CN109082326B - Biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil and preparation method thereof - Google Patents
Biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil and preparation method thereof Download PDFInfo
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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
- C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special 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
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- 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
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- C10M2201/0413—Carbon; Graphite; Carbon black used as base material
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- 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
- C10M2229/00—Organic 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
- C10M2229/04—Siloxanes with specific structure
- C10M2229/048—Siloxanes with specific structure containing carboxyl groups
- C10M2229/0485—Siloxanes with specific structure containing carboxyl groups used as base material
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- 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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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- 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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Abstract
The invention relates to a biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil and a preparation method thereof, wherein the lubricating oil base oil is prepared from the following materials in parts by mass: 80-100 parts of biomass fatty acid, 3-5 parts of dibenzoyl peroxide, 50-60 parts of acrylate, 3.5-4.5 parts of graphene oxide, 31-38 parts of hydroxyl-terminated dimethyl diphenyl polysiloxane, 16-20 parts of diethylene glycol and 2-4 parts of p-toluenesulfonic acid. Oleic acid and ricinoleic acid from vegetable oil ester are used as main raw materials, and the prepared biomass base oil has the functions of high temperature resistance, oxidation resistance and long lubrication durability by carrying out graft copolymerization modification of acrylic ester, graft modification of graphene oxide and esterification modification of hydroxy silicone oil and diethylene glycol on the raw materials, and has the characteristics of scientific and reasonable process route, simple process operation, lower cost and remarkable economic benefit.
Description
Technical Field
The invention relates to a biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil and a preparation method thereof.
Background
Lubricating oil is an indispensable component in mechanical operation, plays roles in reducing friction and wear, protecting machinery, cooling, cleaning, sealing, prolonging service life and the like, is widely applied to mechanical equipment in various industries such as engineering machinery, electric power, automobiles, steel, ships, machine tools and the like, has continuously increased lubricating oil demand in China in recent years, has the consumption of more than 6.0 ten thousand tons in China in 2016 and has become the second largest lubricating oil market in the world. Due to the limitation and worry of the main source of petroleum resources of the lubricating oil base oil and the serious damage to the natural environment caused by the leakage, overflow, evaporation or improper treatment of the lubricating oil, the currently developed biomass environment-friendly lubricating oil base oil is concerned by society and markets (Anjunxin, Luling. the supply and demand status and development trend of the lubricating oil base oil at home and abroad. market observation 2015 (1): 11-19).
The lubricating oil consists of two parts, namely base oil and additives, wherein the base oil is a main body of the lubricating oil, the proportion of the base oil in the lubricating oil is generally 70-99%, the performance of the lubricating oil is mainly determined by the base oil, the quality of the base oil is directly related to the quality of the lubricating oil, and the additives such as a viscosity stabilizer, a dispersing agent, a detergent, an antiwear agent, an antioxidant, a friction regulator and the like are used for making up for the deficiencies of certain performance aspects of the lubricating oil (Wu Shang, the development trend of the lubricating oil base oil in China, the contemporary petrochemical industry, 2009, 17 (5): 16-21). The lubricating oil base oil comprises mineral oil, synthetic oil and biomass oil, wherein the mineral base oil accounts for about 90 percent at present, the mineral oil is derived from petroleum crude oil and mainly comprises hydrocarbons and non-hydrocarbons with high boiling point and large relative molecular mass, and the lubricating oil has the advantages of high temperature resistance, good lubricating effect and difficult degradation and has great environmental pollution in the preparation process and after use. The synthetic oil mainly comprises synthetic grease, polyether, silicone oil, fluorine-containing oil and the like, has the characteristics of high thermal decomposition temperature, oxidation resistance, high temperature resistance and the like, and has high cost and great pollution in the preparation process. The biomass oil is mainly vegetable oil, has the advantages of obvious environmental protection and low pollution, has good lubricating effect, renewable resources and low cost, and has the defect of poor oxidation resistance and high temperature resistance. The common lubricant base oil is prepared by reasonably compounding mineral oil, synthetic oil and biomass base oil. At present, the proportion of biomass oil in the base oil of lubricating oil is very low, and is generally about 1-5%. As the biomass base oil has the advantages of environmental protection, regeneration, good lubricating effect and the like, the biomass base oil becomes a research hotspot in recent years, the social demand is continuously increased, and the unprecedented opportunity is provided for the research and development and industrialization of the biomass base oil (Wang Xiuwen, Chen Enhan, Yan Ka. research on the relationship between the structure composition and the performance of the lubricating oil base oil, application chemical industry, 2014, 43 (3): 539-.
