CN108559577A - A kind of preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil - Google Patents
A kind of preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil Download PDFInfo
- Publication number
- CN108559577A CN108559577A CN201810550096.7A CN201810550096A CN108559577A CN 108559577 A CN108559577 A CN 108559577A CN 201810550096 A CN201810550096 A CN 201810550096A CN 108559577 A CN108559577 A CN 108559577A
- Authority
- CN
- China
- Prior art keywords
- modified graphene
- diisocyanate
- energy
- lubricating oil
- antiwear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of preparation methods of diisocyanate modified graphene antiwear and energy-saving lubricant oil, including prepare modified graphene and be surface modified to it, are ground to modified graphene high speed shear and ultrahigh speed, last dehydration finished product；The present invention coats one layer of lipophilic organic matter on the surface of graphene, it can avoid the two-dimensional layer structure of the mechanical agitation and grinding destruction graphene of strength, to prepare, the number of plies is relatively low and complete modified graphene, give full play to the characteristic of low layer number graphene antiwear and reducing friction, diisocyanate is connected with the modified graphene of lipophile long chain organic amine, low layer number modified graphene made from grinding can be made evenly dispersed in lubricating oil, it avoids reuniting again, the present invention prepares modified graphene lubricating oil in such a way that chemical modification and physical dispersion are combined, modified graphene structural integrity in lubricating oil, the number of plies is low, it is uniformly dispersed and stablizes, make lubricating oil that there is the lubricant effect of antiwear and energy-saving.
Description
Technical field
The present invention relates to lubricating oil field more particularly to a kind of diisocyanate modified graphene antiwear and energy-saving lubricant oils
Preparation method.
Background technology
Friction is the common problem of movable machinery, from space mechanism to land equipment, from micromachine to ultra-large type aviation
Mother ship carrier is related to friction and wear problem invariably as long as being related to mechanical movement.It is more and more severe with the operating condition of modern mechanical
It carves, high-precision, high reliability and the requirement in terms of the long-life that condition becomes increasingly complex and constantly promoted, it is original to breaking through
The high-performance lubriation material of lubriation material performance boundary and the demand of technology are also more and more urgent.
Lubricating oil be a kind of one kind being made of base oil and various additives have lubrication, wear-resistant, anti-attrition, heat dissipation,
The functions such as peace and quiet, antioxygen are in the mixture of one.With the progress of science and technology, mechanical equipment uses work(with higher and higher
Rate and use space so that traditional lubrication oil cannot be satisfied increasingly harsher mechanical friction condition and therefore add in lubricating oil
Add functional material, auxiliary to increase the lubricating ability of lubricating oil, is one of high perofmrnace lubricating oils R＆D direction.
Functionalization graphene modification of lubricating oils dispersion liquid is to disperse skill using Nanotribology as theoretical direction, with nano material
Art is a kind of novel antiwear and energy-saving self-repair function lube product of support, it has excellent antiwear and antifriction and energy-saving ring
Protect effect.Nano-graphene modification of lubricating oils is added in car engine lubrication system, the cold start-up mill of engine can be reduced
50% or more damage increases cylinder seal and improves cylinder pressure.Engine uses nano-graphene modification of lubricating oils for a period of time
Afterwards, one layer of superhard ultra-thin graphene nano protective film is just formed on cylinder liner-piston group.At this point, oil leak once occurs for lubricating system
The failures such as burn oil, in the case where engine lacks lubricating oil, automobile can also drive safely a very long time, this is civilian
It is meaningful on automobile and military jumbo field.
Graphene has nonpolar multilayered structure characteristic, and single-layer graphene is easy to that group occurs under van der Waals interaction
Poly- phenomenon, it is difficult to uniform dispersion wherein, multi-layer graphene structure cannot be complete the characteristic of the antiwear and reducing friction of graphene
It brings into play, limits its application in lubricating area, therefore lubrication can be dispersed in by functionalization graphene thin slice is homogeneous
The functionalization graphene lubricating oil of obtained single layer or low layer number is the difficult point of the prior art in oil.Obtain evenly dispersed work(
Energy graphite alkene suspended dispersed lubricating oil must satisfy condition:Long fibre is destroyed to tangle bond state, aggregate is overcome to adsorb by force
Power stablizes carbon nanomaterial dispersity, there are three types of the method for solution is usual：First, with ultrahigh rotating speed (1400rpm) dispersion machine
A large amount of energy input dispersions are carried out, principle is can be partially formed very strong turbulent flow using high speed agitator, usually to object
Material has very strong dispersion and emulsion effect；Second is that using ultrahigh speed (13000rpm) colloid mill, ultrahigh speed colloid mill by stator and
The relative motion of rotor generates great shearing force to instantaneous dispersing after the nano carbon material abrasive lapping in lubricating oil；Third, adopting
With continuous ultrasonic dispersion machine, energy conversion is carried out to carbon nanomaterial graphene using the ultrasonic wave of different capacity, to reach
To the purpose of dispersed graphite olefinic carbon nano material.
