CN107201071A - A kind of graphene sheet Conductive mica oil tank static electricity conductive anticorrosive paint and preparation method thereof - Google Patents
A kind of graphene sheet Conductive mica oil tank static electricity conductive anticorrosive paint and preparation method thereof Download PDFInfo
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- 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
- C09D5/24—Electrically-conducting paints
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- 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
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Abstract
The invention discloses a kind of graphene-sheets of conductive mica oil tank static electricity conductive anticorrosive paint and preparation method thereof, the coating is using epoxy resin as matrix resin, using modified graphene and Conductive mica as two-component conductive filler, using Isocyanates curing agent.This coating has preferable static conductive, thermal conductivity, Corrosion Protection etc., and this method technique is simple, and raw material sources are extensive.The graphene that the present invention is provided-sheets of conductive mica oil tank static electricity conductive anticorrosive paint preparation method mainly includes：The synthesis of modified graphene, the synthesis of isocyanate trimer and the preparation of oil tank static electricity conductive anticorrosive paint, it is used as two-component conductive filler using graphene and sheets of conductive mica, epoxy resin is matrix resin, adds appropriate solvent, obtains graphene sheet Conductive mica oil tank static conductive coating.
Description
Technical field
The present invention relates to a kind of oil tank static electricity conductive anticorrosive paint, led more particularly to a kind of graphene-sheet
Electric mica oil tank static electricity conductive anticorrosive paint and preparation method thereof, belongs to static conductive coating production technical field.
Background technology
Static conductive coating generally refers to be coated on electrical insulator base material, accumulates quiet with conducting electric current and can eliminate
One class specific functionality coating of electric charge, electromagnetic shielding and electrical heating ability, is broadly divided into admixing type and intrinsically conducting coating,
It is widely used in the every field such as electronic apparatus, building, chemical industry equipment, military affairs.Admixing type electrically-conducting paint is
Incorporation metal particle makes the conductive energy of high polymer, this electric conductivity and the intrinsic spy of non-polymer in insulation high polymer
Property, its conducting process is to provide conducting carriers to realize by the electrically conductive particles mixed, such as graphite, carbon black, mica.It is intrinsic
Type electrically-conducting paint is that, using conduction high polymer as basic film forming matter, " intrinsic " electric conductivity possessed in itself with high polymer makes painting
Layer is conductive, and conductive polymer molecules itself provides conducting carriers.Because conducting polymer composite synthesizes difficult more, cost
It is higher, it is main at present to use admixing type technology, mainly it is made up of conductive filler, resin, diluent and auxiliary agent.
Graphene be it is in recent years newfound by single layer of carbon atom it is tightly packed into a kind of carbon with two-dimensional slice structure
Material, each carbon atom passes throughKey is connected with three carbon atoms closed on, with high mechanical property, while its intensity
High and good conductivity, is excellent conductive filler.The carrier mobility of graphene reaches 200000cm2V-1s-1, more than commercial silicon
More than 10 times of piece mobility, with than silver or copper also high conductance (106Scm-1), while its theoretical specific surface area is up to
2600m2/ g, has more prominent performance compared to traditional carbon conductive filler.The A's of Publication No. CN 101508855
Chinese patent discloses a kind of watersoluble plumbago electrically-conducting paint and preparation method thereof, and its adhesive force is 2-3 grades, but adhesive force is poor；
The A of Publication No. CN 103131232 disclose a kind of high-performance water-based graphene conductive coating and preparation method thereof, publication number
CN104163928A discloses a kind of conductive and heat-conductive graphene slurry and coating, and the conductive filler consumption of two patents is more,
Cause painting color deeper, the coating transparency or richness of formation be not high；The A of Publication No. CN 102254584 China is specially
Profit discloses a kind of common conductive slurry based on graphene filler, is mutually combined and is filled out as conduction with conductive material by the use of graphene
Material, with good electric conductivity, but electrocondution slurry amount of filler is more, and the consumption of especially graphene is more, and cost is high, and
There are problems that it is difficult scattered, with resin compatible is slightly worse, adhesive force.
