CN109777577B - Lubricating oil based on siloxane modified graphene and preparation method thereof - Google Patents
Lubricating oil based on siloxane modified graphene and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lubricating oil based on siloxane modified graphene and a preparation method thereof, wherein the lubricating oil comprises the following components in parts by weight: 75-95 parts of base oil; 5-10 parts of a tackifier; 0.1-1 part of pour point depressant; 2-7 parts of a detergent; 1-5 parts of ashless dispersant; 0.5-3 parts of antioxidant preservative; 1-3 parts of siloxane modified graphene; the siloxane modified graphene is prepared from graphene oxide, polysiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product; the silane coupling agent is prepared from vinyl triethoxysilane and N-aminoethyl-gamma-aminopropyltriethoxysilane in a mass ratio of 1-3: 1. The method can effectively improve the dispersion stability of the graphene, has the advantages of easily available materials, low cost and simple process, and can be used for industrial production.
Description
Technical Field
The invention relates to the field of lubricating oil, and particularly relates to lubricating oil based on siloxane modified graphene and a preparation method thereof.
Background
The lubricating performance of an engine is closely related to the safety, environmental protection, energy conservation and other performances of an automobile, and with the continuous improvement of the engine performance, the requirement on the lubricating aspect is increasingly complex and severe, and graphene oxide as a carbonaceous new material with a two-dimensional structure has a series of excellent properties such as high specific surface area, thermal conductivity, mechanical property and the like, so that a certain amount of graphene needs to be added into lubricating oil in order to improve the engine lubricating performance and realize antifriction and energy conservation, but how to prevent the lubricating oil added with the graphene oxide from generating layering and precipitation is a technical problem which needs to be faced by researchers.
Although the chinese patent application with application number 201810421587.1 discloses a graphene lubricating oil and a preparation method thereof, which can effectively solve the problem that graphene is easy to agglomerate and precipitate, egg oil is adopted, so that the cost is extremely high, and the condition requirements are harsh, which is not favorable for industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the lubricating oil based on the siloxane modified graphene and the preparation method thereof, which can effectively improve the dispersion stability of the graphene, have the advantages of easily available materials, low cost and simple process, and can be used for industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first technical scheme is as follows:
the lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polysiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
further, the silane coupling agent is prepared from vinyl triethoxysilane (A-151) and N-aminoethyl-gamma-aminopropyltriethoxysilane (KH-791) in a mass ratio of 1-3: 1.
Further, the preparation method of the siloxane modified graphene comprises the following steps:
step 1, mixing N-aminoethyl-gamma-aminopropyltriethoxysilane and water in a mass ratio of 1: 5, adding the N-aminoethyl-gamma-aminopropyltriethoxysilane into water, and uniformly dispersing to obtain an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution for later use; according to the mass ratio of the vinyltriethoxysilane to the absolute ethyl alcohol of 1: 5, dissolving the vinyltriethoxysilane by using absolute ethanol to obtain a vinyltriethoxysilane solution for later use;
and 2, adding graphene oxide into the aqueous solution of N-aminoethyl-gamma-aminopropyltriethoxysilane, ultrasonically dispersing for 5 hours at 80 ℃, adding a vinyl triethoxy silanol solution, adding polysiloxane, adjusting the pH value to 4 with acetic acid, ultrasonically dispersing for 2 hours at 100 ℃, naturally cooling to room temperature, filtering, washing for 3-5 times with an ethanol solution with the volume concentration of 40-50%, and drying at 60 ℃ to obtain the graphene oxide film.
Further, the polysiloxane is polydimethylsiloxane.
Further, in the step 1, the graphene oxide adopts few layers of graphene oxide.
Furthermore, the number of the few-layer graphene oxide layers is less than or equal to 3.