But be easy to destroy the two-dimensional slice structure of graphene using the mechanical dispersion of strength, and after dispersion still
It can reunite again, be difficult merely completely, equably by graphene using high-strength, high energy physical mechanical dispersing method therefore
It is homogeneous to be distributed in lubricating oil.
Invention content
The present invention is imperfect for graphene-structured in the graphene lubricating oil of existing preparation and the problem of being easy to reunite, carries
For a kind of preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of diisocyanate modified graphene antiwear and energy-saving
The preparation method of lubricating oil, which is characterized in that include the following steps：
A, diisocyanate modified graphene is prepared
A1, in-situ synthesis prepare graphite oxide
200 mesh natural flake graphites of 10g are added slowly with stirring the big of the 2000ml equipped with the 230ml concentrated sulfuric acids
In beaker, temperature change maintains (0 ± 1) DEG C, is slow added into the mixture of 5g sodium nitrate and 30g potassium permanganate, (35 ±
3) 2h is reacted in DEG C water bath with thermostatic control, is stirred lower heat preservation 30min, is slowly added to 460ml water, adjusts bath temperature and rise to 98 DEG C,
And 15min is maintained, it is diluted to 1400ml with warm water, the hydrogen peroxide of 5-10ml 5wt% is added, is filtered after standing 20-24h, is used
5% hydrochloric acid fully washs filter cake 5-6 times, until the sulfate ion in filtrate is not measured with barium chloride solution inspection, by gains
Matter is centrifuged repeatedly washing to supernatant to neutrality with deionized water again, is placed in drying in 35-40 DEG C of vacuum drying chamber, is aoxidized
Graphite；
A2, diisocyanate are ester modified
Graphite oxide obtained by 1g steps A1 is weighed to be put into 250ml DMAC, it is ultrasonic under the ultrasonic power of 200-250W
1.5-2h is transferred in 80-85 DEG C of water-bath, and 8 grams of diisocyanate are added, and temperature constant magnetic stirring reacts 4-6h, reduces temperature
To 60-65 DEG C, 5 grams of phenylhydrazines are added, continues temperature constant magnetic stirring and reacts 4-6h, reduce temperature to room temperature, dichloromethane is used in filtering
Washing 2-3 times is placed in 35-40 DEG C of vacuum drying chamber dry, obtained diisocyanate modified graphene；
B, surface modification diisocyanate modified graphene
Diisocyanate modified graphene obtained by step A is subjected to Host range 10h in the alcoholic solution of organic amine, will be hanged
Supernatant liquid passes through centrifugal filtration, and the modification stone that diisocyanate is connected with lipophile organic amine long chain is made after vacuum drying
Black alkene；
C, the preliminary dispersion of high speed shear mixing
Add after the diisocyanate modified graphene of surface modification obtained by step B is mixed with commercially available SN 5w-40 lubricating oil
Enter into the stainless steel cauldron with stirring and high speed zigzag high speed dispersor, reacting kettle jacketing is arrived using heat-conducting oil heating
50-80 DEG C, reaction kettle main agitator is started, dispersion aids after stirring 30-60min, is pressed lubricating oil by agitator speed 48rpm
The 0.5-5% of weight is added in reaction kettle, after at the uniform velocity stirring 30-60min, then by suspension stabilizer by lubrication weight of oil
0.5-2.5% is added in reaction kettle, after at the uniform velocity stirring 10-30min, high speed dispersor is started, gradually by the rotating speed of dispersion machine
2800rpm is adjusted, it is strong pre-dispersed to the modified graphene progress in lubricating oil, persistently stir 8h；
D, ultrahigh speed colloid mill disperses
The reaction kettle that the diisocyanate modified graphene lubricating oil tentatively disperseed is filled in step C is passed through into circulation motor
It is connected with ultrahigh speed colloid mill, starts motor, be gradually promoted to ultrahigh speed colloid mill rotating speed by motor inverter
14000rpm carries out ultrahigh speed grinding distribution 3-5h to diisocyanate modified graphene lubricating oil；
E, diisocyanate modified graphene antiwear and energy-saving lubricant oil is prepared
Diisocyanate modified graphene lubricating oil is put into precipitation tank and carries out isolation precipitation, recycles bulky grain solid formation
Matter carries out next batch ultrahigh speed grinding distribution, by insulating liquid by concatenated the two poles of the earth supersonic generator, controls supersonic frequency
For 20Hz, power 500-1400W, flow 2-8L/min, ultrasonic temperature is 0-12 DEG C, finally by the graphite after ultrasonic disperse
Alkene lubricating oil vacuumizes dehydration, deaeration in 120-180 DEG C of vacuum machine, obtains diisocyanate after being down to room temperature filtering and changes
Property graphene antiwear and energy-saving lubricant oil.