At present, the application proportion of biomass base oil in lubricating oil in China is low, the biomass base oil accounts for about 1% of the consumption proportion of the lubricating oil, and the biomass base oil in developed countries reaches 5%. The main reasons are that the chemical structure of the biomass base oil generally contains double bonds, which results in that the biomass base oil cannot resist high temperature and has poor oxidation stability, and meanwhile, the biomass vegetable oil contains triglyceride, which results in that the biomass vegetable oil has poor hydrolysis stability. In order to overcome the instability of double bonds and glyceride groups in the biomass oil, the biomass base oil is modified by mainly adopting methods of preparing dibasic acid esters by saponification-cracking of vegetable oil and preparing polyol esters by hydrolysis-esterification of vegetable oil in China, but the technical processes have the defects of high pollution, poor economy, difficulty in controlling the product structure, more performance defects and the like, and can not meet the performance requirements of the lubricating oil base oil; the method mainly prepares multi-branched polyolefin base oil through double decomposition of vegetable oil ester abroad, improves the molecular branching degree through epoxy-ring opening of the vegetable oil ester, improves the oxidation stability and the low-temperature fluidity through oleic acid addition, and has the problems of high catalyst cost, difficult separation of the catalyst, more byproducts, difficult separation of a final product and the like (upland crossing, blazing, celebration, and the like, the structural innovation and the industrial development of the bio-based lubricating oil base oil, the petroleum institute, 2018, 34 (2): 203-216).
Disclosure of Invention
The invention aims to provide a biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil and a preparation method thereof.
In order to achieve the purpose, the invention provides a biomass high-temperature-resistant oxidation-resistant long-durability lubricating oil base oil which is prepared from the following materials in parts by mass:
80-100 parts of biomass fatty acid, 3-5 parts of dibenzoyl peroxide, 50-60 parts of acrylate, 3.5-4.5 parts of graphene oxide, 31-38 parts of hydroxyl-terminated dimethyl diphenyl polysiloxane, 16-20 parts of diethylene glycol and 2-4 parts of p-toluenesulfonic acid.
The biomass fatty acid is prepared from vegetable oleic acid and ricinoleic acid in a mass ratio of 1.3: 1; the vegetable oil acid is a light yellow transparent oily liquid, the acid value is 195-206 mg KOH/g, the saponification value is 195-207 mg KOH/g, and the iodine value is 120-145I2100g, the freezing point is 5-12 ℃; ricinoleic acid is colorless or slightly yellow viscous liquid with acid value of190 to 203mgKOH/g, a saponification value of 188 to 196mgKOH/g, a hydroxyl value of 135 to 155mgKOH/g, and an iodine value of 82 to 86I2100g, the freezing point is 6-10 ℃.
The graphene oxide is obtained by freeze drying of a graphene oxide nanosheet layer dispersion liquid, the graphene oxide content of the graphene oxide dispersion liquid is 0.5%, the planar size of each layer is 60-530 nm, the thickness of each layer is 2.6-6.5 nm, the graphene oxide is a 2-6 graphene oxide monolithic layer aggregate, and the oxygen content of the graphene oxide is 16.6% -19.3%.
The hydroxyl-terminated dimethyl diphenyl polysiloxane has a boiling point greater than 300 ℃, a flash point greater than 230 ℉ and a density of 1.05g/cm3The average relative molecular mass was 293 g/mol.