Furthermore, the preparation method of the few-layer graphene oxide comprises the following steps: by the Hummer method, 2g of flake graphite powder was put into a 250mL beaker, and 1g of NaNO was added thereto in an ice-water bath3Then 46mL of H with the mass concentration of 98 percent is added2SO4After stirring well, 6g of KMnO was slowly added4Keeping the temperature of the solution at 20 ℃ for at least 5min, then heating to 35 ℃ and keeping for 30 min; adding 92mL of water, stirring for 15min, and raising the temperature to about 98 ℃; and then adding 80mL of hydrogen peroxide with the volume concentration of 3% at 60 ℃, centrifuging for 30min at the rotating speed of 7200 r/min, cleaning residues with hot water at 60 ℃ until the pH of the upper-layer suspension is 7, dispersing the obtained powder into water again, performing ultrasonic treatment for 15min, filtering black residues to obtain uniform suspension, and performing spray drying to obtain few-layer graphene oxide.
Further, the base oil is prepared from 650SN base oil, 150SN base oil and 150BS base oil according to a mass ratio of 65-75: 5-15: 2-10 are compounded;
the tackifier is prepared from ethylene propylene copolymer and polymethacrylate according to a mass ratio of 3-10: 1 is compounded;
the pour point depressant is a polyethylene-fumarate copolymer;
the detergent is prepared from medium-base-number synthetic calcium sulfonate, high-base-number synthetic calcium sulfonate and sulfurized calcium alkyl phenate according to a mass ratio of 0.5-2.5: 1.5-2.5: 0.1-1.5;
the ashless dispersant is a succinimide dispersant, and the succinimide dispersant is prepared by mixing polyisobutylene bis-succinimide and polyisobutylene polysuccinimide according to the weight ratio of 1.5-3.5: 0.5-1.5;
the antioxidant preservative is prepared from butyl octyl zinc thiophosphate and dioctyl alkaline zinc thiophosphate in a mass ratio of 1-3: 3-6.
The second technical scheme is as follows:
a preparation method of lubricating oil based on siloxane modified graphene comprises the following steps:
firstly, weighing raw materials in parts by weight, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step two, heating the pour point depressant to 55 ℃;
step three, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step four, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step five, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersing additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method, the modification of the graphene oxide is carried out in two steps, firstly, N-aminoethyl-gamma-aminopropyltriethoxysilane is adopted to carry out primary modification on the graphene oxide, and then, a composite modifier consisting of vinyl triethoxysilane, N-aminoethyl-gamma-aminopropyltriethoxysilane and polysiloxane mixture is adopted to carry out secondary modification on the graphene oxide under an acidic condition, so that the agglomeration of the graphene can be effectively slowed down or even avoided, the dispersion stability of the graphene is improved, the dispersion, storage stability and wear-reducing and wear-resisting properties of the lubricating oil are improved, and the energy consumption is saved.
2. According to the invention, acetic acid with volatility is adopted to adjust the pH of the solution in the graphene modification process, the pH of the solution is gradually increased along with the volatilization of the acetic acid in the high-temperature modification process, and compared with the method adopting non-volatile acid, the method has a remarkable influence on the modification effect of the second-step composite modification.
3. The type of the modifier used for modifying the graphene oxide, the modification sequence of the modifier and the type (volatile acid) of the pH regulator are all keys influencing the modification effect of the graphene, and the graphene agglomeration can be slowed only by modifying the graphene oxide by adopting the steps disclosed by the invention, so that the dispersion stability of the graphene oxide is effectively improved.
4. In the invention, polysiloxane and N-aminoethyl-gamma-aminopropyltriethoxysilane are not only indispensable for modifying graphene oxide, but also cannot be replaced by other similar modifiers.
All parameters in the process of preparing the lubricating oil by the method play a critical role, the lubricating oil prepared by the method can effectively improve the dispersion stability of the graphene and improve the lubricity of an automobile engine, so that the energy consumption caused by friction is saved, the materials are easy to obtain, the cost is low, the process is simple, and the industrial production can be carried out.
Detailed Description
The present invention will be described in further detail with reference to examples.
650SN base oil adopts Yanshan quadrifilar 650SN base oil.
150SN base oil is Yanshan Diandian 150SN base oil.
