CN114540100B - Antioxidant for biodegradable lubricating oil, preparation method thereof and lubricating oil - Google Patents
Antioxidant for biodegradable lubricating oil, preparation method thereof and lubricating oil Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating 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
- C10M169/04—Mixtures of base-materials and additives
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
- C10M2207/2895—Partial esters containing free hydroxy groups used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
Abstract
The invention belongs to the field of lubricating oil, and particularly relates to an antioxidant composition for lubricating oil, a preparation method of the antioxidant composition and the lubricating oil. Which comprises the following steps: 1-10 parts of modified mesoporous carbon sphere nano particles loaded with rosmarinic acid; 1 to 10 portions of p, p' -diisooctyl diphenylamine. The rosmarinic acid-mesoporous carbon sphere nano-particles with the ordered pore structure are synthesized by a hydrothermal method, and are combined with the traditional high-temperature-resistant antioxidant pair and p' -diisooctyl diphenylamine to show surprising oxidation resistance, and the oxidation time is remarkably prolonged compared with that of the two nano-particles when the rosmarinic acid-mesoporous carbon sphere nano-particles are used alone.
Description
Technical Field
The invention belongs to the technical field of lubricating oil additives. More particularly, it relates to an antioxidant for biodegradable lubricating oil, a preparation method thereof and lubricating oil.
Background
Biodegradable lubricating oil is understood to be a lubricating oil which is digested, metabolized and decomposed by microorganisms present in nature into carbon dioxide, water and tissue intermediates, and is measured as the percentage of the lubricating oil which is degraded by the microorganisms under certain conditions and for a certain period of time. At present, vegetable oil is a potential substitute for preparing environment-friendly lubricating oil, has the advantages of high viscosity index, good viscosity-temperature performance, good abrasion resistance, no toxicity, easy biodegradation, no adverse effect on the environment, and poor thermal oxidation stability, hydrolytic stability and low-temperature fluidity [1] These properties are caused by the molecular structure of vegetable oils, and the triglyceride structure of vegetable oils is mainly composed of oleic acid, linoleic acid, etc., and a large number of unsaturated double bonds C = C and activated carbon atoms are present.
For a lubricating oil system using vegetable oil as base oil, the additive is added to inhibit the free radical oxidation reaction generated in the vegetable oil and improve the oxidation stability of the vegetable oil. If the metal passivator is added, the metal passivator and metal ions such as iron, copper, manganese and the like in the use environment of the lubricating oil form a complex compound to inhibit the catalytic action of the metal ions on the free radical oxidation reaction; adding a chain growth terminator to convert the hydrocarbon-based radical into a stable neutral compound by supplying a hydrogen atom, terminating the chain growth reaction, and preventing the generation of a peroxide radical by the chain growth reaction; the pour point depressant is added to change the growth direction and the crystal shape of the wax by molecular adsorption or eutectic crystal in the molecular chain or at the tail end of the crystalline wax to prevent the formation of a spatial network structure, thereby reducing the adsorption, solvation and encapsulation effects on the liquid oil and improving the low-temperature fluidity of the vegetable oil [2] . Thus, vegetable oils are currently degradable lubricating oilsThe problem of the research is how to improve the oxidation stability.
Reference documents:
[1]Fox N J,Stachowiak G W.Vegetable oil-based lubricants—A review ofoxidation[J].Tribology International,2007,40(7):1035-1046.
[2] ding Jianhua, fang Jianhua, jiang Zeqi, zheng Zhe biodegradable lubricating oils overview [ J ] synthetic lubricating materials, 2017,44 (02): 38-43.
Disclosure of Invention
According to the invention, the mesoporous carbon sphere nano-particles with the ordered pore structure are synthesized by a hydrothermal method, the surface of the mesoporous carbon sphere nano-particles is oxidized and modified to be used as a carrier of a rosmarinic acid antioxidant, and experiments prove that the mesoporous carbon sphere nano-particles-rosmarinic acid has oxidation resistance obviously superior to that of rosmarinic acid.
It is an object of the present invention to provide an antioxidant composition for lubricating oils comprising:
1-10 parts of modified mesoporous carbon sphere nano particles loaded with rosmarinic acid;
1 to 10 portions of p, p' -diisooctyl diphenylamine.
