CN111718638A - Functionalized graphene-water-based epoxy resin anticorrosive material and preparation method thereof - Google Patents
Functionalized graphene-water-based epoxy resin anticorrosive material and preparation method thereof Download PDFInfo
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- CN111718638A CN111718638A CN202010686528.4A CN202010686528A CN111718638A CN 111718638 A CN111718638 A CN 111718638A CN 202010686528 A CN202010686528 A CN 202010686528A CN 111718638 A CN111718638 A CN 111718638A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
The invention relates to the technical field of epoxy resin, and discloses a functionalized graphene-water-based epoxy resin anticorrosive material which comprises the following formula raw materials and components: functionalized graphene, epoxy resin, a curing agent, a curing accelerator and a defoaming agent. The method comprises the following steps of carrying out esterification reaction on polyvinyl alcohol grafted by graphene and carboxyl of DL-serine, carrying out phosphorylation esterification reaction on phosphoric acid and hydroxyl of serine to obtain amphiphilic phosphorylated serine-polyvinyl alcohol grafted graphene containing phosphate groups of metal slow-release groups, carrying out chemical covalent modification on functionalized graphene into a matrix of epoxy resin, promoting conversion of oleophilic epoxy resin to hydrophilicity by using an amphiphilic serine-polyvinyl alcohol esterification product component, uniformly dispersing the graphene, improving barrier property of the epoxy resin to air and water, inhibiting corrosion reaction of a ferrous metal anode in seawater, and enabling the aqueous epoxy resin material to show excellent chemical corrosion resistance and electrochemical corrosion resistance.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to a functionalized graphene-water-based epoxy resin anticorrosive material and a preparation method thereof.
Background
The metal corrosion refers to the damage of metal under the chemical or electrochemical action of surrounding media such as air, water and the like, and often under the combined action of physical, mechanical or biological factors, and can be chemically corroded and electrochemically corroded according to the corrosion, wherein the chemical corrosion is the corrosion caused by the chemical action of metal in dry gas and non-electrolyte solution, a compound generated by the chemical corrosion is unstable and easy to volatilize or dissolve, the compound is not firmly combined with the metal, a corrosion product can fall off, the electrochemical corrosion is the damage caused by the electrochemical action generated between the metal and the electrolyte solution, and current is generated in the corrosion process.
The epoxy resin is a thermosetting resin, molecules of the epoxy resin contain more than two epoxy groups, the epoxy resin can be cured and crosslinked with a curing agent containing active hydrogen, the epoxy resin has good insulating property, corrosion resistance and mechanical property, products mainly comprise high-temperature-resistant glue, optical glue, sealant, latent curing glue and the like, and in the fields of mechanical buildings, electronic appliances, aerospace and aviation and the like, the waterborne epoxy resin has the advantages of strong adaptability, good environmental protection and the like.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the high-efficiency functionalized graphene-water-based epoxy resin anticorrosive material and the preparation method thereof, and solves the problems that the epoxy resin has limited anticorrosive performance and does not have the electrochemical anticorrosive effect.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a functionalized graphene-water-based epoxy resin anticorrosive material comprises: the graphene-epoxy resin curing agent comprises the following raw materials and components, namely functionalized graphene, epoxy resin, a curing agent, a curing accelerator and a defoaming agent, wherein the mass ratio of the functionalized graphene to the epoxy resin is 10-30:100:45-55:0.2-1: 0.5-1.
Preferably, the curing agent is an acid anhydride curing agent, and the curing accelerator is an amine curing accelerator.
Preferably, the preparation method of the functionalized graphene-waterborne epoxy resin anticorrosive material comprises the following steps:
(1) adding a distilled water solvent and graphene oxide into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic dispersion instrument for ultrasonic dispersion treatment, adding polyvinyl alcohol, heating to 90-100 ℃, performing ultrasonic reflux reaction for 5-10 hours, placing the solution in an ice water bath for cooling, performing vacuum drying to remove the solvent, washing a solid product with distilled water and ethanol, and drying to obtain the polyvinyl alcohol grafted graphene.
