CN108531038A - A kind of sea water resistance graphene modified anti-corrosive coating and preparation method thereof - Google Patents

A kind of sea water resistance graphene modified anti-corrosive coating and preparation method thereof Download PDF

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CN108531038A
CN108531038A CN201810365119.7A CN201810365119A CN108531038A CN 108531038 A CN108531038 A CN 108531038A CN 201810365119 A CN201810365119 A CN 201810365119A CN 108531038 A CN108531038 A CN 108531038A
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王树立
朱建康
饶永超
赵书华
白浩然
冯大成
才政
陈磊
黄俊尧
陈锋
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Changzhou University
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • 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
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    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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    • 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
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    • C—CHEMISTRY; METALLURGY
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Abstract

A kind of sea water resistance graphene modified anti-corrosive coating of the present invention, it includes following parts by weight of component, component A, 20%~30% epoxy resin, 3%~10%Fe3O4@TiO2/ rGO composite materials, 20%~30% deionized water, 1%~5% zinc powder, 5%~10% trbasic zinc phosphate, 5%~10% talcum powder, 5%~15% calcium carbonate, 3%~10% aqueous dispersion, 0.5%~3% coupling agent, 1.5%~5% other auxiliary agent B components, 15%~30% curing agent；Coating of the present invention is with Fe3O4@TiO2/ rGO composite materials are formed in the surface of material, the Fe of nucleocapsid3O4@TiO2Nanometer has efficient photocatalytic effect, by ocean organic-biological oxygenolysis, while generating photic cathodic protection, has antisepsis to basis material.The unique laminated structures of rGO can improve the adhesive force of coating, while can also form Physical barriers, by the optimization of this universality energy, coating be made to have good antifouling antiseptic property.It can be widely applied to the oil-gas pipeline under marine environment, the facilities such as steel frame construction field.

Description

A kind of sea water resistance graphene modified anti-corrosive coating and preparation method thereof
Technical field
The invention belongs to anti-corrosion of metal engineering fields, and in particular to a kind of antifouling anticorrosive paint of marine environment metallic graphite carbon alkene Preparation method can also be applied to other anti-corrosion of metal fields.
Background technology
With marine oil gas field industrial expansion, offshore production, floating mode facility (FPSO), submerged pipeline etc. is continuously increased, The etching problem that it is faced under marine environment is also increasingly serious.Structure of steel product under marine environment, by salt fog, wind, rain, day The influence of the multiple actions such as light, surface are readily formed mordant moisture film.Thin water film occurs the effect of steel greatly The process of gas corrosion meets the rule of electrochemical corrosion in electrolyte.The characteristics of this process is that oxygen is accessible to steel surface, Steel corrosion speed is controlled by oxygen polarization process.Impurities influence corrosion of steel very big in air, rich in marine environment Containing a large amount of sea salt particle, these salt particle impurity are dissolved in the moisture film of steel surface, so that this layer of moisture film is become corrosivity very strong Electrolyte, further speeded up corrosion progress, in addition to this, in marine environment under microbial action material etching problem It is one of the important feature of marine corrosion, influence of the marine microorganism to material corrosion is significantly complicated, shows different from normal The corrosion new problem of rule, since various metals and its alloy or the sensibility of nonmetallic materials microbial corrosion resistance are different, usually Copper, chromium and macromolecule polymeric material compare microbial corrosion resistance, can be handled, in basis material by the surface to material Middle addition microbial corrosion resistance element applies the nano-oxide etc. of antimicrobial corrosion in metal surface, and then reaches prevention The purpose of SRB corrosion.Nano-titanium dioxide (TiO2), have good anti-weather, anti-light corrosive nature, it is non-toxic the advantages that, It, can be with by the photohole and electronics for generating Strong oxdiative reproducibility under its photocatalysis as antimicrobial corrosion material By coating surface organic-biological oxygenolysis, to reduce the biological corrosion harm that marine organisms are brought, and will not bring Secondary pollution is the research hotspot of marine anti-pollution material, be applied in recent years it is antifouling, in antifouling anticorrosive paint, but TiO2(rutile titania Mine) photochemical catalyst energy gap be 3.2eV, to play its photocatalysis performance, it is necessary to by wavelength be less than 387nm purple The irradiation of outer light, however in sunlight, mostly visible light, ultraviolet light only account for 4% or so, when wide more than or equal to forbidden band The light action of degree is in TiO2Surface after, TiO2Inside will produce the hole of electronics and strong oxidizing property with strong reducing property, however The hole of high activity and electronics can combine quickly again, and be discharged with thermal energy and the energy of other forms, its photocatalysis is caused to be imitated Rate reduces, and limits its extensive use in antifouling anticorrosive paint.Graphene is most thin in the world anticorrosion material, is possessed super High intensity, excellent barrier property, high stability and the good electric conductivity advantage of energy have anticorrosive paint comprehensive performance relatively strong Castering action.Have simultaneously, Environmental Safety, the characteristics such as non-secondary pollution, in recent years, domestic and international many scholars answer graphene With among coating, the antiseptic property for improving coating and shock resistance.The high surface energy product of graphene, intensity Van der Waals force and π-π effects make it easily reunite, and cannot form stable chemical combination between water, organic solvent and polymer and build, lead to it Interface binding power between resin is faint, poor compatibility, is also easy to produce phase separation, seriously affects coating performance.