A preparation method of biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil comprises the following steps:
step one, preparing modified biomass fatty acid:
stirring 80-100 parts of biomass fatty acid and 200-250 parts of toluene, heating to 75-85 ℃, adding 3-5 parts of dibenzoyl peroxide, stirring, dropwise adding 50-60 parts of acrylic ester at a constant speed within 40-50 minutes, reacting for 3-3.5 hours under a heat preservation condition, and distilling under reduced pressure to obtain a distillation product, namely modified biomass fatty acid;
step two, preparing graphene oxide modified biomass fatty acid:
mixing 80-100 parts of modified biomass fatty acid obtained in the step one with 3.5-4.5 parts of graphene oxide and 1-2 parts of p-toluenesulfonic acid, ultrasonically dispersing for 50-60 minutes, heating to 120-130 ℃, stirring and reacting for 4-4.5 hours to obtain a product, namely graphene oxide modified biomass fatty acid;
step three, preparing the biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil:
and (3) mixing 80-100 parts of graphene oxide modified biomass fatty acid obtained in the second step, 31-38 parts of hydroxyl terminated dimethyl diphenyl polysiloxane, 16-20 parts of monoethylene glycol and 1-2 parts of p-toluenesulfonic acid, and reacting at 130-150 ℃ for 5-6 hours to prepare the biological high-temperature-resistant anti-oxidation long-durability lubricating oil base oil.
The step oneThe biomass fatty acid is prepared from vegetable oleic acid and ricinoleic acid according to the mass ratio of 1.3:1, wherein the vegetable oleic acid is light yellow transparent oily liquid, the acid value is 195-206 mg KOH/g, the saponification value is 195-207 mg KOH/g, and the iodine value is 120-145I2100g, the freezing point is 5-12 ℃; the ricinoleic acid is colorless or slightly yellow viscous liquid, the acid value is 190-203 mgKOH/g, the saponification value is 188-196 mgKOH/g, the hydroxyl value is 135-155 mgKOH/g, and the iodine value is 82-86I2100g, the freezing point is 6-10 ℃.
In the step one, the acrylic ester is composed of ethyl acrylate and butyl acrylate according to the mass ratio of 1: 2.
The graphene oxide in the second step is obtained by freeze drying of graphene oxide nano-sheet layer dispersion liquid, the graphene oxide content of the graphene oxide dispersion liquid is 0.5%, the sheet size is 60 nm-530 nm, the sheet thickness is 2.6-6.5 nm, the graphene oxide dispersion liquid is a 2-6 graphene oxide single-sheet layer aggregate, and the oxygen content of the graphene oxide is 16.6% -19.3%.
And the unit power during the ultrasonic treatment in the step two is 2000W, and the frequency is 20 Hz.
The hydroxyl-terminated dimethyldiphenylpolysiloxane in step three above had a boiling point of greater than 300 ℃, a flash point of greater than 230 ℃ F., a density of 1.05g/cm3, and an average relative molecular mass of 293 g/mol.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, double bonds are eliminated, the branching degree is increased, the oxidation resistance and the viscosity-temperature performance are improved through the graft modification of the acrylate, the heat transfer, heat conduction, lubrication, high temperature resistance and oxidation resistance are improved through the graft modification of the graphene oxide, and the lubrication performance and the stability are improved through the esterification modification of the hydroxyl silicone oil and the monoethylene glycol;
(2) after the solvent and water are removed from the product prepared by the method, further separation and purification are not needed;
(3) the preparation method disclosed by the invention is simple in process, convenient to operate, low in cost, economic and practical.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention include, but are not limited to, the scope shown in the following examples.
The invention provides a biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil which is prepared from the following materials in parts by mass:
80-100 parts of bio-based fatty acid, 3-5 parts of dibenzoyl peroxide, 50-60 parts of acrylate, 3.5-4.5 parts of graphene oxide nanosheet layer, 31-38 parts of hydroxyl-terminated dimethyl diphenyl polysiloxane, 16-20 parts of monoethylene glycol and 2-4 parts of p-toluenesulfonic acid.
A preparation method of biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil comprises the following steps:
step one, preparing modified biomass fatty acid: putting 80-100 parts of biomass fatty acid and 200-250 parts of toluene into a reaction kettle with a reflux device, stirring and heating to 75-85 ℃, adding 3-5 parts of dibenzoyl peroxide, stirring, dropwise adding 50-60 parts of acrylate at a constant speed within 40-50 minutes, reacting for 3-3.5 hours under heat preservation, distilling under reduced pressure, removing toluene in a system, and obtaining a product which is a graft copolymer of the acrylate and the biomass fatty acid, namely the modified biomass fatty acid.
