CN111363290A - Polyaniline-graphene grafted alkyd resin anticorrosive material and preparation method thereof - Google Patents
Polyaniline-graphene grafted alkyd resin anticorrosive material and preparation method thereof Download PDFInfo
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- CN111363290A CN111363290A CN202010394113.XA CN202010394113A CN111363290A CN 111363290 A CN111363290 A CN 111363290A CN 202010394113 A CN202010394113 A CN 202010394113A CN 111363290 A CN111363290 A CN 111363290A
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Abstract
The invention relates to the technical field of anticorrosive materials, and discloses a polyaniline-graphene grafted alkyd resin anticorrosive material which comprises the following formula raw materials and components: polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluoro octyl ethyl methacrylate, methyl methacrylate and azobisisobutyronitrile. According to the anticorrosive material of polyaniline-graphene grafted alkyd resin, aniline and aniline grafted graphene are subjected to polymerization reaction to obtain polyaniline chemically covalent grafted graphene, perfluoro octyl ethyl methacrylate, glycidyl methacrylate and alkyd resin containing unsaturated ethylenic bonds are copolymerized, amino groups of the aniline grafted graphene are subjected to ring-opening reaction with epoxy groups, and the aniline grafted graphene is introduced into a molecular chain of the alkyd resin, so that the compatibility and the dispersibility of the polyaniline and the graphene with the alkyd resin are improved, and the excellent anticorrosive performance of the alkyd resin material is enhanced.
Description
Technical Field
The invention relates to the technical field of anticorrosive materials, in particular to an anticorrosive material of polyaniline-graphene grafted alkyd resin and a preparation method thereof.
Background
The corrosion refers to the process of loss and destruction of metal materials and polymer materials under the action of surrounding media such as water, air and the like, mainly comprises chemical corrosion, electrochemical corrosion and biological corrosion, the material corrosion phenomenon can cause resource waste and huge economic loss, the problems of environmental pollution, social hazard and the like are caused, and the development of the application of a new technology is seriously hindered.
Alkyd resins can be divided into drying alkyd resins, non-drying alkyd resins and long-oil alkyd resins, the alkyd resins have the advantages of easily available raw materials, simple process, good comprehensive performance of paint films and the like, the performances of the alkyd resins can be modified by acrylic resin modification, organic cinnamon modification, styrene modification, graphene nano material modification and other methods, and the alkyd resins are widely applied to the fields of paints, coatings, ships and the like, so that the development of alkyd resin materials with more excellent anticorrosive performance is required.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a polyaniline-graphene grafted alkyd resin anticorrosive material and a preparation method thereof, which solve the problem that a graphene nano material is easy to agglomerate in alkyd resin and solve the problem of insufficient anticorrosive performance of the alkyd resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the polyaniline-graphene grafted alkyd resin anticorrosive material comprises the following raw materials and components, and is characterized in that: the polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and azodiisobutyronitrile in a mass ratio of 0.5-3:100:5-12:3-8:2-5: 0.15-0.3.
Preferably, the preparation method of the polyaniline-graphene grafted alkyd resin anticorrosive material comprises the following steps:
(1) adding a distilled water solvent, graphene oxide and silver acetate into a reaction bottle, placing the reaction bottle in an ultrasonic disperser, uniformly dispersing by ultrasonic, pouring the solution into a high-pressure reaction kettle, heating to 190 ℃ for 170-5 ℃, reacting for 10-20h, drying the solution in vacuum to remove the solvent, placing the solid mixed product in an atmosphere furnace, heating at the rate of 2-5 ℃/min to 320 ℃, carrying out heat preservation and calcination for 2-4h, placing the calcined product in 18-25% nitric acid solution, carrying out uniform stirring reaction for 2-4h at the temperature of 70-90 ℃, filtering to remove the solvent, washing the solid product with distilled water until the solid product is neutral, and preparing the three-dimensional porous graphene oxide.
(2) Introducing nitrogen into a reaction bottle, adding an anhydrous toluene solvent and three-dimensional porous graphene oxide, adding thionyl chloride after ultrasonic dispersion is uniform, heating to 100 ℃ and 120 ℃, stirring at a constant speed for reaction for 25-35h, distilling the solution under reduced pressure to remove the solvent, washing a solid product with anhydrous dichloromethane, and drying to prepare the acylchlorinated graphene.
(3) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent and acylchlorinated graphene, uniformly dispersing by ultrasonic, adding 4- (BOC-amino) phenol, reacting at 60-80 ℃ under uniform stirring for 15-25h, adding a dichloromethane solvent and trifluoroacetic acid, reacting at uniform stirring for 1-3h, filtering, washing and drying the solution to obtain the aniline grafted graphene.
