pressure antiwear agent in this example differs from that of example 5 in that:
s3: weighing 3g of intermediate B, 20g of cystamine, 0.7g of N-hydroxysuccinimide, 0.2g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and 300mL of phosphate buffer solution, placing the mixture in a flask, mixing and stirring uniformly, adding 0.1g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide once every 20min, repeating the addition for 5 times, and finally dialyzing the obtained mixed solution by using deionized water to obtain an intermediate C;
the rest of the procedure is the same as in example 5;
the production process of the modified high-load gear oil in this example was the same as in example 5.
Example 8
The modified high-bearing gear oil of the embodiment comprises the following components in percentage by weight: 12% of extreme pressure antiwear agent, 1% of polydimethylsiloxane, 1% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 84% of cocoa butter;
the preparation method of the extreme pressure antiwear agent in this example is the same as that of example 7;
the production process of the modified high-bearing gear oil in the embodiment comprises the following steps:
according to the formula, 840g of cocoa butter, 120g of extreme pressure antiwear agent, 10g of polydimethylsiloxane, 10g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, and uniformly mixed and stirred to obtain the compound.
Example 9
The modified high-bearing gear oil of the embodiment comprises the following components in percentage by weight: 10% of extreme pressure antiwear agent, 1% of polydimethylsiloxane, 1% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 86% of cocoa butter;
the preparation method of the extreme pressure antiwear agent in this example is the same as that of example 7;
the production process of the modified high-bearing gear oil in the embodiment comprises the following steps:
according to the formula, 860g of cocoa butter, 100g of extreme pressure antiwear agent, 10g of polydimethylsiloxane, 10g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, and uniformly mixed and stirred to obtain the compound.
Comparative example
Comparative example 1
The modified high-bearing gear oil of the comparative example comprises the following components in percentage by weight: 10% of carbon powder, 1% of polydimethylsiloxane, 1% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 86% of cocoa butter;
the production process of the modified high-bearing gear oil in the comparative example comprises the following steps:
according to the formula, 860g of cocoa butter, 100g of carbon powder, 10g of polydimethylsiloxane, 10g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, mixed and stirred uniformly.
Comparative example 2
The modified high-bearing gear oil of the comparative example comprises the following components in percentage by weight: 10% of extreme pressure antiwear agent, 1% of polydimethylsiloxane, 1% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 86% of cocoa butter;
the extreme pressure antiwear agent in this comparative example was prepared by a method comprising the steps of:
s1: weighing 5g of carbon powder, 150mL of absolute ethyl alcohol, 5mL of ammonia water with the concentration of 20%, 10mL of deionized water and 3.0g of gamma-methacryloxypropyl trimethoxysilane, placing in a flask, performing ultrasonic dispersion for 2h, stirring at room temperature for 10h, filtering to precipitate after the reaction is finished, and washing with absolute ethyl alcohol to obtain an intermediate A;
s2: weighing 5g of intermediate A, 20mL of absolute ethyl alcohol, 2g of oleic acid monomer and 0.05g of azodiisobutyronitrile, placing the mixture into a three-neck flask provided with a condenser tube and a nitrogen-introducing pipe, introducing nitrogen for 10min, heating to 70 ℃, reacting for 15h while stirring, filtering the product, and washing with acetone to obtain the product;
the production process of the modified high-bearing gear oil in the comparative example comprises the following steps:
according to the formula, 860g of cocoa butter, 100g of extreme pressure antiwear agent, 10g of polydimethylsiloxane, 10g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, and uniformly mixed and stirred to obtain the compound.
Comparative example 3
The modified high-bearing gear oil of the comparative example comprises the following components in percentage by weight: 10% of extreme pressure antiwear agent, 1% of polydimethylsiloxane, 1% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 86% of cocoa butter;
the extreme pressure antiwear agent in this comparative example was prepared by a method comprising the steps of:
s1: weighing 5g of carbon powder, 150mL of absolute ethyl alcohol, 5mL of ammonia water with the concentration of 20%, 10mL of deionized water and 3.0g of gamma-methacryloxypropyl trimethoxysilane, placing in a flask, performing ultrasonic dispersion for 2h, stirring at room temperature for 10h, filtering to precipitate after the reaction is finished, and washing with absolute ethyl alcohol to obtain an intermediate A;
s2: weighing 5g of intermediate A, 20mL of absolute ethyl alcohol, 2g of oleic acid monomer and 0.05g of azodiisobutyronitrile, placing the mixture into a three-neck flask provided with a condenser pipe and a nitrogen-introducing pipe, introducing nitrogen for 10min, heating to 70 ℃, reacting for 15h while stirring, filtering the product, and washing with acetone to obtain intermediate B;
s3: weighing 3g of intermediate B, 15g of cystamine, 0.45g of N-hydroxysuccinimide, 0.2g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and 300mL of phosphate buffer solution, placing the mixture in a flask, mixing and stirring uniformly, adding 0.05g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide once every 20min, repeating the addition for 5 times, and finally dialyzing the obtained mixed solution by using deionized water;
the production process of the modified high-bearing gear oil in the comparative example comprises the following steps:
according to the formula, 860g of cocoa butter, 100g of extreme pressure antiwear agent, 10g of polydimethylsiloxane, 10g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, and uniformly mixed and stirred to obtain the finished product.
Comparative example 4
The modified high-bearing gear oil of the comparative example comprises the following components in percentage by weight: 10% of vulcanized isobutene, 1% of polydimethylsiloxane, 1% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 86% of cocoa butter;
the production process of the modified high-bearing gear oil in the comparative example comprises the following steps:
according to the formula, 860g of cocoa butter, 100g of vulcanized isobutene, 10g of polydimethylsiloxane, 10g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, and uniformly mixed and stirred to obtain the finished product.
Comparative example 5
The modified high-bearing gear oil of the comparative example comprises the following components in percentage by weight: 5% of sulfurized isobutylene, 5% of dodecyl octyl phosphite, 1% of polydimethylsiloxane, 1% of hydroquinone, 1% of sodium dodecyl benzene sulfonate, 1% of polyethylene glycol and 86% of cocoa butter;
the production process of the modified high-bearing gear oil in the comparative example comprises the following steps:
according to the formula, 860g of cocoa butter, 50g of vulcanized isobutene, 50g of dodecyl octyl phosphite, 10g of polydimethylsiloxane, 10g of hydroquinone, 10g of sodium dodecyl benzene sulfonate and 10g of polyethylene glycol are respectively weighed, mixed and stirred uniformly.
Performance test
Detection method
1. Method for measuring wear resistance and bearing capacity of gear oil
The test method comprises the following steps: GB3142-82
Test equipment: MJ-800 type four-ball testing machine
Rotational speed: 1450rpm
(1) Taking gear oil samples of examples 1-9 and comparative examples 1-5, wherein the fixed load is 400N, the friction time is 1h, and the diameter of grinding marks is measured;
(2) increasing the load, and measuring the maximum seizure-free load PB value and the sintering load PD value of the gear oil samples of examples 1 to 9 and comparative examples 1 to 5, respectively;
(3) the bearing capacity and the wear resistance of the gear oil are judged by the sizes of the grinding mark diameter, the maximum non-seizing load PB value and the sintering load PD value, and the smaller the grinding mark diameter is, the larger the maximum non-seizing load PB value and the sintering load PD value are, so that the better the bearing capacity and the wear resistance of the gear oil are.
Analysis of results
As can be seen from the data of examples 1-3 and comparative examples 1-5 in fig. 1-3, the grinding mark diameter of the gear oil in the examples is obviously reduced, and the maximum seizure free load PB value and the sintering load PD value are obviously increased, which indicates that the inorganic nanoparticles, the coated fatty acid polymer, the sulfur-containing compound and the phosphorus-containing compound in the extreme pressure antiwear agent have synergistic effect on the wear resistance and the bearing capacity of the gear oil, so that the wear resistance and the bearing capacity of the gear oil are obviously improved.
As can be seen from the data of examples 3-5 in FIGS. 1-3, as the addition of N-hydroxysuccinimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide increases, the wear scar diameter decreases, the maximum seizure free load PB and sintering load PD increases, indicating that the wear resistance and load carrying capacity of the gear oil can be improved, but when the addition of N-hydroxysuccinimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide reaches a certain value, the addition is increased again, and the wear resistance and load carrying capacity can be maintained substantially unchanged, even slightly reduced.
As can be seen from the data of examples 5 to 7 in fig. 1 to 3, as the addition amount of the cystamine compound increases, the diameter of the grinding marks decreases, the maximum seizure free load PB value and the sintering load PD value increase, which indicates that the wear resistance and the bearing capacity of the gear oil can be improved, but when the addition amount of the cystamine compound reaches a certain value, the addition amount is increased again, and the wear resistance and the bearing capacity can be kept substantially unchanged.
As can be seen from the data of examples 7 to 9 in fig. 1 to 3, as the addition amount of the extreme pressure antiwear agent increases, the diameter of the grinding marks decreases first and then increases, and the maximum seizure free load PB value and the sintering load PD value increase first and then decrease, which indicates that there is an optimum value for the addition amount of the extreme pressure antiwear agent, and when the addition amount of the extreme pressure antiwear agent is greater than the optimum value, the improvement of the wear resistance and the bearing capacity of the gear oil is not facilitated.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (6)