Polyisobutylene polysuccinimide (T161) is a high molecular weight polyisobutylene polysuccinimide available from mallow china lubricant additive additives ltd; kinematic viscosity (100 ℃), 300-2S; flash point (open cup) is more than or equal to 170 ℃; nitrogen content, 1.0-1.2% (m/m); water content less than or equal to 0.08% (m/m); total base number, 15-30mg KOH/g.
Polyisobutylene bis-succinimide T154 is a high nitrogen, chlorine free polyisobutylene bis-succinimide available from California Huamei lubricating oil additives Inc.; density (20 ℃), 890-kg/m3(ii) a Kinematic viscosity (100 ℃), 150-2S; flash point (open cup) is more than or equal to 170 ℃; nitrogen content, 1.1-1.3% (m/m); the chroma (dilution) is less than or equal to 7 moisture; less than or equal to 0.1 percent (m/m); total base number, 15-30mg KOH/g.
Zinc butyl octyl dithiophosphate (T202): purchased from orthodox chemical company, Inc., Guangzhou.
Alkaline zinc salt of dioctyl sulfur and phosphorus (T203): purchased from petty chemical limited, ca.
The preparation method of the few-layer graphene oxide used in the invention comprises the following steps: using a Hummer method, in a 250mL volume2g of crystalline flake graphite powder was added to a beaker, and 1g of NaNO was added thereto in an ice-water bath3Then 46mL of H with the mass concentration of 98 percent is added2SO4After stirring well, 6g of KMnO was slowly added4Keeping the temperature of the solution at 20 ℃ for at least 5min, then heating to 35 ℃ and keeping for 30 min; adding 92mL of water, stirring for 15min, and raising the temperature to about 98 ℃; and then adding 80mL of hydrogen peroxide with the volume concentration of 3% at 60 ℃, centrifuging for 30min at the rotating speed of 7200 r/min, cleaning residues with hot water at 60 ℃ until the pH of the upper-layer suspension is 7, dispersing the obtained powder into water again, performing ultrasonic treatment for 15min, filtering black residues to obtain uniform suspension, and performing spray drying to obtain few-layer graphene.
In the invention, the polysiloxane is polydimethylsiloxane.
Example 1
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polydimethylsiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent is prepared from vinyl triethoxysilane (A-151) and N-aminoethyl-gamma-aminopropyltriethoxysilane (KH-791) in a mass ratio of 2: 1.
The manufacturing method comprises the following steps:
step one, preparing siloxane modified graphene: step A, according to the mass ratio of N-aminoethyl-gamma-aminopropyltriethoxysilane to water of 1: 5, adding the N-aminoethyl-gamma-aminopropyltriethoxysilane into water, and uniformly dispersing to obtain an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution for later use; according to the mass ratio of the vinyltriethoxysilane to the absolute ethyl alcohol of 1: 5, dissolving the vinyltriethoxysilane by using absolute ethanol to obtain a vinyltriethoxysilane solution for later use;
b, adding graphene oxide into an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution, ultrasonically dispersing for 5 hours at 80 ℃, adding a vinyl triethoxy silanol solution, adding polydimethylsiloxane, adjusting the pH value to be 4 by using acetic acid, ultrasonically dispersing for 2 hours at 100 ℃, naturally cooling to room temperature, filtering, washing for 4 times by using an ethanol solution with the volume concentration of 45%, and drying at 60 ℃ to obtain siloxane modified graphene;
weighing the raw materials in parts by weight, firstly, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step three, heating the pour point depressant to 55 ℃;
step four, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step five, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step six, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersant additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
Example 2
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polydimethylsiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent is prepared from vinyl triethoxysilane and N-aminoethyl-gamma-aminopropyltriethoxysilane in a mass ratio of 2: 1.
The manufacturing method comprises the following steps: the same as in example 1.
Example 3
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polydimethylsiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent is prepared from vinyl triethoxysilane and N-aminoethyl-gamma-aminopropyltriethoxysilane in a mass ratio of 2: 1.
The manufacturing method comprises the following steps: the same as in example 1.
Comparative example 1
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide and a silane coupling agent in a mass ratio of 1: 2, preparing the product;
the silane coupling agent is prepared from vinyl triethoxysilane and N-aminoethyl-gamma-aminopropyltriethoxysilane in a mass ratio of 1-3: 1.