(4) Adding 2.5-4% by mass of hydrochloric acid solution and aniline grafted graphene into a reaction bottle, after uniformly dispersing by ultrasonic, adding aniline at 0-5 ℃, dropwise adding ammonium persulfate solution, stirring at a constant speed for reaction for 5-10h, filtering, washing and drying the solution, and thus obtaining the polyaniline grafted graphene.
(5) Adding an isopropanol solvent and alkyd resin into a reaction bottle, stirring uniformly, then simultaneously dropwise adding glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and an initiator azobisisobutyronitrile, stirring at a constant speed at 70-80 ℃ for reaction for 3-6h, then adding polyaniline grafted graphene, placing in an ultrasonic disperser for ultrasonic dispersion uniformly, heating to 70-90 ℃, reacting for 5-10h, adding triethylamine to adjust the pH of the solution to be neutral, carrying out a high-speed emulsification process, pouring the emulsion into a film-forming mold, drying and curing to form a film, thus preparing the polyaniline-graphene grafted alkyd resin anticorrosive material.
Preferably, the ultrasonic disperser includes ultrasonic instrument, ultrasonic instrument below fixedly connected with ultrasonic probe, the inside below of ultrasonic disperser is provided with the base, base top swing joint has adjusting device, adjusting device fixedly connected with adjusts the pole, adjust pole swing joint and connect the bobble, connect bobble swing joint to rotate the bobble, rotate bobble swing joint and have the draw-in groove, draw-in groove top fixedly connected with backup pad, backup pad top are provided with the reaction bottle.
Preferably, the mass ratio of the graphene oxide to the silver acetate is 6-10: 1.
Preferably, the mass ratio of the three-dimensional porous graphene oxide to the thionyl chloride is 80-100: 1.
Preferably, the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol to the trifluoroacetic acid is 1:5-8: 15-25.
Preferably, the mass ratio of the aniline grafted graphene to the aniline to the ammonium persulfate is 0.5-4:10: 22-26.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the anticorrosive material of polyaniline-graphene grafted alkyd resin is characterized in that silver acetate is used for carrying out high-temperature etching on graphene oxide to prepare three-dimensional porous graphene oxide, the three-dimensional porous graphene oxide has a rich mesoporous structure and a large specific surface area, oxygen-containing groups such as surface carboxyl groups can be improved, the carboxyl groups react with thionyl chloride to obtain acylchlorinated graphene with a high grafting rate, the acyl chloride groups react with phenolic hydroxyl groups of 4- (BOC-amino) phenol to obtain aniline grafted graphene through a BOC deprotection process, aniline and aniline grafted graphene are subjected to polymerization reaction through an in-situ polymerization method to obtain polyaniline chemically covalent grafted graphene, under the action of an initiator azodiisobutyronitrile, perfluoro octyl ethyl methacrylate with strong hydrophobicity, glycidyl methacrylate containing an epoxy group and alkyd resin containing unsaturated olefinic bonds are copolymerized, and the amino group of the aniline grafted graphene and the epoxy group in the alkyd resin are subjected to ring-opening reaction, so that the aniline grafted graphene is introduced into a molecular chain of the alkyd resin in a chemical bond combination mode, the compatibility and the dispersibility of the polyaniline and the graphene with the alkyd resin are greatly improved, and the problem that the mechanical property of the material is influenced due to the agglomeration of the dispersed graphene in the alkyd resin material is solved.
According to the polyaniline-graphene grafted alkyd resin anticorrosive material, perfluoro octyl ethyl methacrylate in a molecular chain of the alkyd resin has strong hydrophobicity, the permeation of water molecules can be reduced through the hydrophobic property of the material, polyaniline in the molecular chain can react with oxygen, the permeation of the oxygen is favorably hindered, the polyaniline-graphene grafted alkyd resin anticorrosive material has a good oxygen shielding effect, nano-graphene is uniformly dispersed in a matrix and a gap of the alkyd resin to form a continuous protective layer, the entering and permeation of corrosive media are inhibited, the chemical corrosion resistance of the material is improved, meanwhile, the polyaniline and the graphene have excellent conductivity, the charge conduction effect is strong, a cathode reaction can be transferred to the surface of the alkyd resin, the metal anode corrosion reaction of a metal material is inhibited, the electrochemical corrosion rate is reduced, and the electrochemical corrosion resistance of the material is improved, endows the alkyd resin material with excellent anticorrosion performance under the synergistic action.
