CN111410905A - Functional graphene modified polyurethane conductive anticorrosive coating and preparation method thereof - Google Patents
Functional graphene modified polyurethane conductive anticorrosive coating and preparation method thereof Download PDFInfo
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Abstract
The invention relates to the technical field of polyurethane materials, and discloses a functional graphene modified polyurethane conductive anticorrosive coating, which comprises the following formula raw materials and components: functionalized graphene, isophorone diisocyanate, polyester polyol, a catalyst, 1, 4-butanediol, 2-dihydroxypropionic acid, a leveling agent and a defoaming agent. According to the functionalized graphene modified polyurethane conductive anticorrosive coating, 4, 4' -triphenylmethane triisocyanate reacts with hydroxyl in graphene oxide, polyester polyol is a polyol monomer and performs copolymerization reaction with isocyanate in graphene, compatibility of graphene and polyurethane is enhanced, graphene enters gaps of a coating material, excellent barrier property is achieved, water molecules and oxygen can be inhibited from permeating into the coating to be contacted with the coating, a three-dimensional conductive network is formed in the polyurethane coating by the graphene, conductivity of the coating is improved, and the coating shows excellent conductivity and anticorrosive property.
Description
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a functional graphene modified polyurethane conductive anticorrosive coating and a preparation method thereof.
Background
The corrosion refers to the process of loss and destruction of materials under the action of surrounding media such as water, air, salt and the like, the corrosion is mainly divided into chemical corrosion and electrochemical corrosion, the chemical corrosion is caused by the chemical action of the materials in dry gas and non-electrolyte solution, no current is generated in the corrosion process, the products of the chemical corrosion exist on the surface of the materials, when the corrosion products are unstable and easy to volatilize or dissolve, the materials are not firmly combined with the materials, the corrosion products can fall off to destroy the materials, the electrochemical corrosion is caused by the electrochemical action generated between metal and the electrolyte solution, the current is generated in the corrosion process, the metal is ionized in the electrolyte solution, when the bonding force of the metal ions and electrons is smaller than that of the metal ions and water molecules, the metal ions are dissolved into electrolyte from the metal surface to form the electrochemical corrosion, chemical corrosion is a great hazard, more than one hundred million metals which are scrapped due to corrosion worldwide every year, and the coating of anticorrosive paint on the surface of materials makes the most economic and effective and universal anticorrosive method.
Polyurethane is a new organic high molecular material, has excellent chemical stability and mechanical property, good heat insulation, sound insulation and resilience, mainly comprises products such as polyurethane foam, polyurethane fiber, polyurethane rubber, elastomer, polyurethane coating and the like, has wide application in the shoe and leather making industry, the household appliance field, the traffic field, the building field and the like, but has low chemical corrosion resistance, lower conductivity and poorer electrochemical corrosion resistance, limits the application of polyurethane coating, graphene is a two-dimensional carbon nano material, has excellent mechanical and electrical properties, has great development potential in the corrosion resistance field, can form a composite material with polyurethane, enhances the corrosion resistance of the polyurethane material through electrochemical protection, barrier shielding and passivation corrosion inhibition, but has poor compatibility with the polyurethane, the mechanical properties of the composite material, such as tensile strength and wear resistance, are seriously affected.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a functional graphene modified polyurethane conductive anticorrosive coating and a preparation method thereof, which solve the problems of poor anticorrosive performance and conductive performance of polyurethane and the problem of poor compatibility of graphene and polyurethane.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a functional graphene modified polyurethane conductive anticorrosive coating comprises the following formula raw materials and components: 0.5-3 parts of functionalized graphene, 30-40 parts of isophorone diisocyanate, 30-57 parts of polyester polyol, 0.5-2 parts of catalyst, 8-14 parts of 1, 4-butanediol, 3-6 parts of 2, 2-dihydroxypropionic acid, 0.5-3 parts of flatting agent and 0.5-2 parts of defoaming agent.
Preferably, the catalyst is dibutyltin dilaurate, the flatting agent is an organic silicon system flatting auxiliary agent, and the defoaming agent is a silane defoaming agent.
Preferably, the preparation method of the functionalized graphene comprises the following steps:
(1) adding concentrated sulfuric acid solvent and graphite into a reaction bottle, stirring at 0-5 deg.C for 30-60min, and adding NaNO3Stirring at a constant speed for reaction for 30-60min, slowly dropwise adding potassium permanganate, stirring at a constant speed for reaction for 2-4h, heating the temperature to 30-40 ℃, stirring at a constant speed for reaction for 3-6h, slowly dropwise adding distilled water solvent, adding hydrogen peroxide solution to neutralize excessive potassium permanganate until the solution is bright yellow, adding dilute hydrochloric acid solution into the solution, standing for 10-20h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the graphene oxide.
