CN110373094A - A kind of graphene anticorrosive paint and preparation method thereof - Google Patents
A kind of graphene anticorrosive paint and preparation method thereof Download PDFInfo
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- CN110373094A CN110373094A CN201910824156.4A CN201910824156A CN110373094A CN 110373094 A CN110373094 A CN 110373094A CN 201910824156 A CN201910824156 A CN 201910824156A CN 110373094 A CN110373094 A CN 110373094A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The present invention relates to a kind of graphene anticorrosive paints and preparation method thereof.The coating includes film-forming components and curing component；Film-forming components include epoxy resin, the thin graphene slurry of 15-35wt%, the zinc powder of 15-40wt%, the talcum powder of 5-15wt%, the feldspar powder of 5-15wt%, the titanium dioxide of 1-5wt%, the polyamide wax of 1-5wt% and the dispersing agent of 0.1-3wt% of 15-30wt%；Thin graphene slurry includes graphene and the first solvent, and mass percentage of the graphene in thin graphene slurry is 5-20wt%；Graphene is no more than 2 microns for the granularity of 1-5 layers of graphene and the graphene.Include thin graphene in the anticorrosive paint, graphene micron order erosion resistant coating can be formed in coating surface, effectively block the contact of external erosion with protected metal, and effectively cut off protected metal electron and outwardly migrate, has reached corrosion-resistant purpose.
Description
Technical field
The present invention relates to anticorrosive paint technology fields more particularly to a kind of graphene anticorrosive paint and preparation method thereof.
Background technique
The whole world causes huge economic loss because of corrosion every year, and in numerous anti-corrosion measures, corrosion-inhibiting coating is most
One of cost-effective method.Commercial industrial antisepsis coating is mostly annular-oxygen and rich zinc antiseptic dope now, relies primarily on zinc powder
Inhibit the electron transfer of metal to reach corrosion-resistant purpose, the epoxy zinc-rich for the use of Zn content being mostly 80% or more in practical application
Priming paint, excessively high Zn content can not only damage the health of user of service, and also unfriendly to environment.Moreover, general feelings
Under condition, single layer coating only has the salt spray proof time of steel 1500 hours.
Industrial annular-oxygen and rich zinc antiseptic dope needs the zinc powder of high concentration and needs to smear 3 layers to reach long-time corrosion-resistant
It is at high cost insufficient with this two o'clock of long construction period to form coating for purpose.
Graphene is a kind of two-dimensional material, since its electron mobility is high, conductive capability is good, intensity is big, the capacity of heat transmission is good
And the electric conductivity with good obstructing capacity, especially graphene can promote the zinc powder in epoxy zinc rich primer better
Cathodic protection effect is played, these make it possible graphene modified epoxy zinc-rich anti-corrosive paint.But graphene itself is easy
Reunite, is not easy to disperse, influences the performance and quality of coating, this limits graphene answering in anticorrosive paint to a certain extent
With.
Industry solves the problems, such as this main thought first is that improving the dispersion of system by way of dispersing agent is added at present
Property to improve effect of the graphene in system, for example, application publication number be CN108485470A Chinese patent application file
Disclosed technical solution joined the components such as KH550, KH560, KH570 as dispersing agent；Application publication number is
Technical solution disclosed in the Chinese patent application file of CN109111825A joined the components such as BYK110, BYK161, BYK170
As dispersing agent；Application publication number is that technical solution disclosed in the Chinese patent application file of CN108250900A joined one kind
Ternary block polymer anionic dispersing agents with A-B-C block structure.This method is relatively simple, but disadvantage is also very bright
Aobvious, the dosage of dispersing agent is larger, and most of dispersing agent is water-soluble component, poor with film forming system compatible result.Separately
One method is the dispersion performance for being modified processing to graphene to improve graphene, for example, application publication number is
Technical solution disclosed in the Chinese patent application file of CN110041801A use molecular weight for 70000 kayexalate
The reunion to inhibit graphene is modified to graphene；Application publication number is the Chinese patent application file of CN108841211A
Disclosed technical solution is using benzoic acid, benzene sulfonic acid, C1~C5 chain fatty acid, ethanol amine or C1~C5 chain fatty alcohol group to stone
Black alkene carries out surface modification；Application publication number is that technical solution disclosed in the Chinese patent application file of CN105505212A passes through
Vinyl benzyl in imidazoles exchanges to the edge of graphene by ion exchange, then polymerize with methyl methacrylate,
A kind of graphene composite material of polymethyl methacrylate is obtained to use as modified graphite olefinic constituent.These method of modifying are all
By carrying out the modification of organic group on the surface of graphene, though the dispersion performance of graphene is improved to a certain extent,
Organic reagent is used in modifying process, some is even with a large amount of organic reagent.
Summary of the invention
In view of the deficiencies in the prior art or insufficient, the technical problem to be solved by the present invention is to be: provide a kind of stone
Black alkene anticorrosive paint and preparation method thereof.