Sheets of conductive mica have nontoxic, tasteless, "dead", light, electrical conductivity it is high, it is with low cost many advantages, such as,
It is also good conductive filler, coordinates graphene, using can not only improve the electric conductivity of coating, can also increase in coating
The mechanical property of strong coating.
Therefore it is to meet the market demand, it is necessary to develop high stability, high electrostatic conductive performance while having anticorrosion concurrently
The oil tank electrically-conducting paint of performance, the problem of presently, there are with solution.
The content of the invention
It is an object of the invention to solve the problem of prior art is present, there is provided a kind of graphene-sheet with deficiency
Conductive mica oil tank static electricity conductive anticorrosive paint and preparation method thereof, graphene made from this method-sheets of conductive mica oil tank
Static electricity conductive anticorrosive paint has preferable static conductive, thermal conductivity, Corrosion Protection etc., and this method technique is simple, raw material sources
Extensively.
The purpose of the present invention can be reached by following measures：
A kind of graphene-sheets of conductive mica oil tank static electricity conductive anticorrosive paint, the coating is using epoxy resin as matrix tree
Fat, using modified graphene and Conductive mica as two-component conductive filler, using Isocyanates curing agent.
In a kind of scheme, the coating contains solvent, or also contains auxiliary agent or pigment.
The proportion by weight of each component is in the coating of the present invention：50~70 parts of epoxy resin, modified graphene 0.1~5
Part, 15~30 parts of Conductive mica, 5~15 parts of Isocyanates curing agent, 5~25 parts of solvent；Or further contain in the coating
There is the component of one or more of following mass parts：1~3 part of auxiliary agent, 1~3.5 part of pigment.
In a kind of scheme, the proportion by weight of each component is in coating of the present invention：50~60 parts of epoxy resin, modified stone
Black 0.3~3 part of alkene, 15~25 parts of Conductive mica, 10~15 parts of Isocyanates curing agent, 5~20 parts of solvent；Or the coating
In component further containing one or more of following mass parts：1~3 part of auxiliary agent, 1~3.5 part of pigment.
Modified graphene in the present invention is the modified graphene of acidification or the modified graphene of grafting processing.
Wherein the modified graphene of acidification is the carboxy-modified graphene being modified by the concentrated sulfuric acid with concentrated nitric acid；Connect
The modified graphene of branch processing is the graphene by silane coupler modified grafted silane coupling agent.
A kind of synthesis step of the modified graphene of acidification is：It is sufficiently stirred for after graphene is mixed with the concentrated sulfuric acid,
Carry out ultrasonic vibration again, then add concentrated nitric acid mixed, then at 130~170 DEG C reaction, after should after filter out product
And dry, obtain the modified graphene of acidification.Wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 4:1.
A kind of synthetic method of the modified graphene of more specifically acidification is as follows：A small amount of graphene is terminated in into 150ml
In single-necked flask, the 50ml concentrated sulfuric acids are then poured into, magnetic agitation 5h, ultrasonic vibration 4h adds concentrated nitric acid (dense sulphur into flask again
Acid is 4 with concentrated nitric acid volume ratio:1), magnetic agitation 30min, the constant-temperature condensation backflow 2h of 150 DEG C or so of immigration, takes out mixing
Thing, and diluted with frozen water, then filtering is repeated with the less filter membrane in aperture, the product after filtering is placed in 50 DEG C of freeze-day with constant temperature
8h is dried in case, that is, obtains carboxy-modified graphene.
It is a kind of be grafted processing the synthesis step of modified graphene be：The ethanol of the silane coupler of first secure ph 4~6
Solution, adds graphene and carries out ultrasonic disperse, then reacted at 50~70 DEG C, washing, filtering and drying after reaction is obtained
To the modified graphene of grafting processing.Wherein silane coupler be gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-γ-
Aminopropyl trimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-γ-ammonia
Propyl-triethoxysilicane, N- (β-aminoethyl)-γ-aminopropyltriethoxy diethoxy silane, polyamino alkyltri silicon
One or more in alkane.