(2) Adding an N, N-dimethylformamide solvent and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, adding 4, 4' -triphenylmethane triisocyanate, putting the mixture into an oil bath pot, heating the mixture to 75-85 ℃ for reaction for 6-12h, adding a reducing agent hydrazine hydrate solution and ammonia water, adjusting the pH of the solution to 8-10, heating the solution to 90-110 ℃, uniformly stirring the solution for reaction for 6-10h, cooling the solution to room temperature, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying the solid product to prepare the diisocyanated functionalized graphene.
Preferably, the graphite, NaNO3The mass ratio of the potassium permanganate to the potassium permanganate is 1:0.4-0.7: 2.8-3.5.
Preferably, the mass ratio of the graphene oxide to the 4, 4' -triphenylmethane triisocyanate to the hydrazine hydrate is 1:15-25: 0.6-1.
Preferably, the oil bath pot includes heating device, heating device top is provided with the oil bath pot, the outer fixedly connected with heat preservation of oil bath pot, heat preservation top fixedly connected with bracing piece, the inside draw-in groove that is provided with of bracing piece, draw-in groove and fixture block swing joint, fixture block fixedly connected with carriage release lever, carriage release lever swing joint have the governing valve, governing valve and expansion clamp swing joint.
Preferably, the preparation method of the functionalized graphene modified polyurethane conductive anticorrosive coating comprises the following steps:
(1) adding 0.5-3 parts of functionalized graphene, 30-40 parts of isophorone diisocyanate and 30-57 parts of polyester polyol into a reaction bottle, adding 0.5-2 parts of dibutyltin dilaurate serving as a catalyst after uniform ultrasonic dispersion, placing the mixture into an oil bath pot, heating the mixture to 70-85 ℃, uniformly stirring the mixture for reaction for 3-5 hours, cooling the temperature to 45-55 ℃, adding an acetone solvent, adjusting the viscosity of the solution, adding 3-6 parts of 2, 2-dihydroxypropionic acid, uniformly stirring the mixture for reaction for 2-3 hours, adding 8-14 parts of 1, 4-butanediol, uniformly stirring the mixture for reaction for 1-3 hours, cooling the solution to room temperature, adding triethylamine to adjust the pH of the solution to be neutral, adding 0.5-3 parts of leveling agent organic silicon system leveling assistant and 0.5-2 parts of defoaming agent silane defoaming agent, and (3) emulsifying at high speed, pouring the emulsion into a polytetrafluoroethylene mold, and curing to form a film to prepare the functionalized graphene modified polyurethane conductive anticorrosive coating.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the functional graphene modified polyurethane conductive anticorrosive coating, high-hydroxyl-content graphene oxide is prepared through an acidification oxidation method, isocyanate groups in 4, 4' -triphenylmethane triisocyanate react with hydroxyl groups in the graphene oxide, hydrazine hydrate is used for reduction to prepare diisocyanated functional graphene, the functional graphene is used as crosslinking neutrality, polyester polyol is used as a polyol monomer and is subjected to copolymerization reaction with two unreacted isocyanates in the graphene, and a chemical covalent bond modification method is used for preparing the functional graphene modified polyurethane coating material, so that the compatibility of the graphene and polyurethane is remarkably enhanced.
According to the functionalized graphene modified polyurethane conductive anticorrosive coating, nano-morphology graphene is uniformly dispersed in the polyurethane coating and enters gaps of a coating material, so that excellent barrier property is achieved, water molecules, oxygen and corrosive media can be inhibited from permeating into the coating and contacting with the material, a good electrochemical anticorrosive effect is achieved, the uniformly dispersed graphene forms a three-dimensional conductive network in the polyurethane coating, the volume resistivity of the material is reduced, the conductivity of the material is improved, electrons lost by Fe in an iron-based metal material can be transferred to the polyurethane coating, a cathode reaction in an electrochemical corrosion reaction is transferred to the polyurethane coating, the generation of hydroxide radicals generated by the cathode reaction and iron ions generated by an anode in a reaction production precipitation is reduced, the metal anode corrosion reaction is hindered, and the dissolution and corrosion of iron in the iron-based metal material are reduced, has good electrochemical corrosion resistance.
Drawings
FIG. 1 is a schematic front view of a heating apparatus;
fig. 2 is an enlarged schematic view of the travel bar.