In order to solve the above-mentioned technical problems, the present invention provides following technical solutions:
A kind of graphene anticorrosive paint includes film-forming components and curing component；
The film-forming components include thin graphene slurry, the 15- of the epoxy resin of 15-30wt%, 15-35wt%
The zinc powder of 40wt%, the talcum powder of 5-15wt%, the feldspar powder of 5-15wt%, the titanium dioxide of 1-5wt%, 1-5wt% polyamides
The dispersing agent of amine wax and 0.1-3wt%；
Wherein, the thin graphene slurry includes graphene and the first solvent, and graphene is starched in the thin graphene
Mass percentage in material is 5-20wt%；
The graphene is no more than 2 microns for the granularity of 1-5 layers of graphene and the graphene.
Preferably, the thin graphene slurry is prepared as follows:
Graphite is subjected to Gas grinding, obtains functionalization crude product；The process conditions of Gas grinding are as follows: pressure 0.5-
1MPa, gas flow 500-5000m3/ h, milling time 10min-24h, grader revolving speed 1000-20000rpm；
The functionalization crude product is removed in the supercritical state, obtains rubble ink alkene；
The rubble ink alkene is classified, the graphene for 1-5 layers is obtained, the graphene is mixed simultaneously with the first solvent
Grinding, obtains the thin graphene slurry.
Preferably, the Gas grinding includes: and graphite is added in Gas grinding machine, then squeeze into compressed gas, makes stone
Black fluidization simultaneously collides with each other to realize Gas grinding；
The graphite is that natural graphite, electrographite, expanded graphite, thermal cracking graphite are any one or more of, preferably
For natural graphite；
The compressed gas is that air, carbon dioxide, inert gas are any one or more of, it is preferable that the compression
The pressure of air is 0.5-1MPa.
Preferably, the overcritical removing includes: that functionalization crude product is introduced into high pressure resistant reaction kettle, is passed through in advance
Add hot medium, changes the object of supercritical fluid by the temperature or pressure or the additional amount of medium of the high pressure resistant reaction kettle of adjusting
Physicochemical property is to match the critical pressure and critical-temperature of the functionalization crude product；
Until when scheduled pressure value, medium is made to enter supercriticality, pressure reducing valve is opened after being stirred enters material
Kettle is depressurized, makes pressure reduction to normal pressure or lower pressure, obtains rubble ink alkene；
The medium includes gas medium and liquid medium；
The gas medium includes any in carbon dioxide, ammonia, butane and butene mixture, nitrogen, sulfur hexafluoride
Kind is a variety of；
The liquid medium includes water, methanol, ethyl alcohol, isopropanol, dinitrophenol, dodecyl sodium sulfate, dodecane
Base sodium sulphate, N,N-dimethylformamide, N-Methyl pyrrolidone are any one or more of；
Preferably, mass percentage x of the liquid medium in the gas mediumLiquidValue are as follows: 0 < xLiquid≤
10%.
Preferably, the classification includes: to be classified using 3~5 grades of cyclone separators to rubble ink alkene, obtains 1-5 layers
Graphene.
Preferably, the epoxy resin is modified epoxy；
The dispersing agent is non-ion aqueous dispersing agent；And/or
First solvent is that dimethylbenzene, hexone, butanol are any one or more of.
Preferably, the curing component includes the Ammonia curing agent of 50-90wt% and the mixed solvent of 10-50wt%.
Preferably,
The Ammonia curing agent is that polyamide, modified diethylaminopropylamine, fatty amine are any one or more of；And/or
The mixed solvent is that dimethylbenzene, hexone, butanol are any one or more of.
Preferably, the granularity of the graphene anticorrosive paint is less than 50 microns；
The graphene anticorrosive paint has the adhesive force not less than 15MPa；
The salt spray resistance duration of the graphene anticorrosive paint is not less than 2800 hours.
A kind of preparation method of the graphene anticorrosive paint, includes the following steps:
By epoxy resin, thin graphene slurry, zinc powder, talcum powder, feldspar powder, titanium dioxide, polyamide wax and dispersing agent
It mixes and grinds, obtain film-forming components of the fineness less than 50 microns；
Then curing component is added and stirs, obtains the graphene anticorrosive paint.
Beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
It include thin graphene in this anticorrosive paint provided by the invention, after coating film forming, thin graphene can be
Coating surface forms graphene micron order erosion resistant coating, effectively blocks the contact of external erosion with protected metal, and effectively cut
Disconnected protected metal electron outwardly migrates, to prevent protected metal and extraneous generation oxidation reaction, has reached anti-corrosion
Purpose.The addition of thin graphene can substantially reduce the dosage of zinc powder, so that the flexibility and adhesive force of the coating after film forming
It is improved.
The present invention provides the dispersion performance that a kind of completely new thinking improves graphene, by Gas grinding, overcritical
Graphene made from the method for removing and multi-stage separation is not inherently easy to reunite, and dispersibility is excellent, when it is applied to film forming system
In after, graphene shows excellent dispersion effect in film forming system.Due to this method provided by the invention without using
Organic reagent carries out base group modification to the surface of graphene and improves its dispersion performance, reduces with high toxicity, high pollution
With the use of high-cost organic reagent.