A kind of synthetic method for the modified graphene for being more specifically grafted processing is as follows：In a certain amount of ethanol solution
In, a small amount of hydrochloric acid is instilled, regulation pH value to 4.5-5.5 adds a certain amount of silane coupler, is configured to 3% mixed solution,
Stirred evenly with glass bar, be fully hydrolyzed it, 90ml graphenes are added in the solution, reactant is placed in constant temperature by ultrasonic disperse 2h
60 DEG C, 6h is stirred, reactant is taken out, is cooled to room temperature, unreacted silane coupler is washed away with acetone, then carried out with filter membrane
Filter, is finally placed in 50 DEG C of vacuum drying chambers and dries 8h, that is, obtain the graphene of grafted silane coupling agent.
Epoxy resin in the present invention can use various epoxy resin of the prior art, it is preferred to use E-35, E-31, E-
20th, the one or more in E-14, E-12, E-06, E-03.
Conductive mica in the present invention uses sheets of conductive mica.
Isocyanates curing agent in the present invention in TDI tripolymers, HDI trimer, TDI/TMP addition products one
Plant or several.
Solvent in the present invention can use dimethylbenzene, n-butanol, cyclohexanone, ethyl acetate and PMA one or more.
Auxiliary agent in the present invention be one kind in zinc naphthenate, zinc Isoocatanoate, BYK-310, BYK-300, TEGO-300 or
It is several.
Pigment in the present invention can be using TR-33 titanium dioxides, 696 titanium whites, 596 titanium whites, N234 carbon blacks, U carbon blacks etc..
The concentrated sulfuric acid in the present invention refers to the concentrated nitric acid in the sulfuric acid solution that mass fraction is more than or equal to 70%, the present invention
Refer to mass fraction for 65% or herein on and concentration be less than fuming nitric aicd salpeter solution.
A kind of preparation method of Isocyanates curing agent is：Add isocyanates in the reactor, add solvent and
Catalyst, stirring and dissolving, heating response NCO%=7.5%-8.5% adds the polymerization inhibitor with catalyst equimolar amounts, after
Cooling discharge after continuous stirring reaction, that is, obtain isocyanate trimer；
Present invention also offers a kind of synthesis step of specific isocyanate trimer：Isocyanic acid is added in the reactor
Ester, adds the dissolving of same amount of stirring solvent, adds catalyst, heating response to NCO%=7.5%-8.5%, add with
The polymerization inhibitor of catalyst equimolar amounts, continues to stir 0.5h, cooling discharge is to obtain isocyanate trimer.
In the preparation of curing agent, further technical scheme is described isocyanates in TDI, MDI, HDI
It is one or more of；Described solvent is the mixing of N,N-dimethylformamide, butyl acetate, ethyl acetate or DMF and dimethylbenzene
Solvent；Described catalyst is a kind of in triethylene diamine, stannous octoate, three-(dimethylamino methyl) phenol or they mixed
Catalyst is closed, catalyst amount is less than the 0.5%-1.0% of raw material gross weight；Described polymerization inhibitor is phosphoric acid, chlorobenzoyl chloride, right
It is a kind of in toluene sulfonic acide；Described heating response temperature is 30-90 DEG C.
Invention further provides a kind of preparation side of graphene-sheets of conductive mica oil tank static electricity conductive anticorrosive paint
Method, it comprises the following steps：It is that matrix resin, modified graphene, Conductive mica, solvent are mixed evenly by epoxy resin,
Or further addition auxiliary agent and pigment are well mixed, and oil tank static electricity conductive anticorrosive paint paint liquid is made；Solidified using preceding add
Agent and solvent, are mixed evenly, and obtain oil tank static electricity conductive anticorrosive paint paint liquid.
Compared with existing static conductive coating the invention has the advantages that：
(1) synthetic method craft of the invention is simple, and course of reaction is easily controllable, and reaction condition is gentle, by modified
Graphene, can be scattered in resin well.
(2) present invention cooperates with graphene and sheets of conductive mica in coating and merely by graphene or sheet
Conductive mica is used to compare in coating, plays equal conductive effect addition and significantly reduces, because flake graphite alkene and sheet are led
Conductive path is more readily formed in electric mica, and electric conductivity is also relatively stablized；
(3) technique remaining is wide, is easy to implement sane production, and product has a extensive future.