Drawings
FIG. 1 is a schematic front view of an ultrasonic disperser;
FIG. 2 is an enlarged schematic view of the adjustment device;
fig. 3 is a schematic view of adjustment lever adjustment.
1. An ultrasonic disperser; 2. an ultrasonic instrument; 3. an ultrasonic probe; 4. a base; 5. an adjustment device; 6. adjusting a rod; 7. connecting the small balls; 8. rotating the big ball; 9. a card slot; 10. a support plate; 11 reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the polyaniline-graphene grafted alkyd resin anticorrosive material comprises the following raw materials and components: the polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and azodiisobutyronitrile in a mass ratio of 0.5-3:100:5-12:3-8:2-5: 0.15-0.3.
The preparation method of the polyaniline-graphene grafted alkyd resin anticorrosive material comprises the following steps:
(1) adding distilled water solvent, graphene oxide and silver acetate with the mass ratio of 6-10:1 into a reaction bottle, placing the reaction bottle into an ultrasonic disperser, wherein the ultrasonic disperser comprises an ultrasonic instrument, an ultrasonic probe is fixedly connected below the ultrasonic instrument, a base is arranged below the inner part of the ultrasonic disperser, an adjusting device is movably connected above the base, an adjusting rod is fixedly connected with the adjusting device, a connecting small ball is movably connected with the adjusting rod, a rotating large ball is movably connected with the connecting small ball, a clamping groove is movably connected with the rotating large ball, a supporting plate is fixedly connected above the clamping groove, a reaction bottle is arranged above the supporting plate, pouring the solution into a high-pressure reaction kettle after the ultrasonic dispersion is uniform, heating the solution to 190 ℃, reacting for 10-20h, drying the solution in vacuum to remove the solvent, placing the solid mixed product into an atmosphere furnace, and raising the temperature, heating to the temperature of 280 ℃ and 320 ℃, keeping the temperature and calcining for 2-4h, placing the calcined product into 18-25% nitric acid solution, stirring at a constant speed at the temperature of 70-90 ℃ for reacting for 2-4h, filtering to remove the solvent, and washing the solid product with distilled water until the solid product is neutral to prepare the three-dimensional porous graphene oxide.
(2) Introducing nitrogen into a reaction bottle, adding an anhydrous toluene solvent and three-dimensional porous graphene oxide, adding thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the anhydrous toluene solvent to the three-dimensional porous graphene oxide is 80-100:1, heating to 100-fold, stirring at a constant speed, reacting for 25-35h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with anhydrous dichloromethane, and drying to prepare the acylchlorinated graphene.
(3) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent and acylchlorinated graphene, performing ultrasonic dispersion uniformly, adding 4- (BOC-amino) phenol, performing uniform stirring reaction at 60-80 ℃ for 15-25h, adding a dichloromethane solvent and trifluoroacetic acid, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol to the trifluoroacetic acid is 1:5-8:15-25, performing uniform stirring reaction for 1-3h, filtering, washing and drying the solution, and thus obtaining the aniline grafted graphene.
(4) Adding 2.5-4% by mass of hydrochloric acid solution and aniline grafted graphene into a reaction bottle, after uniformly dispersing by ultrasonic waves, adding aniline at 0-5 ℃, and dropwise adding ammonium persulfate solution, wherein the mass ratio of the aniline grafted graphene to the aniline to the ammonium persulfate is 0.5-4:10:22-26, stirring at a constant speed for reaction for 5-10h, filtering, washing and drying the solution, and thus obtaining the polyaniline grafted graphene.
(5) Adding an isopropanol solvent and alkyd resin into a reaction bottle, stirring uniformly, then simultaneously dropwise adding glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and an initiator azobisisobutyronitrile, stirring at a constant speed at 70-80 ℃ for reaction for 3-6h, then adding polyaniline grafted graphene, placing in an ultrasonic disperser for ultrasonic dispersion uniformly, heating to 70-90 ℃, reacting for 5-10h, adding triethylamine to adjust the pH of the solution to be neutral, carrying out a high-speed emulsification process, pouring the emulsion into a film-forming mold, drying and curing to form a film, thus preparing the polyaniline-graphene grafted alkyd resin anticorrosive material.