The dosage of dispersing agent in this graphene anticorrosive paint provided by the invention is lower, substantially increases the simultaneous of system
Capacitive.
This graphene anticorrosive paint preparation process provided by the invention is simply controllable, and cost is relatively low.
This graphene anti-corrosion coating adhesive force provided by the invention is stronger, is presented with preferable anti-corrosion effect, single
The anti-corrosion duration of coating is promoted, and can be reduced smear layer and be counted to 2 layers.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of graphene anticorrosive paint in first aspect, and the graphene anticorrosive paint includes film forming group
Point and curing component；
The film-forming components include thin graphene slurry, the 15- of the epoxy resin of 15-30wt%, 15-35wt%
The zinc powder of 40wt%, the talcum powder of 5-15wt%, the feldspar powder of 5-15wt%, the titanium dioxide of 1-5wt%, 1-5wt% polyamides
The dispersing agent of amine wax and 0.1-3wt%；
Wherein, the thin graphene slurry includes graphene and the first solvent, and the first solvent can be dimethylbenzene, methyl
Isobutyl ketone, butanol are any one or more of, and mass percentage of the graphene in the thin graphene slurry is
5-20wt% (for example, can for 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%,
13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%)；
The graphene is no more than 2 microns for the granularity of 1-5 layers of graphene and the graphene.
Specifically, accounting of the epoxy resin in the film-forming components can for 15wt%, 16wt%, 17wt%,
18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%,
29wt%, 30wt%；Accounting of the thin graphene slurry in the film-forming components can for 15wt%, 16wt%,
17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%,
28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%；The zinc powder is in the film forming group
Point in accounting can for 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%,
23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%,
34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%；The talcum powder is in the film-forming components
Accounting can for 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%,
15wt%；Accounting of the feldspar powder in the film-forming components can for 5wt%, 6wt%, 7wt%, 8wt%, 9wt%,
10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%；Accounting of the titanium dioxide in the film-forming components can
Think 1wt%, 2wt%, 3wt%, 4wt%, 5wt%；Accounting of the polyamide wax in the film-forming components can be
1wt%, 2wt%, 3wt%, 4wt%, 5wt%；Accounting of the dispersing agent in the film-forming components can for 0.1wt%,
0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%.Certainly, the sum of above-mentioned each component is 100%.
It include thin graphene in this anticorrosive paint provided by the invention, after coating film forming, thin graphene can be
Coating surface forms graphene micron order erosion resistant coating, effectively blocks the contact of external erosion with protected metal, and effectively cut
Disconnected protected metal electron outwardly migrates, to prevent protected metal and extraneous generation oxidation reaction, has reached anti-corrosion
Purpose.The addition of this thin graphene improves the anti-corrosion duration of single coating, and reduces smear layer and count to 2 layers, prevents simultaneously
Rotten effect is improved.In addition, the addition of this thin graphene can substantially reduce the dosage of zinc powder, so that the painting after film forming
The flexibility and adhesive force of layer are improved.
Preferably, the thin graphene slurry used in the present invention is prepared as follows: graphite is carried out air-flow
Grinding, obtains functionalization crude product；The process conditions of Gas grinding are as follows: pressure 0.5-1MPa (can for 0.5MPa, 0.6MPa,
0.7MPa, 0.8MPa, 0.9MPa, 1MPa), gas flow 500-5000m3/ h (can be 500m3/h、600m3/h、700m3/h、
800m3/h、900m3/h、1000m3/h、1100m3/h、1200m3/h、1300m3/h、1400m3/h、1500m3/h、1600m3/h、
1700m3/h、1800m3/h、1900m3/h、2000m3/h、2100m3/h、2200m3/h、2300m3/h、2400m3/h、2500m3/
h、2600m3/h、2700m3/h、2800m3/h、2900m3/h、3000m3/h、3100m3/h、3200m3/h、3300m3/h、
3400m3/h、3500m3/h、3600m3/h、3700m3/h、3800m3/h、3900m3/h、4000m3/h、4100m3/h、4200m3/
h、4300m3/h、4400m3/h、4500m3/h、4600m3/h、4700m3/h、4800m3/h、4900m3/h、5000m3/ h), grinding
Time 10min-24h (can for 10min, 30min, 50min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h,
13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, for 24 hours), (grader is located at Gas grinding machine to grader
Inside, according to the rank of the good grader of standard setting, rank is not reached during grinding cannot enter subsequent processing,
Be further continued for grinding) revolving speed 1000-20000rpm (can for 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm,
1500rpm,1600rpm,1700rpm,1800rpm,1900rpm,2000rpm)；
The functionalization crude product is removed in the supercritical state, obtains rubble ink alkene；
The rubble ink alkene is classified, the graphene for 1-5 layers is obtained, the graphene is mixed simultaneously with the first solvent
Grinding, obtains the thin graphene slurry.