(2) Adding a dimethyl sulfoxide solvent and polyvinyl alcohol grafted graphene into a reaction bottle, ultrasonically dispersing uniformly, adding a sulfuric acid solution to adjust the pH of the solution to 2-4, adding DL-serine, heating to 100-130 ℃, stirring at a constant speed for reaction for 12-24h, cooling, filtering, washing and drying the solution to prepare the amphiphilic serine-polyvinyl alcohol grafted graphene.
(3) Adding a dimethyl sulfoxide solvent and serine-polyvinyl alcohol grafted graphene into a reaction bottle, adding phosphoric acid and a catalyst urea after uniform ultrasonic dispersion, heating to 120-140 ℃, stirring at a constant speed for reaction for 5-10h, cooling, filtering, washing and drying the solution to obtain the phosphorylated serine-polyvinyl alcohol grafted graphene, namely the functionalized graphene.
(4) Adding a distilled water solvent and functionalized graphene into a reaction bottle, adding epoxy resin after uniform ultrasonic dispersion, performing a high-speed emulsification process, adding an anhydride curing agent, an amine curing accelerator and a defoaming agent, stirring uniformly, pouring the emulsion into a mold, and performing thermosetting crosslinking to prepare the functionalized graphene-waterborne epoxy resin anticorrosive material.
Preferably, the constant temperature ultrasonic dispersion appearance in step (1) includes that insulating layer, insulating layer inner wall are fixed with the ultrasonic apparatus, insulating layer inner wall fixedly connected with fixture block, fixture block fixedly connected with spring beam, spring beam swing joint have the cardboard, insulating layer inside below fixedly connected with base, the base top is provided with the reaction bottle.
Preferably, the mass ratio of the graphene oxide to the polyvinyl alcohol in the step (1) is 1: 5-20.
Preferably, the mass ratio of the polyvinyl alcohol grafted graphene to the DL-serine in the step (2) is 100: 15-35.
Preferably, the mass ratio of the serine-polyvinyl alcohol grafted graphene to the phosphoric acid to the urea in the step (3) is 100:80-200: 3-15.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the functionalized graphene-water-based epoxy resin anticorrosive material, hydroxyl of polyvinyl alcohol reacts with oxygen-containing groups of graphene oxide, the polyvinyl alcohol is grafted to a lamellar structure of the graphene, the grafted polyvinyl alcohol component and the carboxyl of DL-serine are subjected to esterification reaction, the serine-polyvinyl alcohol esterification product has good amphipathy, phosphoric acid and the hydroxyl in the serine component are subjected to phosphorylation esterification reaction by taking urea as a catalyst to prepare the amphiphilic phosphorylated serine-polyvinyl alcohol grafted graphene containing the phosphate group of the metal slow-release group, namely the functionalized graphene, which is used as a modified filler, in the ring opening process of an anhydride curing agent and epoxy resin, and simultaneously reacting amino of a serine component in the functionalized graphene with an anhydride curing agent to chemically and covalently modify the functionalized graphene into a matrix of the epoxy resin.
According to the functionalized graphene-water-based epoxy resin anticorrosive material, the amphiphilic serine-polyvinyl alcohol esterification product component promotes lipophilic epoxy resin to be converted into hydrophilic, the hydrophilicity and the water resistance of the epoxy resin are improved, the graphene is uniformly dispersed into gaps and a matrix of the epoxy resin, the barrier property of the epoxy resin is improved, the phenomenon that air, water and other corrosive media permeate the epoxy resin is reduced, the chemical corrosion resistance of the epoxy resin is enhanced, meanwhile, the graphene with excellent conductivity inhibits the corrosion reaction of a ferrous metal anode in seawater, the electrochemical corrosion rate is reduced, the graphene can transfer electrons lost by anode iron to the surface of a coating, the cathode reaction is transferred to the surface of the coating to occur, and OH generated by the cathode reaction is inhibited-Fe formed by reaction with anode3+The reaction hinders the proceeding of anode reaction, reduces the dissolution and corrosion of the iron-based material, and the phosphate group in the functionalized graphene can be used as an anionic metal corrosion inhibitor, so that the water-based epoxy resin material shows excellent chemical corrosion resistance and electrochemical corrosion resistance under the synergistic action.
Drawings
FIG. 1 is a schematic front view of a constant temperature ultrasonic disperser;
FIG. 2 is a schematic top view of an ultrasound machine;
FIG. 3 is a schematic top view of a spring rod;
FIG. 4 is a schematic top view of a reaction flask.