(4) flake graphite alkene and sheets of conductive mica act synergistically in coating system can form three-dimensional shape conductive mesh
Network, can not only strengthen the electric conductivity of coating, and its special construction can also significantly increase the mechanical property of coating, have concurrently simultaneously
Certain Corrosion Protection.
Embodiment
Illustrate the present invention below by way of specific embodiment, but the present invention is not merely defined in these embodiments.
The preparation of carboxy-modified graphene
2.0g graphenes are placed in 150ml single-necked flasks, the 50ml concentrated sulfuric acids, magnetic agitation 5h, ultrasound is then poured into
4h-5h is vibrated, then into flask adds concentrated nitric acid (concentrated sulfuric acid and concentrated nitric acid volume ratio is 4:1), magnetic agitation 30min, is moved into
150 DEG C or so of constant-temperature condensation backflow 2h, takes out mixture, and is diluted with frozen water, then is repeated with the less filter membrane in aperture
Filtering, until being adjusted to PH close to 7, the product after filtering is placed in 50 DEG C of thermostatic drying chambers 8h is dried, that is, obtain carboxylic
The graphene powder that base is modified, also known as modified graphene (acidifying).
The preparation of grafted silane coupling agent graphene
In 50ml ethanol solution, 10-20 drop hydrochloric acid is instilled, regulation pH value to 4.5-5.5 is added a certain amount of
Silane coupler, be configured to 3% mixed solution, stirred evenly with glass bar, be fully hydrolyzed it, in the solution add 90ml graphite
Reactant is placed in 60 DEG C of constant temperature by alkene, ultrasonic disperse 2h, stirs 2-6h, is taken out reactant, is cooled to room temperature, is washed away with acetone
Unreacted silane coupler, then filtered with filter membrane, finally it is placed in 50 DEG C of vacuum drying chambers and dries 10h, that is, is grafted
The modified graphene of the graphene of silane coupler, also known as silane coupler grafting processing.
The preparation of TDI tripolymers
The synthesis of toluene diisocyanate trimer：Equipped with reflux condensing tube, three mouthfuls of reactions of thermometer and agitator
A certain amount of toluene di-isocyanate(TDI) is added in bottle, same amount of dimethylbenzene stirring and dissolving is added, catalyst three-(dimethylamine is added
Ylmethyl) phenol, 60 DEG C of reactions are heated to, during to NCO%=8.6%, the polymerization inhibitor chlorobenzoyl chloride with catalyst equivalent are added,
Continue to stir 0.5h, be diluted to dimethylbenzene and produce TDI tripolymers containing 53% admittedly.
Conductive mica uses sheets of conductive mica.
Embodiment 1
The preparation of graphene-sheets of conductive mica Static Electric ity Conduc tive Antic：By above-mentioned modified graphene (acid
Change) 0.5 part, 10 parts of TDI tripolymers, 20.5 parts of Conductive mica, 3 parts of cyclohexanone, 7 parts of dimethylbenzene, 2 parts of n-butanol, epoxy resin
55 parts, well mixed, obtained grayish paint liquid is stirred at room temperature, admittedly containing 55.8% (120 DEG C/1g/2h), viscosity 120.3s (applies 4
Cup, 25 DEG C), it is that oil tank conductive coating is made by technique making sheet.Performance is shown in Table 1 after testing.
Embodiment 2
From the modified graphene of acidification.Paint is carried out according to the method for embodiment 1, control modified graphene etc. is added
The ratio of thing, 1 part of modified graphene (acidifying), 10 parts of TDI tripolymers, 19 parts of Conductive mica, 3 parts of cyclohexanone, 7 parts of dimethylbenzene,
2 parts of n-butanol, 55 parts of epoxy resin is stirred at room temperature well mixed, and grayish paint liquid is made, admittedly containing 57.5% (120 DEG C/1g/
2h), viscosity 125.9s (applying 4 glasss, 25 DEG C), is that oil tank conductive coating is made by technique making sheet.Performance is shown in Table 1 after testing.