Graphite is ground into micron order crude product in a manner of Gas grinding by production method provided by the invention, the crude product
For the non-form the few-layer graphene alkene of micron order, the intrinsic performance of graphene is utmostly played, this is because Gas grinding is in process of lapping
In only use compressed air, without destroyed as the methods of oxidation-reduction method graphene ontology generation defect.In addition, this hair
It is bright that also the process conditions of Gas grinding are optimized, when limitation crushes pressure, gas flow, grader revolving speed and grinding
Between, so that graphite ontology not made defect occur, also avoid that grinding splitting time is long, and pollutant is discharged in low efficiency, generates amorphous
Phase is conducive to dispersion and intercalation under supercriticality, the crude product ground under process conditions provided by the invention
Granularity will not make graphite agglomeration occur close to 2 microns.
Production method provided by the invention is not only innovatively by the organic of Gas grinding stripping method and supercritical fluid method
In conjunction with, but also consider and remove incomplete situation in the presence of to graphite, therefore by 3-5 grades of grading plant to graphene
Crude product is classified, and can not only separate graphite and graphene, 1-5 layers of thin graphene also can be obtained.
To sum up, the present invention provides the dispersion performance that a kind of completely new thinking improves graphene, by Gas grinding, surpass
Graphene made from the method for critical removing and multi-stage separation is not inherently easy to reunite, and dispersibility is excellent, when it is applied to film forming
After in system, graphene shows excellent dispersion effect in film forming system.Since this method provided by the invention is not necessarily to
Base group modification is carried out using surface of the organic reagent to graphene and improves its dispersion performance, is reduced with high toxicity, high dirt
The use of metachromia and high-cost organic reagent.
In addition, since thin graphene shows excellent dispersion performance, the aid dispersion ingredient dispersion agents in the present invention
Dosage it is lower, substantially increase the compatibility of system.
The anti-corrosion duration of single coating is also improved using thin graphene made from this method, smear layer can be reduced and count to 2
Layer.
Mass percentage of the thin graphene in the thin graphene slurry is 5-20wt%, this content is hair
The optimal scheme that bright people obtains afterwards after study.When the too high levels of thin graphene, the dispersion performance of graphene is reduced.
In some preferred embodiments, the step of Gas grinding includes: that graphite is added to Gas grinding machine
In, then squeeze into compressed gas, make graphite fluidizedization and collide with each other to realize Gas grinding.The graphite can be natural stone
Ink, electrographite, expanded graphite, thermal cracking graphite are any one or more of, preferably natural graphite, can reduce and be produced into
This.The compressed gas is can be any one or more of with air, carbon dioxide, inert gas (such as nitrogen, argon gas), preferably
Ground, the pressure of the compressed air are 0.5-1MPa, for example, can for 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa,
0.9MPa、1MPa。
In some preferred embodiments, the step of overcritical removing includes: to be introduced into functionalization crude product
In high pressure resistant reaction kettle, it is passed through pre-heated medium, passes through the temperature or pressure of the high pressure resistant reaction kettle of adjusting or adding for medium
Enter amount to change the physicochemical properties of supercritical fluid to match the critical pressure and critical-temperature of the functionalization crude product,
Conducive to the dispersion of non-few layer crude product and the intercalation to graphite of supercritical fluid, thus preferably removing graphite obtain it is more excellent
The high purity graphite alkene of matter；Until when scheduled pressure value, medium is made to enter supercriticality, pressure reducing valve is opened after being stirred to be made
Material enters pressure reduction vessel, makes pressure reduction to normal pressure or lower pressure, and supercritical medium expands, and releases energy and overcomes stone
Model ylid bloom action power between layer of ink obtains rubble ink alkene.Preferably, before opening pressure reducing valve, by the pressure tune in pressure reduction vessel
Section is 0.01-0.1MPa, and is adjusted to normal pressure after the completion of material decompression, then by pressure；Preferably, by the pressure reduction vessel
Interior temperature maintains the boiling point of liquid medium or more.
Medium used in the stage is optimized in the present invention, and the medium includes gas medium and liquid medium；Institute
It is any one or more of comprising carbon dioxide, ammonia, butane and butene mixture, nitrogen, sulfur hexafluoride to state gas medium；Institute
It states liquid medium and includes water, methanol, ethyl alcohol, isopropanol, dinitrophenol, dodecyl sodium sulfate, lauryl sodium sulfate, N,
Dinethylformamide, N-Methyl pyrrolidone are any one or more of.More preferably, it is preferable that the liquid medium exists
Mass percentage x in the gas mediumLiquidValue are as follows: 0 < xLiquid≤ 10%.
In some preferred embodiments, the step of classification includes: using multi-cyclone to step (2)
Rubble ink alkene obtained carries out multiple fractionation, obtains the thin graphene for meeting number of plies requirement；Preferably, using 3~5 grades of whirlwind
Separator carries out the classification to obtain 1-5 layers of thin graphene product；It is highly preferred that by institute in the 1st grade of cyclone separator
The thick graphite or graphene of collection carry out Gas grinding again；With by thickness graphite or stone collected in the 2nd grade of cyclone separator
Black alkene carries out overcritical removing again；Preferably, in classification process, the cyclone separator is heated so that the rotation
The temperature of wind separator maintains the boiling point of liquid medium or more.
