CN108559577B - Preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil - Google Patents
Preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil Download PDFInfo
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- CN108559577B CN108559577B CN201810550096.7A CN201810550096A CN108559577B CN 108559577 B CN108559577 B CN 108559577B CN 201810550096 A CN201810550096 A CN 201810550096A CN 108559577 B CN108559577 B CN 108559577B
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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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
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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
- 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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- 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
- C10M2201/04—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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- 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
Abstract
The invention discloses a preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil, which comprises the steps of preparing modified graphene, carrying out surface modification on the modified graphene, carrying out high-speed shearing and ultrahigh-speed grinding on the modified graphene, and finally carrying out dehydration treatment to obtain a finished product; according to the invention, the lipophilic organic matter is coated on the surface of the graphene, so that the two-dimensional layer structure of the graphene can be prevented from being damaged by strong mechanical stirring and grinding, the complete modified graphene with a lower layer number is prepared, the wear-resistant and wear-reducing characteristics of the low-layer graphene are fully exerted, the diisocyanate is connected with the modified graphene of the lipophilic long molecular chain organic amine, the low-layer modified graphene prepared by grinding can be uniformly dispersed in lubricating oil, and re-agglomeration is avoided.
Description
Technical Field
The invention relates to the field of lubricating oil, in particular to a preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil.
Background
Friction is a common problem for moving machinery, from space machinery to ground equipment, from micromachines to ultra-large aircraft carriers, as long as mechanical motion is involved, and friction and wear problems are not involved. With increasingly strict and complex operating conditions of modern machinery and continuously improved requirements on high precision, high reliability and long service life, the requirements on high-performance lubricating materials and technologies for breaking through the performance limit of the original lubricating materials are also increasingly urgent.
The lubricating oil is a mixture which is composed of base oil and various additives and has the functions of lubrication, wear resistance, friction reduction, heat dissipation, cleanness, antioxidation and the like. With the progress of science and technology, mechanical equipment has higher and higher use power and use space, so that the conventional lubricating oil cannot meet the more and more rigorous mechanical friction conditions, and therefore, the lubricating oil is added with functional materials to assist in increasing the lubricating capacity of the lubricating oil, and is one of the research and development directions of high-performance lubricating oil.
The functionalized graphene modified lubricating oil dispersion liquid is a novel wear-resistant energy-saving self-repairing functional lubricating oil product which is guided by the theory of nano-tribology and supported by a nano-material dispersion technology, and has excellent wear-resistant friction-reducing, energy-saving and environment-friendly effects. The nano graphene modified lubricating oil is added into an automobile engine lubricating system, so that the cold start abrasion of an engine can be reduced by more than 50%, the air cylinder sealing performance is improved, and the air cylinder pressure is improved. After the engine uses the nano graphene modified lubricating oil for a period of time, a layer of ultra-hard ultra-thin graphene nano protective film is formed on the cylinder sleeve and the piston ring. In this case, once the lubricating system has a fault of oil leakage, engine oil burning and the like, the automobile can run safely for a long time under the condition that the engine is lack of lubricating oil, which is significant in the fields of civil automobiles and military heavy equipment.
Graphene has a nonpolar multi-layer structure characteristic, single-layer graphene is easy to agglomerate under the action of van der waals force and is difficult to uniformly disperse in the graphene, and the multi-layer graphene structure cannot fully exert the anti-wear and anti-wear characteristics of the graphene, so that the application of the graphene in the lubricating field is limited, and therefore, the difficulty in the prior art is that whether functionalized graphene sheets can be uniformly dispersed in lubricating oil to prepare single-layer or low-layer functionalized graphene lubricating oil. The uniformly dispersed functionalized graphene suspension dispersion lubricating oil has to meet the conditions of destroying the long fiber entanglement bonding state, overcoming the strong adsorption force of aggregates and stabilizing the dispersion state of carbon nano materials, and the solving methods generally comprise three methods: firstly, a dispersing machine with ultrahigh rotating speed (1400rpm) is used for inputting and dispersing a large amount of energy, and the principle is that a high-speed stirrer can form strong turbulence locally, so that the dispersing and emulsifying device has strong dispersing and emulsifying effects on materials; secondly, an ultra-high speed (13000rpm) colloid mill is adopted, and the ultra-high speed colloid mill generates great shearing force through the relative motion of a stator and a rotor so as to instantly disperse the nano carbon material in the lubricating oil after grinding; and thirdly, performing energy conversion on the graphene which is a carbon nano material by adopting a continuous ultrasonic dispersion machine and adopting ultrasonic waves with different powers so as to achieve the purpose of dispersing the graphene carbon nano material.