Embodiment 3
From the modified graphene of acidification.Paint is carried out according to the method for embodiment 1, control modified graphene etc. is added
The ratio of thing, 1.5 parts of modified graphene (acidifying), 10 parts of TDI tripolymers, 18.5 parts of Conductive mica, 3 parts of cyclohexanone, dimethylbenzene 7
Part, 2 parts of n-butanol, 55 parts of epoxy resin is stirred at room temperature well mixed, and grayish paint liquid is made, admittedly containing 56.5% (120 DEG C/
1g/2h), viscosity 123.5s (applying 4 glasss, 25 DEG C), is that oil tank conductive coating is made by technique making sheet.Performance is shown in Table 2 after testing.
Embodiment 4
The modified graphene of processing is grafted from silane coupler.Paint, the modified stone of control are carried out according to the method for embodiment 1
The ratio of the additives such as black alkene, 0.5 part of modified graphene (grafting), 10 parts of TDI tripolymers, 20.5 parts of Conductive mica, cyclohexanone 3
Part, well mixed, obtained grayish paint liquid is stirred at room temperature in 7 parts of dimethylbenzene, 2 parts of n-butanol, 55 parts of epoxy resin, admittedly contain
58.7% (120 DEG C/1g/2h), viscosity 127.4s (applies 4 glasss, 25 DEG C), is that oil tank conductive coating is made by technique making sheet.Through inspection
Survey performance and be shown in Table 2.
Embodiment 5
The modified graphene of processing is grafted from silane coupler.Paint, the modified stone of control are carried out according to the method for embodiment 1
The ratio of the additives such as black alkene, 1.0 parts of modified graphene (grafting), 10 parts of TDI tripolymers, 19 parts of Conductive mica, cyclohexanone 3
Part, well mixed, obtained grayish paint liquid is stirred at room temperature in 7 parts of dimethylbenzene, 2 parts of n-butanol, 55 parts of epoxy resin, admittedly contain
59.5% (120 DEG C/1g/2h), viscosity 130.5s (applies 4 glasss, 25 DEG C), is that oil tank conductive coating is made by technique making sheet.Through inspection
Survey performance and be shown in Table 2.
Embodiment 6
The modified graphene of processing is grafted from silane coupler.Paint, the modified stone of control are carried out according to the method for embodiment 1
The ratio of the additives such as black alkene, 1.5 parts of modified graphene (grafting), 10 parts of TDI tripolymers, 18.5 parts of Conductive mica, cyclohexanone 3
Part, well mixed, obtained grayish paint liquid is stirred at room temperature in 7 parts of dimethylbenzene, 2 parts of n-butanol, 55 parts of epoxy resin, admittedly contain
60.5% (120 DEG C/1g/2h), viscosity 135.6s (applies 4 glasss, 25 DEG C), is that oil tank conductive coating is made by technique making sheet.Through inspection
Survey performance and be shown in Table 2.
Comparative example 1
The preparation of sheets of conductive mica Static Electric ity Conduc tive Antic：By 10 parts of TDI tripolymers, Conductive mica 21
Part, well mixed, obtained grayish paint is stirred at room temperature in 3 parts of cyclohexanone, 7 parts of dimethylbenzene, 2 parts of n-butanol, 55 parts of epoxy resin
Liquid, is that oil tank conductive coating is made by technique making sheet admittedly containing 56.2% (120 DEG C/1g/2h), viscosity 125s (applies 4 glasss, 25 DEG C).
Performance is shown in Table 1 after testing.
Comparative example 2
The preparation of unmodified graphene Static Electric ity Conduc tive Antic：By 1.5 parts of graphene, TDI tripolymers 10
Part, well mixed, system is stirred at room temperature in 10 parts of titanium dioxide, 3 parts of cyclohexanone, 7 parts of dimethylbenzene, 2 parts of n-butanol, 55 parts of epoxy resin
Grayish paint liquid is obtained, admittedly containing 45.8% (120 DEG C/1g/2h), viscosity 108s (applies 4 glasss, 25 DEG C), is to be made by technique making sheet
Oil tank conductive coating.Performance is shown in Table 1 after testing.