1-constant temperature ultrasonic dispersion instrument; 2-a heat insulation layer; 3-an ultrasonic device; 4-clamping blocks; 5-a spring rod; 6-clamping plate; 7-a base; 8-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a functionalized graphene-water-based epoxy resin anticorrosive material comprises: the modified graphene-epoxy resin modified epoxy resin coating comprises the following raw materials and components, namely, functionalized graphene, epoxy resin, an anhydride curing agent, an amine curing accelerator and a defoaming agent, wherein the mass ratio of the functionalized graphene to the amine curing accelerator is 10-30:100:45-55:0.2-1: 0.5-1.
The preparation method of the functionalized graphene-waterborne epoxy resin anticorrosive material comprises the following steps:
(1) adding distilled water solvent and graphene oxide into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a heat-insulating layer, an ultrasonic device is fixed on the inner wall of the heat-insulating layer, a clamping block is fixedly connected to the inner wall of the heat-insulating layer, a spring rod is fixedly connected to the clamping block, a clamping plate is movably connected to the spring rod, a base is fixedly connected to the lower portion of the inner portion of the heat-insulating layer, a reaction bottle is arranged above the base, ultrasonic dispersing treatment is carried out, then polyvinyl alcohol is added, the mass ratio of the polyvinyl alcohol to the graphene oxide is 5-20:1, the solution is heated to 90-100 ℃, ultrasonic reflux reaction is carried out for 5-10 hours, the solution is placed in an ice water bath for cooling.
(2) Adding a dimethyl sulfoxide solvent and polyvinyl alcohol grafted graphene into a reaction bottle, performing ultrasonic dispersion uniformly, adding a sulfuric acid solution to adjust the pH of the solution to 2-4, adding DL-serine at a mass ratio of 15-35:100 to the polyvinyl alcohol grafted graphene, heating to 100-phase 130 ℃, stirring at a constant speed for reaction for 12-24 hours, cooling, filtering, washing and drying the solution, and thus obtaining the amphiphilic serine-polyvinyl alcohol grafted graphene.
(3) Adding a dimethyl sulfoxide solvent and serine-polyvinyl alcohol grafted graphene into a reaction bottle, adding phosphoric acid and a catalyst urea after ultrasonic dispersion is uniform, wherein the mass ratio of the dimethyl sulfoxide solvent to the serine-polyvinyl alcohol grafted graphene is 100:80-200:3-15, heating to 120 plus materials, stirring at a constant speed, reacting for 5-10h, cooling, filtering, washing and drying the solution, and preparing the phosphorylated serine-polyvinyl alcohol grafted graphene, namely the functionalized graphene.
(4) Adding a distilled water solvent and functionalized graphene into a reaction bottle, adding epoxy resin after uniform ultrasonic dispersion, performing a high-speed emulsification process, adding an anhydride curing agent, an amine curing accelerator and a defoaming agent, stirring uniformly, pouring the emulsion into a mold, and performing thermosetting crosslinking to prepare the functionalized graphene-waterborne epoxy resin anticorrosive material.
Example 1
(1) Adding distilled water solvent and graphene oxide into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a heat-insulating layer, an ultrasonic device is fixed on the inner wall of the heat-insulating layer, a clamping block is fixedly connected to the inner wall of the heat-insulating layer, a spring rod is fixedly connected to the clamping block, a clamping plate is movably connected to the spring rod, a base is fixedly connected to the lower portion of the inner portion of the heat-insulating layer, a reaction bottle is arranged above the base, ultrasonic dispersing treatment is carried out, then polyvinyl alcohol is added, the mass ratio of polyvinyl alcohol to graphene oxide is 5:1, heating is carried out to 90 ℃, ultrasonic reflux reaction is carried out for 5 hours, the solution is placed in an ice water bath to be cooled, vacuum.
(2) Adding a dimethyl sulfoxide solvent and polyvinyl alcohol grafted graphene into a reaction bottle, performing ultrasonic dispersion uniformly, adding a sulfuric acid solution to adjust the pH of the solution to 4, adding DL-serine at a mass ratio of 15:100 to the polyvinyl alcohol grafted graphene, heating to 100 ℃, stirring at a constant speed for reaction for 12 hours, cooling, filtering, washing and drying the solution to obtain the amphiphilic serine-polyvinyl alcohol grafted graphene.