However, the two-dimensional lamellar structure of graphene is easily destroyed by adopting strong mechanical dispersion, and the graphene is still agglomerated again after dispersion, so that the graphene is difficult to be completely and uniformly dispersed in the lubricating oil by adopting a high-strength and high-energy physical mechanical dispersion method.
Disclosure of Invention
The invention provides a preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil, aiming at the problems that graphene in the existing prepared graphene lubricating oil is incomplete in structure and easy to agglomerate.
The technical scheme for solving the technical problems is as follows: a preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil is characterized by comprising the following steps:
A. preparation of diisocyanate-modified graphene
A1 preparation of graphite oxide by in-situ synthesis
Slowly adding 10g of 200-mesh natural crystalline flake graphite into a 2000ml big beaker filled with 230ml of concentrated sulfuric acid under stirring, keeping the temperature change at (0 +/-1) DEG C, slowly adding a mixture of 5g of sodium nitrate and 30g of potassium permanganate, reacting for 2h in a constant-temperature water bath of (35 +/-3) DEG C, keeping the temperature for 30min under stirring, slowly adding 460ml of water, adjusting the temperature of the water bath to 98 ℃, keeping for 15min, diluting to 1400ml with warm water, adding 5-10ml of 5wt% hydrogen peroxide, standing for 20-24h, filtering, fully washing a filter cake for 5-6 times with 5% hydrochloric acid until sulfate ions in a filtrate cannot be detected by using a barium chloride solution, repeatedly centrifugally washing the obtained substance to a neutral supernatant by using deionized water, and drying in a vacuum drying box at 35-40 ℃ to obtain graphite oxide;
a2 modification of diisocyanate
Weighing 1g of graphite oxide obtained in the step A1, putting the graphite oxide into 250ml of DMAC (dimethylacetamide), carrying out ultrasonic treatment for 1.5-2h under the ultrasonic power of 200-85W, transferring the graphite oxide into a water bath kettle at the temperature of 80-85 ℃, adding 8 g of diisocyanate, carrying out constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to 60-65 ℃, adding 5g of phenylhydrazine, continuing the constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to room temperature, filtering, washing with dichloromethane for 2-3 times, and drying in a vacuum drying box at the temperature of 35-40 ℃ to obtain diisocyanate modified graphene;
B. surface modification diisocyanate modified graphene
B, carrying out infiltration reaction on the diisocyanate modified graphene obtained in the step A in an alcoholic solution of organic amine for 10 hours, carrying out centrifugal filtration on the suspension, and carrying out vacuum-pumping drying to obtain modified graphene with diisocyanate connected with a lipophilic organic amine long molecular chain;
C. high shear mixing preliminary dispersion
Mixing the surface-modified diisocyanate modified graphene obtained in the step B with commercially available SN 5w-40 lubricating oil, adding the mixture into a stainless steel reaction kettle with a stirring and high-speed serrated high-speed dispersing machine, heating a reaction kettle jacket to 50-80 ℃ by adopting heat conducting oil, starting a main stirrer of the reaction kettle, enabling the rotating speed of the stirrer to be 48rpm, stirring for 30-60min, adding an auxiliary dispersing agent into the reaction kettle according to 0.5-5% of the weight of the lubricating oil, stirring for 30-60min at a constant speed, adding a suspension stabilizer into the reaction kettle according to 0.5-2.5% of the weight of the lubricating oil, stirring for 10-30min at a constant speed, starting the high-speed dispersing machine, gradually adjusting the rotating speed of the dispersing machine to 2800rpm, strongly pre-dispersing the modified graphene in the lubricating oil, and continuously stirring for 8 h;
D. ultra high speed colloid mill dispersion