Example 1
(1) Adding distilled water solvent, graphene oxide and silver acetate with the mass ratio of 6:1 into a reaction bottle, placing the reaction bottle into an ultrasonic disperser, wherein the ultrasonic disperser comprises an ultrasonic instrument, an ultrasonic probe is fixedly connected below the ultrasonic instrument, a base is arranged below the inner part of the ultrasonic disperser, an adjusting device is movably connected above the base, an adjusting rod is fixedly connected with the adjusting device, a connecting small ball is movably connected with the adjusting rod, a rotating large ball is movably connected with the connecting small ball, a clamping groove is movably connected with the rotating large ball, a supporting plate is fixedly connected above the clamping groove, a reaction bottle is arranged above the supporting plate, after the ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, heating to 170 ℃, reacting for 10h, carrying out vacuum drying on the solution to remove the solvent, placing a solid mixed product into an atmosphere furnace, heating to the temperature of 2 ℃/min, heating to 280 ℃, carrying out heat preservation and, and (3) stirring at a constant speed at 90 ℃ for reaction for 2h, filtering to remove the solvent, and washing the solid product with distilled water until the solid product is neutral to prepare the three-dimensional porous graphene oxide.
(2) Introducing nitrogen into a reaction bottle, adding an anhydrous toluene solvent and three-dimensional porous graphene oxide, adding thionyl chloride after ultrasonic dispersion is uniform, heating to 100 ℃, stirring at a constant speed for reaction for 25 hours, distilling the solution under reduced pressure to remove the solvent, washing a solid product with anhydrous dichloromethane, and drying to prepare the acyl chlorinated graphene.
(3) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent and acylchlorinated graphene, performing ultrasonic dispersion uniformly, adding 4- (BOC-amino) phenol, performing uniform stirring reaction at 80 ℃ for 15 hours, adding a dichloromethane solvent and trifluoroacetic acid, performing uniform stirring reaction for 1 hour, filtering, washing and drying the solution to obtain the aniline grafted graphene, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol to the trifluoroacetic acid is 1:5: 15.
(4) Adding a hydrochloric acid solution with the mass fraction of 2.5% and aniline grafted graphene into a reaction bottle, after uniform ultrasonic dispersion, adding aniline at 5 ℃, and dropwise adding an ammonium persulfate solution, wherein the mass ratio of the aniline grafted graphene to the aniline to the ammonium persulfate is 0.5:10:22, stirring at a constant speed for reaction for 5 hours, filtering, washing and drying the solution, and thus obtaining the polyaniline grafted graphene.
(5) Adding an isopropanol solvent and alkyd resin into a reaction bottle, stirring uniformly, then simultaneously dropwise adding glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and an initiator azobisisobutyronitrile, stirring at a constant speed at 70 ℃ for reaction for 3 hours, then adding polyaniline grafted graphene, wherein the polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and azodiisobutyronitrile are placed in an ultrasonic disperser with the mass ratio of 0.5:100:5:3:2:0.15 for uniform ultrasonic dispersion, heated to 70 ℃, reacted for 5 hours, added with triethylamine to adjust the pH value of the solution to be neutral, subjected to a high-speed emulsification process, poured into a film forming mold, and drying, curing and film-forming to prepare the polyaniline-graphene grafted alkyd resin anticorrosive material.
Example 2
(1) Adding distilled water solvent, graphene oxide and silver acetate with the mass ratio of 7:1 into a reaction bottle, placing the reaction bottle into an ultrasonic disperser, wherein the ultrasonic disperser comprises an ultrasonic instrument, an ultrasonic probe is fixedly connected below the ultrasonic instrument, a base is arranged below the inner part of the ultrasonic disperser, an adjusting device is movably connected above the base, an adjusting rod is fixedly connected with the adjusting device, a connecting small ball is movably connected with the adjusting rod, a rotating large ball is movably connected with the connecting small ball, a clamping groove is movably connected with the rotating large ball, a supporting plate is fixedly connected above the clamping groove, a reaction bottle is arranged above the supporting plate, after the ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, heating to 190 ℃, reacting for 12h, carrying out vacuum drying on the solution to remove the solvent, placing a solid mixed product into an atmosphere furnace, heating to 280 ℃ at the speed of 5 ℃/min, carrying out heat preservation and calcination, and (3) stirring at a constant speed at 90 ℃ for reaction for 2h, filtering to remove the solvent, and washing the solid product with distilled water until the solid product is neutral to prepare the three-dimensional porous graphene oxide.
(2) Introducing nitrogen into a reaction bottle, adding an anhydrous toluene solvent and three-dimensional porous graphene oxide, adding thionyl chloride after ultrasonic dispersion is uniform, heating to 120 ℃, stirring at a constant speed for reaction for 35 hours, distilling the solution under reduced pressure to remove the solvent, washing a solid product with anhydrous dichloromethane, and drying to prepare the acyl chlorinated graphene.