The manufacturing method comprises the following steps:
step one, preparing siloxane modified graphene:
step A, according to the mass ratio of N-aminoethyl-gamma-aminopropyltriethoxysilane to water of 1: 5, adding the N-aminoethyl-gamma-aminopropyltriethoxysilane into water, and uniformly dispersing to obtain an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution for later use; according to the mass ratio of the vinyltriethoxysilane to the absolute ethyl alcohol of 1: 5, dissolving the vinyltriethoxysilane by using absolute ethanol to obtain a vinyltriethoxysilane solution for later use;
b, adding graphene oxide into an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution, ultrasonically dispersing for 5 hours at 80 ℃, adding a vinyl triethoxy silanol solution, adjusting the pH value to be 4 by using acetic acid, ultrasonically dispersing for 2 hours at 100 ℃, naturally cooling to room temperature, filtering, washing for 4 times by using an ethanol solution with the volume concentration of 45%, and drying at 60 ℃ to obtain siloxane modified graphene;
weighing the raw materials in parts by weight, firstly, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step three, heating the pour point depressant to 55 ℃;
step four, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step five, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step six, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersant additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
Comparative example 2
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide and polydimethylsiloxane according to a mass ratio of 1: 1, preparing;
the manufacturing method comprises the following steps:
step one, preparing modified graphene:
according to the mass ratio of graphene oxide to 50% volume concentration ethanol solution of 1: 10, ultrasonically dispersing graphene oxide in an ethanol solution at 80 ℃, then adding polydimethylsiloxane, adjusting the pH to 4 with acetic acid, ultrasonically dispersing for 2h at 100 ℃, naturally cooling to room temperature, filtering, washing for 4 times with an ethanol solution with the volume concentration of 45%, and drying at 60 ℃ to obtain modified graphene;
weighing the raw materials in parts by weight, firstly, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step three, heating the pour point depressant to 55 ℃;
step four, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step five, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step six, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersing additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene/clean pour point depressant.
Comparative example 3
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polydimethylsiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent adopts vinyl triethoxysilane.
The manufacturing method comprises the following steps:
step one, preparing siloxane modified graphene: step A, mixing vinyl triethoxysilane and absolute ethanol in a mass ratio of 1: 5, dissolving the vinyltriethoxysilane by using absolute ethanol to obtain a vinyltriethoxysilane solution for later use;
step B, according to the mass ratio of graphene oxide to water of 1: 5, ultrasonically dispersing graphene oxide in water at 80 ℃, then adding a vinyl triethoxy silanol solution, adding polydimethylsiloxane, adjusting the pH value to 4 by using acetic acid, ultrasonically dispersing for 2 hours at 100 ℃, naturally cooling to room temperature, filtering, washing for 4 times by using an ethanol solution with the volume concentration of 45%, and drying at 60 ℃ to obtain siloxane modified graphene;
weighing the raw materials in parts by weight, firstly, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step three, heating the pour point depressant to 55 ℃;
step four, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step five, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step six, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersant additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
Comparative example 4
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polydimethylsiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent adopts N-aminoethyl-gamma-aminopropyltriethoxysilane.
The manufacturing method comprises the following steps:
step one, preparing siloxane modified graphene: step A, according to the mass ratio of N-aminoethyl-gamma-aminopropyltriethoxysilane to water of 1: adding N-aminoethyl-gamma-aminopropyltriethoxysilane into water, dispersing uniformly to obtain an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution for later use, and then mixing the N-aminoethyl-gamma-aminopropyltriethoxysilane with absolute ethanol according to the mass ratio of 1: 10 weighing absolute ethyl alcohol for later use;
b, adding graphene oxide into an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution, performing ultrasonic dispersion at 80 ℃ for 5 hours, adding absolute ethyl alcohol, adding polydimethylsiloxane, adjusting the pH to 4 with acetic acid, performing ultrasonic dispersion at 100 ℃ for 2 hours, naturally cooling to room temperature, filtering, washing for 4 times with an ethanol solution with a volume concentration of 45%, and drying at 60 ℃ to obtain siloxane modified graphene;
weighing the raw materials in parts by weight, firstly, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step three, heating the pour point depressant to 55 ℃;
step four, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step five, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step six, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersant additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
Comparative example 5
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polyamide and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent is prepared from vinyl triethoxysilane (A-151) and N-aminoethyl-gamma-aminopropyltriethoxysilane (KH-791) in a mass ratio of 1-3: 1.