Invention content
For a kind of insufficient existing for background technology, of the invention its soil resistance of antifouling anti-corrosion material of marine environment graphene Can, antiseptic property etc. is excellent.The principle of the present invention is：By nano-TiO2It is carried on the magnetic Fe with spinel structure3O4Table Face forms the Fe with nucleocapsid structure3O4It receives composite material, KH-550 silane coupling agents is then utilized, to composite material surface Functional modification is carried out, the composite material of functionalization is grafted on to the surface of graphene oxide (GO), reduction treatment is carried out to GO Redox graphene (rGO) is obtained, finally, obtains nucleocapsid Fe3O4@TiO2/ rGO trielement composite materials.Nucleocapsid structure Fe3O4@TiO2Nanometer, wherein magnetic Fe3O4The a small amount of Fe decomposed3+TiO can be effectively reduced2Energy gap width, reduce light The compound probability in raw hole and electronics, compares nano-TiO2, composite material specific surface area significantly increases, and photoresponse range increases, Photocatalysis efficiency significantly improves, to more effectively by coating surface organic-biological oxygenolysis, reduce what marine organisms were brought Biological corrosion endangers；And the electronics of generation is excited under its photocatalysis, it is transferred to metal surface, metal surface is made to be in one The state of kind electron rich, metal surface makes the reduction of its point because of electron rich, to make metal be in cathodic protection, Reach etch-proof purpose；Nano-TiO2The bending strength and tensile strength and impact strength of epoxy can be improved；Spinelle The nanometer Fe of structure3O4The mechanical strength of coating can be improved；Nucleocapsid structure Fe3O4@TiO2It is grafted on the surface graphene (rGO), By the unique laminated structure properties of rGO, coating is divided into minizone, effectively reduces the internal stress of coating, improves coating Flexibility, war of resistance impact and wearability；RGO can have an effect in the active medium with metal surface, form densification Physical barriers, to effectively prevent H2O,O2The infiltration of equal micro-molecular gas, improves the physical barrier of coating.Pass through this The optimization of universality energy reduces the corrosion caused by the factors such as marine organisms, coating breakage under marine environment and accelerates.
The present invention proposes a kind of marine anticorrosion composite coating material, is two-component it includes following parts by weight of component,
Component A, 20%~30% epoxy resin；
3%~10%Fe3O4@TiO2/ rGO composite materials (self-control)；
20%~30% deionized water；
1%~5% zinc powder；
5%~10% trbasic zinc phosphate；
5%~10% talcum powder；
5%~15% calcium carbonate；
3%~10% aqueous dispersion (self-control)；
0.5%~3% coupling agent；
1.5%~5% other auxiliary agents；
B component, 15%~30% curing agent.
Further, the epoxy resin is selected from aqueous epoxy resins (aqueous epoxy resins F0704, solid content 50%)
Further, the dispersant is homemade base epoxy phosphate ester water-borne dispersions.
Further, the antifoaming agent is (DD-171 aqueous defoamers) or (one in B-091, B-092 aqueous defoamer Kind or two kinds).
Further, the levelling agent is BYK-307 organosilicon levelling agents.
Further, the coupling agent is KH550.
Further, the adhesion promoter is DP-02, one or both of DP-10.
Further, the curing agent is (waterborne curing agent F0705).
Marine anticorrosion composite coating of the present invention can be prepared according to conventional Paint preparation technology.
Functionalization nucleocapsid Fe3O4@TiO2/rGO through the following steps that realize：
(1) GO is synthesized by improved hummer methods.