(3) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent and acylchlorinated graphene, performing ultrasonic dispersion uniformly, adding 4- (BOC-amino) phenol, performing uniform stirring reaction at 70 ℃ for 20 hours, adding a dichloromethane solvent and trifluoroacetic acid, performing uniform stirring reaction for 3 hours, filtering, washing and drying the solution, and thus obtaining the aniline grafted graphene.
(4) Adding a hydrochloric acid solution with the mass fraction of 3% and aniline grafted graphene into a reaction bottle, after uniformly dispersing by ultrasonic, adding aniline at 5 ℃, dropwise adding an ammonium persulfate solution, wherein the mass ratio of the aniline grafted graphene to the aniline to the ammonium persulfate is 1:10:23, stirring at a constant speed for reaction for 8 hours, filtering, washing and drying the solution, and thus obtaining the polyaniline grafted graphene.
(5) Adding an isopropanol solvent and alkyd resin into a reaction bottle, stirring uniformly, then simultaneously dropwise adding glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and an initiator azobisisobutyronitrile, stirring at a constant speed at 70 ℃ for reacting for 6 hours, then adding polyaniline grafted graphene, wherein the polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and azodiisobutyronitrile are placed in an ultrasonic disperser with the mass ratio of 1:100:6:4:2.5:0.2 for uniform ultrasonic dispersion, heated to 90 ℃, reacted for 10 hours, added with triethylamine to adjust the pH value of the solution to be neutral, subjected to a high-speed emulsification process, poured into a film forming mold, and drying, curing and film-forming to prepare the polyaniline-graphene grafted alkyd resin anticorrosive material.
Example 3
(1) Adding distilled water solvent, graphene oxide and silver acetate with the mass ratio of 8:1 into a reaction bottle, placing the reaction bottle into an ultrasonic disperser, wherein the ultrasonic disperser comprises an ultrasonic instrument, an ultrasonic probe is fixedly connected below the ultrasonic instrument, a base is arranged below the inner part of the ultrasonic disperser, an adjusting device is movably connected above the base, an adjusting rod is fixedly connected with the adjusting device, a connecting small ball is movably connected with the adjusting rod, a rotating large ball is movably connected with the connecting small ball, a clamping groove is movably connected with the rotating large ball, a supporting plate is fixedly connected above the clamping groove, a reaction bottle is arranged above the supporting plate, after the ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, heating to 180 ℃, reacting for 150h, vacuum drying the solution to remove the solvent, placing a solid mixed product into an atmosphere furnace, heating to 300 ℃ at the heating rate of 3 ℃/min, keeping the temperature and calcining for 3h, and (3) uniformly stirring and reacting for 3h at 80 ℃, filtering to remove the solvent, and washing the solid product with distilled water until the solid product is neutral to prepare the three-dimensional porous graphene oxide.
(2) Introducing nitrogen into a reaction bottle, adding an anhydrous toluene solvent and three-dimensional porous graphene oxide, adding thionyl chloride after ultrasonic dispersion is uniform, heating to 110 ℃, stirring at a constant speed for reaction for 30 hours, distilling the solution under reduced pressure to remove the solvent, washing a solid product with anhydrous dichloromethane, and drying to prepare the acyl chlorinated graphene.
(3) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent and acylchlorinated graphene, performing ultrasonic dispersion uniformly, adding 4- (BOC-amino) phenol, performing uniform stirring reaction at 70 ℃ for 20 hours, adding a dichloromethane solvent and trifluoroacetic acid, performing uniform stirring reaction for 2 hours, filtering, washing and drying the solution to obtain the aniline grafted graphene, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol to the trifluoroacetic acid is 1:6.5: 20.
(4) Adding a hydrochloric acid solution with the mass fraction of 3.5% and aniline grafted graphene into a reaction bottle, after uniformly dispersing by ultrasonic, adding aniline at 2 ℃, and dropwise adding an ammonium persulfate solution, wherein the mass ratio of the aniline grafted graphene to the aniline to the ammonium persulfate is 3:10:24, stirring at a constant speed for reaction for 10 hours, filtering, washing and drying the solution, and thus obtaining the polyaniline grafted graphene.
(5) Adding an isopropanol solvent and alkyd resin into a reaction bottle, stirring uniformly, then simultaneously dropwise adding glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and an initiator azobisisobutyronitrile, stirring at a constant speed at 80 ℃ for reaction for 3 hours, then adding polyaniline grafted graphene, wherein the polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and azodiisobutyronitrile are placed in an ultrasonic disperser with the mass ratio of 2.5:100:10:7:4:0.25 for uniform ultrasonic dispersion, heated to 90 ℃, reacted for 10 hours, added with triethylamine to adjust the pH value of the solution to be neutral, subjected to a high-speed emulsification process, poured into a film forming mold, and drying, curing and film-forming to prepare the polyaniline-graphene grafted alkyd resin anticorrosive material.