The manufacturing method comprises the following steps:
step one, preparing siloxane modified graphene: step A, according to the mass ratio of N-aminoethyl-gamma-aminopropyltriethoxysilane to water of 1: 5, adding the N-aminoethyl-gamma-aminopropyltriethoxysilane into water, and uniformly dispersing to obtain an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution for later use; according to the mass ratio of the vinyltriethoxysilane to the absolute ethyl alcohol of 1: 5, dissolving the vinyltriethoxysilane by using absolute ethanol to obtain a vinyltriethoxysilane solution for later use;
b, adding graphene oxide into an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution, ultrasonically dispersing for 5 hours at 80 ℃, adding a vinyl triethoxy silanol solution, adding polyamide, adjusting the pH value to be 4 by using acetic acid, ultrasonically dispersing for 2 hours at 100 ℃, naturally cooling to room temperature, filtering, washing for 4 times by using an ethanol solution with the volume concentration of 45%, and drying at 60 ℃ to obtain siloxane modified graphene;
weighing the raw materials in parts by weight, firstly, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step three, heating the pour point depressant to 55 ℃;
step four, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step five, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step six, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersant additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
Comparative example 6
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polydimethylsiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent is prepared from vinyl triethoxysilane (A-151) and N-aminoethyl-gamma-aminopropyltriethoxysilane (KH-791) in a mass ratio of 2: 1.
The manufacturing method comprises the following steps:
step one, preparing siloxane modified graphene: step A, according to the mass ratio of N-aminoethyl-gamma-aminopropyltriethoxysilane to water of 1: 5, adding the N-aminoethyl-gamma-aminopropyltriethoxysilane into water, and uniformly dispersing to obtain an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution for later use; according to the mass ratio of the vinyltriethoxysilane to the absolute ethyl alcohol of 1: 5, dissolving the vinyltriethoxysilane by using absolute ethanol to obtain a vinyltriethoxysilane solution for later use;
b, adding graphene oxide into an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution, ultrasonically dispersing for 5 hours at 80 ℃, adding a vinyl triethoxy silanol solution, adding polydimethylsiloxane, adjusting the pH to 4 with phosphoric acid, ultrasonically dispersing for 2 hours at 100 ℃, naturally cooling to room temperature, filtering, washing for 4 times with an ethanol solution with the volume concentration of 45%, and drying at 60 ℃ to obtain siloxane modified graphene;
weighing the raw materials in parts by weight, firstly, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step three, heating the pour point depressant to 55 ℃;
step four, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step five, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step six, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersant additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
Comparative example 7
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polydimethylsiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent is prepared from vinyl triethoxysilane (A-151) and 3-glycidoxypropyltrimethoxysilane (KH-560) in a mass ratio of 2: 1.