1. The modified high-bearing gear oil is characterized by comprising the following components in percentage by weight: 8-12% of extreme pressure antiwear agent, 0.5-2% of polydimethylsiloxane, 0.5-2% of hydroquinone, 1-1.5% of sodium dodecyl benzene sulfonate, 1-1.5% of polyethylene glycol and the balance of vegetable oil; the vegetable oil is one or more of olive oil, palm oil, castor oil, cocoa butter and rapeseed oil;
the extreme pressure antiwear agent is prepared by a method comprising the following steps:
s1: taking inorganic nano material, absolute ethyl alcohol, alkali liquor, deionized water and silane coupling agent, uniformly mixing, performing ultrasonic dispersion for 1-3h, stirring at room temperature for reaction for 8-12h, and filtering, precipitating and washing after the reaction is finished to obtain an intermediate material A;
s2: dissolving the intermediate material A, unsaturated fatty acid monomers and azodiisobutyronitrile in absolute ethyl alcohol, introducing inert gas, heating to 60-80 ℃, reacting for 12-18h while stirring, filtering and washing the product to obtain an intermediate material B; the unsaturated fatty acid is one of acrylic acid, palmitoleic acid and oleic acid;
s3: taking an intermediate material B, a cystamine compound, N-hydroxysuccinimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and a phosphate buffer salt solution, uniformly mixing and stirring, then adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide once every 20-30min, repeatedly adding 4-7 times, and finally dialyzing the obtained mixed solution with deionized water to obtain an intermediate material C; the cystamine compound is one or more of cystamine, D-cystine, cystamine sulfate, cystamine hydrochloride, tertiary Ding Yangtan group-cystamine hydrochloride, N-bis (acryloyl) cystamine and di-tertiary butoxycarbonyl-cystamine;
s4: dissolving the intermediate material C in ethanol, slowly dripping phosphate compound at 22-25deg.C, maintaining the reaction temperature at 30-40deg.C, stirring for reacting for 12-24 hr, and distilling under reduced pressure to remove ethanol; the phosphate is one of tributyl phosphate, dibutyl phosphate, triethyl phosphite, dibutyl phosphite, tributyl phosphite, dioctyl phosphite and dodecyl octyl phosphite.
2. The modified high-load gear oil according to claim 1, wherein in step S1, the inorganic nanoparticles are one of carbon powder, nano silica and nano titania; the silane coupling agent is one of vinyl trimethoxy silane, propenyl trimethoxy silane, methyl vinyl dimethoxy silane, methyl propenyl diethoxy silane and gamma-methacryloxypropyl trimethoxy silane.
3. The modified high-load gear oil according to claim 1, wherein the cystamine compound is one of D-cystine, N-bis (acryl) cystamine and cystamine.
4. The modified high-load gear oil according to claim 1, wherein the phosphate ester is one of triethyl phosphite, dioctyl phosphite and dodecyloctyl phosphite.
5. The modified high-load gear oil according to claim 1, wherein in the step S3, the mass ratio of the intermediate B, the cystamine compound, the N-hydroxysuccinimide and the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is 1 (5-10): 0.15-0.3.
6. A process for producing the modified high-load gear oil according to claim 1, comprising the steps of:
respectively weighing vegetable oil, extreme pressure antiwear agent, polydimethylsiloxane, hydroquinone, sodium dodecyl benzene sulfonate and polyethylene glycol according to a formula, and uniformly mixing and stirring.
CN202311270694.6A 2023-09-28 2023-09-28 Modified high-bearing gear oil and production process thereof Active CN117025286B (en)