Example 4
(1) Adding distilled water solvent, graphene oxide and silver acetate with the mass ratio of 10:1 into a reaction bottle, placing the reaction bottle into an ultrasonic disperser, wherein the ultrasonic disperser comprises an ultrasonic instrument, an ultrasonic probe is fixedly connected below the ultrasonic instrument, a base is arranged below the inner part of the ultrasonic disperser, an adjusting device is movably connected above the base, an adjusting rod is fixedly connected with the adjusting device, a connecting small ball is movably connected with the adjusting rod, a rotating large ball is movably connected with the connecting small ball, a clamping groove is movably connected with the rotating large ball, a supporting plate is fixedly connected above the clamping groove, a reaction bottle is arranged above the supporting plate, after the ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, heating to 170 ℃, reacting for 20h, carrying out vacuum drying on the solution to remove the solvent, placing a solid mixed product into an atmosphere furnace, heating to 320 ℃ at the rate of 5 ℃/min, carrying out heat preservation and calcination, and (3) uniformly stirring and reacting for 4h at 90 ℃, filtering to remove the solvent, and washing the solid product with distilled water until the solid product is neutral to prepare the three-dimensional porous graphene oxide.
(2) Introducing nitrogen into a reaction bottle, adding an anhydrous toluene solvent and three-dimensional porous graphene oxide, adding thionyl chloride after ultrasonic dispersion is uniform, heating to 120 ℃, stirring at a constant speed for reaction for 25 hours, distilling the solution under reduced pressure to remove the solvent, washing a solid product with anhydrous dichloromethane, and drying to prepare the acyl chlorinated graphene.
(3) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent and acylchlorinated graphene, performing ultrasonic dispersion uniformly, adding 4- (BOC-amino) phenol, performing uniform stirring reaction at 80 ℃ for 25 hours, adding a dichloromethane solvent and trifluoroacetic acid, performing uniform stirring reaction for 2 hours, filtering, washing and drying the solution to obtain the aniline grafted graphene, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol to the trifluoroacetic acid is 1:7.5: 23.
(4) Adding a hydrochloric acid solution with the mass fraction of 4% and aniline grafted graphene into a reaction bottle, after uniformly dispersing by ultrasonic, adding aniline at 0 ℃, and dropwise adding an ammonium persulfate solution, wherein the mass ratio of the aniline grafted graphene to the aniline to the ammonium persulfate is 3.5:10:25, stirring at a constant speed for reaction for 8 hours, filtering, washing and drying the solution, and thus obtaining the polyaniline grafted graphene.
(5) Adding an isopropanol solvent and alkyd resin into a reaction bottle, stirring uniformly, then simultaneously dropwise adding glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and an initiator azobisisobutyronitrile, stirring at a constant speed at 80 ℃ for reacting for 6 hours, then adding polyaniline grafted graphene, wherein the polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and azodiisobutyronitrile are placed in an ultrasonic disperser with the mass ratio of 2.5:100:11:7:3.5:0.25 for uniform ultrasonic dispersion, heated to 90 ℃, reacted for 5 hours, added with triethylamine to adjust the pH value of the solution to be neutral, subjected to a high-speed emulsification process, poured into a film forming mold, and drying, curing and film-forming to prepare the polyaniline-graphene grafted alkyd resin anticorrosive material.
Example 5
(1) Adding distilled water solvent, graphene oxide and silver acetate with the mass ratio of 10:1 into a reaction bottle, placing the reaction bottle into an ultrasonic disperser, wherein the ultrasonic disperser comprises an ultrasonic instrument, an ultrasonic probe is fixedly connected below the ultrasonic instrument, a base is arranged below the inner part of the ultrasonic disperser, an adjusting device is movably connected above the base, an adjusting rod is fixedly connected with the adjusting device, a connecting small ball is movably connected with the adjusting rod, a rotating large ball is movably connected with the connecting small ball, a clamping groove is movably connected with the rotating large ball, a supporting plate is fixedly connected above the clamping groove, a reaction bottle is arranged above the supporting plate, after the ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, heating to 190 ℃, reacting for 20h, vacuum drying the solution to remove the solvent, placing a solid mixed product into an atmosphere furnace, heating to 320 ℃ at the rate of 5 ℃/min, keeping the temperature and calcining for 4h, and (3) uniformly stirring and reacting for 4h at 90 ℃, filtering to remove the solvent, and washing the solid product with distilled water until the solid product is neutral to prepare the three-dimensional porous graphene oxide.