In some preferred embodiments, the epoxy resin is modified epoxy.
In some preferred embodiments, the dispersing agent is non-ion aqueous dispersing agent.
In some preferred embodiments, the curing component include 50-90wt% (can for 50wt%,
55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 75wt%, 90wt%) Ammonia curing agent and 10-
50wt% (for example, can for 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%,
Mixed solvent 50wt%).It is highly preferred that the Ammonia curing agent is polyamide, in modified diethylaminopropylamine, fatty amine
It is any one or more；The mixed solvent is that dimethylbenzene, hexone, butanol are any one or more of.
This graphene anticorrosive paint provided by the invention is had excellent performance, and the granularity of the graphene anticorrosive paint is less than 50
Micron, to guarantee that the coating surface after coating film forming is smooth, the graphene anticorrosive paint has the attachment not less than 15MPa
The salt spray resistance duration of power, the graphene anticorrosive paint is not less than 2800 hours.
Most comprehensively, graphene anticorrosive paint provided by the invention includes:
1. film-forming components
The film-forming components include thin graphene slurry, the 15- of the epoxy resin of 15-30wt%, 15-35wt%
The zinc powder of 40wt%, the talcum powder of 5-15wt%, the feldspar powder of 5-15wt%, the titanium dioxide of 1-5wt%, 1-5wt% polyamides
The dispersing agent of amine wax and 0.1-3wt%；
The thin graphene slurry includes graphene and the first solvent, and graphene is in the thin graphene slurry
Mass percentage is 5-20wt%, and graphene is more than 2 microns for the granularity of 1-5 layers of graphene and the graphene；
The epoxy resin is modified epoxy；
The dispersing agent is non-ion aqueous dispersing agent；
First solvent is that dimethylbenzene, hexone, butanol are any one or more of；
The graphene slurry is prepared as follows:
Graphite is subjected to Gas grinding, obtains functionalization crude product；The process conditions of Gas grinding are as follows: pressure 0.5-
1MPa, gas flow 500-5000m3/ h, milling time 10min-24h, grader revolving speed 1000-20000rpm；
The functionalization crude product is removed in the supercritical state, obtains rubble ink alkene；
The rubble ink alkene is classified, the graphene for 1-5 layers is obtained, the graphene is mixed simultaneously with the first solvent
Grinding, obtains the thin graphene slurry；
The Gas grinding includes: graphite to be added in Gas grinding machine, then squeeze into compressed gas, makes graphite fluidizedization
And it collides with each other to realize Gas grinding；
The graphite is that natural graphite, electrographite, expanded graphite, thermal cracking graphite are any one or more of, preferably
For natural graphite；
The compressed gas is that air, carbon dioxide, inert gas are any one or more of, it is preferable that the compression
The pressure of air is 0.5-1MPa；
The overcritical removing includes: that functionalization crude product is introduced into high pressure resistant reaction kettle, is passed through pre-heated
Medium changes the physical chemistry of supercritical fluid by the temperature or pressure or the additional amount of medium of the high pressure resistant reaction kettle of adjusting
Property is to match the critical pressure and critical-temperature of the functionalization crude product；
Until when scheduled pressure value, medium is made to enter supercriticality, pressure reducing valve is opened after being stirred enters material
Kettle is depressurized, makes pressure reduction to normal pressure or lower pressure, obtains rubble ink alkene；
The medium includes gas medium and liquid medium；
The gas medium includes any in carbon dioxide, ammonia, butane and butene mixture, nitrogen, sulfur hexafluoride
Kind is a variety of；
The liquid medium includes water, methanol, ethyl alcohol, isopropanol, dinitrophenol, dodecyl sodium sulfate, dodecane
Base sodium sulphate, N,N-dimethylformamide, N-Methyl pyrrolidone are any one or more of；
Preferably, mass percentage x of the liquid medium in the gas mediumLiquidValue are as follows: 0 < xLiquid≤
10%；
The classification includes: to be classified using 3~5 grades of cyclone separators to rubble ink alkene, obtains 1-5 layers of graphite
Alkene.
2. curing component；
The curing component includes the Ammonia curing agent of 50-90wt% and the mixed solvent of 10-50wt%；The Ammonia is solid
Agent is that polyamide, modified diethylaminopropylamine, fatty amine are any one or more of；The mixed solvent is dimethylbenzene, first
Base isobutyl ketone, butanol are any one or more of.