Diisocyanate described in step A2 is one kind in IPDI, MDI or HDI.
The alcoholic solution of organic amine described in step B be methylethanolamine polyvinyl alcohol water solution or triethanolamine it is different
Propanol solution.
The diisocyanate modified graphene of surface modification described in step C and the commercially available SN 5w-40 lubricate weight of oil
Than 1:100-1:40.
Dispersion aids described in step C is in succimide, dodecyl sodium sulfate, cetyl trimethylammonium bromide
One kind；The suspension stabilizer is in polyvinylpyrrolidone, dodecyl calcium mahogany sulfonate, succinic acid iso-octyl sodium sulfonate
One kind.
The rotating speed of dispersion machine described in step C is 1400-2800rpm.
The beneficial effects of the invention are as follows：
1) present invention prepares graphene oxide using in-situ synthesis, compared to commercially available graphene oxide is directly used, certainly
Oxygenerating graphite can guarantee that graphite oxide has uniform granularity and uniform lamellar structure, ensure the product of subsequent reactions product
Matter；
2) present invention diisocyanate modified graphene, coats one layer of organic matter on the surface of graphene, can avoid strength
Mechanical agitation and grinding destroy the two-dimensional layer structure of graphene, the number of plies is relatively low and complete modified graphene to preparing,
Give full play to the characteristic of low layer number graphene antiwear and reducing friction；
3) present invention is surface modified diisocyanate modified graphene, and obtained diisocyanate is connected with lipophile
The modified graphene of long chain can make low layer number modified graphene made from grinding evenly dispersed in lubricating oil, avoid again
Secondary reunion；
4) present invention prepares modified graphene lubricating oil, lubricating oil in such a way that chemical modification and physical dispersion are combined
Middle modified graphene structural integrity, the number of plies is low, is uniformly dispersed and stablizes, and lubricating oil is made to have long-acting lubricant effect.
Specific implementation mode
Below in conjunction with example, present invention is described, and the given examples are served only to explain the present invention, is not intended to limit this
The range of invention.
Embodiment 1
A kind of preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil, includes the following steps：
A, diisocyanate modified graphene is prepared
A1, in-situ synthesis prepare graphite oxide
200 mesh natural flake graphites of 10g are added slowly with stirring the big of the 2000ml equipped with the 230ml concentrated sulfuric acids
In beaker, temperature change maintains (0 ± 1) DEG C, is slow added into the mixture of 5g sodium nitrate and 30g potassium permanganate, (35 ±
3) 2h is reacted in DEG C water bath with thermostatic control, is stirred lower heat preservation 30min, is slowly added to 460ml water, adjusts bath temperature and rise to 98 DEG C,
And 15min is maintained, it is diluted to 1400ml with warm water, the hydrogen peroxide of 5-10ml 5wt% is added, is filtered after standing 20-24h, is used
5% hydrochloric acid fully washs filter cake 5-6 times, until the sulfate ion in filtrate is not measured with barium chloride solution inspection, by gains
Matter is centrifuged repeatedly washing to supernatant to neutrality with deionized water again, is placed in drying in 35-40 DEG C of vacuum drying chamber, is aoxidized
Graphite；
A2, diisocyanate are ester modified
Graphite oxide obtained by 1g steps A1 is weighed to be put into 250ml DMAC, it is ultrasonic under the ultrasonic power of 200-250W
1.5-2h is transferred in 80-85 DEG C of water-bath, and 8 grams of IPDI are added, and temperature constant magnetic stirring reacts 4-6h, reduces temperature to 60-65
DEG C, 5 grams of phenylhydrazines are added, continues temperature constant magnetic stirring and reacts 4-6h, reduce temperature to room temperature, filtering washs 2-3 with dichloromethane
It is secondary, dry, obtained diisocyanate modified graphene is placed in 35-40 DEG C of vacuum drying chamber；
B, surface modification diisocyanate modified graphene
Diisocyanate modified graphene obtained by step A is infiltrated in the polyvinyl alcohol water solution of methylethanolamine
10h is reacted, suspension is passed through into centrifugal filtration, diisocyanate is made after vacuum drying and is connected with lipophile organic amine length point
The modified graphene of subchain；
C, the preliminary dispersion of high speed shear mixing
In mass ratio by the diisocyanate modified graphene with commercially available SN 5w-40 lubricating oil of surface modification obtained by step B
1:It is added to after 100 mixing in the stainless steel cauldron with stirring and high speed zigzag high speed dispersor, reacting kettle jacketing is adopted
With heat-conducting oil heating to 50-80 DEG C, reaction kettle main agitator is started, agitator speed 48rpm will help dispersion after stirring 30min
Agent succimide 0.5% is added in reaction kettle as lubrication weight of oil, after at the uniform velocity stirring 30min, then by suspension stabilizer
Polyvinylpyrrolidone is added to by the 0.5% of lubrication weight of oil in reaction kettle, after at the uniform velocity stirring 10min, starts high speed dispersion
Machine, it is strong pre-dispersed to the modified graphene progress in lubricating oil gradually by the rotational speed regulation of dispersion machine to 1400rpm, continue
Stir 8h；
D, ultrahigh speed colloid mill disperses