Further, it comprises:
3-10 parts of modified mesoporous carbon sphere nano particles loaded with rosmarinic acid;
3-10 parts of p, p' -diisooctyl diphenylamine.
Further, it is characterized in that it comprises:
5 parts of modified mesoporous carbon sphere nano particles loaded with rosmarinic acid;
5 parts of p, p' -diisooctyl diphenylamine.
P, p' -diisooctyldiphenylamine molecular formula C 28 H 44 N, a molecular structure shown in formula 1 below, is a commonly used high temperature resistant antioxidant, and is widely used in lubricating oils.
The rosmarinic acid is extracted from flowers and leaves of natural plant rosmarinic acidThe obtained environment-friendly antioxidant with strong antioxidant capacity has a molecular formula of C 18 H 16 O 8 The molecular structure is shown in the following formula 2, and the CAS number is 20283-92-5.
In tests, the antioxidant capacity of the antioxidant prepared by compounding p, p' -diisooctyldiphenylamine and rosmarinic acid in specific types and proportions of base oil is improved to a certain extent, but the compatibility problem of rosemary and the base oil needs to be noticed.
The mesoporous material is a material with an ordered pore channel structure with the pore diameter of 2-50 nm, has a large specific surface area, a large pore volume and an ordered and open pore channel structure, and does not have the application of mesoporous carbon sphere nanoparticles for loading rosmarinic acid antioxidant and for lubricating oil antioxidation at present.
The inventor uses the mesoporous carbon sphere nano-particle with the surface modified by oxidation as a carrier to load the rosmarinic acid to prepare the mesoporous carbon sphere nano-particle-rosmarinic acid, and the oxidation resistance of the mesoporous carbon sphere nano-particle-rosmarinic acid is multiplied compared with that of the rosmarinic acid. In addition, the mesoporous carbon sphere nanoparticles are of an ordered multi-pore spherical structure, so that the friction coefficient can be effectively reduced, the engine abrasion is reduced, and the function of a friction modifier can be exerted at the same time.
The surface of mesoporous carbon sphere particles is subjected to oxidation modification, and oxygen-containing functional groups are introduced to the surfaces of the nanoparticles, so that the suspension stability of the nanoparticles in lubricating oil is improved, the compatibility of rosmarinic acid and a lubricating oil system is improved, the mesoporous carbon sphere nanoparticles and rosmarinic acid can be uniformly dispersed in the oil material after being stirred for 10-30 min at the temperature of 30-50 ℃, and the mesoporous carbon sphere nanoparticles and rosmarinic acid are not layered after standing and have good stability. In addition, since the surface of the unmodified mesoporous carbon sphere nanoparticles has high hydrophobicity, it is difficult to disperse the mesoporous carbon sphere nanoparticles in a rosmarinic acid-water solution, and the surface of the mesoporous carbon sphere nanoparticles is oxidized, so that the hydrophilicity and the dispersibility of the mesoporous carbon sphere nanoparticles can be improved.
Tests show that the mesoporous carbon sphere nanoparticle-rosmarinic acid is combined with p, p' -diisooctyl diphenylamine, and surprisingly, the integral antioxidant capacity is improved by times compared with a single agent, the oxidative decomposition of lubricating oil can be effectively inhibited, and the function of a friction modifier is exerted.
Furthermore, in the composition, the weight ratio of the modified mesoporous carbon sphere nanoparticles loaded with the rosmarinic acid to the p' -diisooctyl diphenylamine is 1.3-1.
Further, in the composition, the weight ratio of the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles to the p-diisooctyldiphenylamine is 1:1, 1, 0.3, 1, 0.5, 1, 0.6, 1, 0.8, more preferably 1:1. Research shows that the effect of multiplied increase of the antioxidant capacity only appears in a specific ratio range of the p, p '-diisooctyldiphenylamine and the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles, and particularly when the ratio of the p, p' -diisooctyldiphenylamine and the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles is 1:1, the combined antioxidant time is remarkably prolonged compared with that of a single agent. While outside this range, there is no significant difference in the antioxidant time of the combination compared to the single dose.