C, connecting the reaction kettle containing the preliminarily dispersed diisocyanate modified graphene lubricating oil in the step C with an ultrahigh-speed colloid mill through a circulating motor, starting the motor, gradually increasing the rotating speed of the ultrahigh-speed colloid mill to 14000rpm through a motor frequency converter, and carrying out ultrahigh-speed grinding dispersion on the diisocyanate modified graphene lubricating oil for 3-5 hours;
E. preparation of diisocyanate modified graphene antiwear energy-saving lubricating oil
Putting the diisocyanate modified graphene lubricating oil into a precipitation tank for isolation precipitation, recovering large-particle solid-phase substances for next-batch ultrahigh-speed grinding and dispersion, passing the isolation solution through a two-pole ultrasonic generator connected in series, controlling the ultrasonic frequency to be 20Hz, the power to be 500 plus 1400W, the flow to be 2-8L/min and the ultrasonic temperature to be 0-12 ℃, finally carrying out vacuum-pumping dehydration and defoaming on the ultrasonically dispersed graphene lubricating oil in a vacuum machine at the temperature of 120 plus 180 ℃, and cooling to normal temperature for filtration to obtain the diisocyanate modified graphene anti-wear energy-saving lubricating oil.
The diisocyanate in the step A2 is one of IPDI, MDI or HDI.
And the alcoholic solution of the organic amine in the step B is a polyvinyl alcohol aqueous solution of methyl ethanolamine or an isopropanol solution of triethanolamine.
And C, the weight ratio of the surface modified diisocyanate modified graphene to the commercially available SN 5w-40 lubricating oil in the step C is 1:100-1: 40.
In the step C, the auxiliary dispersing agent is one of succinimide, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide; the suspension stabilizer is one of polyvinylpyrrolidone, calcium dodecyl petroleum sulfonate and sodium isooctyl succinate.
The rotation speed of the dispersion machine in step C is 1400-2800 rpm.
The invention has the beneficial effects that:
1) compared with the method of directly using the commercially available graphene oxide, the method of preparing the graphene oxide by using the in-situ synthesis method has the advantages that the self-made graphite oxide can ensure that the graphite oxide has uniform granularity and uniform lamellar structure, and the quality of subsequent reaction products is ensured;
2) according to the invention, diisocyanate is used for modifying graphene, and a layer of organic matter is coated on the surface of graphene, so that the damage to the two-dimensional layer structure of graphene caused by powerful mechanical stirring and grinding can be avoided, and thus the complete modified graphene with lower layers is prepared, and the characteristics of wear resistance and wear reduction of the graphene with low layers are fully exerted;
3) according to the invention, the surface modification is carried out on the diisocyanate modified graphene to prepare the modified graphene with the diisocyanate connected with the lipophilic long molecular chain, so that the low-layer modified graphene prepared by grinding can be uniformly dispersed in lubricating oil, and re-agglomeration is avoided;
4) the modified graphene lubricating oil is prepared by combining chemical modification and physical dispersion, and the modified graphene in the lubricating oil has the advantages of complete structure, low layer number, uniform and stable dispersion, so that the lubricating oil has a long-acting lubricating effect.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
A preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil comprises the following steps:
A. preparation of diisocyanate-modified graphene
A1 preparation of graphite oxide by in-situ synthesis