The graphene anticorrosive paint has the advantage that
(1) for the granularity of graphene anticorrosive paint less than 50 microns, the coating surface after guaranteeing coating film forming is smooth；
(2) graphene anticorrosive paint has the adhesive force not less than 15MPa；
(3) the salt spray resistance duration of graphene anticorrosive paint is not less than 2800 hours；
(4) graphene anticorrosive paint has used a kind of dispersion performance of completely new thinking improvement graphene, without using having
Machine reagent carries out base group modification to the surface of graphene and improves its dispersion performance, reduce with high toxicity, high pollution and
The use of high-cost organic reagent；
(5) the anti-corrosion duration of the single coating of graphene anticorrosive paint is promoted, and can be reduced smear layer and be counted to 2 layers；
(6) thin graphene used of graphene anticorrosive paint has excellent dispersion performance, reduces dispersing agent
Dosage improves the compatibility of system；
(7) content of the zinc powder of graphene anticorrosive paint reduces, so that the flexibility of the coating after film forming and adhesive force obtain
To improve；
(8) preparation process of graphene anticorrosive paint is simply controllable, and cost is relatively low.
The present invention provides a kind of preparation method of graphene anticorrosive paint in second aspect, which includes such as
Lower step:
By epoxy resin, thin graphene slurry, zinc powder, talcum powder, feldspar powder, titanium dioxide, polyamide wax and dispersing agent
It mixes and grinds, obtain film-forming components of the fineness less than 50 microns；
Then curing component is added and stirs, obtains the graphene anticorrosive paint.
The preparation method is simply controllable, and without complex device, high production efficiency, manufacturing cost is low.Furthermore it is also possible to respectively
Make film-forming components and curing component, by the two separate storage, when use mixed use, favorable anti-corrosion effect can equally be made
Graphene anticorrosive paint.
It is the embodiment that the present invention enumerates below.
Embodiment 1
Present embodiments provide a kind of method for producing thin graphene, the equipment that this method is provided using embodiment 1 into
Row, specifically comprises the following steps:
S1, natural graphite is added in Gas grinding machine, then squeezes into compressed air, pressure 0.8MPa makes natural
Graphite fluidizedization simultaneously collides with each other to realize Gas grinding, the process conditions of Gas grinding are as follows: pressure 0.8MPa, gas flow
3000m3/ h, milling time 16h, grader revolving speed 10000rpm, obtain functionalization crude product after grinding, which is
The non-form the few-layer graphene alkene of micron order, granularity is uniformly dispersed close to 2 microns, not easy to reunite.
The step of S2, overcritical removing: functionalization crude product made from step (1) is introduced into high pressure resistant reaction kettle,
It is passed through pre-heated medium, super face is changed by the temperature or pressure or the additional amount of medium of the high pressure resistant reaction unit of adjusting
The physicochemical properties of boundary's fluid are to match the critical pressure and critical-temperature of the functionalization crude product；Until scheduled pressure value
When, so that medium is entered supercriticality, pressure reducing valve is opened after being stirred makes material enter pressure reduction vessel, makes pressure reduction to normal
Pressure or lower pressure, obtain rubble ink alkene；Before opening pressure reducing valve, the pressure in pressure reduction vessel is adjusted to 0.06MPa, and
And normal pressure is adjusted to after the completion of material decompression, then by pressure；Temperature in the pressure reduction vessel is maintained into liquid medium
It is more than boiling point.
The step of S3, classification: 4 classifications are carried out to rubble ink alkene made from step (2) using 4 grades of cyclone separators, are obtained
To thin graphene；Thickness graphite collected in 1st grade of cyclone separator or graphene are subjected to Gas grinding again；With by
Collected thickness graphite or graphene carry out overcritical removing again in 2 grades of cyclone separators；In classification process, to the rotation
Wind separator is heated so that the temperature of the cyclone separator maintains the boiling point of liquid medium or more.
The number of plies of thin graphene obtained is at 1-5 layers, and the granularity of graphene is no more than 2 microns.
Embodiment 2
Present embodiments provide a kind of method for producing thin graphene, the equipment that this method is provided using embodiment 1 into
Row, step is substantially the same with embodiment 1, the difference is that:
In S1, expanded graphite is added in Gas grinding machine, then squeezes into compression carbon dioxide, pressure is
0.5MPa makes expanded graphite fluidization and collides with each other to realize Gas grinding, the process conditions of Gas grinding are as follows: pressure
0.5MPa, gas flow 500m3It is thick to obtain functionalization after grinding by/h, milling time 10min, grader revolving speed 1000rpm
Product.
In S3,5 classifications are carried out using 5 grades of cyclone separators.
The number of plies of thin graphene obtained is at 1-5 layers, and the granularity of graphene is no more than 2 microns.
Embodiment 3
Present embodiments provide a kind of method for producing thin graphene, the equipment that this method is provided using embodiment 1 into
Row, step is substantially the same with embodiment 1, the difference is that:
In S1, natural graphite is added in Gas grinding machine, then squeeze into compressed nitrogen, pressure 1MPa makes day
Right graphite fluidizedization simultaneously collides with each other to realize Gas grinding, the process conditions of Gas grinding are as follows: pressure 1MPa, gas flow
5000m3/ h, for 24 hours, grader revolving speed 20000rpm obtains functionalization crude product to milling time after grinding.
In S3,3 classifications are carried out using 3 grades of cyclone separators.
The number of plies of thin graphene obtained is at 1-5 layers, and the granularity of graphene is no more than 2 microns.