Further, the preparation method of the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles comprises the following steps:
s1, melting phenol, adding sodium hydroxide, uniformly stirring, adding a formaldehyde solution with the volume fraction of 37%, and stirring at 70-80 ℃ for 20-35 min to obtain phenolic resin;
s2, adding a triblock copolymer into the phenolic resin, and stirring for 10-16 h at the temperature of 60-80 ℃; then reacting for 15-30 h at 100-140 ℃, and drying the reaction liquid to obtain powder; placing the powder in an inert atmosphere, and roasting at 700 ℃ for 1-3 h to obtain mesoporous carbon sphere nano-particles;
s3, dispersing the mesoporous carbon sphere nano particles in hydrogen peroxide, performing ultrasonic treatment for 1-4 h, drying at 80-100 ℃, and collecting solid powder to obtain modified mesoporous carbon sphere nano particles;
and S4, dispersing the modified mesoporous carbon sphere nanoparticles into a rosmarinic acid-water solution, carrying out ultrasonic treatment for 10-20 min, continuing stirring for 12-24 h, centrifuging, collecting precipitate, and drying to obtain the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles.
Further, in the step S4, the weight ratio of the modified mesoporous carbon sphere nanoparticles to the rosmarinic acid is 1:1-1.5. Furthermore, the weight ratio of the two is 1.
The invention also aims to provide lubricating oil containing the antioxidant composition. In particular, the lubricating oil is biodegradable.
Further, in principle, the biodegradable lubricating oil further comprises a base oil and an additive, wherein the base oil comprises one of, but not limited to, vegetable oil, synthetic ester, polyalphaolefin (PAOs), or a combination of two or more thereof. In particular, the vegetable oil includes, but is not limited to, rapeseed oil, peanut oil, olive oil, castor oil, palm oil, corn oil, cottonseed oil, soybean oil, and sunflower oil. The synthetic ester is formed by esterifying organic acid and organic alcohol under the catalysis, and includes but is not limited to monoester, dibasic acid diester, dihydric alcohol diester, dimer acid ester, polymeric oleate, neopentyl polyol mixed acid ester and the like.
Specifically, the base oil is prepared from rapeseed oil, trimethylolpropane oleate and poly-alpha olefin according to the weight ratio of 10-15: 1-5:1-3. Furthermore, the weight ratio of the three components is 10.
Tests show that the base oil with specific combination and proportion has larger influence on oxidation resistance effect, and screening shows that the oxidation resistance combination of the modified mesoporous carbon sphere nano particles loaded with rosmarinic acid and p, p' -diisooctyldiphenylamine has the longest oxidation time in the base oil consisting of rapeseed oil, trimethylolpropane oleate and poly-alpha olefin with specific proportion.
The invention has the following beneficial effects:
the rosmarinic acid-mesoporous carbon sphere nano-particles with the ordered pore structure are synthesized by a hydrothermal method, and are combined with the traditional high-temperature-resistant antioxidant pair and 'diisooctyl diphenylamine', the remarkable oxidation resistance is shown, and the oxidation time is remarkably prolonged compared with that of the two used alone.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Preparation of rosmarinic acid-mesoporous carbon sphere nanoparticles (Ra-OMCN)
S1, melting 1.2g of phenol, adding 30ml of 0.1mol/L sodium hydroxide solution, uniformly stirring, adding 4.2ml of 37% volume fraction formaldehyde solution, heating to 75 ℃, and stirring for 25min to obtain phenolic resin;
s2, dissolving 1.92g of triblock copolymer in 30ml of deionized water to obtain a mixed solution, adding the mixed solution into the phenolic resin, and stirring at 65 ℃ for 15 hours; then reacting for 24 hours at 120 ℃, and drying the reaction liquid to obtain powder; placing the powder in a nitrogen atmosphere, and roasting at 700 ℃ for 2.5h to obtain mesoporous carbon sphere nanoparticles;
s3, dispersing 100mg of the mesoporous carbon sphere nano particles in 50ml of hydrogen peroxide, performing ultrasonic treatment for 2h, drying at 100 ℃, and collecting solid powder to obtain modified mesoporous carbon sphere nano particles;
s4, dispersing the rosmarinic acid in deionized water to prepare a rosmarinic acid-water solution with the mass fraction of 3%; dispersing the modified mesoporous carbon sphere nanoparticles into a rosmarinic acid-water solution, carrying out ultrasonic treatment for 15min, continuing stirring for 16h, centrifuging, collecting precipitates, and drying to obtain the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles; the weight ratio of the modified mesoporous carbon sphere nanoparticles to the rosmarinic acid is 1.2.