(2) Introducing nitrogen into a reaction bottle, adding an anhydrous toluene solvent and three-dimensional porous graphene oxide, adding thionyl chloride after ultrasonic dispersion is uniform, heating to 120 ℃, stirring at a constant speed for reaction for 35 hours, distilling the solution under reduced pressure to remove the solvent, washing a solid product with anhydrous dichloromethane, and drying to prepare the acyl chlorinated graphene.
(3) Introducing nitrogen into a reaction bottle, adding an anhydrous tetrahydrofuran solvent and acylchlorinated graphene, performing ultrasonic dispersion uniformly, adding 4- (BOC-amino) phenol, performing uniform stirring reaction at 80 ℃ for 25 hours, adding a dichloromethane solvent and trifluoroacetic acid, performing uniform stirring reaction for 3 hours, filtering, washing and drying the solution to obtain the aniline grafted graphene, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol to the trifluoroacetic acid is 1:8: 25.
(4) Adding a hydrochloric acid solution with the mass fraction of 4% and aniline grafted graphene into a reaction bottle, after uniformly dispersing by ultrasonic, adding aniline at 5 ℃, and dropwise adding an ammonium persulfate solution, wherein the mass ratio of the aniline grafted graphene to the aniline to the ammonium persulfate is 4:10:26, stirring at a constant speed for reaction for 10 hours, filtering, washing and drying the solution, and thus obtaining the polyaniline grafted graphene.
(5) Adding an isopropanol solvent and alkyd resin into a reaction bottle, stirring uniformly, then simultaneously dropwise adding glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and an initiator azobisisobutyronitrile, stirring at a constant speed at 80 ℃ for reacting for 6 hours, then adding polyaniline grafted graphene, wherein the polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and azodiisobutyronitrile are placed in an ultrasonic disperser with the mass ratio of 3:100:12:8:5:0.3 for uniform ultrasonic dispersion, heated to 90 ℃, reacted for 10 hours, added with triethylamine to adjust the pH value of the solution to be neutral, subjected to a high-speed emulsification process, poured into a film forming mold, and drying, curing and film-forming to prepare the polyaniline-graphene grafted alkyd resin anticorrosive material.
The alkyd resin anticorrosive materials of examples 1 to 5 were placed in a JYWX-250 alternating composite salt spray test chamber for salt spray resistance test and anticorrosive property test.
| Examples | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Resistance to salt fog | 114 | 139 | 96 | 102 | 87 |
In summary, the anticorrosive material of polyaniline-graphene grafted alkyd resin is prepared by etching graphene oxide at high temperature by using silver acetate, so as to obtain three-dimensional porous graphene oxide, has rich mesoporous structure and huge specific surface area, can improve oxygen-containing groups such as surface carboxyl, the carboxyl reacts with thionyl chloride to obtain acylchlorinated graphene with high grafting rate, the acyl chloride group reacts with phenolic hydroxyl of 4- (BOC-amino) phenol, aniline grafted graphene is obtained by BOC deprotection process, aniline and aniline grafted graphene undergo polymerization reaction by in-situ polymerization to obtain polyaniline chemically covalent grafted graphene, perfluorooctyl ethyl methacrylate with strong hydrophobicity under the action of azodiisobutyronitrile as an initiator, glycidyl methacrylate containing epoxy groups and alkyd resin containing unsaturated ethylenic bonds are copolymerized, and the amino group of the aniline grafted graphene and the epoxy group in the alkyd resin are subjected to ring-opening reaction, so that the aniline grafted graphene is introduced into a molecular chain of the alkyd resin in a chemical bond combination mode, the compatibility and the dispersibility of the polyaniline and the graphene with the alkyd resin are greatly improved, and the problem that the mechanical property of the material is influenced due to the agglomeration of the dispersed graphene in the alkyd resin material is solved.
The perfluorooctyl ethyl methacrylate in the molecular chain of the alkyd resin has strong hydrophobicity, can reduce the penetration of water molecules through the hydrophobic property of the material, and polyaniline in molecular chains can react with oxygen, thus being beneficial to blocking the permeation of oxygen and having good oxygen shielding effect, the nano-graphene is uniformly dispersed in the matrix and gaps of the alkyd resin, form a continuous protective layer to inhibit the entry and penetration of corrosive media, improve the chemical corrosion resistance of the material, meanwhile, the polyaniline and the graphene have excellent conductivity and strong charge conduction effect, can transfer cathode reaction to the surface of alkyd resin for reaction, thereby inhibiting the metal anode corrosion reaction of the metal material, reducing the electrochemical corrosion rate, improving the electrochemical corrosion resistance of the material, and endowing the alkyd resin material with excellent corrosion resistance under the synergistic action.