1. A heating device; 2. oil bath pan; 3. a heat-insulating layer; 4. a support bar; 5. a card slot; 6. a clamping block; 7. a travel bar; 8. adjusting a valve; 9. provided is a telescopic clamp.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a functional graphene modified polyurethane conductive anticorrosive coating comprises the following formula raw materials and components: 0.5-3 parts of functionalized graphene, 30-40 parts of isophorone diisocyanate, 30-57 parts of polyester polyol, 0.5-2 parts of dibutyltin dilaurate serving as a catalyst, 8-14 parts of 1, 4-butanediol, 3-6 parts of 2, 2-dihydroxypropionic acid, 0.5-3 parts of a leveling agent organic silicon system leveling agent and 0.5-2 parts of a defoaming agent silane defoaming agent.
The preparation method of the functionalized graphene comprises the following steps:
(1) adding concentrated sulfuric acid solvent and graphite into a reaction bottle, stirring at 0-5 deg.C for 30-60min, and adding NaNO3Stirring at constant speed for reaction for 30-60min, slowly dropwise adding potassium permanganate with the mass ratio of 1:0.4-0.7:2.8-3.5, stirring at constant speed for reaction for 2-4h, heating to 30-40 ℃, stirring at constant speed for reaction for 3-6h, slowly dropwise adding distilled water solvent, adding hydrogen peroxide solution to neutralize excessive potassium permanganate until the solution is bright yellow, adding dilute hydrochloric acid solution into the solution, standing for 10-20h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the graphene oxide.
(2) Adding N, N-dimethylformamide solvent and graphene oxide into a reaction bottle, adding 4,4 '-triphenylmethane triisocyanate after ultrasonic dispersion is uniform, placing the mixture into an oil bath pot, wherein the oil bath pot comprises a heating device, the upper part of the heating device is provided with an oil bath pot, the outer layer of the oil bath pot is fixedly connected with a heat preservation layer, the upper part of the heat preservation layer is fixedly connected with a supporting rod, the inner part of the supporting rod is provided with a clamping groove, the clamping groove is movably connected with a clamping block, the clamping block is fixedly connected with a moving rod, the moving rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a telescopic clamp, heating is carried out to 75-85 ℃, reacting for 6-12h, and then adding a reducing agent hydrazine hydrate solution and ammonia water, wherein the mass ratio of the graphene oxide, the 4, 4' -triphenyl, and adjusting the pH value of the solution to 8-10, heating to 90-110 ℃, uniformly stirring for reaction for 6-10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the diisocyanated functionalized graphene.
The preparation method of the functionalized graphene modified polyurethane conductive anticorrosive coating comprises the following steps:
(1) adding 0.5-3 parts of functionalized graphene, 30-40 parts of isophorone diisocyanate and 30-57 parts of polyester polyol into a reaction bottle, adding 0.5-2 parts of dibutyltin dilaurate serving as a catalyst after uniform ultrasonic dispersion, placing the mixture into an oil bath pot, heating the mixture to 70-85 ℃, uniformly stirring the mixture for reaction for 3-5 hours, cooling the temperature to 45-55 ℃, adding an acetone solvent, adjusting the viscosity of the solution, adding 3-6 parts of 2, 2-dihydroxypropionic acid, uniformly stirring the mixture for reaction for 2-3 hours, adding 8-14 parts of 1, 4-butanediol, uniformly stirring the mixture for reaction for 1-3 hours, cooling the solution to room temperature, adding triethylamine to adjust the pH of the solution to be neutral, adding 0.5-3 parts of leveling agent organic silicon system leveling assistant and 0.5-2 parts of defoaming agent silane defoaming agent, and (3) emulsifying at high speed, pouring the emulsion into a polytetrafluoroethylene mold, and curing to form a film to prepare the functionalized graphene modified polyurethane conductive anticorrosive coating.
Example 1
(1) Preparing a graphene oxide component 1: adding concentrated sulfuric acid solvent and graphite into a reaction bottle, stirring at 5 deg.C for 30min, and adding NaNO3Stirring at a constant speed for reaction for 30min, slowly dropwise adding potassium permanganate with the mass ratio of 1:0.4:2.8, stirring at a constant speed for reaction for 2h, heating to 30 ℃, stirring at a constant speed for reaction for 3h, slowly dropwise adding a distilled water solvent, adding a hydrogen peroxide solution to neutralize excessive potassium permanganate until the solution is bright yellow, adding a dilute hydrochloric acid solution into the solution, standing for 10h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the graphene oxide component 1.