The reaction kettle that the diisocyanate modified graphene lubricating oil tentatively disperseed is filled in step C is passed through into circulation motor
It is connected with ultrahigh speed colloid mill, starts motor, be gradually promoted to ultrahigh speed colloid mill rotating speed by motor inverter
14000rpm carries out ultrahigh speed grinding distribution 3-5h to diisocyanate modified graphene lubricating oil；
E, diisocyanate modified graphene antiwear and energy-saving lubricant oil is prepared
Diisocyanate modified graphene lubricating oil is put into precipitation tank and carries out isolation precipitation, recycles bulky grain solid formation
Matter carries out next batch ultrahigh speed grinding distribution, by insulating liquid by concatenated the two poles of the earth supersonic generator, controls supersonic frequency
For 20Hz, power 500-1400W, flow 2-8L/min, ultrasonic temperature is 0-12 DEG C, finally by the graphite after ultrasonic disperse
Alkene lubricating oil vacuumizes dehydration, deaeration in 120-180 DEG C of vacuum machine, obtains diisocyanate after being down to room temperature filtering and changes
Property graphene antiwear and energy-saving lubricant oil.
Embodiment 2
A kind of preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil, includes the following steps：
A, diisocyanate modified graphene is prepared
A1, in-situ synthesis prepare graphite oxide
200 mesh natural flake graphites of 10g are added slowly with stirring the big of the 2000ml equipped with the 230ml concentrated sulfuric acids
In beaker, temperature change maintains (0 ± 1) DEG C, is slow added into the mixture of 5g sodium nitrate and 30g potassium permanganate, (35 ±
3) 2h is reacted in DEG C water bath with thermostatic control, is stirred lower heat preservation 30min, is slowly added to 460ml water, adjusts bath temperature and rise to 98 DEG C,
And 15min is maintained, it is diluted to 1400ml with warm water, the hydrogen peroxide of 5-10ml 5wt% is added, is filtered after standing 20-24h, is used
5% hydrochloric acid fully washs filter cake 5-6 times, until the sulfate ion in filtrate is not measured with barium chloride solution inspection, by gains
Matter is centrifuged repeatedly washing to supernatant to neutrality with deionized water again, is placed in drying in 35-40 DEG C of vacuum drying chamber, is aoxidized
Graphite；
A2, diisocyanate are ester modified
Graphite oxide obtained by 1g steps A1 is weighed to be put into 250ml DMAC, it is ultrasonic under the ultrasonic power of 200-250W
1.5-2h is transferred in 80-85 DEG C of water-bath, and 8 grams of MDI are added, and temperature constant magnetic stirring reacts 4-6h, reduces temperature to 60-65
DEG C, 5 grams of phenylhydrazines are added, continues temperature constant magnetic stirring and reacts 4-6h, reduce temperature to room temperature, filtering washs 2-3 with dichloromethane
It is secondary, dry, obtained diisocyanate modified graphene is placed in 35-40 DEG C of vacuum drying chamber；
B, surface modification diisocyanate modified graphene
Diisocyanate modified graphene obtained by step A is subjected to Host range in the aqueous isopropanol of triethanolamine
Suspension is passed through centrifugal filtration by 10h, and diisocyanate, which is made, after vacuum drying is connected with lipophile organic amine long chain
Modified graphene；
C, the preliminary dispersion of high speed shear mixing
In mass ratio by the diisocyanate modified graphene with commercially available SN 5w-40 lubricating oil of surface modification obtained by step B
1:It is added to after 70 mixing in the stainless steel cauldron with stirring and high speed zigzag high speed dispersor, reacting kettle jacketing uses
Heat-conducting oil heating starts reaction kettle main agitator, agitator speed 48rpm, after stirring 45min, by dispersion aids to 50-80 DEG C
Dodecyl sodium sulfate is added to by the 2.2% of lubrication weight of oil in reaction kettle, after at the uniform velocity stirring 45min, then will be suspending stabilized
Agent dodecyl calcium mahogany sulfonate is added to by the 1.5% of lubrication weight of oil in reaction kettle, after at the uniform velocity stirring 20min, starts height
Fast dispersion machine is gradually adjusted the speed of dispersion machine to 2100rpm, and strong pre- point is carried out to the modified graphene in lubricating oil
It dissipates, persistently stirs 8h；
D, ultrahigh speed colloid mill disperses
The reaction kettle that the diisocyanate modified graphene lubricating oil tentatively disperseed is filled in step C is passed through into circulation motor
It is connected with ultrahigh speed colloid mill, starts motor, be gradually promoted to ultrahigh speed colloid mill rotating speed by motor inverter
14000rpm carries out ultrahigh speed grinding distribution 3-5h to diisocyanate modified graphene lubricating oil；
E, diisocyanate modified graphene antiwear and energy-saving lubricant oil is prepared
Diisocyanate modified graphene lubricating oil is put into precipitation tank and carries out isolation precipitation, recycles bulky grain solid formation
Matter carries out next batch ultrahigh speed grinding distribution, by insulating liquid by concatenated the two poles of the earth supersonic generator, controls supersonic frequency
For 20Hz, power 500-1400W, flow 2-8L/min, ultrasonic temperature is 0-12 DEG C, finally by the graphite after ultrasonic disperse
Alkene lubricating oil vacuumizes dehydration, deaeration in 120-180 DEG C of vacuum machine, obtains diisocyanate after being down to room temperature filtering and changes
Property graphene antiwear and energy-saving lubricant oil.