Comparative example 3
From the preparation of acidification modified graphene Static Electric ity Conduc tive Antic：By above-mentioned modified graphene
1.5 parts of (acidifying), 10 parts of TDI tripolymers, 10 parts of titanium dioxide, 3 parts of cyclohexanone, 7 parts of dimethylbenzene, 2 parts of n-butanol, epoxy resin 55
Part, it is stirred at room temperature well mixed, grayish paint liquid is made, admittedly containing 44.56% (120 DEG C/1g/2h), viscosity 105s (4 glasss are applied,
25 DEG C), it is that oil tank conductive coating is made by technique making sheet.Performance is shown in Table 1 after testing.
Comparative example 4
The modified graphene for being grafted processing from silane coupler prepares Static Electric ity Conduc tive Antic：Will be above-mentioned
1.5 parts of modified graphene (grafting), 10 parts of TDI tripolymers, 10 parts of titanium dioxide, 3 parts of cyclohexanone, 7 parts of dimethylbenzene, 2 parts of n-butanol,
55 parts of epoxy resin, is stirred at room temperature well mixed, obtained grayish paint liquid, admittedly containing 45.0% (120 DEG C/1g/2h), viscosity
106.3s (applies 4 glasss, 25 DEG C), is that oil tank conductive coating is made by technique making sheet.Performance is shown in Table 1 after testing.
Table 1：Oil tank conductive paint performance test report obtained by the present invention
Table 2：Oil tank conductive paint performance test report obtained by the present invention
Claims (10)
1. a kind of graphene-sheets of conductive mica oil tank static electricity conductive anticorrosive paint, it is characterised in that the coating is with epoxy resin
For matrix resin, using modified graphene and Conductive mica as two-component conductive filler, using Isocyanates curing agent.
2. graphene according to claim 1-sheets of conductive mica oil tank static electricity conductive anticorrosive paint, it is characterised in that should
Coating contains solvent, or also contains auxiliary agent or pigment.
3. graphene according to claim 2-sheets of conductive mica oil tank static electricity conductive anticorrosive paint, it is characterised in that should
The proportion by weight of each component is in coating：50~70 parts of epoxy resin, 0.1~5 part of modified graphene, Conductive mica 15~30
Part, 5~15 parts of Isocyanates curing agent, 5~25 parts of solvent；Or further containing one or more of following matter in the coating
Measure the component of part：1~3 part of auxiliary agent, 1~3.5 part of pigment.
4. graphene according to claim 3-sheets of conductive mica oil tank static electricity conductive anticorrosive paint, it is characterised in that should
The proportion by weight of each component is in coating：50~60 parts of epoxy resin, 0.3~3 part of modified graphene, Conductive mica 15~25
Part, 10~15 parts of Isocyanates curing agent, 5~20 parts of solvent；Or further containing one or more of as follows in the coating
The component of mass parts：1~3 part of auxiliary agent, 1~3.5 part of pigment.
5. graphene-sheets of conductive mica oil tank static electricity conductive anticorrosive according to any one in Claims 1 to 4 is applied
Material, it is characterised in that the modified graphene is the modified graphene of acidification or the modified graphene of grafting processing；It is described
The modified graphene of acidification is the carboxy-modified graphene being modified by the concentrated sulfuric acid with concentrated nitric acid；The grafting processing
Modified graphene is the graphene by silane coupler modified grafted silane coupling agent.
6. graphene according to claim 5-sheets of conductive mica oil tank static electricity conductive anticorrosive paint, it is characterised in that institute
The synthesis step for stating the modified graphene of acidification is：It is sufficiently stirred for after graphene is mixed with the concentrated sulfuric acid, then carries out ultrasound
Concussion, then add concentrated nitric acid mixed, then at 130~170 DEG C reaction, after should after filter out product and drying, obtain
To the modified graphene of acidification；The synthesis step of modified graphene of the grafting processing is：First secure ph 4~6
The ethanol solution of silane coupler, adds graphene and carries out ultrasonic disperse, then reacted at 50~70 DEG C, after reaction
Washing, filtering and drying, obtains the modified graphene of grafting processing.
7. graphene according to claim 6-sheets of conductive mica oil tank static electricity conductive anticorrosive paint, it is characterised in that institute
In the synthesis for the modified graphene for stating acidification, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 4:1；It is grafted the modified graphite of processing
In the synthesis of alkene, the silane coupler is gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-γ-aminopropyl trimethoxy
Base silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy
Silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy diethoxy silane, one kind in polyamino alkyltrialkoxysilaneand or
It is several.