(2) Preparing a functionalized graphene component 1: adding N, N-dimethylformamide solvent and graphene oxide component 1 into a reaction bottle, adding 4,4 '-triphenylmethane triisocyanate after ultrasonic dispersion is uniform, placing the mixture into an oil bath pot, wherein the oil bath pot comprises a heating device, the upper part of the heating device is provided with an oil bath pot, the outer layer of the oil bath pot is fixedly connected with a heat preservation layer, the upper part of the heat preservation layer is fixedly connected with a supporting rod, the inner part of the supporting rod is provided with a clamping groove, the clamping groove is movably connected with a clamping block, the clamping block is fixedly connected with a moving rod, the moving rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a telescopic clamp, heating is carried out to 75 ℃ for reaction for 6 hours, and then adding a reducing agent hydrazine hydrate solution and ammonia water, wherein the mass ratio of the graphene oxide, the 4, 4' triphenylmethane triisocyanate and the hydrazine hydrate, and (3) stirring at a constant speed for reaction for 6h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the diisocyanated functionalized graphene component 1.
(3) Preparing a functional graphene modified polyurethane conductive anticorrosive coating material 1: adding 0.5 part of functionalized graphene component 1, 30 parts of isophorone diisocyanate and 57 parts of polyester polyol into a reaction bottle, adding 0.5 part of dibutyltin dilaurate serving as a catalyst after uniform ultrasonic dispersion, placing the mixture into an oil bath pot, heating the mixture to 70 ℃, stirring at a constant speed for reaction for 3 hours, cooling the temperature to 45 ℃, adding an acetone solvent, adjusting the viscosity of the solution, adding 3 parts of 2, 2-dihydroxypropionic acid, stirring at a constant speed for reaction for 2 hours, adding 8 parts of 1, 4-butanediol, stirring at a constant speed for reaction for 1 hour, cooling the solution to room temperature, adding triethylamine to adjust the pH of the solution to be neutral, adding 0.5 part of a leveling agent, an organic silicon system leveling agent and 0.5 part of a defoaming agent, emulsifying at a high speed, pouring an emulsion into a polytetrafluoroethylene mold, and curing to form a film, thus obtaining the functionalized graphene modified polyurethane conductive anticorrosive coating material 1.
Example 2
(1) Preparing a graphene oxide component 2: adding concentrated sulfuric acid solvent and graphite into a reaction bottle, stirring at 0 deg.C for 60min, and adding NaNO3Stirring at a constant speed for reaction for 60min, slowly dropwise adding potassium permanganate with the mass ratio of 1:0.5:2.8, stirring at a constant speed for reaction for 4h, heating to 40 ℃, stirring at a constant speed for reaction for 6h, slowly dropwise adding a distilled water solvent, adding a hydrogen peroxide solution to neutralize excessive potassium permanganate until the solution is bright yellow, adding a dilute hydrochloric acid solution into the solution, standing for 10h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the graphene oxide component 2.
(2) Preparing a functionalized graphene component 2: adding N, N-dimethylformamide solvent and graphene oxide component 2 into a reaction bottle, adding 4,4 '-triphenylmethane triisocyanate after ultrasonic dispersion is uniform, placing the mixture into an oil bath pot, wherein the oil bath pot comprises a heating device, the upper part of the heating device is provided with an oil bath pot, the outer layer of the oil bath pot is fixedly connected with a heat preservation layer, the upper part of the heat preservation layer is fixedly connected with a supporting rod, the inner part of the supporting rod is provided with a clamping groove, the clamping groove is movably connected with a clamping block, the clamping block is fixedly connected with a moving rod, the moving rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a telescopic clamp, heating is carried out to 85 ℃ for reaction for 6 hours, and then adding a reducing agent hydrazine hydrate solution and ammonia water, wherein the mass ratio of the graphene oxide, the 4, 4' triphenylmethane triisocyanate and the hydrazine hydrate, and (3) stirring at a constant speed for reaction for 10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the diisocyanated functionalized graphene component 2.
(3) Preparing a functional graphene modified polyurethane conductive anticorrosive coating material 2: adding 1 part of functionalized graphene component 2, 32 parts of isophorone diisocyanate and 51 parts of polyester polyol into a reaction bottle, adding 0.8 part of dibutyltin dilaurate serving as a catalyst after uniform ultrasonic dispersion, placing the mixture into an oil bath pot, heating the mixture to 85 ℃, stirring at a constant speed for 5 hours, reducing the temperature to 55 ℃, adding an acetone solvent, adjusting the viscosity of the solution, adding 4 parts of 2, 2-dihydroxypropionic acid, stirring at a constant speed for 2 hours, adding 9.5 parts of 1, 4-butanediol, stirring at a constant speed for 3 hours, cooling the solution to room temperature, adding triethylamine to adjust the pH of the solution to be neutral, adding 1 part of a leveling agent, an organic silicon system leveling agent and 0.7 part of a defoaming agent, emulsifying at a high speed, pouring an emulsion into a polytetrafluoroethylene mold, and curing to form a film, thus obtaining the functionalized graphene modified polyurethane conductive anticorrosive coating material 2.