Step two, preparing graphene oxide modified biomass fatty acid: mixing 80-100 parts of modified biomass fatty acid prepared in the first step with 3.5-4.5 parts of graphene oxide and 1-2 parts of p-toluenesulfonic acid, ultrasonically dispersing for 50-60 minutes, adding into a reaction kettle equipped with a water separator and a reflux device, heating to 120-130 ℃, and reacting for 4-4.5 hours under stirring to obtain a product, namely graphene oxide modified biomass fatty acid.
Step three, preparing the biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil: and (3) sequentially adding 80-100 parts of the graphene oxide modified biomass fatty acid obtained in the second step, 31-38 parts of hydroxyl-terminated dimethyl diphenyl polysiloxane, 16-20 parts of monoethylene glycol and 1-2 parts of p-toluenesulfonic acid into a reaction kettle with a water separator and a reflux device, and reacting at 130-150 ℃ for 5-6 hours to obtain the high-temperature-resistant, antioxidant and long-durability biomass lubricating oil base oil.
The graphene oxide is obtained by freeze drying of graphene oxide nanosheet layer dispersion liquid prepared by a Hummers method, and the content of graphene oxide in the graphene oxide dispersion liquid is 0.5%. The planar size of the lamella is 60-530 nm, the thickness of the lamella is 2.6-6.5 nm, graphene oxide in the dispersion liquid is formed by gathering 2-6 single lamella layers, and the oxygen content of the graphene oxide is 16.6% -19.3%.
And the unit power during the ultrasonic treatment in the step two is 2000W, and the frequency is 20 Hz.
The acrylic ester is composed of ethyl acrylate and butyl acrylate according to the mass ratio of 1: 2.
The technical indexes of the hydroxyl-terminated dimethyl diphenyl polysiloxane are as follows: boiling point greater than 300 ℃, flash point greater than 230 ℉ and density of 1.05g/cm3The average relative molecular mass was 293 g/mol.
The biomass fatty acid is prepared from vegetable oleic acid and ricinoleic acid according to the mass ratio of 1.3:1, wherein the vegetable oleic acid is light yellow transparent oily liquid, the acid value is 195-206 mgKOH/g, the saponification value is 195-207 mgKOH/g, and the iodine value is 120-145I2100g, the freezing point is 5-12 ℃; the ricinoleic acid is colorless or slightly yellow viscous liquid, the acid value is 190-203 mgKOH/g, the saponification value is 188-196 mgKOH/g, the hydroxyl value is 135-155 mgKOH/g, and the iodine value is 82-86I2100g, and the freezing point is 6-10 ℃.
According to the invention, the double bonds of biomass oleic acid from vegetable oil are eliminated through graft copolymerization modification of acrylate, the branching degree is increased, the oxidation resistance and the viscosity-temperature performance are improved, and the heat transfer, heat conduction, lubrication, high temperature resistance and oxidation resistance are improved through the graft modification of graphene oxide; the lubricating property and stability of the hydroxy silicone oil and the monoethylene glycol are improved through esterification modification, and meanwhile, the preparation method disclosed by the invention has the characteristics of simple process, low cost, less pollution, environmental friendliness, cleanness and the like. The biomass lubricating oil base oil obtained by the preparation method disclosed by the invention can work at 150-250 ℃ for a long time, and the service cycle of the biomass lubricating oil base oil can reach about 2 kilometres if the biomass lubricating oil base oil is prepared into automobile engine lubricating oil.
The present invention will be described in detail with reference to the following embodiments.
Example one
A preparation method of biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil comprises the following steps:
step one, preparing modified biomass fatty acid:
putting 80 parts of biomass fatty acid and 200 parts of toluene into a reaction kettle with a reflux device, stirring, heating to 75 ℃, adding 3 parts of dibenzoyl peroxide, stirring, dropwise adding 50 parts of acrylic ester at a constant speed within 40 minutes, reacting for 3 hours under a heat preservation condition, and then distilling under reduced pressure to remove toluene in a system, wherein a product is a graft copolymer of the acrylic ester and the biomass fatty acid, namely the modified biomass fatty acid.