By stirring 3g powdered graphites and 1.5gNaNO3It is added and contains 75ml98%H2SO4Three-neck flask in mix and it is cold But cool down, in addition, being slowly added to 9gKMnO into mixed solution4, rotating speed keeps 300r/min, continues 2h, slow into reactant It is slow that 150ml deionized waters are added, after stirring 15min in 98 DEG C of oil baths, by 30% H2O2Be added mixture in, it is static for 24 hours Afterwards, it is washed, is centrifuged repeatedly with HCl solution and deionized water.Finally, by product, drying for 24 hours, obtains GO at 55 DEG C.
(2) preparation of nano ferriferrous oxide particle
The ethylene glycol of the ferrous sulfate heptahydrate and 50ml of 3g is added in the three-neck flask of 250ml, and through solution in nitrogen Protection is lower to be mixed 30min, and 50% H of 20ml0.5% is then added dropwise2O2Aqueous solution, temperature is maintained at 50 DEG C, It is persistently stirred to react 4h, by the ammonia spirit of addition 25%, reaction mixture is maintained under alkaline environment (pH=13), it will The nano particle dialysis of synthesis for 24 hours, is detached by magnetic field, and the nanometer of precipitation four is finally aoxidized three by decantation and redisperse purifying Iron particle water and methanol wash for several times, filtering, until pH=7.
(3) nucleocapsid structure Fe3O4@TiO2The preparation of nanocomposite
Fe is prepared using sol-gel method3O4@TiO2Nanocomposite measures the absolute ethyl alcohol and 10mlTi of 36ml (OC4H9)4, it is placed in beaker, with vigorous stirring, by Ti (OC4H9)4It is added drop-wise in absolute ethyl alcohol dropwise and is prepared into solution B；It measures 3ml deionized waters, 5ml absolute ethyl alcohols are put into beaker and are uniformly mixed, 0.5g nano ferriferrous oxides are added into mixed liquor, hold Continuous ultrasonic disperse 20min, adjusts pH >=3, solution A is made；Solution B is vigorously stirred, while solution being added dropwise into B solution A；Solution gradually becomes newborn brown, continues to stir 2h, puts and be aged in air for 24 hours, form wet colloidal sol, in drying box at 80 DEG C Dry to form dry colloidal sol for 24 hours, grind into powder calcines 2h for 400 DEG C in Muffle furnace, obtains nucleocapsid Fe3O4@TiO2Nanometer Composite material.
(4) nucleocapsid structure Fe3O4@TiO2Nanocomposite functionalization
Using KH-550 MODIFIED Fes3O4@TiO2Nanocomposite weighs 2gKH-550 and 144g absolute ethyl alcohols, is added to It is stirred evenly in three-necked flask, deionized water is slowly added into mixed liquor, continue to stir 45min, pH=10 is adjusted with ammonium hydroxide, By 5g (Fe3O4@TiO2) nanocomposite be added mixture in, 1.5h is persistently stirred, finally by product deionized water and nothing Water-ethanol washs repeatedly, and centrifuges, and final product is dried for 24 hours at 55 DEG C.
(5) nucleocapsid structure Fe3O4@TiO2Nanocomposite is grafted GO
By the nucleocapsid Fe of functionalization3O4@TiO2Anhydrous second of nanocomposite (0.35g) ultrasonic disperse in 250ml Uniform suspension is formed in alcohol, suspension is slowly added in 45.6mlGO (1mg/ml) solution under mild agitation, is continued 1h is stirred, product is washed repeatedly, and is dried for 24 hours at 55 DEG C.
(6)Fe3O4@TiO2The preparation of/rGO hybrids
By the nucleocapsid Fe of functionalization3O4@TiO2Anhydrous second of nanocomposite (0.35g) ultrasonic disperse in 250ml Uniform suspension is formed in alcohol, suspension is slowly added in 45.6mlGO (1mg/ml) solution under mild agitation, to mixed It closes and 3mol/L NaBH is added in solution4Solution (pH=11) temperature is maintained at 80 DEG C, persistently stirs 3h, and products therefrom is anti- After backwashing is washed, centrifugation, and is dried for 24 hours at 55 DEG C.
(7) preparation of nutgall acid-based epoxy phosphate water-borne dispersions
To equipped with thermometer, it is added in mixing three-necked flask in the three-necked flask of mechanical agitator and condensing unit The tetrabutylammonium bromide (TBAB) of the gallic acid (GA) of 17.12g, the epoxychloropropane (ECP) of 45.26g and 8.6g, mixing Object stirs 30min at room temperature, and the temperature of reaction mixture is controlled and is stirred 3 hours at 120 DEG C, is cooled to room temperature, and slowly adds Enter NaOH (10mol/L) solution, solution is heated to 30 DEG C, continues to stir 3h, later by the distillation water washing three of liquid 50ml It is secondary, it is used in combination anhydrous sodium sulfate to dry 24 hours, removes excessive unreacted EPC at 60 DEG C with rotary vacuum evaporator, obtain To yellow viscous liquid gallic acid base epoxy
The acetone of gallic acid the base epoxy 20g and 20g of above-mentioned preparation is taken to be placed in equipped with thermometer, mechanical agitator In three neck reactors of condensing unit, temperature is maintained at 60 DEG C, by 18gH3PO4With in the mixed liquor 30min of 20g acetone slowly It instills in mixture, the reaction was continued under the mechanical agitation of 500rmp, and 3h finally adds until mixture reaches constant acid value Enter the PH7-8 that KOH solution adjusts reaction mixture, obtains water phase infanticide acid-based epoxy phosphate.
Take the infanticide acid-based epoxy phosphate and 5g nucleocapsid structures Fe of the above-mentioned preparations of 5g3O4@TiO2/ rGO composite materials add Enter into the distilled water of 50ml, and ultrasound two hours in ultrasonic disperse instrument of the 500W equipped with heat sink, obtains infanticide acidic group Epoxy phosphate ester Fe3O4@TiO2/ rGO composite material water-borne dispersions.
Advantageous effect
The marine anti-pollution anticorrosion coating material of the present invention, using the Fe of nucleocapsid structure3O4@TiO2/ rGO trielement composite materials It is added in aqueous epoxy resin systems for main stuffing, the Fe of nucleocapsid structure3O4@TiO2Nanocomposite compares nanometer TiO2, specific surface area significantly increases, and photoresponse range expands, by its efficient photocatalytic effect will, the organic life of coating surface Object oxygenolysis reduces the biological corrosion harm that marine organisms are brought, to reach self-cleaning purpose；And its illumination is made The electronics generated with lower excitation, moves to metal surface, forms the state of electron rich, cause metal potential drop lower in cathode Protection, and then reach etch-proof purpose；The nanometer Fe of spinel structure3O4Mechanical strength and the shock resistance of coating can be improved Intensity；Nucleocapsid Fe3O4@TiO2The surfaces rGO are grafted on, by the unique laminated structure properties of rGO, coating are divided into small Section effectively reduces the internal stress of coating, improves the flexibility of coating, war of resistance impact and wearability；RGO can with gold The active medium of metal surface is had an effect, and fine and close Physical barriers are formed, to effectively prevent H2O,O2Equal micro-molecular gas Infiltration, improve the physical barrier of coating.By this various improvement, enhance the antifouling antiseptic property of coating, promotes coating Comprehensive performance.It can be widely applied to the oil-gas pipeline under marine environment, the facilities such as steel frame construction field.
Description of the drawings
Fig. 1 is functionalization nucleocapsid structure Fe3O4@TiO2The self assembling process figure of nanocomposite；
Fig. 2 is the Fe of nucleocapsid structure3O4@TiO2The self assembly of/GO trielement composite materials, reduction process figure；
Specific implementation mode
With reference to specific example, the present invention is further elaborated.
Case study on implementation one
A kind of marine anti-pollution anticorrosion coating material, material composition in mass ratio are：
Component A, 30% epoxy resin；
5%Fe3O4@TiO2/ rGO composite materials；
20% deionized water；
5% nano zinc powder；
6% trbasic zinc phosphate；
5% talcum powder；
5% calcium carbonate；
6% aqueous dispersion；
2% coupling agent；
1% other auxiliary agents；
B component, 15% curing agent.
Examples detailed above is only the citing for clearly illustrating the thought of the invention and being done, and simultaneously non-present invention is specifically real Apply the restriction of mode.For the engineers and technicians of fields, other can also be made on the basis of the above description Various forms of variations and replacement.There is no need and unable to enumerate all case study on implementation.It is hereby stated that every basic herein The replacement of the upper similar substance amplified out changes, within the invention scope of the claims.

Claims (4)

1. a kind of sea water resistance graphene modified anti-corrosive coating and preparation method thereof of the present invention, it includes following parts by weight of component, A Component, 20%~30% epoxy resin, 3%~10%Fe3O4@TiO2/ rGO composite materials (self-control), 20%~30% deionization It is water, 1%~5% zinc powder, 5%~10% trbasic zinc phosphate, 5%~10% talcum powder, 5%~15% calcium carbonate, 3%~10% aqueous Dispersant, 0.5%~3% coupling agent, 1.5%~5% other auxiliary agent B components, 15%~30% curing agent.
2. sea water resistance graphene modified anti-corrosive coating as described in claim 1 and preparation method thereof, it is characterised in that：The ring Oxygen resin is selected from aqueous epoxy resins (aqueous epoxy resins F0704, solid content 50%), dispersant is homemade nutgall acidic group Epoxy phosphate ester water-borne dispersions, antifoaming agent are (DD-171 aqueous defoamers) or (one in B-091, B-092 aqueous defoamer Kind or two kinds), the levelling agent be BYK-307 organosilicon levelling agents, coupling agent KH550, the adhesion promoter are DP- One or both of 02, DP-10, curing agent is (waterborne curing agent F0705).
3. a kind of sea water resistance graphene as described in claim 1 is modified antifouling anticorrosive paint, it is characterised in that：Functionalization nucleocapsid Structure Fe3O4@TiO2/ rGO through the following steps that realize：
(1) GO is synthesized by improved hummer methods.
By stirring 3g powdered graphites and 1.5gNaNO3It is added and contains 75ml98%H2SO4Three-neck flask in mix and cooling drop Temperature, in addition, being slowly added to 9gKMnO into mixed solution4, rotating speed holding 300r/min, persistently 2h, slowly adds into reactant Enter 150ml deionized waters, after stirring 15min in 98 DEG C of oil baths, by 30% H2O2Be added mixture in, it is static for 24 hours after, use HCl solution and deionized water are washed repeatedly, centrifugation.Finally, by product, drying for 24 hours, obtains GO at 55 DEG C.
(2) preparation of nano ferriferrous oxide particle
The ethylene glycol of the ferrous sulfate heptahydrate and 50ml of 3g is added in the three-neck flask of 250ml, and through solution in nitrogen protection 50% H of 20ml0.5% is then added dropwise in lower mixing 30min2O2Aqueous solution, temperature is maintained at 50 DEG C, continues It is stirred to react 4h, by the way that 25% ammonia spirit is added, reaction mixture is maintained under alkaline environment (pH=13), will be synthesized Nano particle dialysis for 24 hours, detached by magnetic field, decantation and redisperse purifying, finally by the nano ferriferrous oxide of precipitation Grain water and methanol wash for several times, filtering, until pH=7.
(3) nucleocapsid Fe3O4@TiO2The preparation of nanocomposite
Fe is prepared using sol-gel method3O4@TiO2Nanocomposite measures the absolute ethyl alcohol and 10mlTi of 36ml (OC4H9)4, it is placed in beaker, with vigorous stirring, by Ti (OC4H9)4It is added drop-wise in absolute ethyl alcohol dropwise and is prepared into solution B；It measures 3ml deionized waters, 5ml absolute ethyl alcohols are put into beaker and are uniformly mixed, 0.5g nano ferriferrous oxides are added into mixed liquor, hold Continuous ultrasonic disperse 20min, adjusts pH >=3, solution A is made；Solution B is vigorously stirred, while solution being added dropwise into B solution A；Solution gradually becomes newborn brown, continues to stir 2h, puts and be aged in air for 24 hours, form wet colloidal sol, is done at 80 DEG C in drying box Dry to form dry colloidal sol for 24 hours, grind into powder calcines 2h for 400 DEG C in Muffle furnace, obtains nucleocapsid Fe3O4@TiO2Nanometer is multiple Condensation material.
(4) nucleocapsid structure Fe3O4@TiO2Nanocomposite functionalization
Using KH-550 MODIFIED Fes3O4@TiO2Nanocomposite weighs 2gKH-550 and 144g absolute ethyl alcohols, is added to three mouthfuls It is stirred evenly in flask, deionized water is slowly added into mixed liquor, continue to stir 45min, pH=10 is adjusted with ammonium hydroxide, by 5g (Fe3O4@TiO2) nanocomposite be added mixture in, 1.5h is persistently stirred, finally by product deionized water and anhydrous second Alcohol washs repeatedly, and centrifuges, and final product is dried for 24 hours at 55 DEG C.
(5) nucleocapsid structure Fe3O4@TiO2Nanocomposite is grafted GO
By the nucleocapsid Fe of functionalization3O4@TiO2Nanocomposite (0.35g) ultrasonic disperse is in the absolute ethyl alcohol of 250ml Uniform suspension is formed, suspension is slowly added in 45.6mlGO (1mg/ml) solution under mild agitation, it is lasting to stir 1h washs product repeatedly, and is dried for 24 hours at 55 DEG C.
(6)Fe3O4@TiO2The preparation of/rGO hybrids
By the nucleocapsid Fe of functionalization3O4@TiO2Nanocomposite (0.35g) ultrasonic disperse is in the absolute ethyl alcohol of 250ml Uniform suspension is formed, suspension is slowly added in 45.6mlGO (1mg/ml) solution under mild agitation, it is molten to mixing 3mol/L NaBH are added in liquid4Solution (pH=11) temperature is maintained at 80 DEG C, persistently stirs 3h, and products therefrom is washed repeatedly It washs, centrifuges, and dried for 24 hours at 55 DEG C.
4. a kind of sea water resistance graphene as described in claim 1 is modified antifouling anticorrosive paint, it is characterised in that：The dispersant To make infanticide acid-based epoxy phosphate aqueous dispersion by oneself.
To equipped with thermometer, it is added 17.12g's in mixing three-necked flask in the three-necked flask of mechanical agitator and condensing unit The tetrabutylammonium bromide (TBAB) of gallic acid (GA), the epoxychloropropane (ECP) of 45.26g and 8.6g, mixture stirs at room temperature 30min is mixed, the temperature of reaction mixture is controlled and is stirred 3 hours at 120 DEG C, is cooled to room temperature, is slowly added to NaOH (10mol/L) solution, solution are heated to 30 DEG C, continue to stir 3h, later by liquid with the distillation water washing of 50ml three times, be used in combination Anhydrous sodium sulfate is dried 24 hours, removes excessive unreacted EPC at 60 DEG C with rotary vacuum evaporator, and it is viscous to obtain yellow Thick liquid gallic acid base epoxy
The acetone of gallic acid the base epoxy 20g and 20g of above-mentioned preparation is taken to be placed in equipped with thermometer, mechanical agitator and cold In three neck reactors of solidifying device, temperature is maintained at 60 DEG C, by 18gH3PO4It is slowly dropped into in the mixed liquor 30min of 20g acetone In mixture, the reaction was continued under the mechanical agitation of 500rmp, and 3h is eventually adding KOH until mixture reaches constant acid value Solution adjusts the PH7-8 of reaction mixture, obtains water phase infanticide acid-based epoxy phosphate.
Take the infanticide acid-based epoxy phosphate and 5g nucleocapsids Fe of the above-mentioned preparations of 5g3O4@TiO2/ rGO composite materials are added to In the distilled water of 50ml, and ultrasound two hours in ultrasonic disperse instrument of the 500W equipped with heat sink, obtain infanticide acid-based epoxy Phosphate Fe3O4@TiO2/ rGO composite material water-borne dispersions.
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CN109943169A (en) * 2019-03-20 2019-06-28 常州大学 A kind of Nano-composite marine anticorrosive paint and preparation method thereof
CN109943169B (en) * 2019-03-20 2020-11-24 常州大学 Nano composite marine anticorrosive paint and preparation method thereof
CN110305580A (en) * 2019-05-06 2019-10-08 吉林大学 A kind of graphene-based hydrophobic type anticorrosive coating and its preparation method and application
CN110305580B (en) * 2019-05-06 2021-06-15 吉林大学 Graphene-based hydrophobic anticorrosive coating and preparation method and application thereof
CN110345338A (en) * 2019-07-05 2019-10-18 合肥卓汇新材料科技有限公司 A method of inhibiting the microbiologic(al) corrosion of metal material pipeline
CN111153440A (en) * 2019-12-31 2020-05-15 陕西斯瑞新材料股份有限公司 Fe for improving thermal emissivity3O4Preparation method and application of coating
CN111153440B (en) * 2019-12-31 2022-04-22 陕西斯瑞新材料股份有限公司 Fe for improving thermal emissivity3O4Preparation method and application of coating
CN112143346A (en) * 2020-10-09 2020-12-29 东北大学 Graphene oxide grafted nano Fe2O3Preparation method of/epoxy composite coating
CN112143346B (en) * 2020-10-09 2021-06-11 东北大学 Graphene oxide grafted nano Fe2O3Preparation method of/epoxy composite coating
CN117126579A (en) * 2023-07-10 2023-11-28 泉州职业技术大学 Graphene marine anticorrosive paint and preparation method thereof

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