Slowly adding 10g of 200-mesh natural crystalline flake graphite into a 2000ml big beaker filled with 230ml of concentrated sulfuric acid under stirring, keeping the temperature change at (0 +/-1) DEG C, slowly adding a mixture of 5g of sodium nitrate and 30g of potassium permanganate, reacting for 2h in a constant-temperature water bath of (35 +/-3) DEG C, keeping the temperature for 30min under stirring, slowly adding 460ml of water, adjusting the temperature of the water bath to 98 ℃, keeping for 15min, diluting to 1400ml with warm water, adding 5-10ml of 5wt% hydrogen peroxide, standing for 20-24h, filtering, fully washing a filter cake for 5-6 times with 5% hydrochloric acid until sulfate ions in a filtrate cannot be detected by using a barium chloride solution, repeatedly centrifugally washing the obtained substance to a neutral supernatant by using deionized water, and drying in a vacuum drying box at 35-40 ℃ to obtain graphite oxide;
a2 modification of diisocyanate
Weighing 1g of graphite oxide obtained in the step A1, putting the graphite oxide into 250ml of DMAC (dimethylacetamide), carrying out ultrasonic treatment for 1.5-2h under the ultrasonic power of 200-250W, transferring the graphite oxide into a water bath kettle at the temperature of 80-85 ℃, adding 8 g of IPDI (isophorone diisocyanate), carrying out constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to 60-65 ℃, adding 5g of phenylhydrazine, continuing the constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to room temperature, filtering, washing with dichloromethane for 2-3 times, and drying in a vacuum drying box at the temperature of 35-40 ℃ to obtain diisocyanate modified graphene;
B. surface modification diisocyanate modified graphene
B, carrying out infiltration reaction on the diisocyanate modified graphene obtained in the step A in a polyvinyl alcohol aqueous solution of methyl ethanolamine for 10 hours, carrying out centrifugal filtration on the suspension, and carrying out vacuum pumping and drying to obtain modified graphene with diisocyanate connected with a lipophilic organic amine long molecular chain;
C. high shear mixing preliminary dispersion
Mixing the surface-modified diisocyanate modified graphene obtained in the step B with commercially available SN 5w-40 lubricating oil according to a mass ratio of 1:100, adding the mixture into a stainless steel reaction kettle with a stirring and high-speed serrated high-speed dispersion machine, heating a reaction kettle jacket to 50-80 ℃ by adopting heat conducting oil, starting a main stirrer of the reaction kettle, rotating the stirrer at 48rpm, stirring for 30min, adding a dispersion aid succinimide into the reaction kettle according to 0.5 percent of the weight of the lubricating oil, stirring for 30min at a constant speed, adding a suspension stabilizer polyvinylpyrrolidone into the reaction kettle according to 0.5 percent of the weight of the lubricating oil, stirring for 10min at a constant speed, starting the high-speed dispersion machine, gradually adjusting the rotating speed of the dispersion machine to 1400rpm, strongly pre-dispersing the modified graphene in the lubricating oil, and continuously stirring for 8 h;
D. ultra high speed colloid mill dispersion
C, connecting the reaction kettle containing the preliminarily dispersed diisocyanate modified graphene lubricating oil in the step C with an ultrahigh-speed colloid mill through a circulating motor, starting the motor, gradually increasing the rotating speed of the ultrahigh-speed colloid mill to 14000rpm through a motor frequency converter, and carrying out ultrahigh-speed grinding dispersion on the diisocyanate modified graphene lubricating oil for 3-5 hours;
E. preparation of diisocyanate modified graphene antiwear energy-saving lubricating oil
Putting the diisocyanate modified graphene lubricating oil into a precipitation tank for isolation precipitation, recovering large-particle solid-phase substances for next-batch ultrahigh-speed grinding and dispersion, passing the isolation solution through a two-pole ultrasonic generator connected in series, controlling the ultrasonic frequency to be 20Hz, the power to be 500 plus 1400W, the flow to be 2-8L/min and the ultrasonic temperature to be 0-12 ℃, finally carrying out vacuum-pumping dehydration and defoaming on the ultrasonically dispersed graphene lubricating oil in a vacuum machine at the temperature of 120 plus 180 ℃, and cooling to normal temperature for filtration to obtain the diisocyanate modified graphene anti-wear energy-saving lubricating oil.