Claims (7)
1. The polyaniline-graphene grafted alkyd resin anticorrosive material comprises the following raw materials and components, and is characterized in that: the polyaniline grafted graphene, alkyd resin, glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and azodiisobutyronitrile in a mass ratio of 0.5-3:100:5-12:3-8:2-5: 0.15-0.3.
2. The anticorrosive material of polyaniline-graphene grafted alkyd resin according to claim 1, characterized in that: the preparation method of the polyaniline-graphene grafted alkyd resin anticorrosive material comprises the following steps:
(1) adding graphene oxide and silver acetate into a distilled water solvent, placing the mixture into an ultrasonic disperser, uniformly dispersing the mixture by ultrasonic, pouring the solution into a high-pressure reaction kettle, heating the mixture to 190 ℃ for reaction at the temperature of 170 ℃ to 20 hours, placing the solid mixed product into an atmosphere furnace, heating the mixture to 320 ℃ at the temperature of 280 ℃ at the temperature of 2-5 ℃/min, carrying out heat preservation and calcination for 2-4 hours, placing the calcined product into 18-25% nitric acid solution, carrying out uniform stirring reaction for 2-4 hours at the temperature of 70-90 ℃, filtering and washing to prepare the three-dimensional porous graphene oxide;
(2) adding three-dimensional porous graphene oxide into an anhydrous toluene solvent, uniformly dispersing by ultrasonic, adding thionyl chloride in a nitrogen atmosphere, heating to 100-120 ℃, reacting for 25-35h, removing the solvent, and washing to prepare the acylchlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion uniformly, adding 4- (BOC-amino) phenol in a nitrogen atmosphere, reacting at 60-80 ℃ for 15-25h, adding a dichloromethane solvent and trifluoroacetic acid, stirring for reacting for 1-3h, filtering, washing and drying to prepare aniline grafted graphene;
(4) adding aniline grafted graphene into a hydrochloric acid solution with the mass fraction of 2.5-4%, after uniform ultrasonic dispersion, adding aniline at 0-5 ℃, dropwise adding an ammonium persulfate solution, reacting for 5-10h, filtering and washing to prepare polyaniline grafted graphene;
(5) adding alkyd resin into an isopropanol solvent, simultaneously dropwise adding glycidyl methacrylate, perfluorooctyl ethyl methacrylate, methyl methacrylate and an initiator azobisisobutyronitrile, reacting at 70-80 ℃ for 3-6h, adding polyaniline grafted graphene, performing ultrasonic dispersion uniformly, heating to 70-90 ℃, reacting for 5-10h, adding triethylamine to adjust the pH value of the solution to be neutral, performing a high-speed emulsification process, pouring the emulsion into a film-forming mold, drying and curing to form a film, and preparing the polyaniline-graphene grafted alkyd resin anticorrosive material.
3. The anticorrosive material of polyaniline-graphene grafted alkyd resin according to claim 2, characterized in that: the ultrasonic disperser comprises an ultrasonic instrument, an ultrasonic probe fixedly connected below the ultrasonic instrument, a base arranged below the inner part of the ultrasonic disperser, an adjusting device movably connected above the base, an adjusting rod fixedly connected with the adjusting device, a small connecting ball movably connected with the adjusting rod, a large rotating ball movably connected with the small connecting ball, a clamping groove movably connected with the large rotating ball, a supporting plate fixedly connected above the clamping groove, and a reaction bottle arranged above the supporting plate.
4. The anticorrosive material of polyaniline-graphene grafted alkyd resin according to claim 2, characterized in that: the mass ratio of the graphene oxide to the silver acetate is 6-10: 1.
5. The anticorrosive material of polyaniline-graphene grafted alkyd resin according to claim 2, characterized in that: the mass ratio of the three-dimensional porous graphene oxide to the thionyl chloride is 80-100: 1.
6. The anticorrosive material of polyaniline-graphene grafted alkyd resin according to claim 2, characterized in that: the mass ratio of the acyl chlorinated graphene to the 4- (BOC-amino) phenol to the trifluoroacetic acid is 1:5-8: 15-25.
7. The anticorrosive material of polyaniline-graphene grafted alkyd resin according to claim 1, characterized in that: the mass ratio of the aniline grafted graphene to the aniline to the ammonium persulfate is 0.5-4:10: 22-26.
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