Example 3
(1) Preparing a graphene oxide component 3: adding concentrated sulfuric acid solvent and graphite into a reaction bottle, stirring at 2 deg.C for 45min, and adding NaNO3Stirring at a constant speed for reaction for 45min, slowly dropwise adding potassium permanganate with the mass ratio of 1:0.6:3.2, stirring at a constant speed for reaction for 3h, heating to 35 ℃, stirring at a constant speed for reaction for 4.5h, slowly dropwise adding a distilled water solvent, adding a hydrogen peroxide solution to neutralize excessive potassium permanganate until the solution is bright yellow, adding a dilute hydrochloric acid solution into the solution, standing for 15h, filtering the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the graphene oxide component 3.
(2) Preparing a functionalized graphene component 3: adding N, N-dimethylformamide solvent and graphene oxide component 3 into a reaction bottle, adding 4,4 '-triphenylmethane triisocyanate after ultrasonic dispersion is uniform, placing the mixture into an oil bath pot, wherein the oil bath pot comprises a heating device, the upper part of the heating device is provided with an oil bath pot, the outer layer of the oil bath pot is fixedly connected with a heat preservation layer, the upper part of the heat preservation layer is fixedly connected with a supporting rod, the inner part of the supporting rod is provided with a clamping groove, the clamping groove is movably connected with a clamping block, the clamping block is fixedly connected with a moving rod, the moving rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a telescopic clamp, heating is carried out to 80 ℃ for reaction for 9 hours, then adding a reducing agent hydrazine hydrate solution and ammonia water, wherein the mass ratio of the graphene oxide, the 4, 4' triphenylmethane triisocyanate and the hydrazine hydrate is, and (3) stirring at a constant speed for reaction for 8h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the diisocyanated functionalized graphene component 3.
(3) Preparing a functional graphene modified polyurethane conductive anticorrosive coating material 3: adding 1.5 parts of functionalized graphene component 3, 35 parts of isophorone diisocyanate and 44 parts of polyester polyol into a reaction bottle, uniformly dispersing by ultrasonic waves, adding 1 part of dibutyltin dilaurate serving as a catalyst, placing the mixture into an oil bath pot, heating to 80 ℃, uniformly stirring for reaction for 4 hours, cooling to 50 ℃, adding an acetone solvent, adjusting the viscosity of the solution, adding 4.5 parts of 2, 2-dihydroxypropionic acid, uniformly stirring for reaction for 2.5 hours, adding 11 parts of 1, 4-butanediol, uniformly stirring for reaction for 2 hours, cooling the solution to room temperature, adding triethylamine to adjust the pH of the solution to be neutral, adding 1.8 parts of a leveling agent, an organic silicon leveling assistant and 1.2 parts of a defoaming agent, performing high-speed emulsification, pouring an emulsion into a polytetrafluoroethylene mold, and curing to form a film, thus preparing the functionalized graphene modified polyurethane conductive anticorrosive coating material 3.
Example 4
(1) Preparing a graphene oxide component 4: adding concentrated sulfuric acid solvent and graphite into a reaction bottle, stirring at 5 deg.C for 60min, and adding NaNO3Stirring at constant speed for reaction for 60min, slowly adding potassium permanganate dropwise at a mass ratio of 1:0.6:3.5, stirring at constant speed for reaction for 4h, heating to 40 deg.C, stirring at constant speed for reaction for 3h,slowly dropwise adding a distilled water solvent, then adding a hydrogen peroxide solution to neutralize excessive potassium permanganate until the solution is bright yellow, adding a dilute hydrochloric acid solution into the solution, standing for 20h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the graphene oxide component 4.
(2) Preparing a functionalized graphene component 4: adding N, N-dimethylformamide solvent and graphene oxide component 4 into a reaction bottle, adding 4,4 '-triphenylmethane triisocyanate after ultrasonic dispersion is uniform, placing the mixture into an oil bath pot, wherein the oil bath pot comprises a heating device, the upper part of the heating device is provided with an oil bath pot, the outer layer of the oil bath pot is fixedly connected with a heat preservation layer, the upper part of the heat preservation layer is fixedly connected with a supporting rod, the inner part of the supporting rod is provided with a clamping groove, the clamping groove is movably connected with a clamping block, the clamping block is fixedly connected with a moving rod, the moving rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a telescopic clamp, heating is carried out to 85 ℃ for reaction for 12 hours, and then adding reducing agent hydrazine hydrate solution and ammonia water, wherein the mass ratio of the graphene oxide, the 4, 4' triphenylmethane triisocyanate and the hydrazine hydrate is, and (3) stirring at a constant speed for reaction for 9 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the diisocyanated functionalized graphene component 4.