Embodiment 3
A kind of preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil, includes the following steps：
A, diisocyanate modified graphene is prepared
A1, in-situ synthesis prepare graphite oxide
200 mesh natural flake graphites of 10g are added slowly with stirring the big of the 2000ml equipped with the 230ml concentrated sulfuric acids
In beaker, temperature change maintains (0 ± 1) DEG C, is slow added into the mixture of 5g sodium nitrate and 30g potassium permanganate, (35 ±
3) 2h is reacted in DEG C water bath with thermostatic control, is stirred lower heat preservation 30min, is slowly added to 460ml water, adjusts bath temperature and rise to 98 DEG C,
And 15min is maintained, it is diluted to 1400ml with warm water, the hydrogen peroxide of 5-10ml 5wt% is added, is filtered after standing 20-24h, is used
5% hydrochloric acid fully washs filter cake 5-6 times, until the sulfate ion in filtrate is not measured with barium chloride solution inspection, by gains
Matter is centrifuged repeatedly washing to supernatant to neutrality with deionized water again, is placed in drying in 35-40 DEG C of vacuum drying chamber, is aoxidized
Graphite；
A2, diisocyanate are ester modified
Graphite oxide obtained by 1g steps A1 is weighed to be put into 250ml DMAC, it is ultrasonic under the ultrasonic power of 200-250W
1.5-2h is transferred in 80-85 DEG C of water-bath, and 8 grams of HDI are added, and temperature constant magnetic stirring reacts 4-6h, reduces temperature to 60-65
DEG C, 5 grams of phenylhydrazines are added, continues temperature constant magnetic stirring and reacts 4-6h, reduce temperature to room temperature, filtering washs 2-3 with dichloromethane
It is secondary, dry, obtained diisocyanate modified graphene is placed in 35-40 DEG C of vacuum drying chamber；
B, surface modification diisocyanate modified graphene
Diisocyanate modified graphene obtained by step A is subjected to Host range in the aqueous isopropanol of triethanolamine
Suspension is passed through centrifugal filtration by 10h, and diisocyanate, which is made, after vacuum drying is connected with lipophile organic amine long chain
Modified graphene；
C, the preliminary dispersion of high speed shear mixing
In mass ratio by the diisocyanate modified graphene with commercially available SN 5w-40 lubricating oil of surface modification obtained by step B
1:It is added to after 40 mixing in the stainless steel cauldron with stirring and high speed zigzag high speed dispersor, reacting kettle jacketing uses
Heat-conducting oil heating starts reaction kettle main agitator, agitator speed 48rpm, after stirring 60min, by dispersion aids to 50-80 DEG C
Cetyl trimethylammonium bromide cetyl trimethylammonium bromide is added to by the 5% of lubrication weight of oil in reaction kettle, at the uniform velocity
After stirring 60min, then suspension stabilizer succinic acid iso-octyl sodium sulfonate 2.5% is added to reaction kettle by lubrication weight of oil
In, after at the uniform velocity stirring 30min, high speed dispersor is started, gradually adjusts the speed of dispersion machine to 2800rpm, in lubricating oil
Modified graphene carry out strong pre-dispersed, persistently stir 8h；
D, ultrahigh speed colloid mill disperses
The reaction kettle that the diisocyanate modified graphene lubricating oil tentatively disperseed is filled in step C is passed through into circulation motor
It is connected with ultrahigh speed colloid mill, starts motor, be gradually promoted to ultrahigh speed colloid mill rotating speed by motor inverter
14000rpm carries out ultrahigh speed grinding distribution 3-5h to diisocyanate modified graphene lubricating oil；
E, diisocyanate modified graphene antiwear and energy-saving lubricant oil is prepared
Diisocyanate modified graphene lubricating oil is put into precipitation tank and carries out isolation precipitation, recycles bulky grain solid formation
Matter carries out next batch ultrahigh speed grinding distribution, by insulating liquid by concatenated the two poles of the earth supersonic generator, controls supersonic frequency
For 20Hz, power 500-1400W, flow 2-8L/min, ultrasonic temperature is 0-12 DEG C, finally by the graphite after ultrasonic disperse
Alkene lubricating oil vacuumizes dehydration, deaeration in 120-180 DEG C of vacuum machine, obtains diisocyanate after being down to room temperature filtering and changes
Property graphene antiwear and energy-saving lubricant oil.
