CN111675901A - Silicon dioxide-graphene oxide modified polyaniline anticorrosive material and preparation method thereof - Google Patents
Silicon dioxide-graphene oxide modified polyaniline anticorrosive material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polyaniline and discloses a silicon dioxide-graphene oxide modified polyaniline anticorrosive material, wherein cyano-modified graphene oxide is hydrolyzed under alkaline conditions to obtain carboxylated graphene with rich carboxyl content, carboxyl on the graphene oxide is subjected to acyl chlorination reaction, then the carboxyl is reacted with 4- (BOC-amino) phenol, and finally a BOC protective group is removed to obtain aminated graphene, chitosan has strong chemical stability and high biocompatibility, free amino contained in a molecular structure can be grafted with polyaniline, so that the processability of polyaniline can be improved, the three-dimensional structure of nano-silicon dioxide is favorable for hindering the transmission of corrosive media, the anticorrosive performance of the material is improved, and the surface tension of the material can be increased by the graphene, so that the surface hydrophobicity of the material is enhanced, and the migration of corrosive substances to a metal substrate is hindered, further improving the corrosion resistance of the material.
Description
Technical Field
The invention relates to the technical field of polyaniline, in particular to a silicon dioxide-graphene oxide modified polyaniline anticorrosive material and a preparation method thereof.
Background
The chitosan is a natural high molecular polymer with rich content, is a main component of shells of crustaceans, belongs to one of natural functional oligosaccharide preservatives, is insoluble in water, soluble in weak acidic organic solvents, and has excellent biological properties such as antimicrobial property and anti-tumor property.
The graphene is a two-dimensional honeycomb network structure consisting of carbon atoms, and due to the special structure of the graphene, the graphene is added into the coating as a reinforcing material, so that the surface tension of the coating can be increased, the surface hydrophobicity of the coating is enhanced, meanwhile, the nano-sheet structure hinders the migration of corrosive substances to a metal substrate, and the corrosion resistance of the material is improved.
Polyaniline is a conductive polymer with high stability and high conductivity, and is widely concerned due to simple synthesis steps, but polyaniline is difficult to dissolve and process in common solvents like other conductive polymers, and the use of polyaniline materials in some aspects is greatly influenced due to limited corrosion resistance of polyaniline, so that the polyaniline materials are necessarily modified by one or more substances.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a silicon dioxide-graphene oxide modified polyaniline anticorrosive material and a preparation method thereof, and solves the problem of low polyaniline anticorrosive performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a silicon dioxide-graphene oxide modified polyaniline anticorrosive material comprises the following steps:
(1) adding graphene oxide into a toluene solvent in a nitrogen atmosphere, performing ultrasonic dispersion and dispersion for 0.5-1.5h by using an ultrasonic device, taking azobisisobutyronitrile as an initiator, wherein the mass ratio of the azobisisobutyronitrile to the graphene oxide is 1:20-40, reacting for 6-9h at 60-80 ℃, filtering and washing a product, drying to obtain cyano-modified graphene oxide, adding sodium hydroxide and the cyano-modified graphene oxide at the mass ratio of 10:10-30 into an ethanol solvent, stirring and reacting for 30-40h at 70-100 ℃, adjusting the pH of the solution to 2-4, filtering, washing with distilled water, and drying to obtain carboxylated graphene with high carboxyl content;
(2) adding thionyl chloride and carboxylated graphene into a flask, performing ultrasonic dispersion for 0.5-2h, performing reflux reaction for 20-30h in a nitrogen atmosphere at the temperature of 80-100 ℃, adding toluene, performing reduced pressure distillation, and removing redundant thionyl chloride to prepare the acyl chlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion for 0.5-1h, adding 4- (BOC-amino) phenol, performing reflux reaction for 10-15h at the temperature of 60-80 ℃ in a nitrogen atmosphere, adding excessive trifluoroacetic acid and dichloromethane, stirring for 0.5-2h, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene;
(4) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethanol solvent, adding glacial acetic acid until the chitosan is dissolved, stirring and reacting for 20-30h at 50-80 ℃, condensing and refluxing, washing and drying to prepare silicon dioxide-chitosan;
(5) adding perfluoroheptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into a 2% acetic acid solution, stirring for reaction for 0.5-2h, filtering, washing and drying a product by using an acetone solution, and preparing the polyaniline modified by the silica-graphene oxide.
Preferably, the ultrasonic dispersion device in the step (1) comprises an ultrasonic groove, the lower surface of the ultrasonic groove is fixedly connected with a base, the right side of the base is fixedly connected with a refrigerating device, the right side of the refrigerating device is fixedly connected with a magnetic device, the right side of the magnetic device is fixedly connected with a damping device, the bottom of the inner wall of the ultrasonic groove is movably connected with a container, the bottom of the inner wall of the container is movably connected with a rotor, the right side of the inner wall of the ultrasonic groove is fixedly connected with an ultrasonic device, the right side of the outer wall of the ultrasonic groove is fixedly connected with a water outlet, the inside of the water outlet is movably connected with a first water stop valve, a water level sensor is fixedly connected above the water outlet, a temperature sensor is fixedly connected on the left side of the outer wall of the ultrasonic groove, and a water inlet is fixedly connected above the temperature sensor, and a water stop valve II is movably connected inside the water inlet.
Preferably, the mass ratio of the thionyl chloride to the carboxylated graphene in the step (2) is 120-200: 1.
Preferably, the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol in the step (3) is 15-30: 100.