Embodiment 4
A kind of graphene anticorrosive paint is present embodiments provided, which includes:
1. film-forming components
Modified epoxy liquid 90kg, polyamide wax 9kg, graphene slurry (thin graphene+two made from embodiment 1
Toluene is made, and the mass percentage of thin graphene is 20wt%) 54kg, dispersing agent 3kg, titanium dioxide 15kg, talcum powder
30kg, feldspar powder 30kg, zinc powder 69kg.
2. curing component
Polyamide 70kg, dimethylbenzene 30kg.
Specific preparation method comprises the following steps:
S1, by modified epoxy liquid, polyamide wax, graphene slurry is dispersed with stirring 20 minutes after dispersant, then
Titanium dioxide, talcum powder, feldspar powder and zinc powder are sequentially added, stirring 15 minutes is continued, is then ground 60 minutes, until fineness is less than
50 microns；
S2, polyamide and dimethylbenzene is added in product obtained into S1, is dispersed with stirring 15 minutes.
In use, matching film-forming components, curing component according to construction demand.
The product is tested to the inhibitor effectiveness of steel using standard ASTMB117 salt spray resistance, obtains following result:
As can be seen that the anti-corrosion duration of this product is much higher than standard priming paint.
The adhesive force of the invention is measured with the method for pulling open, is greater than 15MPa, and adhesive force is excellent.
Embodiment 5
A kind of graphene anticorrosive paint is present embodiments provided, which includes:
1. film-forming components
Modified epoxy liquid 45kg, polyamide wax 3kg, graphene slurry (thin graphene+two made from embodiment 2
Toluene is made, and the mass percentage of thin graphene is 5wt%) 99kg, dispersing agent 9kg, titanium dioxide 15kg, talcum powder
39kg, feldspar powder 45kg, zinc powder 45kg.
2. curing component
Polyamide 50kg, dimethylbenzene 50kg.
Specific preparation method comprises the following steps:
S1, by modified epoxy liquid, polyamide wax, graphene slurry is dispersed with stirring 20 minutes after dispersant, then
Titanium dioxide, talcum powder, feldspar powder and zinc powder are sequentially added, stirring 15 minutes is continued, is then ground 60 minutes, until fineness is less than
50 microns；
S2, polyamide and dimethylbenzene is added in product obtained into S1, is dispersed with stirring 15 minutes.
In use, matching film-forming components, curing component according to construction demand.
The product is tested to the inhibitor effectiveness of steel using standard ASTMB117 salt spray resistance, obtains following result:
| This product | Standard epoxy zinc rich primer | |
| Coating thickness/micron | 80 | 80 |
| Salt spray resistance duration/hour | 2800 | 1500 |
As can be seen that the anti-corrosion duration of this product is much higher than standard priming paint.
The adhesive force of the invention is measured with the method for pulling open, is greater than 15MPa, and adhesive force is excellent.
Embodiment 6
A kind of graphene anticorrosive paint is present embodiments provided, which includes:
1. film-forming components
Modified epoxy liquid 75kg, polyamide wax 15kg, graphene slurry (thin graphene+two made from embodiment 3
Toluene is made, and the mass percentage of thin graphene is 15wt%) 75kg, dispersing agent 1.5kg, titanium dioxide 4.5kg, talcum powder
15kg, feldspar powder 15kg, zinc powder 99kg.
2. curing component
Polyamide 6 0kg, dimethylbenzene 40kg.
Specific preparation method comprises the following steps:
S1, by modified epoxy liquid, polyamide wax, graphene slurry is dispersed with stirring 20 minutes after dispersant, then
Titanium dioxide, talcum powder, feldspar powder and zinc powder are sequentially added, stirring 15 minutes is continued, is then ground 60 minutes, until fineness is less than
50 microns；
S2, polyamide and dimethylbenzene is added in product obtained into S1, is dispersed with stirring 15 minutes.
In use, matching film-forming components, curing component according to construction demand.
The product is tested to the inhibitor effectiveness of steel using standard ASTMB117 salt spray resistance, obtains following result:
| This product | Standard epoxy zinc rich primer | |
| Coating thickness/micron | 80 | 80 |
| Salt spray resistance duration/hour | 3500 | 1500 |
As can be seen that the anti-corrosion duration of this product is much higher than standard priming paint.
The adhesive force of the invention is measured with the method for pulling open, is greater than 15MPa, and adhesive force is excellent.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of graphene anticorrosive paint, which is characterized in that include film-forming components and curing component；
The film-forming components include the epoxy resin of 15-30wt%, the thin graphene slurry of 15-35wt%, 15-40wt%
Zinc powder, the talcum powder of 5-15wt%, the feldspar powder of 5-15wt%, the titanium dioxide of 1-5wt%, 1-5wt% polyamide wax and
The dispersing agent of 0.1-3wt%；
Wherein, the thin graphene slurry includes graphene and the first solvent, and graphene is in the thin graphene slurry
Mass percentage be 5-20wt%；
The graphene is no more than 2 microns for the granularity of 1-5 layers of graphene and the graphene.