8. graphene-sheets of conductive mica oil tank static electricity conductive anticorrosive according to any one in Claims 1 to 4 is applied
Material, it is characterised in that the epoxy resin is the one or more in E-35, E-31, E-20, E-14, E-12, E-06, E-03；
The Conductive mica is sheets of conductive mica, and the Isocyanates curing agent is selected from TDI tripolymers, HDI trimer, TDI/
One or more in TMP addition products；The solvent is dimethylbenzene, n-butanol, cyclohexanone, ethyl acetate, PMA one kind or several
Kind；The auxiliary agent is the one or more in zinc naphthenate, zinc Isoocatanoate, BYK310, BYK300, TEGO300；The pigment is
One or more in TR-33 titanium whites, 696 titanium whites, 596 titanium whites, N234 carbon blacks, U carbon blacks.
9. graphene according to claim 8-sheets of conductive mica oil tank static electricity conductive anticorrosive paint, it is characterised in that institute
The preparation method for stating Isocyanates curing agent is：Isocyanates is added in the reactor, solvent and catalyst is added, and is stirred
Dissolving, heating response NCO%=7.5%-8.5% adds the polymerization inhibitor with catalyst equimolar amounts, continues after stirring reaction
Cooling discharge, that is, obtain isocyanate trimer；Wherein isocyanates is the one or more in TDI, MDI, HDI；Described
Solvent is the mixed solvent of N,N-dimethylformamide, butyl acetate, ethyl acetate or DMF and dimethylbenzene；Described catalyst
For a kind of or their mixed catalyst in triethylene diamine, stannous octoate, three-(dimethylamino methyl) phenol, catalyst is used
0.5%-1.0% of the amount less than raw material gross weight；Described polymerization inhibitor is one kind in phosphoric acid, chlorobenzoyl chloride, p-methyl benzenesulfonic acid；
Described heating response temperature is 30-90 DEG C.
10. the preparation method of graphene-sheets of conductive mica oil tank static electricity conductive anticorrosive paint described in claim 4, it is special
Levy and be to comprise the following steps：It is that matrix resin, modified graphene, Conductive mica, solvent are mixed evenly by epoxy resin,
Or further addition auxiliary agent and pigment are well mixed, and oil tank static electricity conductive anticorrosive paint paint liquid is made；Solidified using preceding add
Agent and solvent, are mixed evenly, and obtain oil tank static electricity conductive anticorrosive paint paint liquid.
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| CN108864899A (en) * | 2017-12-29 | 2018-11-23 | 厦门中凯新材石墨烯科技有限公司 | A kind of double tank skin graphene anti-corrosion resins and preparation method thereof and application method |
| CN109943190A (en) * | 2019-01-31 | 2019-06-28 | 北京化工大学 | A kind of static electricity conductive anticorrosive function and service coating material, preparation method and application |
| CN110183939A (en) * | 2019-06-26 | 2019-08-30 | 陕西科技大学 | A kind of preparation method of graphene/anti-corrosive paint of epoxy resin |
| CN110330652A (en) * | 2019-06-26 | 2019-10-15 | 兴业皮革科技股份有限公司 | A kind of preparation method of the graphene-based polysiloxanes of low-viscosity and the method for reducing graphene-based silicone cross degree |
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| CN111205738A (en) * | 2020-03-06 | 2020-05-29 | 涂创时代(苏州)科技开发有限公司 | Low-zinc anticorrosive composition compounded by graphene and flaky conductive material and application thereof |
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| CN108003388A (en) * | 2017-11-30 | 2018-05-08 | 山东省圣泉生物质石墨烯研究院 | A kind of Conductive mica, Preparation method and use |
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| CN111205738B (en) * | 2020-03-06 | 2021-08-17 | 涂创时代(苏州)科技开发有限公司 | Low-zinc anticorrosive composition compounded by graphene and flaky conductive material and application thereof |
| CN113831801A (en) * | 2021-10-29 | 2021-12-24 | 闽江学院 | Coating for inhibiting ink migration and preparation method and application thereof |
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