Example 2
A preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil comprises the following steps:
A. preparation of diisocyanate-modified graphene
A1 preparation of graphite oxide by in-situ synthesis
Slowly adding 10g of 200-mesh natural crystalline flake graphite into a 2000ml big beaker filled with 230ml of concentrated sulfuric acid under stirring, keeping the temperature change at (0 +/-1) DEG C, slowly adding a mixture of 5g of sodium nitrate and 30g of potassium permanganate, reacting for 2h in a constant-temperature water bath of (35 +/-3) DEG C, keeping the temperature for 30min under stirring, slowly adding 460ml of water, adjusting the temperature of the water bath to 98 ℃, keeping for 15min, diluting to 1400ml with warm water, adding 5-10ml of 5wt% hydrogen peroxide, standing for 20-24h, filtering, fully washing a filter cake for 5-6 times with 5% hydrochloric acid until sulfate ions in a filtrate cannot be detected by using a barium chloride solution, repeatedly centrifugally washing the obtained substance to a neutral supernatant by using deionized water, and drying in a vacuum drying box at 35-40 ℃ to obtain graphite oxide;
a2 modification of diisocyanate
Weighing 1g of graphite oxide obtained in the step A1, putting the graphite oxide into 250ml of DMAC (dimethylacetamide), carrying out ultrasonic treatment for 1.5-2h under the ultrasonic power of 200-250W, transferring the graphite oxide into a water bath kettle at the temperature of 80-85 ℃, adding 8 g of MDI (diphenylmethane diisocyanate), carrying out constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to 60-65 ℃, adding 5g of phenylhydrazine, continuing the constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to room temperature, filtering, washing with dichloromethane for 2-3 times, and drying in a vacuum drying box at the temperature of 35-40 ℃ to obtain diisocyanate modified graphene;
B. surface modification diisocyanate modified graphene
B, carrying out infiltration reaction on the diisocyanate modified graphene obtained in the step A in an isopropanol solution of triethanolamine for 10 hours, carrying out centrifugal filtration on the suspension, and carrying out vacuum pumping and drying to obtain modified graphene with diisocyanate connected with a lipophilic organic amine long molecular chain;
C. high shear mixing preliminary dispersion
Mixing the surface-modified diisocyanate modified graphene obtained in the step B with commercially available SN 5w-40 lubricating oil according to a mass ratio of 1:70, adding the mixture into a stainless steel reaction kettle with a stirring and high-speed serrated high-speed dispersion machine, heating a reaction kettle jacket to 50-80 ℃ by adopting heat conducting oil, starting a main stirrer of the reaction kettle, rotating the stirrer at 48rpm, stirring for 45min, adding sodium dodecyl sulfate serving as a dispersion aid into the reaction kettle according to 2.2% of the weight of the lubricating oil, stirring for 45min at a constant speed, adding calcium dodecyl petroleum sulfonate serving as a suspension stabilizer into the reaction kettle according to 1.5% of the weight of the lubricating oil, stirring for 20min at a constant speed, starting the high-speed dispersion machine, gradually adjusting the speed of the dispersion machine to 2100rpm, strongly pre-dispersing the modified graphene in the lubricating oil, and continuously stirring for 8 h;
D. ultra high speed colloid mill dispersion
C, connecting the reaction kettle containing the preliminarily dispersed diisocyanate modified graphene lubricating oil in the step C with an ultrahigh-speed colloid mill through a circulating motor, starting the motor, gradually increasing the rotating speed of the ultrahigh-speed colloid mill to 14000rpm through a motor frequency converter, and carrying out ultrahigh-speed grinding dispersion on the diisocyanate modified graphene lubricating oil for 3-5 hours;
E. preparation of diisocyanate modified graphene antiwear energy-saving lubricating oil
Putting the diisocyanate modified graphene lubricating oil into a precipitation tank for isolation precipitation, recovering large-particle solid-phase substances for next-batch ultrahigh-speed grinding and dispersion, passing the isolation solution through a two-pole ultrasonic generator connected in series, controlling the ultrasonic frequency to be 20Hz, the power to be 500 plus 1400W, the flow to be 2-8L/min and the ultrasonic temperature to be 0-12 ℃, finally carrying out vacuum-pumping dehydration and defoaming on the ultrasonically dispersed graphene lubricating oil in a vacuum machine at the temperature of 120 plus 180 ℃, and cooling to normal temperature for filtration to obtain the diisocyanate modified graphene anti-wear energy-saving lubricating oil.