Step two, preparing graphene oxide modified biomass fatty acid:
and (3) mixing 80 parts of modified biomass fatty acid prepared in the first step with 3.5 parts of graphene oxide and 1 part of p-toluenesulfonic acid, ultrasonically dispersing for 50 minutes, adding into a reaction kettle equipped with a water separator and a reflux device, heating to 120 ℃, and reacting for 4 hours under stirring to obtain a product, namely graphene oxide modified biomass fatty acid.
Step three, preparing the biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil:
and (2) sequentially adding 80 parts of the graphene oxide modified biomass fatty acid obtained in the second step, 31 parts of hydroxyl-terminated dimethyl diphenyl polysiloxane, 16 parts of monoethylene glycol and 1 part of p-toluenesulfonic acid into a reaction kettle with a water separator and a reflux device, and reacting at 130 ℃ for 5 hours to obtain the biological high-temperature-resistant oxidation-resistant long-durability lubricating oil base oil, wherein the performances of the base oil are shown in Table 1.
Example two
A preparation method of biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil comprises the following steps:
step one, preparing modified biomass fatty acid:
putting 90 parts of biomass fatty acid and 230 parts of toluene into a reaction kettle with a reflux device, stirring, heating to 80 ℃, adding 4 parts of dibenzoyl peroxide, stirring, dropwise adding 55 parts of acrylic ester at a constant speed within 45 minutes, reacting for 3.2 hours under a heat preservation condition, and then distilling under reduced pressure to remove the toluene in the system, wherein the product is a graft copolymer of the acrylic ester and the biomass fatty acid, namely the modified biomass fatty acid.
Step two, preparing graphene oxide modified biomass fatty acid:
and (3) mixing 90 parts of modified biomass fatty acid prepared in the first step with 4.0 parts of graphene oxide and 1.5 parts of p-toluenesulfonic acid, ultrasonically dispersing for 55 minutes, adding into a reaction kettle equipped with a water separator and a reflux device, heating to 125 ℃, and reacting for 4.2 hours under stirring to obtain a product, namely graphene oxide modified biomass fatty acid.
Step three, preparing the biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil:
and (3) sequentially adding 90 parts of graphene oxide modified biomass fatty acid obtained in the step (II), 34 parts of hydroxyl-terminated dimethyl diphenyl polysiloxane, 18 parts of monoethylene glycol and 1.5 parts of p-toluenesulfonic acid into a reaction kettle with a water separator and a reflux device, and reacting at 140 ℃ for 5.5 hours to obtain the biomass high-temperature-resistant oxidation-resistant long-durability lubricating oil base oil, wherein the performances of the base oil are shown in Table 1.
EXAMPLE III
A preparation method of biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil comprises the following steps:
step one, preparing modified biomass fatty acid:
100 parts of biomass fatty acid and 250 parts of toluene are put into a reaction kettle with a reflux device, stirred and heated to 85 ℃, 5 parts of dibenzoyl peroxide is added, stirred and 60 parts of acrylic ester is dripped at a constant speed within 50 minutes, the heat preservation reaction is carried out for 3.5 hours, then the toluene in the system is removed by reduced pressure distillation, and the product is acrylic ester and biomass fatty acid graft copolymer, namely the modified biomass fatty acid.
Step two, preparing graphene oxide modified biomass fatty acid:
and (3) mixing 100 parts of modified biomass fatty acid prepared in the first step with 4.5 parts of graphene oxide and 2 parts of p-toluenesulfonic acid, ultrasonically dispersing for 60 minutes, adding into a reaction kettle equipped with a water separator and a reflux device, heating to 130 ℃, and reacting for 4.5 hours under stirring to obtain a product, namely graphene oxide modified biomass fatty acid.
Step three, preparing the biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil:
and (2) sequentially adding 100 parts of the graphene oxide modified biomass fatty acid obtained in the second step, 38 parts of hydroxyl-terminated dimethyl diphenyl polysiloxane, 20 parts of monoethylene glycol and 2 parts of p-toluenesulfonic acid into a reaction kettle with a water separator and a reflux device, and reacting at 150 ℃ for 6 hours to obtain the biological high-temperature-resistant oxidation-resistant long-durability lubricating oil base oil, wherein the performances of the base oil are shown in Table 1.