With high power scanning transmission electron microscope to diisocyanate modified graphene antiwear and energy-saving lubricant oil obtained by embodiment 1-3 into
Row characterization finds that the diisocyanate modified graphene number of plies is within 7 layers in gained lubricating oil, and accounting is not less than within 5 layers
40%, the content of single layer is not less than 20%, and diisocyanate modified graphene layer average length is 1 μm, and mean breadth is
400nm, form is complete and is evenly distributed.
By diisocyanate modified graphene antiwear and energy-saving lubricant oil obtained by embodiment 1-3 in SD-2000 abrasion testers
Upper to carry out wear-resistant, energy-efficient performance test, data are shown in Table 1, table 2 and table 3.
1. embodiment of table, 1 gained diisocyanate modified graphene antiwear and energy-saving lubricant oil wears endurance check comparison
2. embodiment of table, 2 gained diisocyanate modified graphene antiwear and energy-saving lubricant oil vehicle oil consumption, wear-resistant noise reduction pair
Than
Note：Test vehicle keeps 110km/h at the uniform velocity to travel 1000km (cruise).
3 embodiment of table, 3 gained diisocyanate modified graphene antiwear and energy-saving lubricant oil deceleration acc power, electricity consumption comparison
In galling testing machine and practical driving experiment and actual heavy load speed reducer it can be seen from table 1-3
Using the diisocyanate modified graphene antiwear and energy-saving lubricant oil of experiment synthesis than using engine motor oil conventional in the market
After industrial gear oil, extreme-pressure anti-wear antifriction effect is significantly improved, and PB/PD values increase, and illustrates that anti-wear lubricating performance improves,
Friction coefficient/wear scar diameter becomes smaller, and illustrates that the energy saving, fuel-efficient of lubricating oil, power saving performance improve, the power of speed reducer and electricity consumption obtain
Average fuel consumption to significant decrease, vehicle reduces, and wear-resistant anti-acoustic capability improves.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil, which is characterized in that including following step
Suddenly：
A, diisocyanate modified graphene is prepared
A1, in-situ synthesis prepare graphite oxide
200 mesh natural flake graphites of 10g are added slowly with stirring to the large beaker of the 2000ml equipped with the 230ml concentrated sulfuric acids
In, temperature change maintains (0 ± 1) DEG C, is slow added into the mixture of 5g sodium nitrate and 30g potassium permanganate, in (35 ± 3) DEG C
2h is reacted in water bath with thermostatic control, is stirred lower heat preservation 30min, is slowly added to 460ml water, adjusts bath temperature and rise to 98 DEG C, and tie up
15min is held, 1400ml is diluted to warm water, the hydrogen peroxide of 5-10ml 5wt% is added, filtered after standing 20-24h, with 5% salt
Sour fully washing filter cake 5-6 times, until not measuring the sulfate ion in filtrate with barium chloride solution inspection, obtained material is used again
Deionized water is centrifuged repeatedly washing to supernatant to neutrality, is placed in drying in 35-40 DEG C of vacuum drying chamber, obtains graphite oxide；
A2, diisocyanate are ester modified
It weighs graphite oxide obtained by 1g steps A1 to be put into 250ml DMAC, the ultrasound 1.5- under the ultrasonic power of 200-250W
2h is transferred in 80-85 DEG C of water-bath, and 8 grams of diisocyanate are added, and temperature constant magnetic stirring reacts 4-6h, reduces temperature to 60-
65 DEG C, 5 grams of phenylhydrazines are added, continues temperature constant magnetic stirring and reacts 4-6h, reduce temperature to room temperature, filtering is washed with dichloromethane
2-3 times, dry, obtained diisocyanate modified graphene is placed in 35-40 DEG C of vacuum drying chamber；
B, surface modification diisocyanate modified graphene
Diisocyanate modified graphene obtained by step A is subjected to Host range 10h in the alcoholic solution of organic amine, by suspension
The modified graphite that diisocyanate is connected with lipophile organic amine long chain is made by centrifugal filtration, after vacuum drying
Alkene；
C, the preliminary dispersion of high speed shear mixing
It is added to after the diisocyanate modified graphene of surface modification obtained by step B is mixed with commercially available SN 5w-40 lubricating oil
In stainless steel cauldron with stirring and high speed zigzag high speed dispersor, reacting kettle jacketing is using heat-conducting oil heating to 50-
80 DEG C, start reaction kettle main agitator, agitator speed 48rpm, after stirring 30-60min, by dispersion aids by lubrication weight of oil