(3) Preparing a functional graphene modified polyurethane conductive anticorrosive coating material 4: adding 2.4 parts of functionalized graphene component 4, 38 parts of isophorone diisocyanate and 37 parts of polyester polyol into a reaction bottle, adding 1.8 parts of dibutyltin dilaurate serving as a catalyst after ultrasonic dispersion is uniform, placing the mixture into an oil bath pot, heating the mixture to 85 ℃, stirring at a constant speed for reaction for 4 hours, cooling the temperature to 55 ℃, adding an acetone solvent, adjusting the viscosity of the solution, adding 5.2 parts of 2, 2-dihydroxypropionic acid, stirring at a constant speed for reaction for 2 hours, adding 12.5 parts of 1, 4-butanediol, stirring at a constant speed for reaction for 2 hours, cooling the solution to room temperature, adding triethylamine to adjust the pH of the solution to be neutral, adding 2.6 parts of a leveling agent, an organic silicon system leveling agent and 1.5 parts of a defoaming agent, emulsifying at a high speed, pouring an emulsion into a polytetrafluoroethylene mold, and curing to form a film, thus obtaining the functionalized graphene modified polyurethane conductive anticorrosive coating material 4.
Example 5
(1) Preparing a graphene oxide component 5: adding concentrated sulfuric acid solvent and graphite into a reaction bottle, stirring at 0 deg.C for 60min, and adding NaNO3Stirring at a constant speed for reaction for 60min, slowly dropwise adding potassium permanganate with the mass ratio of 1:0.7:3.5, stirring at a constant speed for reaction for 4h, heating to 40 ℃, stirring at a constant speed for reaction for 6h, slowly dropwise adding a distilled water solvent, adding a hydrogen peroxide solution to neutralize excessive potassium permanganate until the solution is bright yellow, adding a dilute hydrochloric acid solution into the solution, standing for 20h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the graphene oxide component 5.
(2) Preparing a functionalized graphene component 5: adding N, N-dimethylformamide solvent and graphene oxide component 5 into a reaction bottle, adding 4,4 ' -triphenylmethane triisocyanate after ultrasonic dispersion is uniform, placing the mixture into an oil bath pot, wherein the oil bath pot comprises a heating device, the upper part of the heating device is provided with an oil bath pot, the outer layer of the oil bath pot is fixedly connected with a heat preservation layer, the upper part of the heat preservation layer is fixedly connected with a supporting rod, the inner part of the supporting rod is provided with a clamping groove, the clamping groove is movably connected with a clamping block, the clamping block is fixedly connected with a moving rod, the moving rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a telescopic clamp, heating is carried out to 85 ℃ for reaction for 12 hours, then adding a reducing agent hydrazine hydrate solution and ammonia water, wherein the mass ratio of the graphene oxide, the 4,4 ' and 4 ' triphenylmethane triisocyanate, and (3) stirring at a constant speed for reaction for 10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the diisocyanated functionalized graphene component 5.
(3) Preparing a functional graphene modified polyurethane conductive anticorrosive coating material 5: adding 3 parts of functionalized graphene component 5, 40 parts of isophorone diisocyanate and 30 parts of polyester polyol into a reaction bottle, adding 2 parts of dibutyltin dilaurate serving as a catalyst after uniform ultrasonic dispersion, placing the mixture into an oil bath pot, heating the mixture to 85 ℃, stirring at a constant speed for 5 hours, reducing the temperature to 55 ℃, adding an acetone solvent, adjusting the viscosity of the solution, adding 6 parts of 2, 2-dihydroxypropionic acid, stirring at a constant speed for 3 hours, adding 14 parts of 1, 4-butanediol, stirring at a constant speed for 3 hours, cooling the solution to room temperature, adding triethylamine to adjust the pH of the solution to be neutral, adding 3 parts of a leveling agent organic silicon system leveling assistant and 2 parts of a defoaming agent silane defoaming agent, emulsifying at a high speed, pouring an emulsion into a polytetrafluoroethylene mold, and curing to form a film to prepare the functionalized graphene modified polyurethane conductive anticorrosive coating material 5.
The functionalized graphene modified polyurethane conductive anticorrosive coating material 1-5 prepared in the embodiment is placed in a SYTH-120 salt dry-wet composite corrosion test box for a salt spray resistance test, and the test standard is GB/T1771-2007.