Example 3
A preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil comprises the following steps:
A. preparation of diisocyanate-modified graphene
A1 preparation of graphite oxide by in-situ synthesis
Slowly adding 10g of 200-mesh natural crystalline flake graphite into a 2000ml big beaker filled with 230ml of concentrated sulfuric acid under stirring, keeping the temperature change at (0 +/-1) DEG C, slowly adding a mixture of 5g of sodium nitrate and 30g of potassium permanganate, reacting for 2h in a constant-temperature water bath of (35 +/-3) DEG C, keeping the temperature for 30min under stirring, slowly adding 460ml of water, adjusting the temperature of the water bath to 98 ℃, keeping for 15min, diluting to 1400ml with warm water, adding 5-10ml of 5wt% hydrogen peroxide, standing for 20-24h, filtering, fully washing a filter cake for 5-6 times with 5% hydrochloric acid until sulfate ions in a filtrate cannot be detected by using a barium chloride solution, repeatedly centrifugally washing the obtained substance to a neutral supernatant by using deionized water, and drying in a vacuum drying box at 35-40 ℃ to obtain graphite oxide;
a2 modification of diisocyanate
Weighing 1g of graphite oxide obtained in the step A1, putting the graphite oxide into 250ml of DMAC (dimethylacetamide), carrying out ultrasonic treatment for 1.5-2h under the ultrasonic power of 200-85W, transferring the graphite oxide into a water bath kettle at the temperature of 80-85 ℃, adding 8 g of HDI, carrying out constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to 60-65 ℃, adding 5g of phenylhydrazine, continuing the constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to room temperature, filtering, washing with dichloromethane for 2-3 times, and drying in a vacuum drying box at the temperature of 35-40 ℃ to obtain diisocyanate modified graphene;
B. surface modification diisocyanate modified graphene
B, carrying out infiltration reaction on the diisocyanate modified graphene obtained in the step A in an isopropanol solution of triethanolamine for 10 hours, carrying out centrifugal filtration on the suspension, and carrying out vacuum pumping and drying to obtain modified graphene with diisocyanate connected with a lipophilic organic amine long molecular chain;
C. high shear mixing preliminary dispersion
Mixing the surface-modified diisocyanate modified graphene obtained in the step B with commercially available SN 5w-40 lubricating oil according to the mass ratio of 1:40, adding the mixture into a stainless steel reaction kettle with a stirring and high-speed serrated high-speed dispersion machine, heating the jacket of the reaction kettle to 50-80 ℃ by adopting heat conducting oil, starting a main stirrer of the reaction kettle, stirring for 60min at the rotating speed of 48rpm of the stirrer, adding the auxiliary dispersant cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium bromide into a reaction kettle according to 5 percent of the weight of the lubricating oil, stirring at constant speed for 60min, adding suspension stabilizer sodium isooctyl succinate 2.5 wt% of lubricating oil into the reaction kettle, stirring at a constant speed for 30min, starting a high-speed dispersion machine, gradually adjusting the speed of the dispersion machine to 2800rpm, strongly pre-dispersing the modified graphene in the lubricating oil, and continuously stirring for 8 h;
D. ultra high speed colloid mill dispersion
C, connecting the reaction kettle containing the preliminarily dispersed diisocyanate modified graphene lubricating oil in the step C with an ultrahigh-speed colloid mill through a circulating motor, starting the motor, gradually increasing the rotating speed of the ultrahigh-speed colloid mill to 14000rpm through a motor frequency converter, and carrying out ultrahigh-speed grinding dispersion on the diisocyanate modified graphene lubricating oil for 3-5 hours;
E. preparation of diisocyanate modified graphene antiwear energy-saving lubricating oil
Putting the diisocyanate modified graphene lubricating oil into a precipitation tank for isolation precipitation, recovering large-particle solid-phase substances for next-batch ultrahigh-speed grinding and dispersion, passing the isolation solution through a two-pole ultrasonic generator connected in series, controlling the ultrasonic frequency to be 20Hz, the power to be 500 plus 1400W, the flow to be 2-8L/min and the ultrasonic temperature to be 0-12 ℃, finally carrying out vacuum-pumping dehydration and defoaming on the ultrasonically dispersed graphene lubricating oil in a vacuum machine at the temperature of 120 plus 180 ℃, and cooling to normal temperature for filtration to obtain the diisocyanate modified graphene anti-wear energy-saving lubricating oil.