(3) Adding a dimethyl sulfoxide solvent and serine-polyvinyl alcohol grafted graphene into a reaction bottle, adding phosphoric acid and a catalyst urea after ultrasonic dispersion is uniform, heating to 120 ℃, stirring at a constant speed for reaction for 5 hours, cooling, filtering, washing and drying the solution, and preparing the phosphorylated serine-polyvinyl alcohol grafted graphene, namely the functionalized graphene.
(4) Adding a distilled water solvent and functionalized graphene into a reaction bottle, adding epoxy resin after uniform ultrasonic dispersion, performing a high-speed emulsification process, adding an anhydride curing agent, an amine curing accelerator and a defoaming agent according to the mass ratio of 10:100:45:0.2:0.5, uniformly stirring, pouring the emulsion into a mold, and performing thermosetting crosslinking to prepare the functionalized graphene-waterborne epoxy resin anticorrosive material 1.
Example 2
(1) Adding distilled water solvent and graphene oxide into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a heat-insulating layer, an ultrasonic device is fixed on the inner wall of the heat-insulating layer, a clamping block is fixedly connected to the inner wall of the heat-insulating layer, a spring rod is fixedly connected to the clamping block, a clamping plate is movably connected to the spring rod, a base is fixedly connected to the lower portion of the inner portion of the heat-insulating layer, a reaction bottle is arranged above the base, ultrasonic dispersing treatment is carried out, then polyvinyl alcohol is added, the mass ratio of polyvinyl alcohol to graphene oxide is 10:1, heating is carried out to 90 ℃, ultrasonic reflux reaction is carried out for 10 hours, the solution is placed in an ice water bath to be cooled, vacuum.
(2) Adding a dimethyl sulfoxide solvent and polyvinyl alcohol grafted graphene into a reaction bottle, performing ultrasonic dispersion uniformly, adding a sulfuric acid solution to adjust the pH of the solution to 2, adding DL-serine at a mass ratio of 22:100 to the polyvinyl alcohol grafted graphene, heating to 120 ℃, stirring at a constant speed for reaction for 18 hours, cooling, filtering, washing and drying the solution to obtain the amphiphilic serine-polyvinyl alcohol grafted graphene.
(3) Adding a dimethyl sulfoxide solvent and serine-polyvinyl alcohol grafted graphene into a reaction bottle, adding phosphoric acid and a catalyst urea after uniformly dispersing by ultrasonic, wherein the mass ratio of the dimethyl sulfoxide solvent to the serine-polyvinyl alcohol grafted graphene to the urea is 100:120:8, heating to 120 ℃, stirring at a constant speed for reaction for 10 hours, cooling, filtering, washing and drying the solution to obtain the phosphorylated serine-polyvinyl alcohol grafted graphene, namely the functionalized graphene.
(4) Adding a distilled water solvent and functionalized graphene into a reaction bottle, adding epoxy resin after uniform ultrasonic dispersion, performing a high-speed emulsification process, adding an anhydride curing agent, an amine curing accelerator and a defoaming agent according to the mass ratio of 15:100:48:0.4:0.6, uniformly stirring, pouring the emulsion into a mold, and performing thermosetting crosslinking to prepare the functionalized graphene-waterborne epoxy resin anticorrosive material 2.
Example 3
(1) Adding distilled water solvent and graphene oxide into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a heat-insulating layer, an ultrasonic device is fixed on the inner wall of the heat-insulating layer, a clamping block is fixedly connected to the inner wall of the heat-insulating layer, a spring rod is fixedly connected to the clamping block, a clamping plate is movably connected to the spring rod, a base is fixedly connected to the lower portion of the inner portion of the heat-insulating layer, a reaction bottle is arranged above the base, ultrasonic dispersing treatment is carried out, then polyvinyl alcohol is added, the mass ratio of polyvinyl alcohol to graphene oxide is 15:1, heating is carried out to 95 ℃, ultrasonic reflux reaction is carried out for 8 hours, the solution is placed in an ice water bath to be cooled, vacuum.