The volume resistivity of the functionalized graphene modified polyurethane conductive anticorrosive coating materials 1-5 prepared in the embodiment is tested by using an EST120 digital high-impedance meter, and the test standard GB/T1410-2006 is obtained.
To sum up, the functionalized graphene modified polyurethane conductive anticorrosive coating is prepared by preparing graphene oxide with high hydroxyl content through an acidification oxidation method, reacting isocyanate groups in 4, 4' -triphenylmethane triisocyanate with hydroxyl groups in the graphene oxide, reducing the reaction product through hydrazine hydrate to prepare diisocyanated functionalized graphene, performing copolymerization reaction on the diisocyanated functionalized graphene and two unreacted isocyanates in the graphene by taking the functionalized graphene as crosslinking neutrality and taking polyester polyol as a polyol monomer, and preparing the functionalized graphene modified polyurethane coating material through a chemical covalent bond modification method, so that the compatibility of the graphene and polyurethane is remarkably enhanced.
The nano-morphology graphene is uniformly dispersed in the polyurethane coating, enters gaps of the coating material, has excellent barrier property, and can inhibit water molecules, oxygen and corrosionThe corrosion medium permeates into the coating to contact with the material, so that a good electrochemical corrosion prevention effect is achieved, the uniformly dispersed graphene forms a three-dimensional conductive network in the polyurethane coating, the volume resistivity of the material is reduced, the conductivity of the material is improved, electrons lost by Fe in the iron-based metal material can be transferred into the polyurethane coating, the cathode reaction in the electrochemical corrosion reaction is transferred into the polyurethane coating, the generation of hydroxide radicals generated by the cathode reaction and iron ions generated by an anode are reduced to generate precipitates, so that the metal anode corrosion reaction is prevented from proceeding, the dissolution and corrosion of iron in the iron-based metal material are reduced, the good electrochemical corrosion prevention performance is achieved, and with the moderate increase of the content of the graphene, the volume resistivity is reduced to 1.21 × 107-3.34×106Omega cm, the polyurethane coating material has excellent conductivity and corrosion resistance, and the salt spray resistance reaches 94-118 h.
Claims (7)
1. The functional graphene modified polyurethane conductive anticorrosive coating comprises the following formula raw materials and components in parts by weight, and is characterized in that: 0.5-3 parts of functionalized graphene, 30-40 parts of isophorone diisocyanate, 30-57 parts of polyester polyol, 0.5-2 parts of catalyst, 8-14 parts of 1, 4-butanediol, 3-6 parts of 2, 2-dihydroxypropionic acid, 0.5-3 parts of flatting agent and 0.5-2 parts of defoaming agent.
2. The functionalized graphene modified polyurethane conductive anticorrosive coating according to claim 1, characterized in that: the catalyst is dibutyltin dilaurate, the flatting agent is an organic silicon system flatting auxiliary agent, and the defoaming agent is a silane defoaming agent.
3. The functionalized graphene modified polyurethane conductive anticorrosive coating according to claim 1, characterized in that: the preparation method of the functionalized graphene comprises the following steps:
(1) adding graphite into concentrated sulfuric acid solvent, stirring at 0-5 deg.C for 30-60min, adding NaNO3Reacting for 30-60min, slowly adding potassium permanganate dropwise, reacting for 2-4h, heating to 30-40 deg.C, reacting for 3-6h, adding distilled water solvent dropwise andneutralizing excessive potassium permanganate with a hydrogen peroxide solution, adding a dilute hydrochloric acid solution, standing for 10-20h, filtering, washing and drying to prepare graphene oxide;
(2) adding graphene oxide into an N, N-dimethylformamide solvent, uniformly dispersing by ultrasonic, adding 4, 4' -triphenylmethane triisocyanate, putting the mixture into an oil bath pot, heating the mixture to 75-85 ℃ for reaction for 6-12h, adding a reducing agent hydrazine hydrate solution and ammonia water, adjusting the pH of the solution to 8-10, heating the solution to 90-110 ℃, reacting for 6-10h, filtering, washing and drying to obtain the diisocyanated functionalized graphene.
4. The functionalized graphene modified polyurethane conductive anticorrosive coating according to claim 3, characterized in that: the graphite and NaNO3The mass ratio of the potassium permanganate to the potassium permanganate is 1:0.4-0.7: 2.8-3.5.
5. The functionalized graphene modified polyurethane conductive anticorrosive coating according to claim 3, characterized in that: the mass ratio of the graphene oxide, the 4, 4' -triphenylmethane triisocyanate to the hydrazine hydrate is 1:15-25: 0.6-1.