The manufacturing method comprises the following steps:
step one, preparing siloxane modified graphene: step A, mixing 3-glycidyl ether oxy-propyl trimethoxy silane and water in a mass ratio of 1: 5, adding 3-glycidoxy propyl trimethoxy silane into water, and uniformly dispersing to obtain a 3-glycidoxy propyl trimethoxy silane water solution for later use; according to the mass ratio of the vinyltriethoxysilane to the absolute ethyl alcohol of 1: 5, dissolving the vinyltriethoxysilane by using absolute ethanol to obtain a vinyltriethoxysilane solution for later use;
b, adjusting the pH value of a 3-glycidyl ether oxypropyltrimethoxysilane aqueous solution to 3.5 by using acetic acid, adding graphene oxide, carrying out ultrasonic dispersion at 80 ℃ for 2 hours, adding a vinyl triethoxy silanol solution, adding polydimethylsiloxane, adjusting the pH value to 4, carrying out ultrasonic dispersion at 100 ℃ for 2 hours, naturally cooling to room temperature, filtering, washing for 4 times by using an ethanol solution with the volume concentration of 45%, and drying at 60 ℃ to obtain siloxane modified graphene;
weighing the raw materials in parts by weight, firstly, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step three, heating the pour point depressant to 55 ℃;
step four, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step five, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step six, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersant additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
Comparative example 8
The lubricating oil based on siloxane modified graphene comprises the following components in parts by weight:
the manufacturing method comprises the following steps:
firstly, weighing raw materials in parts by weight, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step two, heating the pour point depressant to 55 ℃;
step three, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step four, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step five, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the graphene oxide, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersing additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the finished product.
Effect example 1 dispersion stability of siloxane-modified graphene
Modified graphene prepared in example 1 and comparative examples 1 to 8 (graphene oxide is adopted in comparative example 8) is mixed according to a mass ratio of 1: 10, dispersing in Yanshan four-line 650SN base oil, standing for 0 day, 2 days, 4 days, 6 days, 8 days, 10 days and 15 days respectively after uniform ultrasonic dispersion, and observing the agglomeration and precipitation phenomena of the target product lubricating oil; additionally setting a blank control, only adding base oil and not adding any graphene; the results are shown in Table 1;
appearance evaluation criteria:
1. the dispersion is stable, and no agglomeration or precipitation phenomenon exists;
2. the dispersion is stable, and slight agglomeration and precipitation phenomena occur;
3. the dispersion is unstable, and the phenomena of agglomeration and precipitation are obvious;
4. the dispersion is extremely unstable, and serious agglomeration and precipitation phenomena occur;
the data in the table show that the dispersion stability of graphene oxide is different due to different modification methods, and the dispersion stability of modified graphene is significantly affected by different modifiers, different types of silane coupling agents, and whether polysiloxane is used.
Effect example 2 storage stability test:
the method comprises the following steps: after the target product lubricating oils prepared in examples 1 to 3 and comparative examples 1 to 8 were respectively left to stand for 0 day, 15 days, 30 days, 60 days, 180 days and 360 days, the phenomena of delamination and precipitation of the target product lubricating oils were observed, and the results are shown in table 1;
appearance evaluation criteria:
1. the dispersion is stable, and the phenomena of agglomeration, layering and precipitation are avoided;
2. the dispersion is stable, and slight agglomeration, layering and precipitation phenomena occur;
3. the dispersion is unstable, and the phenomena of agglomeration, delamination and precipitation are obvious;
4. the dispersion is extremely unstable, and serious agglomeration, delamination and precipitation phenomena occur;
TABLE 2 lubricating oils prepared in the examples and comparative examples agglomerate, delaminate, and precipitate after storage
As can be seen from the data in the table, the modification methods of graphene oxide are different, the dispersion stability is also different, and the difference of the modifier, the difference of the type of the silane coupling agent, and whether polysiloxane is used have a significant influence on the delamination and precipitation phenomena of the lubricating oil due to the aggregation of graphene.
The embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (2)
1. The lubricating oil based on siloxane modified graphene is characterized by comprising the following components in parts by weight:
the siloxane modified graphene is prepared from graphene oxide, polysiloxane and a silane coupling agent in a mass ratio of 1: 1: 2, preparing the product;
the silane coupling agent is prepared from vinyl triethoxysilane and N-aminoethyl-gamma-aminopropyltriethoxysilane in a mass ratio of 1-3: 1, preparing a composition;
the preparation method of the siloxane modified graphene comprises the following steps:
step 1, mixing N-aminoethyl-gamma-aminopropyltriethoxysilane and water in a mass ratio of 1: 5, adding the N-aminoethyl-gamma-aminopropyltriethoxysilane into water, and uniformly dispersing to obtain an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution for later use; according to the mass ratio of the vinyltriethoxysilane to the absolute ethyl alcohol of 1: 5, dissolving the vinyltriethoxysilane by using absolute ethanol to obtain a vinyltriethoxysilane solution for later use;
step 2, adding graphene oxide into an N-aminoethyl-gamma-aminopropyltriethoxysilane aqueous solution, performing ultrasonic dispersion at 80 ℃ for 5 hours, adding a vinyl triethoxy silanol solution, adding polysiloxane, adjusting the pH to 4 with acetic acid, performing ultrasonic dispersion at 100 ℃ for 2 hours, naturally cooling to room temperature, filtering, washing with an ethanol solution with the volume concentration of 40-50% for 3-5 times, and drying at 60 ℃ to obtain the graphene oxide/silicon dioxide;
in the step 2, the graphene oxide adopts few layers of graphene oxide;
the base oil is prepared from 650SN base oil, 150SN base oil and 150BS base oil according to a mass ratio of 65-75: 5-15: 2-10 are compounded;
the tackifier is prepared from ethylene propylene copolymer and polymethacrylate according to a mass ratio of 3-10: 1 is compounded;
the pour point depressant is a polyethylene-fumarate copolymer;
the detergent is prepared from medium-base-number synthetic calcium sulfonate, high-base-number synthetic calcium sulfonate and sulfurized calcium alkyl phenate according to a mass ratio of 0.5-2.5: 1.5-2.5: 0.1-1.5;
the ashless dispersant is a succinimide dispersant, and the succinimide dispersant is prepared by mixing polyisobutylene bis-succinimide and polyisobutylene polysuccinimide according to the weight ratio of 1.5-3.5: 0.5-1.5;
the antioxidant preservative is prepared from butyl octyl zinc thiophosphate and dioctyl alkaline zinc thiophosphate in a mass ratio of 1-3: 3-6.
2. The method for preparing the lubricating oil based on the siloxane-modified graphene according to claim 1, comprising the following steps:
firstly, weighing raw materials in parts by weight, uniformly mixing different detergents and different ashless dispersants, and preheating to 75 ℃ to obtain a detergent dispersant additive;
step two, heating the pour point depressant to 55 ℃;
step three, uniformly mixing a plurality of antioxidant preservatives, and preheating to 55 ℃;
step four, uniformly mixing a plurality of tackifiers, and preheating to 135 ℃;
and step five, adding the base oil into a blending tank, heating to 75 ℃ under the stirring condition of the rotating speed of 1350 revolutions per minute, sequentially adding the siloxane modified graphene, the preheated tackifier, the preheated pour point depressant, the preheated detergent dispersing additive and the preheated antioxidant preservative, stirring to be uniformly dispersed at 75 ℃, filtering and subpackaging to obtain the modified graphene oxide/silica gel composite material.
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| CN110373251B (en) * | 2019-07-18 | 2021-09-28 | 南京理工大学 | Graphene/lanthanum borate/kaolin composite lubricating oil additive |
| CN110373247B (en) * | 2019-07-18 | 2021-09-21 | 南京理工大学 | Functional graphene/montmorillonite/lanthanum borate composite lubricating oil additive |
| CN110483972A (en) * | 2019-08-09 | 2019-11-22 | 创隆科技有限公司 | Modified plastics and preparation method thereof based on few layer of graphene |
| CN110483971A (en) * | 2019-08-09 | 2019-11-22 | 创隆科技有限公司 | Modified plastics and preparation method thereof based on few layer of graphene |
| CN110607028A (en) * | 2019-09-17 | 2019-12-24 | 创隆科技有限公司 | Modified plastic based on few-layer graphene and preparation method thereof |
| CN110872491B (en) * | 2019-11-22 | 2021-06-29 | 东莞市登喜达表面处理科技有限公司 | Graphene heat conduction oil and preparation method thereof |
| CN112079951B (en) * | 2020-09-01 | 2022-10-11 | 唐山浩昌杰环保科技发展有限公司 | Lubricating oil pour point depressant and preparation method thereof |
| CN115491248A (en) * | 2022-10-19 | 2022-12-20 | 陈梓昊 | Lubricating oil containing modified graphene material and preparation method thereof |
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