TABLE 1 Properties of the products prepared in the examples
Table 1 the data was determined according to the following method: the flash point is tested according to GB/T267-88, the pour point is tested according to GB/T3535-2006, the thermal stability is tested according to SH/T0680-1999, the oxidation stability is tested according to SH/T0193-2008, the kinematic viscosity is tested according to GB/T11137-1989, the viscosity index is tested according to NFT60-136-2004, and the biodegradability is tested according to CEC L-33-A-93.
As can be seen from the test results in Table 1, the biomass lubricating oil base oil prepared by the preparation method disclosed by the invention has good thermal stability, has no loss at 300 ℃, and can be used within the range of 150-250 ℃; the oxidation stability is good, and the antioxidant property is good; the biomass lubricating oil base oil obtained by the preparation method disclosed by the invention has the performance indexes for preparing high-performance lubricating oil of various grades, and has a wide application prospect.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (10)
1. The high-temperature-resistant anti-oxidation long-durability biomass lubricating oil base oil is characterized in that:
the material is prepared from the following materials in parts by mass:
80-100 parts of vegetable oil fatty acid, 3-5 parts of dibenzoyl peroxide, 50-60 parts of acrylate, 3.5-4.5 parts of graphene oxide, 31-38 parts of hydroxyl-terminated dimethyl diphenyl polysiloxane, 16-20 parts of diethylene glycol and 2-4 parts of p-toluenesulfonic acid;
the preparation method comprises the following steps:
step one, preparing modified biomass fatty acid:
stirring 80-100 parts of vegetable oil fatty acid and 200-250 parts of toluene, heating to 75-85 ℃, adding 3-5 parts of dibenzoyl peroxide, stirring, dropwise adding 50-60 parts of acrylic ester at a constant speed within 40-50 minutes, reacting for 3-3.5 hours under a heat preservation condition, and carrying out reduced pressure distillation to obtain a distillation product which is modified biomass fatty acid;
step two, preparing graphene oxide modified biomass fatty acid:
mixing 80-100 parts of modified biomass fatty acid obtained in the step one with 3.5-4.5 parts of graphene oxide and 1-2 parts of p-toluenesulfonic acid, ultrasonically dispersing for 50-60 minutes, heating to 120-130 ℃, stirring and reacting for 4-4.5 hours to obtain a product, namely graphene oxide modified biomass fatty acid;
step three, preparing the biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil:
and (3) mixing 80-100 parts of graphene oxide modified biomass fatty acid obtained in the second step, 31-38 parts of hydroxyl terminated dimethyl diphenyl polysiloxane, 16-20 parts of monoethylene glycol and 1-2 parts of p-toluenesulfonic acid, and reacting at 130-150 ℃ for 5-6 hours to prepare the biological high-temperature-resistant anti-oxidation long-durability lubricating oil base oil.
2. The biomass high temperature resistant anti-oxidation long-durability lubricating oil base oil according to claim 1, characterized in that:
the vegetable oil fatty acid is composed of vegetable oleic acid and ricinoleic acid according to the mass ratio of 1.3: 1; the vegetable oil acid is light yellow transparent oily liquid,an acid value of 195 to 206mg KOH/g, a saponification value of 195 to 207mg KOH/g, an iodine value of 120 to 145I2100g, the freezing point is 5-12 ℃; the ricinoleic acid is colorless or slightly yellow viscous liquid, the acid value is 190-203 mgKOH/g, the saponification value is 188-196 mgKOH/g, the hydroxyl value is 135-155 mgKOH/g, and the iodine value is 82-86I2100g, the freezing point is 6-10 ℃.
3. The biomass high temperature resistant anti-oxidation long-durability lubricating oil base oil according to claim 1, characterized in that:
the graphene oxide is obtained by freeze drying of a graphene oxide nanosheet layer dispersion liquid, the graphene oxide mass fraction of the graphene oxide dispersion liquid is 0.5%, the planar size of each layer is 60-530 nm, the thickness of each layer is 2.6-6.5 nm, the graphene oxide is a 2-6 graphene oxide monolithic layer aggregate, and the oxygen content of the graphene oxide is 16.6-19.3%.