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CN101379168A (en) * 2006-01-12 2009-03-04 阿肯色大学评议会 Nanoparticle compositions and methods for making and using the same
KR101832855B1 (en) * 2016-11-15 2018-02-28 주식회사 루브캠코리아 Gear oil having improved lubrication properties
CN113831947A (en) * 2021-08-09 2021-12-24 江苏国平油品科技有限公司 Gear oil for synthetic port machinery and preparation method thereof

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US9228149B2 (en) * 2012-07-02 2016-01-05 Exxonmobil Research And Engineering Company Enhanced durability performance of lubricants using functionalized metal phosphate nanoplatelets
US9422502B2 (en) * 2014-03-31 2016-08-23 Exxonmobil Research And Engineering Company Low viscosity, low volatility lubricating oil basestocks
WO2018213627A1 (en) * 2017-05-17 2018-11-22 Quadion Llc Zwitterionic monomers, polyzwitterionic polymers formed therefrom, surface functionalization and surface modification

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101379168A (en) * 2006-01-12 2009-03-04 阿肯色大学评议会 Nanoparticle compositions and methods for making and using the same
KR101832855B1 (en) * 2016-11-15 2018-02-28 주식회사 루브캠코리아 Gear oil having improved lubrication properties
CN113831947A (en) * 2021-08-09 2021-12-24 江苏国平油品科技有限公司 Gear oil for synthetic port machinery and preparation method thereof

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