Examples 1 to 3 and comparative examples 1 to 4 biodegradable lubricating oils (parts by weight)
Note: MC-01 refers to p, p' -diisooctyldiphenylamine; ra is rosmarinic acid; TMPTO means trimethylolpropane oleate.
Examples 1 to 3 and comparative examples 1 to 4 lubricating oil preparation methods: adding antioxidant into base oil, and stirring at 40 deg.C for 20 min.
Antioxidant stability test
Respectively filling the lubricating oils of the examples 1-3 and the comparative examples 1-4 into triangular flasks, plugging the triangular flasks, violently shaking for 1min, placing the triangular flasks in a drying oven at 105 +/-3 ℃ for 8h, taking out the triangular flasks, and cooling to room temperature; after the triangular flask is vigorously shaken for 1min, the lubricating oil is rapidly poured into a clean centrifugal tube to 50ml of scale mark, the centrifugal tube is put into a constant-temperature bath at 90 +/-3 ℃ for heating for 5min, and is centrifuged at 600r/min for 30min, the centrifugal tube is taken out, and whether the lubricating oil is layered, turbid or precipitated is observed. The results are shown in table 1 below.
Table 1:
| sample (I) | Results of stability test |
| Example 1 | Without demixing, turbidity or precipitation |
| Example 2 | Without the phenomenon of demixing, turbidity or precipitation |
| Example 3 | Without demixing, turbidity or precipitation |
| Comparative example 1 | Without demixing, turbidity or precipitation |
| Comparative example 2 | Without demixing, turbidity or precipitation |
| Comparative example 3 | Without demixing, turbidity or precipitation |
| Comparative example 4 | With demixing and turbidity |
As can be seen from table 1, the stability of rosmarinic acid in the base oil composed of rapeseed oil, trimethylolpropane oleate, and polyalphaolefin is poor, and the stability of rosmarinic acid in the lubricating oil can be improved by using the modified mesoporous carbon sphere nanoparticles as the carrier of rosmarinic acid.
Test for stability against Oxidation
(1) The oxidation stability of the lubricating oil was determined by the rotating oxygen bomb method. The specific method comprises the following steps: a glass sample holder containing a sample, distilled water and a copper catalyst coil was placed in an oxygen bomb equipped with a pressure gauge, oxygen gas at a pressure of 620kPa was injected at room temperature, the oxygen bomb was put in an oil bath at 150 ℃ and rotated axially at an angle of 30 ℃ to the horizontal plane at a speed of 100r/min, when a specified pressure drop was reached, the test was stopped, the test time was recorded, and the oxidation stability of the sample was evaluated in min as indicated by the test time of the oxygen bomb, and the results are shown in Table 2.
(2) A300 ml sample was taken out and put in a test tube, the test tube was put in an oil bath at 95 ℃ and air was blown thereto at 10. + -. 0.5L/h for 120 hours, and the change in the acid value of the lubricating oil was measured, and the results are shown in Table 2.
Table 2:
note: the blank control contained no antioxidant.
And (4) conclusion: the base oil composition without antioxidant (rapeseed oil, trimethylolpropane oleate and poly-alpha olefin) has poor antioxidant performance, and the antioxidant Ra-OMCN + MC-01, ra-OMCN and MC-01 can improve the antioxidant performance of the lubricating oil to different degrees and have different base oil performances, wherein Ra-OMCN + MC-01 is more than Ra + MC-01 and more than Ra-OMCN, and the antioxidant performance is obviously improved after the antioxidant Ra-OMCN + MC-01 is added.