6. The functionalized graphene modified polyurethane conductive anticorrosive coating according to claim 3, characterized in that: the oil bath pot comprises a heating device, an oil bath pot body is arranged above the heating device, a heat preservation layer is fixedly connected to the outer layer of the oil bath pot body, a support rod is fixedly connected to the upper portion of the heat preservation layer, a clamping groove is formed in the support rod, the clamping groove is movably connected with a clamping block, a moving rod is fixedly connected with the clamping block, a moving rod is movably connected with a regulating valve, and the regulating valve is movably connected with a telescopic.
7. The functionalized graphene modified polyurethane conductive anticorrosive coating according to claim 1, characterized in that: the preparation method of the functional graphene modified polyurethane conductive anticorrosive coating comprises the following steps:
(1) adding 0.5-3 parts of functionalized graphene and 30-40 parts of isophorone diisocyanate into 30-57 parts of polyester polyol, adding 0.5-2 parts of dibutyltin dilaurate serving as a catalyst after uniform ultrasonic dispersion, placing the mixture into an oil bath pot, heating the mixture to 70-85 ℃, reacting for 3-5 hours, cooling the temperature to 45-55 ℃, adding an acetone solvent, adjusting the viscosity of the solution, adding 3-6 parts of 2, 2-dihydroxypropionic acid, reacting for 2-3 hours, adding 8-14 parts of 1, 4-butanediol, reacting for 1-3 hours, adding triethylamine to adjust the pH of the solution to be neutral, adding 0.5-3 parts of a leveling agent, an organic silicon system leveling agent and 0.5-2 parts of a defoaming agent, performing high-speed emulsification, pouring an emulsion into a polytetrafluoroethylene mold, and curing to form a film, and preparing the functionalized graphene modified polyurethane conductive anticorrosive coating.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608436A (en) * | 2020-12-14 | 2021-04-06 | 武汉材料保护研究所有限公司 | Polyurethane modified graphene microchip and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804169A (en) * | 2015-05-22 | 2015-07-29 | 烟台大学 | Preparation method of graphene-modified polyurethane conductive coating |
| CN106750087A (en) * | 2016-12-15 | 2017-05-31 | 陕西高新实业有限公司 | The preparation method of Graphene Waterborne PU Composite |
| CN107793901A (en) * | 2017-10-20 | 2018-03-13 | 安徽快来防水防腐有限公司 | A kind of production method for the poly-aspartate polyurea water-proof corrosion-inhibiting coating that graphene is modified |
-
2020
- 2020-04-26 CN CN202010338258.8A patent/CN111410905A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804169A (en) * | 2015-05-22 | 2015-07-29 | 烟台大学 | Preparation method of graphene-modified polyurethane conductive coating |
| CN106750087A (en) * | 2016-12-15 | 2017-05-31 | 陕西高新实业有限公司 | The preparation method of Graphene Waterborne PU Composite |
| CN107793901A (en) * | 2017-10-20 | 2018-03-13 | 安徽快来防水防腐有限公司 | A kind of production method for the poly-aspartate polyurea water-proof corrosion-inhibiting coating that graphene is modified |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608436A (en) * | 2020-12-14 | 2021-04-06 | 武汉材料保护研究所有限公司 | Polyurethane modified graphene microchip and preparation method thereof |
| CN112745476A (en) * | 2020-12-30 | 2021-05-04 | 桐乡市鸿信科技合伙企业(有限合伙) | Graphene modified polyurethane resin material with high thermal stability and preparation method thereof |
| CN113057636A (en) * | 2021-03-01 | 2021-07-02 | 上海英科心电图医疗产品有限公司 | Anti-interference graphene electrocardioelectrode and preparation method thereof |
| CN112940282A (en) * | 2021-03-05 | 2021-06-11 | 陕西科技大学 | Composite modified graphene modified waterborne polyurethane emulsion and preparation method thereof |
| CN114369406A (en) * | 2022-02-15 | 2022-04-19 | 江苏冠军科技集团股份有限公司 | Graphene zinc powder anticorrosion primer for high-flash-point steel structure and preparation method thereof |
| CN114539902B (en) * | 2022-03-01 | 2022-12-20 | 刘志强 | Coating for automobile chassis for off-road vehicle |
| CN114539902A (en) * | 2022-03-01 | 2022-05-27 | 刘志强 | Coating for automobile chassis for off-road vehicle |
| CN114773534A (en) * | 2022-03-24 | 2022-07-22 | 广东邦固化学科技有限公司 | Conductive PUA composite emulsion and preparation method thereof |
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