2. graphene anticorrosive paint according to claim 1, which is characterized in that the thin graphene slurry is according to as follows
It is prepared by method:
Graphite is subjected to Gas grinding, obtains functionalization crude product；The process conditions of Gas grinding are as follows: pressure 0.5-1MPa, gas
Body flow 500-5000m3/ h, milling time 10min-24h, grader revolving speed 1000-20000rpm；
The functionalization crude product is removed in the supercritical state, obtains rubble ink alkene；
The rubble ink alkene is classified, the graphene for 1-5 layers is obtained, the graphene is mixed and ground with the first solvent
Mill, obtains the thin graphene slurry.
3. graphene anticorrosive paint according to claim 2, which is characterized in that the Gas grinding includes: to add graphite
Enter into Gas grinding machine, then squeeze into compressed gas, make graphite fluidizedization and collides with each other to realize Gas grinding；
The graphite is that natural graphite, electrographite, expanded graphite, thermal cracking graphite are any one or more of, preferably day
Right graphite；
The compressed gas is that air, carbon dioxide, inert gas are any one or more of, it is preferable that the compressed air
Pressure be 0.5-1MPa.
4. graphene anticorrosive paint according to claim 2, which is characterized in that the overcritical removing includes: by function
Change crude product to be introduced into high pressure resistant reaction kettle, be passed through pre-heated medium, by adjust high pressure resistant reaction kettle temperature or
Pressure or the additional amount of medium change the physicochemical properties of supercritical fluid to match the critical of the functionalization crude product
Pressure and critical-temperature；
Until when scheduled pressure value, medium is made to enter supercriticality, pressure reducing valve is opened after being stirred makes material enter decompression
Kettle makes pressure reduction to normal pressure or lower pressure, obtains rubble ink alkene；
The medium includes gas medium and liquid medium；
The gas medium include any one of carbon dioxide, ammonia, butane and butene mixture, nitrogen, sulfur hexafluoride or
It is a variety of；
The liquid medium includes water, methanol, ethyl alcohol, isopropanol, dinitrophenol, dodecyl sodium sulfate, dodecyl sulphur
Sour sodium, N,N-dimethylformamide, N-Methyl pyrrolidone are any one or more of；
Preferably, mass percentage x of the liquid medium in the gas mediumLiquidValue are as follows: 0 < xLiquid≤ 10%.
5. graphene anticorrosive paint according to claim 2, which is characterized in that the classification includes: to be revolved using 3~5 grades
Wind separator is classified rubble ink alkene, obtains 1-5 layers of graphene.
6. graphene anticorrosive paint according to claim 1, which is characterized in that the epoxy resin is modified epoxy tree
Rouge；
The dispersing agent is non-ion aqueous dispersing agent；And/or
First solvent is that dimethylbenzene, hexone, butanol are any one or more of.
7. graphene anticorrosive paint according to claim 1, which is characterized in that the curing component includes 50-90wt%
Ammonia curing agent and 10-50wt% mixed solvent.
8. graphene anticorrosive paint according to claim 7, which is characterized in that
The Ammonia curing agent is that polyamide, modified diethylaminopropylamine, fatty amine are any one or more of；And/or
The mixed solvent is that dimethylbenzene, hexone, butanol are any one or more of.
9. graphene anticorrosive paint according to claim 1, which is characterized in that the granularity of the graphene anticorrosive paint is small
In 50 microns；
The graphene anticorrosive paint has the adhesive force not less than 15MPa；
The salt spray resistance duration of the graphene anticorrosive paint is not less than 2800 hours.
10. a kind of preparation method of any one of claim 1 to 9 graphene anticorrosive paint, which is characterized in that including as follows
Step:
By epoxy resin, thin graphene slurry, zinc powder, talcum powder, feldspar powder, titanium dioxide, polyamide wax and dispersant
And grind, obtain film-forming components of the fineness less than 50 microns；
Then curing component is added and stirs, obtains the graphene anticorrosive paint.
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| CN110760211A (en) * | 2019-11-29 | 2020-02-07 | 西安交通大学 | Anticorrosive paint and preparation method thereof |
| CN111117484A (en) * | 2019-12-27 | 2020-05-08 | 宁波知源新材料有限公司 | Anticorrosive composition containing sheet-like carbon material |
| CN111690283A (en) * | 2020-05-18 | 2020-09-22 | 上海帕吉索纳米技术有限公司 | High-concentration salt-spray-resistant graphene slurry and preparation method thereof |
| CN112280358A (en) * | 2020-10-29 | 2021-01-29 | 湖南省德谦新材料有限公司 | Graphene antistatic coating |
| CN112592642A (en) * | 2020-12-16 | 2021-04-02 | 石墨烯科技有限公司 | Graphene primer and preparation method thereof |
| CN112708327A (en) * | 2020-12-28 | 2021-04-27 | 杭州泓蓝环保科技有限公司 | Graphene anticorrosive paint and preparation method thereof |
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Application publication date: 20191025 |