0.5-5% be added in reaction kettle, at the uniform velocity stir 30-60min after, then by suspension stabilizer by lubrication weight of oil 0.5-
2.5% is added in reaction kettle, after at the uniform velocity stirring 10-30min, high speed dispersor is started, gradually by the rotational speed regulation of dispersion machine
It is strong pre-dispersed to the modified graphene progress in lubricating oil to 2800rpm, persistently stir 8h；
D, ultrahigh speed colloid mill disperses
The reaction kettle that the diisocyanate modified graphene lubricating oil tentatively disperseed is filled in step C by circulation motor and is surpassed
Colloid mills connect, and start motor, ultrahigh speed colloid mill rotating speed is gradually promoted to 14000rpm by motor inverter, right
Diisocyanate modified graphene lubricating oil carries out ultrahigh speed grinding distribution 3-5h；
E, diisocyanate modified graphene antiwear and energy-saving lubricant oil is prepared
Diisocyanate modified graphene lubricating oil is put into precipitation tank and carries out isolation precipitation, recycling bulky grain solid matter into
Row next batch ultrahigh speed grinding distribution, by insulating liquid by concatenated the two poles of the earth supersonic generator, control supersonic frequency is
20Hz, power 500-1400W, flow 2-8L/min, ultrasonic temperature is 0-12 DEG C, finally by the graphene after ultrasonic disperse
Lubricating oil vacuumizes dehydration, deaeration in 120-180 DEG C of vacuum machine, is down to after room temperature filtering that obtain diisocyanate ester modified
Graphene antiwear and energy-saving lubricant oil.
2. the preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil according to claim 1, feature
It is, diisocyanate described in step A2 is one kind in IPDI, MDI or HDI.
3. the preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil according to claim 1, feature
It is, the alcoholic solution of organic amine described in step B is the polyvinyl alcohol water solution of methylethanolamine or the isopropyl of triethanolamine
Alcoholic solution.
4. the preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil according to claim 1, feature
It is, the diisocyanate modified graphene of surface modification described in step C and the commercially available SN 5w-40 lubricating oil weight ratios
1:100-1:40。
5. the preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil according to claim 1, feature
It is, dispersion aids described in step C is in succimide, dodecyl sodium sulfate, cetyl trimethylammonium bromide
It is a kind of.
6. the preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil according to claim 1, feature
It is, suspension stabilizer described in step C is polyvinylpyrrolidone, dodecyl calcium mahogany sulfonate, succinic acid iso-octyl sulphur
One kind in sour sodium.
7. the preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil according to claim 1, feature
It is, the rotating speed of dispersion machine described in step C is 1400-2800rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810550096.7A CN108559577B (en) | 2018-05-31 | 2018-05-31 | Preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810550096.7A CN108559577B (en) | 2018-05-31 | 2018-05-31 | Preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108559577A true CN108559577A (en) | 2018-09-21 |
| CN108559577B CN108559577B (en) | 2021-03-02 |
Family
ID=63552691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810550096.7A Active CN108559577B (en) | 2018-05-31 | 2018-05-31 | Preparation method of diisocyanate modified graphene anti-wear energy-saving lubricating oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108559577B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484757A (en) * | 2020-04-17 | 2020-08-04 | 连云港杜钟新奥神氨纶有限公司 | Modified graphene oxide and preparation method thereof |
| CN111863366A (en) * | 2020-07-15 | 2020-10-30 | 广东骄阳热能科技有限公司 | Electromagnetic liquid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191023A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Surface modified solid particles, preparation method and application thereof |
| US8048931B2 (en) * | 2005-10-14 | 2011-11-01 | The Trustees Of Princeton University | Emulsifier containing thermally exfoliated graphite oxide |
| CN105295028A (en) * | 2015-08-03 | 2016-02-03 | 杭州师范大学 | Graphene in-situ modified nylon 6 composite and preparation method and application thereof |
| CN106085551A (en) * | 2016-05-31 | 2016-11-09 | 烟台恒诺化工科技有限公司 | A kind of graphene-based wear-resistant self-repair material of high molecular nanometer alloy and its preparation method and application |
| CN106244289A (en) * | 2016-07-07 | 2016-12-21 | 重庆德领科技有限公司 | Dispersibility and the good modified graphene lubricating oil of affinity and preparation method thereof |