4. The biomass high temperature resistant anti-oxidation long-durability lubricating oil base oil according to claim 1, characterized in that:
the boiling point of the hydroxyl-terminated dimethyl diphenyl polysiloxane is more than 300 ℃, the flash point is more than 110 ℃, and the density is 1.05g/cm3The average relative molecular mass was 293 g/mol.
5. The preparation method of the biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil is characterized by comprising the following steps of:
the method comprises the following steps:
step one, preparing modified biomass fatty acid:
stirring 80-100 parts of vegetable oil fatty acid and 200-250 parts of toluene, heating to 75-85 ℃, adding 3-5 parts of dibenzoyl peroxide, stirring, dropwise adding 50-60 parts of acrylic ester at a constant speed within 40-50 minutes, reacting for 3-3.5 hours under a heat preservation condition, and carrying out reduced pressure distillation to obtain a distillation product which is modified biomass fatty acid;
step two, preparing graphene oxide modified biomass fatty acid:
mixing 80-100 parts of modified biomass fatty acid obtained in the step one with 3.5-4.5 parts of graphene oxide and 1-2 parts of p-toluenesulfonic acid, ultrasonically dispersing for 50-60 minutes, heating to 120-130 ℃, stirring and reacting for 4-4.5 hours to obtain a product, namely graphene oxide modified biomass fatty acid;
step three, preparing the biomass high-temperature-resistant anti-oxidation long-durability lubricating oil base oil:
and (3) mixing 80-100 parts of graphene oxide modified biomass fatty acid obtained in the second step, 31-38 parts of hydroxyl terminated dimethyl diphenyl polysiloxane, 16-20 parts of monoethylene glycol and 1-2 parts of p-toluenesulfonic acid, and reacting at 130-150 ℃ for 5-6 hours to prepare the biological high-temperature-resistant anti-oxidation long-durability lubricating oil base oil.
6. The method for preparing the biomass high temperature resistant anti-oxidation long-durability lubricating oil base oil according to claim 5, characterized in that:
the vegetable oil fatty acid in the step one is composed of vegetable oleic acid and ricinoleic acid according to the mass ratio of 1.3: 1; the vegetable oil acid is a light yellow transparent oily liquid, the acid value is 195-206 mg KOH/g, the saponification value is 195-207 mg KOH/g, and the iodine value is 120-145I2100g, the freezing point is 5-12 ℃; the ricinoleic acid is colorless or slightly yellow viscous liquid, the acid value is 190-203 mgKOH/g, the saponification value is 188-196 mgKOH/g, the hydroxyl value is 135-155 mgKOH/g, and the iodine value is 82-86I2100g, the freezing point is 6-10 ℃.
7. The method for preparing the biomass high temperature resistant anti-oxidation long-durability lubricating oil base oil according to claim 5, characterized in that:
in the first step, the acrylic ester is composed of ethyl acrylate and butyl acrylate according to the mass ratio of 1: 2.
8. The method for preparing the biomass high temperature resistant anti-oxidation long-durability lubricating oil base oil according to claim 5, characterized in that:
and step two, the graphene oxide is obtained by freeze drying of graphene oxide nano-sheet layer dispersion liquid, the graphene oxide mass fraction of the graphene oxide dispersion liquid is 0.5%, the sheet layer plane size is 60-530 nm, the sheet layer thickness is 2.6-6.5 nm, the graphene oxide dispersion liquid is a 2-6 graphene oxide single-sheet layer aggregate, and the oxygen content of the graphene oxide is 16.6-19.3%.
9. The method for preparing the biomass high temperature resistant anti-oxidation long-durability lubricating oil base oil according to claim 5, characterized in that:
and step two, the unit power of ultrasonic treatment is 2000W, and the frequency is 20 Hz.
10. The method for preparing the biomass high temperature resistant anti-oxidation long-durability lubricating oil base oil according to claim 5, characterized in that:
the boiling point of the hydroxyl-terminated dimethyl diphenyl polysiloxane in the step three is more than 300 ℃, the flash point is more than 110 ℃, and the density is 1.05g/cm3The average relative molecular mass was 293 g/mol.
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