The diisocyanate modified graphene anti-wear energy-saving lubricating oil obtained in examples 1 to 3 is characterized by a high-power scanning transmission electron microscope, and it is found that the number of diisocyanate modified graphene layers in the obtained lubricating oil is within 7, the content of 5 layers is not less than 40%, the content of a single layer is not less than 20%, the average length of the diisocyanate modified graphene layers is 1 μm, the average width is 400nm, and the shape is complete and uniform in distribution.
The diisocyanate modified graphene antiwear energy-saving lubricating oil obtained in examples 1-3 was subjected to antiwear and energy-saving performance tests on an SD-2000 abrasion tester, and the data are shown in tables 1, 2 and 3.
TABLE 1 comparison of the wear-resistant and wear-resistant tests of the diisocyanate-modified graphene anti-wear and energy-saving lubricating oil obtained in example 1
Table 2 comparison of oil consumption, abrasion resistance and noise reduction of diisocyanate modified graphene abrasion-resistant energy-saving lubricating oil vehicle obtained in example 2
Note: the test vehicles all kept driving at a constant speed of 110km/h for 1000km (constant speed cruise).
Table 3 comparison of power and electricity consumption of the diisocyanate modified graphene antiwear energy-saving lubricating oil speed reducer obtained in example 3
As can be seen from tables 1 to 3, when the diisocyanate-modified graphene anti-wear energy-saving lubricating oil synthesized by the metal wear testing machine, the actual driving experiment and the actual heavy-load speed reducer using experiment is compared with the conventional engine oil and industrial gear oil in the market, the extreme pressure anti-wear and anti-wear effects are obviously improved, the PB/PD value is increased, which indicates that the anti-wear lubricating performance is improved, the friction coefficient/wear scar diameter is reduced, which indicates that the energy-saving, oil-saving and power-saving performance of the lubricating oil is improved, the power and electricity consumption of the speed reducer are obviously reduced, the average of the vehicle is reduced, and the anti-wear and noise-reduction performance is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil is characterized by comprising the following steps:
A. preparation of diisocyanate-modified graphene
A1 preparation of graphite oxide by in-situ synthesis
Slowly adding 10g of 200-mesh natural crystalline flake graphite into a 2000ml big beaker filled with 230ml of concentrated sulfuric acid under stirring, keeping the temperature change at (0 +/-1) DEG C, slowly adding a mixture of 5g of sodium nitrate and 30g of potassium permanganate, reacting for 2h in a constant-temperature water bath of (35 +/-3) DEG C, keeping the temperature for 30min under stirring, slowly adding 460ml of water, adjusting the temperature of the water bath to 98 ℃, keeping for 15min, diluting to 1400ml with warm water, adding 5-10ml of 5wt% hydrogen peroxide, standing for 20-24h, filtering, fully washing a filter cake for 5-6 times with 5% hydrochloric acid until sulfate ions in a filtrate cannot be detected by using a barium chloride solution, repeatedly centrifugally washing the obtained substance to a neutral supernatant by using deionized water, and drying in a vacuum drying box at 35-40 ℃ to obtain graphite oxide;
a2 modification of diisocyanate
Weighing 1g of graphite oxide obtained in the step A1, putting the graphite oxide into 250ml of DMAC (dimethylacetamide), carrying out ultrasonic treatment for 1.5-2h under the ultrasonic power of 200-85W, transferring the graphite oxide into a water bath kettle at the temperature of 80-85 ℃, adding 8 g of diisocyanate, carrying out constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to 60-65 ℃, adding 5g of phenylhydrazine, continuing the constant-temperature magnetic stirring reaction for 4-6h, reducing the temperature to room temperature, filtering, washing with dichloromethane for 2-3 times, and drying in a vacuum drying box at the temperature of 35-40 ℃ to obtain diisocyanate modified graphene;