| CN106634144A (en) * | 2016-12-29 | 2017-05-10 | 湖南湘江关西涂料有限公司 | Preparation method for aqueous dispersion of cationic graphene and application thereof |
-
2018
- 2018-05-31 CN CN201810550096.7A patent/CN108559577B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8048931B2 (en) * | 2005-10-14 | 2011-11-01 | The Trustees Of Princeton University | Emulsifier containing thermally exfoliated graphite oxide |
| CN101191023A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Surface modified solid particles, preparation method and application thereof |
| CN105295028A (en) * | 2015-08-03 | 2016-02-03 | 杭州师范大学 | Graphene in-situ modified nylon 6 composite and preparation method and application thereof |
| CN106085551A (en) * | 2016-05-31 | 2016-11-09 | 烟台恒诺化工科技有限公司 | A kind of graphene-based wear-resistant self-repair material of high molecular nanometer alloy and its preparation method and application |
| CN106244289A (en) * | 2016-07-07 | 2016-12-21 | 重庆德领科技有限公司 | Dispersibility and the good modified graphene lubricating oil of affinity and preparation method thereof |
| CN106634144A (en) * | 2016-12-29 | 2017-05-10 | 湖南湘江关西涂料有限公司 | Preparation method for aqueous dispersion of cationic graphene and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484757A (en) * | 2020-04-17 | 2020-08-04 | 连云港杜钟新奥神氨纶有限公司 | Modified graphene oxide and preparation method thereof |
| CN111484757B (en) * | 2020-04-17 | 2021-10-22 | 连云港杜钟新奥神氨纶有限公司 | Modified graphene oxide and preparation method thereof |
| CN111863366A (en) * | 2020-07-15 | 2020-10-30 | 广东骄阳热能科技有限公司 | Electromagnetic liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108559577B (en) | 2021-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108559577A (en) | A kind of preparation method of diisocyanate modified graphene antiwear and energy-saving lubricant oil | |
| CN107805530B (en) | Graphene/manganous manganic oxide composite nano lubricating additive and synthetic method thereof | |
| CN111440651B (en) | Preparation method of black phosphorus alkene/graphene oxide composite water-based lubricant additive | |
| CN105670737A (en) | Preparation method of graphene lubricating additive | |
| CN105969478B (en) | A kind of preparation method of the composite lubricated material of line borate/stannic oxide/graphene nano | |
| CN107057799B (en) | Functionalized graphene powder, lubricating oil containing functionalized graphene powder, and preparation method and application of functionalized graphene powder | |
| CN106190432A (en) | A kind of modified graphene lubricating oil of polymolecularity and preparation method thereof | |
| CN108117913B (en) | Preparation method and application of spherical graphene lubricating additive | |
| CN110681324B (en) | Graphene oxide hybrid multi-wall self-lubricating micro-nano capsule and preparation method thereof | |
| CN106883904A (en) | A kind of modified finished lube preparation method of Graphene | |
| CN106085551B (en) | A kind of graphene-based wear-resistant self-repair material of high molecular nanometer alloy and its preparation method and application | |
| CN101698808B (en) | Plate-strip steel cold-rolling emulsified oil containing nanometer hexagonal boron nitride particles, and preparation method | |
| CN113773892B (en) | Preparation method of lipophilic black phosphorus lubricating oil | |
| CN110028810A (en) | A kind of preparation method and applications of composite modified nano yttrium oxide | |
| CN104962354B (en) | A kind of lubricating grease and preparation method thereof | |
| CN108559576A (en) | A kind of graphene coated nano copper lubricating oil additive and preparation method thereof | |
| CN106566592A (en) | Method for preparing expanded graphene lubricant additive, expanded graphene lubricant additive, and lubricant | |
| CN109439384A (en) | A kind of preparation method of the nano lubricating oil compound additive of three-layer nuclear shell structure | |
| CN113308286B (en) | Lubricating oil modifier and modified lubricating oil | |
| CN110760365B (en) | Graphene oxide/silicon dioxide-aluminum oxide nano composite water-based lubricant and preparation method thereof | |
| CN114479985A (en) | Composite material coated with black phosphorus quantum dots and preparation method and application thereof | |
| CN111909751A (en) | High-temperature extreme-pressure wear-resistant lubricating oil and preparation method thereof | |
| CN115746936B (en) | Composite nanofiber, preparation method and application thereof, wide-temperature-range wear-resistant self-repairing lubricating grease and preparation method thereof | |
| CN114480001B (en) | Molybdenum disulfide nano lubricating oil capable of stably existing and preparation method thereof | |
| CN108102762B (en) | Functionalized graphene-attapulgite composite nanomaterial, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |