CN110205023A - With hydrophobic, antiseptic property composite Nano coating material and its preparation method and application - Google Patents

With hydrophobic, antiseptic property composite Nano coating material and its preparation method and application Download PDF

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CN110205023A
CN110205023A CN201910541557.9A CN201910541557A CN110205023A CN 110205023 A CN110205023 A CN 110205023A CN 201910541557 A CN201910541557 A CN 201910541557A CN 110205023 A CN110205023 A CN 110205023A
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hydrophobic
nonessential
graphene oxide
solvent
nano
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李滨
游波
程鹏
秦建波
王玉
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Chongqing Academy of Science and Technology
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Chongqing Academy of Science and Technology
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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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention provides a kind of with hydrophobic, antiseptic property composite Nano coating material and its preparation method and application, using in-situ chemical modification technology, in surface of graphene oxide grafted hydrophobic nanoparticle, the hydrophobic nano particle is coated on graphene oxide layer surface, form multilevel structure, enhance the dispersibility of graphene oxide, hydrophobicity and the effect for obstructing steam, the significant increase resistance to steam of coating and antiseptic property；The particle modified graphene oxide of hydrophobic nano, polyorganosiloxane resin, solvent, nonessential blending resin, nonessential curing agent, nonessential pigments and fillers and nonessential coating additive are blended, film-forming under conditions of temperature is -30~300 DEG C, obtains having hydrophobic, antiseptic property composite Nano coating material.It is able to ascend that coating is hydrophobic and antiseptic property, avoids substrate corrosion failure, preparation method process flow is simple, and raw material is simple and easy to get, practical.

Description

With hydrophobic, antiseptic property composite Nano coating material and preparation method thereof and Using
Technical field
The present invention relates to chemical fields, and in particular to it is a kind of with hydrophobic, antiseptic property composite Nano coating material and Preparation method and application.
Background technique
Metal erosion is all industrial existing huge problem all the time.According to statistics, because of metal erosion, the annual wave in the whole world The resource of expense accounts for 1/5th of current year utilization rate, is the several times that various natural calamities cause economic loss summation.With economy Development and the improvement of people's living standards, demand of the people to metal material increasingly increases, to the attention degree of anti-corrosion of metal Also growing day by day.The surface coverings such as construction material, automobile, marine facility, instrument and equipment are easy during using and transporting The erosion of steam, salt fog, leads to metal erosion, influences the use of metal material, even results in safety problem.Corrosion-inhibiting coating is to protect Metal is protected from the conventional means of corrosion.Coating can resist to a certain degree steam, salt fog is invaded as metal surface protection materials Erosion, plays antisepsis.Tradition containing chromium, cobalt anticorrosive paint because of its toxicity, be forbidden to use at present.Therefore new painting is found Layer material realizes that anti-corrosion demand is the research hotspot of current paint field.
It introduces inorganic filler at present and modified resin is to prepare the most common method of anticorrosive paint.CN108504259A is disclosed A kind of anticorrosive paint, joined the inorganic fillers such as quartz sand, calcium carbonate, with silane coupler modified epoxy in the epoxy Resin is prepared for the excellent anticorrosive paint of antiseptic property.CN108948962A discloses a kind of anticorrosive paint, is with epoxy resin Matrix resin introduces fumed silica and is prepared for that caking property is good, anticorrosive paint at low cost, moisture-proof, waterproof. CN109161274A discloses a kind of conductive anti-corrosion coating, utilizes citric acid, chitosan, conductive black, stannic chloride and trichlorine oxygen Conductive anti-corrosion coating is prepared after mixing with epoxy resin in P Modification graphene.CN109021774A discloses a kind of anti-corrosion Coating participates in aliphatic epoxy resin using silane coupling agent and is copolymerized, the long-effective corrosion that adhesive force is good, stability is high is prepared Coating.Codolar etc. is prepared for the zinc rich primer with antiseptic property using hollow glass micropearl and zinc powder, can effectively protect Metal and stainless steel surface are protected from corrosion (US20150210863A1).The polyolefin modified epoxy of long-chain such as Nishiguchi Resin is prepared for the anticorrosive paint of superelevation adhesive force.High adhesion force to greatly promote between coating and matrix almost without bubble Protective effect (US20160200916A1) of the anticorrosive paint to substrate.But the above method it is different degrees of there are filler use The problems such as amount is big, bad anti-corrosion effect, poor mechanical property.
Polysiloxanes is using Si-O-Si inorganic network structure as the polymer of skeleton.Si-h bond has high bond energy, long bond distance The characteristics of, there is excellent weatherability, heat resistance and Corrosion Protection.Graphene and its derivative have excellent mechanical property Energy, electric property, heat-conductive characteristic, chemical stability, adsorption capacity etc. are widely used in functional coating neck, can prepare anti- The coating of the multiple functions such as burn into scratch-resistant, heat-resisting, conductive, super-hydrophobic.Modified graphene oxide is added in polysiloxanes, Can while promoting coating antiseptic performance, solve silicone cross density is excessive, internal stress increases, it is brittle it is easy to crack, The all good anticorrosive paint of antiseptic property, mechanical property can be prepared in the problems such as scratch resistant performance is poor.
Summary of the invention
The object of the present invention is to provide a kind of with hydrophobic, antiseptic property composite Nano coating material and its preparation side Method, is able to ascend that coating is hydrophobic and antiseptic property, avoids substrate corrosion failure, preparation method process flow is simple, raw material letter Singly it is easy to get, it is practical.
It is of the present invention that there is hydrophobic, antiseptic property composite Nano coating material, using in-situ chemical modification technology, The grafted hydrophobic nanoparticle on graphene oxide, the hydrophobic nano particle are coated on graphene oxide layer surface, shape At the particle modified graphene oxide of the hydrophobic nano of multilevel structure, the dispersibility, hydrophobicity and resistance of graphene oxide are enhanced The effect of water proof vapour, the significant increase resistance to steam of coating and antiseptic property.
By the particle modified graphene oxide of hydrophobic nano, polyorganosiloxane resin, solvent, nonessential blending resin, it is non-must Curing agent, nonessential pigments and fillers and nonessential coating additive is needed to be blended, film-forming under conditions of temperature is -30~300 DEG C.
The polyorganosiloxane resin general formula are as follows:
Wherein, R1、R2、R3、R4Independently selected from following independent repetitive :-CH3、-CH2,-CH=CH2、-PH、-CH (O)CH-、-CH2CH2CH2OCH2-、-OCONH-、-COO-、-CONH-、-NH3,-N=C=O ,-SH ,-CH2O-、-CH (CH3)-、-CH(CH3)2And-(Si (CH3)2O)e-Si(CH3)2In any, wherein R1、R3、R4It can be same functional group Group, a, b, c, d, e are each independently 0~1000 integer.Si-O-Si repetitive structure and organic group in polysiloxane backbone It is connected directly, makes it have the characteristic of organic and inorganic materials, the organic-inorganic hybrid structure of this molecular level improves painting Mechanical performance, weatherability and the antiseptic property of layer, obtaining has hydrophobic, antiseptic property composite Nano coating material.
In terms of coating material gross mass, the particle modified graphene oxide of hydrophobic nano accounts for 0.1~30wt%, poly- silicon Oxygen alkane resin accounts for 20~89.9wt%, and solvent accounts for 10~79.9wt%, and nonessential blending resin accounts for 0~50wt%, nonessential solid Agent accounts for 0~30wt%, and nonessential pigments and fillers account for 0~50wt%, and nonessential coating additive accounts for 0~30.0wt%, coating material Gross mass be the particle modified graphene oxide of hydrophobic nano used, polyorganosiloxane resin, solvent, nonessential blending resin, Nonessential curing agent, nonessential pigments and fillers and nonessential coating additive quality sum.
Further, the solvent is water, alcohols solvent, alcohol ethers solvent, ether solvent, ketones solvent, lipid in coating One or more of solvent, aromatic hydrocarbon solvent, fat hydrocarbon solvent and halogenated hydrocarbon solvent.The non-limiting example of solvent Including water, methanol, ethyl alcohol, isopropanol, methyl acetate, ethyl acetate, propyl acetate, ethyl acetate, benzene,toluene,xylene, third Ketone, espeleton, methylisobutylketone, ether, butyl ether, pentane, hexane, octane, glycol monoethyl ether, ethylene glycol monoethyl ether, second Glycol monobutyl ether, glycol methyl ether acetate, 2-Butoxyethyl acetate, dimethyl carbonate, dimethyl adipate, glutaric acid two Methyl esters or dimethyl succinate.
The nonessential blending resin includes epoxy resin, acrylate, fluorocarbon resin, polyurethane resin, amino One or more of resin, alkyd resin and polyester resin.The non-limiting example of nonessential blending resin includes bisphenol-A ring Oxygen resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, A Hydrogenated Bisphenol A F epoxy resin, Hydromethyl bisphenol Resin, Hydroxyl acrylic resin, carboxy acrylic ester resin, Epocryl, polyurethane acrylate resin, polytetrafluoro Vinyl, polyvinylidene fluoride resin, polytrifluorochloroethylene/vinyl ether resin, polyfluoroethylene resin, oxygen solidify polyurethane Modified oil, moisture-cure polyurethane resin, polyhydroxy polyurethane resin, acrylated polyurethane resin, Lauxite, melamine first Urea formaldehyde, methyl-etherified melamine resin, butylated melamine-formaldehyde resin, long oil alkyd, medium oil alcohol Acid resin hydroxy polyester resin, short oil-ity alcohol acid resin, carboxyl polyester resin, unsaturated polyester resin or epoxy group polyester tree Rouge.
The nonessential curing agent is amine curing agent, amides curing agent, acid anhydride type curing agent, polyurethanes curing agent One or more of with amino resins class curing agent.The non-limiting example of nonessential curing agent includes ethylenediamine, diethyl Triamine, trientine, tetraethylenepentamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, hydroxyethyl ethylenediamine, diethyl Hydramine, isophorone diamine, bis- (4- amino -3- methylcyclohexyl) methane, bis- (4- aminocyclohexyl) methane, isophthalic diformazan Amine, m-phenylene diamine (MPD), diaminodiphenyl-methane, dicyanodiamine, adipic dihydrazide, hydroxyethyl ethylenediamine, 3- urea propyl front three Oxysilane, r- aminopropyltriethoxywerene werene, N- normal-butyl -3- aminopropyl trimethoxysilane, double-[3- (trimethoxy Silicon)-propyl] it is-amine, 3- diethylin propyl trimethoxy silicane, modified by cardanol amine, M-aminophenol modified to tert-butyl o Amine, 2,6 di t butyl phenol modified amine, benzoic acid, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, epoxy acrylate, epoxy polyurethane, polyisocyanic acid vinegar have toluene two different Cyanate, 4,4 1 methyl diphenylene diisocyanates, isophorone diisocyanate, hexamethylene-diisocyanate, 1,12 10 Dioxane diisocyanate, methyl diphenylene diisocyanate, more phenyl polymethine polyisocyanates, -1,5 diisocyanate of naphthalene Ester, aliphatic hexamethylene diisocyanate, isocyanates methoxy silane, isocyanates Ethoxysilane, isocyanate-containing alkyl Methoxy silane, isocyanate-containing alkyl Ethoxysilane 3- isocyanate group propyl-triethoxysilicane, Lauxite, melamine Amine-formaldehyde resins, methyl-etherified melamine resin or butylated melamine-formaldehyde resin.
The nonessential pigments and fillers are one or more of inorganic color stuffing and organic pigments and fillers.Nonessential pigments and fillers Non-limiting example includes titanium dioxide, talcum powder, barium sulfate, zinc oxide, precipitated silica, calcium carbonate, diamond dust, quartz Sand, corundum, schist, floating bead, iron oxide red, micaceous iron oxide, mica powder, attapulgite, silicate fiber, flake asbestos.
The nonessential coating additive is defoaming agent, dispersing agent, wetting agent, coalescing agent, thickener, levelling agent, anti-ageing One or more of agent, ultraviolet absorber and pH adjusting agent.
Further, the particle modified graphene oxide of hydrophobic nano is to utilize inorganic nano presoma, decentralized medium, hydrophobic Modifying agent, nonessential hydrophobic inorganic nanometer presoma, nonessential catalyst, nonessential modified additive, are changed by in-situ chemical Property technology, chemical modification is carried out to graphene oxide, active force between the inorganic nano presoma and graphene oxide is model One of De Huali, hydrogen bond action, electrostatic interaction, hydrophobe balanced action, ionic bond, covalent bond and ionic-covalent bonds or It is several.
Further, the inorganic nano presoma is metal alkoxide, silane coupling agent, titanate coupling agent, Aluminate idol Join one or more of agent, organosilicon and silicon fluoride.It is used inorganic in the particle modified graphene oxide preparation of hydrophobic nano Nanometer presoma non-limiting example includes four n-butoxy zirconiums, tributoxy-boron, γ-glycidyl ether oxygen propyl trimethoxy Silane, 3- triethoxysilyl -1- propylamine gamma-aminopropyl-triethoxy-silane, γ-(methacryloxypropyl) propyl front three Oxysilane, butyl titanate, two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters, (two is pungent for isopropyl three Base phosphoric acid acyloxy) titanate esters, three iso stearate isopropyl titanates, Di(dioctylpyrophosphato) ethylene titanate, four Isopropyl two (dioctyl phosphito acyloxy) titanate esters, isopropyl triisostearoyltitanate, tetraisopropyl titanate, distearyl Acyl-oxygen isopropyl Aluminate, three isopropyl ester of aluminic acid, three benzyl ester of aluminic acid, distearyl acyl-oxygen isopropyl Aluminate, hydroxy silicon oil, silicic acid Tetra-ethyl ester, trimethyl silicane alkoxy esters of silicon acis, trimethoxymethylsila,e, 1,3- dimercaptopropane aminopropyl triethoxysilane, Trimethylolpropane, silester, methyl silicate, methyltrimethoxysilane, phenyltrimethoxysila,e, three ethoxy of vinyl Base silane, vinyltrimethoxysilane, triethoxy ethyl silane, 17 fluorine ruthenium trimethoxysilanes, perfluoro capryl three Ethoxysilane or Trimethlyfluorosilane.
The decentralized medium is water, aqueous acid, aqueous alkali, saline solution, alcohols solvent, alcohol ethers solvent, ethers One or more of solvent, ketones solvent, lipid solvent, aromatic hydrocarbon solvent, fat hydrocarbon solvent and halogenated hydrocarbon solvent； In hydrophobic nano particle modified graphene oxide preparation decentralized medium non-limiting example used include water, aqueous hydrochloric acid solution, Aqueous acetic acid, aqueous sulfuric acid, phosphate aqueous solution, sodium hydrate aqueous solution, ammonium hydroxide, potassium hydroxide aqueous solution, sodium carbonate Solution, ammonium carbonate solution, methanol, ethyl alcohol, isopropanol, tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, benzene, first Benzene, dimethylbenzene, acetone, espeleton, methylisobutylketone, ether, butyl ether, pentane, hexane, octane, glycol monoethyl ether, second two Alcohol list ether, ethylene glycol monobutyl ether, glycol methyl ether acetate, 2-Butoxyethyl acetate, dimethyl carbonate, adipic acid diformazan Ester, dimethyl glutarate, dimethyl succinate, N, N-dimethylformamide or dimethyl sulfoxide.
The hydrophobic modifier is the glycerol of the saturated fatty acid of C8-C50, the unsaturated fatty acid of C8-C50, C8-C50 One or more of ester, Hydrophobic silicate, the hydrophobic silicones of C3-C50, silicon fluoride of C3-C50.Hydrophobic nano Hydrophobic modifier non-limiting example used includes octanoic acid, capric acid, lauric acid, cardamom in the preparation of particle modified graphene oxide Acid, palmitic acid, stearic acid, arachidic acid, linoleic acid, linolenic acid, arachidonic acid, glycerol trioleate, palmitin, Glycerol tristearate, silica, silicone oil, 17 fluorine ruthenium trimethoxysilanes, perfluoro capryl triethoxysilane or three Methyl silicon fluoride.
The nonessential hydrophobic inorganic nanometer presoma is the unsaturated fat of the saturated fatty acid of C8-C50, C8-C50 Acid, the glyceride of C8-C50, Hydrophobic silicate, the hydrophobic silicones of C3-C50, C3-C50 one of silicon fluoride or It is several.Nonessential hydrophobic inorganic nanometer presoma used is non-limiting in the particle modified graphene oxide preparation of hydrophobic nano Example includes octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, linoleic acid, linolenic acid, arachidonic Acid, glycerol trioleate, palmitin, glycerol tristearate, silica, silicone oil, 17 fluorine decyl trimethoxies Base silane, perfluoro capryl triethoxysilane or Trimethlyfluorosilane.
The nonessential catalyst is organic acid, inorganic acid, hydroxide, ammonium hydroxide, sodium alkoxide, lewis acid and lewis base One or more of.Nonessential catalyst non-limiting example used in the particle modified graphene oxide preparation of hydrophobic nano Including formic acid, acetic acid, benzoic acid, tartaric acid, oxalic acid, citric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, sulfuric acid, hydrochloric acid, Nitric acid, perchloric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, aluminium hydroxide, ammonium hydroxide, sodium ethoxide, sodium methoxide, benzyl alcohol sodium, Alchlor, boron trifluoride, sulfur trioxide, ferric bromide, water or methanol.
The nonessential modified additive is one of pH adjusting agent, defoaming agent, wetting agent, dispersing agent, thickener or several Kind.Nonessential auxiliary agent non-limiting example used includes that coating is common in hydrophobic nano particle modified graphene oxide preparation PH adjusting agent, defoaming agent, wetting agent, dispersing agent or thickener, additionally it is possible to be aqueous paint additive, solvent based coating auxiliary agent, UV Coating material solidified auxiliary agent, no-solvent type coating additive or powder coating additive.
Further, the polysiloxanes is the irregular three-D network-like structure that trifunctional or four-functional group form, packet Multiple Si-O-Si keys and at least two organic groups are included, the organic group connects at least one Si-O-Si key.
Further, the organic group is alkyl, phenyl, amino, epoxy group, vinyl, acyloxy, sulfydryl and isocyanic acid One or more of in ester group, which is connected to the coupling part on the silicon of a Si-O-Si key, wherein the connection Part are as follows:-(CH2)f, wherein f is 1~10 integer；Or-(CH2)gCONH(CH2)h, wherein g and h stand alone as 1~10 it is whole Number.
Further, at least part of the Si-O-Si key includes colloidal silicon dioxide.
A kind of preparation method with hydrophobic, antiseptic property composite Nano coating material comprising following steps:
The preparation of the particle modified graphene oxide of S1 hydrophobic nano,
S1.1,50~1000 parts by weight are added in the graphene oxide of 1 parts by weight, the nonessential modified additive of 0~2 parts by weight Decentralized medium in, disperse 0.1~48 hour；
S1.2, by 0.1~100 parts by weight of inorganic nanometer presoma, the nonessential hydrophobic inorganic nanometer of 0~100 parts by weight The nonessential catalyst of presoma, 0~100 parts by weight is added in the decentralized medium of 50~1000 parts by weight, and dispersion 0.1~48 is small When；
S1.3, S1.1 products therefrom is added in S1.2 products therefrom, reacts 1 under conditions of temperature is 5~200 DEG C ~50 hours,
S1.4, S1.3 reaction products therefrom is separated, is washed, 0.1~100 parts by weight hydrophobic modifier is added, Temperature is reacted 0.1~50 hour under conditions of being 0~200 DEG C, then by products therefrom separation, washing, obtains hydrophobic nano grain The particle modified graphene oxide of hydrophobic nano in fold scraps of paper shape that attached bag is covered；
The preparation of S2 composite Nano coating material,
S2.1, temperature be 1~100 DEG C under conditions of, the particle modified graphene oxide of the hydrophobic nano that S1 is obtained, Polyorganosiloxane resin and nonessential blending resin are added in solvent and mix, and stir under conditions of revolving speed is 100~1500rpm Uniformly；
S2.2, nonessential pigments and fillers, nonessential coating additive are added in solvent and are mixed, revolving speed be 100~ It is stirred evenly under conditions of 5000rpm；
S2.3, S2.1 products therefrom is added in S2.2 products therefrom, under conditions of revolving speed is 100~1500rpm It stirs evenly；
S2.4, nonessential curing agent is added in S2.3 products therefrom, under conditions of revolving speed is 100~1500rpm It stirs evenly, film-forming at being then -30~300 DEG C in temperature obtains having hydrophobic, antiseptic property composite Nano coating Material.
Above-mentioned has hydrophobic, antiseptic property composite Nano coating material to ocean engineering, communications and transportation, energy work All kinds of metal devices carry out the application in preservative treatment in industry, production equipment or urban operating mechanism, avoid component failure.
Compared with prior art, the present invention has the following advantages:
1, the present invention utilizes inorganic nano presoma, decentralized medium, nonessential catalyst, nonessential auxiliary agent, passes through original position Chemical modification technique carries out chemical modification to graphene oxide, obtains having nanoparticle/graphene oxide of multilevel structure to change Property compound.Inorganic nano presoma by Van der Waals force, hydrogen bond action, electrostatic interaction, hydrophobe balanced action, ionic bond, Covalent bond and ionic-covalent bonds make hydrophobic inorganic nanoparticle be coated on oxidation stone in conjunction with surface of graphene oxide group Black alkene sheet surfaces form multilevel structure.Inorganic nano-particle enhances the dispersibility of graphene oxide, improves nano combined Order inside coating material, the hydrophobic grouping of inorganic nano-particle play the role of obstructing steam, improve hydrophobic performance.
2, the present invention is by setting the particle modified graphene oxide of hydrophobic nano, polyorganosiloxane resin, nonessential blending Rouge, solvent, nonessential curing agent, nonessential pigments and fillers and nonessential auxiliary agent are blended, in -30~300 DEG C of film-formings, due to changing The addition of property graphene, effectively improves the hydrophobic and antiseptic property of coating material, avoids substrate corrosion failure.
3, preparation method process of the invention is simple, and raw material is simple and easy to get, practical.
Detailed description of the invention
Fig. 1 is the scanning electron microscope micrograph for the particle modified graphene oxide of hydrophobic nano that embodiment one obtains；
Fig. 2 is the scanning electron microscope micrograph for the composite Nano coating cross sections that embodiment one obtains, in which: A is polysiloxanes Coating, B are the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating；
Fig. 3 is the water contact angle test result figure of the obtained composite Nano coating of embodiment two and comparative example, and wherein C is poly- Silicon coating, D are composite Nano coating；
Fig. 4 is electrochemical impedance spectroscopy of the obtained composite Nano coating of embodiment three under different time, and wherein E is poly- silicon Oxygen alkane coating, F are composite Nano coating.
Specific embodiment
The present invention will be described in detail below with reference to specific embodiments.
Unless otherwise specified, the particle modified graphene oxide/polysiloxanes of hydrophobic nano is prepared in following embodiment Each step of composite Nano coating all carries out under normal pressure.
The microstructure of the particle modified graphene oxide of hydrophobic nano obtained and composite Nano coating is by German Zeiss 55 field emission scanning electron microscope of company Ultra is observed to obtain.
The water contact angle data of coating are by German Data physics company OWCA 15plus contact angle System water contact angle tester is tested to obtain.
The antiseptic property data (electrochemical alternate impedance spectrum) of coating are to characterize coating using chem workstation CHI604B What the corrosion behavior in 3.5wt%NaCl solution obtained.
Embodiment one weighs 200mg graphene oxide powder and is placed in 200ml anhydrous ethanol solvent, and ultrasonic disperse 2 hours Obtain reaction solution.1.0g tetraethyl orthosilicate and 17 fluorine ruthenium trimethoxysilane of 0.5g are added in reaction solution again, together When be added 2~3 drop acetic acid as catalyst, stir 24 hours, received under conditions of temperature is 60 DEG C, revolving speed is 500rpm Rice corpuscles modified graphene dispersion liquid.Then separation product is filtered, and is washed respectively 3 times with acetone and deionized water.Then exist 2.0g perfluoro capryl triethoxysilane is added in product and carries out hydrophobically modified, reacts 24 hours at 80 DEG C, is obtained after reaction Product dry 12 hours at 60 DEG C, the particle modified graphene oxide of hydrophobic nano is made.
Morphology observation is carried out, referring to Fig. 1, hydrophobic Nano particles of silicon dioxide is coated on sheet graphene oxide table Face forms multilevel structure.
Weigh the particle modified graphene oxide of hydrophobic nano made from 100mg and 50g polyorganosiloxane resin, 10g hydroxyl first It after the mixing of base bisphenol A epoxide resin, is added in 30g ethylene glycol monoethyl ether, is stirred evenly under conditions of revolving speed is 300rpm Obtain reaction system.Reaction system is added in 5gr- aminopropyltriethoxywerene werene, 0.5g dispersing agent, 0.01g defoaming agent again, It is stirred evenly under conditions of revolving speed is 800rpm, it is compound to obtain the particle modified graphene oxide/polysiloxanes of hydrophobic nano Nano-coating material.
Above-mentioned composite Nano coating material is coated on the substrate that cleaning was polished with bar, solidifies 48 under room temperature Hour, the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating is obtained, its pattern is observed, Referring to fig. 2, composite Nano coating is compared with polysiloxane coating coarse surface structure, the work with stronger hydrophobicity and barrier steam With.
Embodiment two weighs 300mg graphene oxide powder and is placed in 200ml sodium hydrate aqueous solution, and 0.05g ammonia is added After water under room temperature, 200rpm revolving speed, stirring obtains reaction solution in 2 hours.By two oleic acid acyloxy (dioctyl of 2.0g isopropyl Phosphoric acid acyloxy) reaction solution, under room temperature, 200rpm revolving speed, mechanical stirring 5 is added in titanate esters and 1.0g Trimethlyfluorosilane Hour, obtain nanometer particle-modified graphene dispersing solution.Then separation product is filtered, and is washed with deionized 3 times.Then exist 3.0 grams of glycerol tristearates are added in product and carry out hydrophobically modified, are reacted 72 hours under conditions of temperature is 40~60 DEG C, The particle modified graphene oxide of hydrophobic nano is made after being freeze-dried 12 hours in product.
Weigh the particle modified graphene oxide of hydrophobic nano made from 100mg and 100g polyorganosiloxane resin, 20g epoxy It after acrylate mixing, is added in 50g methylisobutylketone, is uniformly mixing to obtain reaction under conditions of revolving speed is 600rpm System.Reaction system is added in 10g3- diethylin propyl trimethoxy silicane, 0.6g thickener, 0.02g defoaming agent, is being turned Speed stirs evenly under conditions of being 700rpm, obtains the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano Coating material.
Above-mentioned composite Nano coating material is coated on the substrate that cleaning was polished with bar, the item for being 80 DEG C in temperature Solidify 5 hours under part, obtains the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating.To its carry out Water contact angle test, referring to Fig. 3, the water contact angle of polysiloxane coating levels off to 0 °, has stronger hydrophily, is unfavorable for base Material anti-corrosion；The water contact angle of composite Nano coating is 148.3 °, and hydrophobicity is strong, can obstruct steam, improves the anti-corrosion of coating Performance.
Embodiment three, weigh 50mg graphene oxide powder be placed in 100ml water, 50ml ethyl alcohol, 30ml isopropanol composition In the mixed solvent is added 0.05g dispersing agent, stirs 2 hours under 500rpm revolving speed.Finely dispersed mixed solution is transferred to Equipped with mechanical agitator, reflux condensing tube, constant pressure funnel 500mL three-necked flask in, three isopropyl ester of 1.0g aluminic acid is added Enter mixed solution, addition 3mg sodium ethoxide is as catalyst, mechanical stirring under conditions of temperature is 40 DEG C, revolving speed is 1000rpm 20 hours, obtain nanometer particle-modified graphene dispersing solution.Then separation product is filtered, and is washed with deionized 3 times.Then 1.0g stearic acid is added in the product and carries out hydrophobically modified, is reacted 12 hours under conditions of temperature is 150 DEG C, after product filters The particle modified graphene oxide of hydrophobic nano is made in freeze-drying 24 hours.
It weighs after the particle modified graphene oxide of hydrophobic nano made from 30mg mixes with 80g polyorganosiloxane resin, adds Enter in 40g toluene, is uniformly mixing to obtain reaction system under conditions of revolving speed is 800rpm.15g adipic dihydrazide, 5g are sunk Reaction system is added in shallow lake silica, 0.3g thickener, 0.1g dispersing agent, 0.01g defoaming agent, in the item that revolving speed is 1000rpm It is stirred evenly under part, obtains the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating material.
Above-mentioned coating material is coated on the substrate that cleaning was polished with bar, it is solid under conditions of temperature is 120 DEG C Change 2 hours, obtains the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating.To its chemical property Test, referring to fig. 4, when frequency is 10-2When HZ, the resistance modulus of polysiloxane coating | Z | it changes over time very greatly, 30 days are existing It is decreased obviously；The resistance modulus of nano-composite coating | Z | it is kept approximately constant in 30 days, shows hydrophobic nano grain obtained Sub- modified graphene oxide/polysiloxanes composite Nano coating has excellent corrosion resistance
Example IV weighs 150mg graphene oxide powder and is placed in 250ml toluene, in the condition that revolving speed is 800rpm Lower dispersion 2 hours.Finely dispersed mixed solution is transferred to equipped with mechanical agitator, reflux condensing tube, constant pressure funnel 500mL three-necked flask in, 5.0g3- triethoxysilyl -1- propylamine gamma-aminopropyl-triethoxy-silane is added mixed Solution is closed, mechanical stirring 24 hours, obtains nanometer particle-modified graphene under conditions of temperature is 80 DEG C, revolving speed is 400rpm Dispersion liquid.Then separation product is filtered, and is washed with deionized 3 times.It is 70 that product, which is added in 2.0g silicone oil in temperature, It is reacted 12 hours under conditions of DEG C, it is 20 hours dry under conditions of temperature is 80 DEG C after suction filtration, hydrophobic nano particle is made Modified graphene oxide.
It weighs the particle modified graphene oxide of hydrophobic nano made from 80mg and 50g polyorganosiloxane resin, 15g is unsaturated It after polyester resin mixing, is added in 25g isopropanol, is uniformly mixing to obtain reaction system under conditions of revolving speed is 500rpm.It will 15g ethylenediamine, 1g zinc oxide, 0.5g dispersing agent, 0.01g defoaming agent and 10g isopropanol are mixed under conditions of revolving speed is 500rpm Reaction system is added after closing uniformly, is stirred evenly under conditions of revolving speed is 1000rpm, obtains the particle modified oxygen of hydrophobic nano Graphite alkene/polysiloxanes composite Nano coating material.
Above-mentioned coating material is coated on the substrate that cleaning was polished with bar, is solidified under conditions of temperature is 80 DEG C 15 hours, obtain the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating.
Embodiment five weighs 120mg graphene oxide powder and is placed in 100g methyl acetate, in the item that revolving speed is 500rpm Disperse 5 hours under part.Finely dispersed mixed solution is transferred to equipped with mechanical agitator, reflux condensing tube.Constant pressure addition leakage In the 500ml three-necked flask of bucket, 10g distearyl acyl-oxygen isopropyl Aluminate, 5g perfluoro capryl triethoxysilane are added mixed Solution is closed, mechanical stirring 10 hours, obtains nanometer particle-modified graphene under conditions of temperature is 60 DEG C, revolving speed is 800rpm Then dispersion liquid filters separation product, and is washed 3 times with methyl acetate.3.0g silicon dioxide gel is then added in the product, It reacts 10 hours, is dredged under conditions of revolving speed is 500rpm within dry 10 hours under conditions of temperature is 200 DEG C after suction filtration Aqueous nanoparticle modified graphene oxide.
Embodiment six weighs 250mg graphene oxide powder and is placed in 200gN, in N-dimethylformamide, is in revolving speed Disperse to obtain reaction solution in 2 hours under conditions of 200rpm.By 5.0g tetra isopropyl two (dioctyl phosphito acyloxy) metatitanic acid Reaction solution is added in ester, 1.0g linoleic acid, 0.5g acetic acid, under conditions of room temperature, revolving speed are 500rpm, mechanical stirring 2 hours, Nanometer particle-modified graphene dispersing solution is obtained, separation product is then filtered.Obtained product is added in 2.0g oleic acid, Revolving speed is that the reaction was continued 20 hours under 500rpm, obtains the particle modified oxygen of hydrophobic nano within dry 5 hours at 100 DEG C after suction filtration Graphite alkene.
Embodiment seven weighs the particle modified graphene oxide of hydrophobic nano made from 60mg embodiment one and the poly- silicon of 90g After oxygen alkane resin, the mixing of 30g polyvinylidene fluoride resin, it is added in 50g methanol, stirring is equal under conditions of revolving speed is 500rpm It is even to obtain reaction system.Bis- (4- amino -3- methylcyclohexyl) methane of 20g, 0.1g dispersing agent, 0.2g levelling agent, 0.01g are disappeared Infusion and 15g methanol under conditions of revolving speed is 500rpm under reaction system is added after mixing, be 500rpm's in revolving speed Under the conditions of stir evenly, obtain the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating material.
Above-mentioned coating material is coated on the substrate that cleaning was polished with bar, solidifies 72 hours under room temperature, obtains To the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating.
Embodiment eight weighs the particle modified graphene oxide of hydrophobic nano made from 75mg embodiment two and the poly- silicon of 100g It after the mixing of oxygen alkane resin, is added in 50g dimethyl carbonate, is uniformly mixing to obtain reactant under conditions of revolving speed is 200rpm System.Reaction is added in 1g isophorone diisocyanate, 0.1g dispersing agent, 0.1g levelling agent, 0.1g thickener, 0.01g defoaming agent System stirs evenly under conditions of revolving speed is 500rpm, obtains the particle modified graphene oxide/polysiloxanes of hydrophobic nano Composite Nano coating material.
Above-mentioned coating material is coated on the substrate that cleaning was polished with bar, solidifies 10 hours under room temperature, obtains To the particle modified graphene oxide of hydrophobic nano/polysiloxanes composite Nano coating.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention Protection scope.

Claims (9)

1. a kind of with hydrophobic, antiseptic property composite Nano coating material, it is characterised in that: using the modified skill of in-situ chemical Art, the grafted hydrophobic nanoparticle on graphene oxide, the hydrophobic nano particle are coated on surface of graphene oxide, are formed The particle modified graphene oxide of the hydrophobic nano of multilevel structure；
By the particle modified graphene oxide of hydrophobic nano, polyorganosiloxane resin, solvent, nonessential blending resin, nonessential solid Agent, nonessential pigments and fillers and nonessential coating additive are blended, and film-forming under conditions of temperature is -30~300 DEG C obtains With hydrophobic, antiseptic property composite Nano coating material；
The polyorganosiloxane resin general formula are as follows:
Wherein, R1、R2、R3、R4Independently selected from following independent repetitive :-CH3、-CH2,-CH=CH2、-PH、-CH(O) CH-、-CH2CH2CH2OCH2-、-OCONH-、-COO-、-CONH-、-NH3,-N=C=O ,-SH ,-CH2O-、-CH(CH3)-、-CH (CH3)2And-(Si (CH3)2O)e-Si(CH3)2In any, wherein R1、R3、R4Can be same functional group, a, b, c, d, E is each independently 0~1000 integer；
In terms of coating gross mass, the particle modified graphene oxide of hydrophobic nano accounts for 0.1~30wt%, polyorganosiloxane resin Accounting for 20~89.9wt%, solvent accounts for 10~79.9wt%, and nonessential blending resin accounts for 0~50wt%, and nonessential curing agent accounts for 0~ 30wt%, nonessential pigments and fillers account for 0~50wt%, and nonessential coating additive accounts for 0~30.0wt%, and coating material gross mass is to make The particle modified graphene oxide of hydrophobic nano, polyorganosiloxane resin, solvent, nonessential blending resin, nonessential solidification Agent, nonessential pigments and fillers and nonessential coating additive quality sum.
2. according to claim 1 have hydrophobic, antiseptic property composite Nano coating material, it is characterised in that: described Solvent is water, alcohols solvent, alcohol ethers solvent, ether solvent, ketones solvent, lipid solvent, aromatic hydrocarbon solvent, rouge in coating One or more of fat hydrocarbon solvent and halogenated hydrocarbon solvent；
The nonessential blending resin include epoxy resin, acrylate, fluorocarbon resin, polyurethane resin, amino resins, One or more of alkyd resin and polyester resin；
The nonessential curing agent is amine curing agent, amides curing agent, acid anhydride type curing agent, polyurethanes curing agent and ammonia One or more of base resinae curing agent；
The nonessential pigments and fillers are one or more of inorganic color stuffing and organic pigments and fillers；
The nonessential coating additive be defoaming agent, dispersing agent, wetting agent, coalescing agent, thickener, levelling agent, age resister, One or more of ultraviolet absorber and pH adjusting agent.
3. according to claim 1 or 2 have hydrophobic, antiseptic property composite Nano coating material, it is characterised in that: dredge Aqueous nanoparticle modified graphene oxide is to utilize inorganic nano presoma, decentralized medium, hydrophobic modifier, nonessential hydrophobic Property inorganic nano presoma, nonessential catalyst, nonessential modified additive, by in-situ chemical modification technology, to graphite oxide Alkene carries out chemical modification, and active force between the inorganic nano presoma and graphene oxide is Van der Waals force, hydrogen bond action, quiet One or more of electro ultrafiltration, hydrophobe balanced action, ionic bond, covalent bond and ionic-covalent bonds.
4. according to claim 3 have hydrophobic, antiseptic property composite Nano coating material, it is characterised in that:
The inorganic nano presoma is metal alkoxide, silane coupling agent, titanate coupling agent, aluminate coupling agent, organosilicon One or more of with silicon fluoride；
The decentralized medium be water, aqueous acid, aqueous alkali, saline solution, alcohols solvent, alcohol ethers solvent, ether solvent, One or more of ketones solvent, lipid solvent, aromatic hydrocarbon solvent, fat hydrocarbon solvent and halogenated hydrocarbon solvent；
The hydrophobic modifier is the saturated fatty acid of C8-C50, the glyceride of the unsaturated fatty acid of C8-C50, C8-C50, dredges One or more of aqueous silicate, the hydrophobic silicones of C3-C50, silicon fluoride of C3-C50；
The nonessential hydrophobic inorganic nanometer presoma be the saturated fatty acid of C8-C50, C8-C50 unsaturated fatty acid, The glyceride of C8-C50, Hydrophobic silicate, the hydrophobic silicones of C3-C50, C3-C50 one of silicon fluoride or several Kind；
The nonessential catalyst is in organic acid, inorganic acid, hydroxide, ammonium hydroxide, sodium alkoxide, lewis acid and lewis base It is one or more of；
The nonessential modified additive is one or more of pH adjusting agent, defoaming agent, wetting agent, dispersing agent, thickener.
5. according to claim 1 or 2 have hydrophobic, antiseptic property composite Nano coating material, it is characterised in that: institute Stating polysiloxanes is the irregular three-D network-like structure that trifunctional or four-functional group form, including multiple Si-O-Si keys and At least two organic groups, the organic group connect at least one Si-O-Si key.
6. according to claim 5 have hydrophobic, antiseptic property composite Nano coating material, it is characterised in that: described Organic group is one or more in alkyl, phenyl, amino, epoxy group, vinyl, acyloxy, sulfydryl and isocyanate group, should Organic group is connected to the coupling part on the silicon of a Si-O-Si key, wherein the coupling part are as follows:
-(CH2)f, wherein f is 1~10 integer；Or-(CH2)gCONH(CH2)h, wherein g and h stands alone as 1~10 integer.
7. according to claim 5 have hydrophobic, antiseptic property composite Nano coating material, it is characterised in that: described At least part of Si-O-Si key includes colloidal silicon dioxide.
8. a kind of preparation method with hydrophobic, antiseptic property composite Nano coating material, it is characterised in that: including walking as follows It is rapid:
The preparation of the particle modified graphene oxide of S1 hydrophobic nano,
S1.1, point that the graphene oxide of 1 parts by weight, the nonessential modified additive of 0~2 parts by weight are added to 50~1000 parts by weight In dispersion media, disperse 0.1~48 hour；
S1.2, by 0.1~100 parts by weight of inorganic nanometer presoma, the nonessential hydrophobic inorganic nanometer forerunner of 0~100 parts by weight The nonessential catalyst of body, 0~100 parts by weight is added in the decentralized medium of 50~1000 parts by weight, disperses 0.1~48 hour；
S1.3, S1.1 products therefrom is added in S1.2 products therefrom, the reaction 1~50 under conditions of temperature is 5~200 DEG C Hour,
S1.4, S1.3 reaction products therefrom is separated, is washed, 0.1~100 parts by weight hydrophobic modifier being added, in temperature 0.1~50h is reacted under conditions of being 0~200 DEG C, then by products therefrom separation, washing, obtains hydrophobic nano particle cladding In the particle modified graphene oxide of hydrophobic nano of fold scraps of paper shape；
The preparation of S2 composite Nano coating material,
S2.1, temperature be 1~100 DEG C under conditions of, the particle modified graphene oxide of the hydrophobic nano that S1 is obtained, poly- silicon Oxygen alkane resin and nonessential blending resin are added in solvent and mix, and stirring is equal under conditions of revolving speed is 100~1500rpm It is even；
S2.2, nonessential pigments and fillers, nonessential coating additive are added in solvent and are mixed, be 100~5000rpm's in revolving speed Under the conditions of stir evenly；
S2.3, S2.1 products therefrom is added in S2.2 products therefrom, is stirred under conditions of revolving speed is 100~1500rpm Uniformly；
S2.4, nonessential curing agent is added in S2.3 products therefrom, is stirred under conditions of revolving speed is 100~1500rpm Uniformly, film-forming at being then -30~300 DEG C in temperature, obtains having hydrophobic, antiseptic property composite Nano coating material Material.
Have hydrophobic, antiseptic property composite Nano coating material to ocean work 9. claim 1~7 is described in any item All kinds of metal devices carry out the application in preservative treatment in journey, communications and transportation, energy industry, production equipment or urban operating mechanism, keep away Exempt from component failure.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110479182A (en) * 2019-09-10 2019-11-22 肯特催化材料股份有限公司 A kind of polyamino Gemini surface active agent and the preparation method and application thereof
CN111040527A (en) * 2019-12-31 2020-04-21 山东华夏神舟新材料有限公司 Heat-reflecting super-hydrophobic PVDF coating and preparation method thereof
CN111607283A (en) * 2020-06-05 2020-09-01 华东理工大学 Modified halloysite, composite coating based on modified halloysite and preparation method of composite coating
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CN112430419A (en) * 2020-11-30 2021-03-02 长沙理工大学 Large-pipe-diameter inner-covering composite hydrophobic coating and preparation method thereof
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150065601A1 (en) * 2013-09-04 2015-03-05 Alfaisal University Novel antimicrobial polymer -graphene-silver nanocomposite
CN106280726A (en) * 2016-08-15 2017-01-04 山东天汇防水材料有限公司 A kind of super-hydrophobic high-cooling property coating and preparation method thereof
CN106752923A (en) * 2016-11-28 2017-05-31 复旦大学 A kind of damage resistant high, abrasion-resistant coatings material and preparation method thereof
US20180242452A1 (en) * 2015-08-10 2018-08-23 The University Of Manchester Electrically conductive materials comprising graphene
CN108727947A (en) * 2018-06-22 2018-11-02 成都新柯力化工科技有限公司 A kind of graphene oxide hydridization anticorrosive paint and preparation method
CN108841211A (en) * 2018-06-13 2018-11-20 重庆市科学技术研究院 A kind of inorganic zinc coating of modified graphene and preparation method thereof
CN109836919A (en) * 2017-09-29 2019-06-04 天津工业大学 A kind of functional graphene oxide corrosion-inhibiting coating and its preparation process

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150065601A1 (en) * 2013-09-04 2015-03-05 Alfaisal University Novel antimicrobial polymer -graphene-silver nanocomposite
US20180242452A1 (en) * 2015-08-10 2018-08-23 The University Of Manchester Electrically conductive materials comprising graphene
CN106280726A (en) * 2016-08-15 2017-01-04 山东天汇防水材料有限公司 A kind of super-hydrophobic high-cooling property coating and preparation method thereof
CN106752923A (en) * 2016-11-28 2017-05-31 复旦大学 A kind of damage resistant high, abrasion-resistant coatings material and preparation method thereof
CN109836919A (en) * 2017-09-29 2019-06-04 天津工业大学 A kind of functional graphene oxide corrosion-inhibiting coating and its preparation process
CN108841211A (en) * 2018-06-13 2018-11-20 重庆市科学技术研究院 A kind of inorganic zinc coating of modified graphene and preparation method thereof
CN108727947A (en) * 2018-06-22 2018-11-02 成都新柯力化工科技有限公司 A kind of graphene oxide hydridization anticorrosive paint and preparation method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AGHILES BOUIBED: "Synthesis and characterization of hybrid materials based on graphene oxide and silica nanoparticles and their effect on the corrosion protection properties of epoxy resin coatings", 《JOURNAL OF ADHESION SCIENCE AND TECHNOLOGY》 *
YANG,BO: "Improving the Thermal Conductivity and Mechanical Properties of Two-component Room Temperature Vulcanized Silicone Rubber by Filling with Hydrophobically Modified SiO2-Graphene Nanohybrids", 《CHINESE JOURNAL OF POLYMER SCIENCE》 *
张新海等: "石墨烯及衍生物在耐磨涂料中的应用", 《涂层与防护》 *

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