B. surface modification diisocyanate modified graphene
B, carrying out infiltration reaction on the diisocyanate modified graphene obtained in the step A in an alcoholic solution of organic amine for 10 hours, carrying out centrifugal filtration on the suspension, and carrying out vacuum-pumping drying to obtain modified graphene with diisocyanate connected with a lipophilic organic amine long molecular chain;
C. high shear mixing preliminary dispersion
Mixing the surface modified diisocyanate graphene obtained in the step B with commercially available SN 5w-40 lubricating oil, adding the mixture into a stainless steel reaction kettle with a stirring and high-speed serrated high-speed dispersing machine, heating a reaction kettle jacket to 50-80 ℃ by adopting heat conducting oil, starting a main stirrer of the reaction kettle, enabling the rotating speed of the stirrer to be 48rpm, stirring for 30-60min, adding an auxiliary dispersing agent into the reaction kettle according to 0.5-5% of the weight of the lubricating oil, stirring for 30-60min at a constant speed, adding a suspension stabilizer into the reaction kettle according to 0.5-2.5% of the weight of the lubricating oil, stirring for 10-30min at a constant speed, starting the high-speed dispersing machine, gradually adjusting the rotating speed of the dispersing machine to 1400-2800rpm, strongly pre-dispersing the modified graphene in the lubricating oil, and continuously stirring for 8 h;
D. ultra high speed colloid mill dispersion
C, connecting the reaction kettle containing the preliminarily dispersed diisocyanate modified graphene lubricating oil in the step C with an ultrahigh-speed colloid mill through a circulating motor, starting the motor, gradually increasing the rotating speed of the ultrahigh-speed colloid mill to 14000rpm through a motor frequency converter, and carrying out ultrahigh-speed grinding dispersion on the diisocyanate modified graphene lubricating oil for 3-5 hours;
E. preparation of diisocyanate modified graphene antiwear energy-saving lubricating oil
Putting the diisocyanate modified graphene lubricating oil into a precipitation tank for isolation precipitation, recovering large-particle solid-phase substances for next-batch ultrahigh-speed grinding and dispersion, passing the isolation solution through two-stage ultrasonic generators connected in series, controlling the ultrasonic frequency to be 20Hz, the power to be 500 plus 1400W, the flow to be 2-8L/min and the ultrasonic temperature to be 0-12 ℃, finally vacuumizing, dehydrating and defoaming the graphene lubricating oil subjected to ultrasonic dispersion in a vacuum machine at the temperature of 120 plus 180 ℃, and cooling to normal temperature for filtration to obtain the diisocyanate modified graphene anti-wear energy-saving lubricating oil.
2. The method for preparing the diisocyanate-modified graphene antiwear energy-saving lubricating oil according to claim 1, wherein the diisocyanate in the step A2 is one of IPDI, MDI or HDI.
3. The preparation method of the diisocyanate-modified graphene antiwear energy-saving lubricating oil according to claim 1, wherein the alcoholic solution of the organic amine in the step B is a polyvinyl alcohol aqueous solution of methyl ethanolamine or an isopropanol solution of triethanolamine.
4. The preparation method of the diisocyanate modified graphene antiwear energy-saving lubricating oil according to claim 1, wherein the weight ratio of the surface modified diisocyanate modified graphene in the step C to the commercially available SN 5w-40 lubricating oil is 1:100-1: 40.
5. The method for preparing the diisocyanate-modified graphene antiwear energy-saving lubricating oil according to claim 1, wherein the dispersion aid in step C is one of succinimide, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide.
6. The method for preparing the diisocyanate-modified graphene antiwear energy-saving lubricating oil according to claim 1, wherein the suspension stabilizer in step C is one of polyvinylpyrrolidone, calcium dodecyl petroleum sulfonate and sodium isooctyl succinate.
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