Abrasion resistance test
The abrasion resistance of the oil product is measured by adopting a four-ball tester, and the method comprises the following steps: three steel balls with the diameter of 12.7mm are clamped in the oil box, and the other steel ball with the same diameter is placed at the top of the three balls and is acted by 392N force to form three-point contact. When the lubricating oil reaches 75 +/-2 ℃, the top ball rotates for 60min at 1200 +/-60 r/min, then the wear scar diameters of three steel balls are measured, and the average value is calculated.
Table 3:
| oil product | Abrasive grain diameter/mm |
| Blank control group | 1.52 |
| Example 1 | 0.60 |
| Example 2 | 0.53 |
| Example 3 | 0.56 |
| Comparative example 1 | 0.72 |
| Comparative example 2 | 1.36 |
| Comparative example 3 | 0.68 |
| Comparative example 4 | 1.44 |
Note: the blank control contained no antioxidant.
Analysis of Table 2 reveals that: the addition of Ra-OMCN + MC-01 or Ra-OMCN can obviously improve the abrasion resistance of the lubricating oil, and shows that the spherical structure of the OMCN can reduce the resistance in the friction process, reduce the friction coefficient and play the role of a friction modifier, and the effect is different in different base oils.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. Biodegradable lubricating oil, characterized in that it consists of the following components:
1 to 10 parts of modified mesoporous carbon sphere nano-particles loaded with rosmarinic acid;
1 to 10 parts of p, p' -diisooctyldiphenylamine;
the balance being base oil;
the base oil is prepared from rapeseed oil, trimethylolpropane oleate and poly-alpha olefin according to the weight ratio of 10 to 15:1 to 5, wherein the weight ratio is 1 to 3;
the weight ratio of the rosmarinic acid-loaded modified mesoporous carbon sphere nano-particles to the' diisooctyl diphenylamine is 1 to 0.3-1;
the preparation method of the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles comprises the following steps:
s1, melting phenol, adding sodium hydroxide, uniformly stirring, adding a formaldehyde solution with the volume fraction of 37%, and stirring at 70-80 ℃ for 20-35min to obtain a phenolic resin;
s2, adding a triblock copolymer into the phenolic resin, and stirring at 60 to 80 ℃ for 10 to 169h; then reacting for 15 to 30h at the temperature of 100 to 140 ℃, and drying the reaction solution to obtain powder; placing the powder in an inert atmosphere, and roasting at 700 ℃ for 1 to 3h to obtain mesoporous carbon sphere nano-particles;
s3, dispersing the mesoporous carbon sphere nano-particles in hydrogen peroxide, carrying out ultrasonic treatment for 1 to 4 hours, drying at 80 to 100 ℃, and collecting solid powder to obtain modified mesoporous carbon sphere nano-particles;
and S4, dispersing the modified mesoporous carbon sphere nanoparticles into a rosmarinic acid-water solution, carrying out ultrasonic treatment for 10 to 20min, continuously stirring for 12 to 24h, centrifuging, collecting precipitates, and drying to obtain the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles.
2. The biodegradable lubricating oil of claim 1, wherein the weight ratio of the rosmarinic acid-loaded modified mesoporous carbon sphere nanoparticles to the p, p' -diisooctyldiphenylamine is 1:1.
3. The biodegradable lubricating oil of claim 1, wherein in the step S4, the weight ratio of the modified mesoporous carbon sphere nanoparticles to the rosmarinic acid is 1 to 1.5.
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| JP2014185209A (en) * | 2013-03-22 | 2014-10-02 | Fuji Oil Co Ltd | Biodegradable lubricant base oil |
| WO2015086516A1 (en) * | 2013-12-09 | 2015-06-18 | Mattias GRAHN | An aqueous lubricant composition, a method for making the same and uses thereof |
| CN109054960B (en) * | 2018-10-16 | 2021-08-31 | 深圳市金晖科技有限公司 | Friction modifier containing nano mesoporous carbon and preparation method thereof |
| CN110973156B (en) * | 2019-11-28 | 2021-09-10 | 自然资源部第三海洋研究所 | Graphene oxide/rosmarinic acid composite material and preparation method thereof |
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