(2) Adding a dimethyl sulfoxide solvent and polyvinyl alcohol grafted graphene into a reaction bottle, performing ultrasonic dispersion uniformly, adding a sulfuric acid solution to adjust the pH of the solution to 3, adding DL-serine at a mass ratio of 30:100 to the polyvinyl alcohol grafted graphene, heating to 115 ℃, stirring at a constant speed for reaction for 18 hours, cooling, filtering, washing and drying the solution to obtain the amphiphilic serine-polyvinyl alcohol grafted graphene.
(3) Adding a dimethyl sulfoxide solvent and serine-polyvinyl alcohol grafted graphene into a reaction bottle, adding phosphoric acid and a catalyst urea after uniformly dispersing by ultrasonic, wherein the mass ratio of the dimethyl sulfoxide solvent to the serine-polyvinyl alcohol grafted graphene to the urea is 100:160:12, heating to 130 ℃, stirring at a constant speed for reaction for 8 hours, cooling, filtering, washing and drying the solution to obtain the phosphorylated serine-polyvinyl alcohol grafted graphene, namely the functionalized graphene.
(4) Adding a distilled water solvent and functionalized graphene into a reaction bottle, adding epoxy resin after uniform ultrasonic dispersion, performing a high-speed emulsification process, adding an anhydride curing agent, an amine curing accelerator and a defoaming agent according to the mass ratio of 25:100:52:0.7:0.8, uniformly stirring, pouring the emulsion into a mold, and performing thermosetting crosslinking to prepare the functionalized graphene-waterborne epoxy resin anticorrosive material 3.
Example 4
(1) Adding distilled water solvent and graphene oxide into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a heat-insulating layer, an ultrasonic device is fixed on the inner wall of the heat-insulating layer, a clamping block is fixedly connected to the inner wall of the heat-insulating layer, a spring rod is fixedly connected to the clamping block, a clamping plate is movably connected to the spring rod, a base is fixedly connected to the lower portion of the inner portion of the heat-insulating layer, a reaction bottle is arranged above the base, ultrasonic dispersing treatment is carried out, then polyvinyl alcohol is added, the mass ratio of polyvinyl alcohol to graphene oxide is 20:1, heating is carried out to 100 ℃, ultrasonic reflux reaction is carried out for 10 hours, the solution is placed in an ice water bath to be cooled, vacuum.
(2) Adding a dimethyl sulfoxide solvent and polyvinyl alcohol grafted graphene into a reaction bottle, performing ultrasonic dispersion uniformly, adding a sulfuric acid solution to adjust the pH of the solution to 2, adding DL-serine according to the mass ratio of 35:100 to the polyvinyl alcohol grafted graphene, heating to 130 ℃, stirring at a constant speed for reaction for 24 hours, cooling, filtering, washing and drying the solution, and thus obtaining the amphiphilic serine-polyvinyl alcohol grafted graphene.
(3) Adding a dimethyl sulfoxide solvent and serine-polyvinyl alcohol grafted graphene into a reaction bottle, adding phosphoric acid and a catalyst urea after uniformly dispersing by ultrasonic, wherein the mass ratio of the dimethyl sulfoxide solvent to the serine-polyvinyl alcohol grafted graphene to the urea is 100:200:15, heating to 140 ℃, stirring at a constant speed for reaction for 10 hours, cooling, filtering, washing and drying the solution to obtain the phosphorylated serine-polyvinyl alcohol grafted graphene, namely the functionalized graphene.
(4) Adding a distilled water solvent and functionalized graphene into a reaction bottle, adding epoxy resin after uniform ultrasonic dispersion, performing a high-speed emulsification process, adding an anhydride curing agent, an amine curing accelerator and a defoaming agent according to the mass ratio of 30:100:55:1:1, uniformly stirring, pouring the emulsion into a mold, and performing thermosetting crosslinking to prepare the functionalized graphene-waterborne epoxy resin anticorrosive material 4.
Comparative example 1
(1) Adding distilled water solvent and graphene oxide into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a heat-insulating layer, an ultrasonic device is fixed on the inner wall of the heat-insulating layer, a clamping block is fixedly connected to the inner wall of the heat-insulating layer, a spring rod is fixedly connected to the clamping block, a clamping plate is movably connected to the spring rod, a base is fixedly connected to the lower portion of the inner portion of the heat-insulating layer, a reaction bottle is arranged above the base, ultrasonic dispersing treatment is carried out, then polyvinyl alcohol is added, the mass ratio of polyvinyl alcohol to graphene oxide is 2:1, heating is carried out to 100 ℃, ultrasonic reflux reaction is carried out for 5 hours, the solution is placed in an ice water bath to be cooled, vacuum.
(2) Adding a dimethyl sulfoxide solvent and polyvinyl alcohol grafted graphene into a reaction bottle, performing ultrasonic dispersion uniformly, adding a sulfuric acid solution to adjust the pH of the solution to 4, adding DL-serine at a mass ratio of 40:100 to the polyvinyl alcohol grafted graphene, heating to 130 ℃, stirring at a constant speed for reaction for 24 hours, cooling, filtering, washing and drying the solution to obtain the amphiphilic serine-polyvinyl alcohol grafted graphene.
(3) Adding a dimethyl sulfoxide solvent and serine-polyvinyl alcohol grafted graphene into a reaction bottle, adding phosphoric acid and a catalyst urea after uniformly dispersing by ultrasonic, wherein the mass ratio of the dimethyl sulfoxide solvent to the serine-polyvinyl alcohol grafted graphene to the urea is 100:50:2, heating to 120 ℃, stirring at a constant speed for reaction for 10 hours, cooling, filtering, washing and drying the solution to obtain the phosphorylated serine-polyvinyl alcohol grafted graphene, namely the functionalized graphene.
(4) Adding a distilled water solvent and functionalized graphene into a reaction bottle, adding epoxy resin after uniform ultrasonic dispersion, performing a high-speed emulsification process, adding an anhydride curing agent, an amine curing accelerator and a defoaming agent in a mass ratio of 5:100:40:0.15:2, uniformly stirring, pouring the emulsion into a mold, and performing thermosetting crosslinking to prepare the functionalized graphene-waterborne epoxy resin comparative anticorrosive material 1.
The water contact angles of the functionalized graphene-water-based epoxy resin anticorrosive materials in the examples and the comparative examples are measured by using a MODEL590 contact angle determinator, and the test standard is GB/T30693-2014.
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Water contact angle | 41.6 | 38.4 | 36.2 | 45.6 | 69.2 |
The functionalized graphene-waterborne epoxy resin anticorrosive materials in the examples and the comparative examples are placed in a CY-90D composite salt spray corrosion test box to be subjected to salt spray resistance and corrosion resistance tests, wherein the test standard is GB/T31588.1-2015.
| Item | 240h | 720h |
| Example 1 | No cracking and no foaming | No cracking and obvious foaming |
| Example 2 | No cracking and no foaming | No cracking and no foaming |
| Example 3 | No cracking and no foaming | No cracking and no foaming |
| Example 4 | No cracking and no foaming | Cracking and foaming are obvious |
| Comparative example 1 | No cracking and obvious foaming | Cracking and foaming are obvious |
Claims (7)
1. A functionalized graphene-waterborne epoxy resin anticorrosive material is characterized in that: the graphene-epoxy resin curing agent comprises the following raw materials and components, namely functionalized graphene, epoxy resin, a curing agent, a curing accelerator and a defoaming agent, wherein the mass ratio of the functionalized graphene to the epoxy resin is 10-30:100:45-55:0.2-1: 0.5-1.
2. The functionalized graphene-aqueous epoxy resin anticorrosive material according to claim 1, characterized in that: the curing agent is an anhydride curing agent, and the curing accelerator is an amine curing accelerator.
3. The functionalized graphene-aqueous epoxy resin anticorrosive material according to claim 1, characterized in that: the preparation method of the functionalized graphene-waterborne epoxy resin anticorrosive material comprises the following steps:
(1) adding graphene oxide into a distilled water solvent, placing the mixture into a constant-temperature ultrasonic dispersion instrument for ultrasonic dispersion treatment, adding polyvinyl alcohol, heating to 90-100 ℃, performing ultrasonic reflux reaction for 5-10 hours, cooling, removing the solvent, washing and drying to prepare polyvinyl alcohol grafted graphene;
(2) adding polyvinyl alcohol grafted graphene into a dimethyl sulfoxide solvent, after uniform ultrasonic dispersion, adding a sulfuric acid solution to adjust the pH of the solution to 2-4, then adding DL-serine, heating to 100-130 ℃, reacting for 12-24h, cooling, filtering, washing and drying to prepare amphiphilic serine-polyvinyl alcohol grafted graphene;
(3) adding serine-polyvinyl alcohol grafted graphene into a dimethyl sulfoxide solvent, adding phosphoric acid and a catalyst urea after ultrasonic dispersion is uniform, heating to the temperature of 120 ℃ and 140 ℃, reacting for 5-10h, cooling, filtering, washing and drying to prepare phosphorylated serine-polyvinyl alcohol grafted graphene, namely functionalized graphene;
(4) adding functionalized graphene into a distilled aqueous solvent, adding epoxy resin after uniform ultrasonic dispersion, performing a high-speed emulsification process, adding an anhydride curing agent, an amine curing accelerator and a defoaming agent, stirring uniformly, pouring the emulsion into a mold, and performing thermosetting crosslinking to prepare the functionalized graphene-waterborne epoxy resin anticorrosive material.
4. The functionalized graphene-aqueous epoxy resin anticorrosive material according to claim 3, characterized in that: the constant-temperature ultrasonic dispersion instrument in the step (1) comprises a heat insulation layer and an ultrasonic device fixed on the inner wall of the heat insulation layer, a fixture block fixedly connected to the inner wall of the heat insulation layer, a spring rod fixedly connected to the fixture block, a clamping plate movably connected to the spring rod, a base fixedly connected to the lower portion inside the heat insulation layer, and a reaction bottle arranged above the base.
5. The functionalized graphene-aqueous epoxy resin anticorrosive material according to claim 3, characterized in that: the mass ratio of the graphene oxide to the polyvinyl alcohol in the step (1) is 1: 5-20.
6. The functionalized graphene-aqueous epoxy resin anticorrosive material according to claim 3, characterized in that: the mass ratio of the polyvinyl alcohol grafted graphene to the DL-serine in the step (2) is 100: 15-35.
7. The functionalized graphene-aqueous epoxy resin anticorrosive material according to claim 3, characterized in that: the mass ratio of the serine-polyvinyl alcohol grafted graphene, the phosphoric acid and the urea in the step (3) is 100:80-200: 3-15.
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| CN114958143A (en) * | 2022-06-11 | 2022-08-30 | 浙江桥母电气有限公司 | Energy-saving mould-pressing corrosion-resistant high-strength cable bridge |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107638805A (en) * | 2017-11-03 | 2018-01-30 | 宁波日新恒力科技有限公司 | A kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol |
| AU2018307573A1 (en) * | 2017-07-26 | 2020-03-05 | Talga Technologies Limited | Functionalised graphene composition |
| KR20200033650A (en) * | 2018-09-20 | 2020-03-30 | 광주과학기술원 | graphene oxide membrane film and method for fabricating the same |
| CN111363312A (en) * | 2020-04-26 | 2020-07-03 | 张杨全 | Phytic acid ammonium salt-graphene modified epoxy resin flame-retardant material and preparation method thereof |
| CN111363311A (en) * | 2020-04-26 | 2020-07-03 | 林科 | Graphene-anhydride curing agent modified waterborne epoxy resin material and preparation method thereof |
-
2020
- 2020-07-16 CN CN202010686528.4A patent/CN111718638A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2018307573A1 (en) * | 2017-07-26 | 2020-03-05 | Talga Technologies Limited | Functionalised graphene composition |
| CN107638805A (en) * | 2017-11-03 | 2018-01-30 | 宁波日新恒力科技有限公司 | A kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol |
| KR20200033650A (en) * | 2018-09-20 | 2020-03-30 | 광주과학기술원 | graphene oxide membrane film and method for fabricating the same |
| CN111363312A (en) * | 2020-04-26 | 2020-07-03 | 张杨全 | Phytic acid ammonium salt-graphene modified epoxy resin flame-retardant material and preparation method thereof |
| CN111363311A (en) * | 2020-04-26 | 2020-07-03 | 林科 | Graphene-anhydride curing agent modified waterborne epoxy resin material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958143A (en) * | 2022-06-11 | 2022-08-30 | 浙江桥母电气有限公司 | Energy-saving mould-pressing corrosion-resistant high-strength cable bridge |
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Application publication date: 20200929 |