Preferably, the mass ratio of the nano silicon dioxide, the isocyanatopropyl triethoxysilane and the chitosan in the step (4) is 15-20:100: 300-.
Preferably, the mass ratio of the perfluoroheptanoic acid, the ammonium persulfate, the aniline, the silica-chitosan and the aminated graphene in the step (5) is 3.5-4.5:210-230:100:8-12: 0.5-2.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the silicon dioxide-graphene oxide modified polyaniline anticorrosive material, cyano-modified graphene oxide is hydrolyzed under an alkaline condition to obtain carboxylated graphene with rich carboxyl content, carboxyl on the graphene oxide is subjected to acyl chlorination reaction, then reacts with 4- (BOC-amino) phenol, and finally BOC protective groups are removed to obtain the aminated graphene.
The silicon dioxide-graphene oxide modified polyaniline anticorrosive material takes isocyanate triethoxy silane as a coupling agent, the obtained silicon dioxide and chitosan are organically combined, amino groups of aniline, aminated graphene and chitosan are polymerized in situ under the initiation action of ammonium persulfate to obtain the silicon dioxide-graphene oxide modified polyaniline anticorrosive material, due to the fact that the chitosan is strong in chemical stability and high in biocompatibility, free amino groups contained in a molecular structure can be grafted with polyaniline, the processability of polyaniline can be improved, meanwhile, under the cross-linking action of the chitosan, the interface compatibility of nano silicon dioxide and polyaniline is improved, the three-dimensional structure of the nano silicon dioxide is beneficial to hindering the transmission of corrosive media, the anticorrosive performance of the material is improved, and due to the fact that the graphene can increase the surface tension of the material, the hydrophobicity of the surface of the material is enhanced, the migration of corrosive substances to a metal substrate is hindered, and the corrosion resistance of the material is further improved.
Drawings
FIG. 1 is a front sectional view of an ultrasonic dispersion apparatus;
FIG. 2 is a schematic front view of an ultrasonic dispersion apparatus.
1-ultrasonic wave groove; 2-a base; 3-a refrigeration device; 4-a magnetic device; 5-a damping device; 6-container; 7-a rotor; 8-ultrasonic device; 9-water outlet; 10-a first water stop valve; 11-a water level sensor; 12-a temperature sensor; 13-a water inlet; and 14-a second water stop valve.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a silicon dioxide-graphene oxide modified polyaniline anticorrosive material comprises the following steps:
(1) in the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic dispersing device comprises an ultrasonic groove, the lower surface of the ultrasonic groove is fixedly connected with a base, the right side of the base is fixedly connected with a refrigerating device, the right side of the refrigerating device is fixedly connected with a magnetic device, the right side of the magnetic device is fixedly connected with a damping device, the bottom of the inner wall of the ultrasonic groove is movably connected with a container, the bottom of the inner wall of the container is movably linked with a rotor, the right side of the inner wall of the ultrasonic groove is fixedly connected with an ultrasonic device, the right side of the outer wall of the ultrasonic groove is fixedly connected with a water outlet, the inside of the water outlet is movably linked with a first water stop valve, a water level sensor is fixedly connected above the water outlet, the left side of the outer wall of the ultrasonic groove is fixedly, performing ultrasonic dispersion and dispersion for 0.5-1.5h, using azobisisobutyronitrile as an initiator, wherein the mass ratio of the azobisisobutyronitrile to the graphene oxide is 1:20-40, reacting at 60-80 ℃ for 6-9h, filtering and washing the product, drying to obtain cyano-modified graphene oxide, adding sodium hydroxide and the cyano-modified graphene oxide into an ethanol solvent at the mass ratio of 10:10-30, stirring and reacting at 70-100 ℃ for 30-40h, adjusting the pH of the solution to 2-4, filtering, washing with distilled water, and drying to obtain carboxylated graphene with high carboxyl content;
(2) adding thionyl chloride and carboxylated graphene into a flask, wherein the mass ratio of the thionyl chloride to the carboxylated graphene is 120-1, performing ultrasonic dispersion for 0.5-2h, performing reflux reaction for 20-30h in a nitrogen atmosphere at 80-100 ℃, adding toluene, performing reduced pressure distillation, removing redundant thionyl chloride, and preparing the acyl chlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion for 0.5-1h, adding 4- (BOC-amino) phenol, performing reflux reaction for 10-15h in a nitrogen atmosphere at the temperature of 60-80 ℃, adding excessive trifluoroacetic acid and dichloromethane, stirring for 0.5-2h, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol is 15-30: 100;
(4) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethanol solvent, wherein the mass ratio of the nano silicon dioxide to the isocyanatopropyl triethoxysilane to the chitosan is 15-20:100:300-600, adding glacial acetic acid until the chitosan is dissolved, stirring and reacting for 20-30h at 50-80 ℃, condensing and refluxing, washing and drying to prepare the silicon dioxide-chitosan;
(5) adding perfluoro-heptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into 2% acetic acid solution, wherein the mass ratio of the perfluoro-heptanoic acid to the ammonium persulfate to the aniline to the silica-chitosan to the aminated graphene is 3.5-4.5: 210: 230:100:8-12:0.5-2, stirring for reaction for 0.5-2h, filtering, washing and drying a product by using acetone solution, and preparing the polyaniline modified by the silica-graphene oxide.
Example 1
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic dispersing device comprises an ultrasonic groove, the lower surface of the ultrasonic groove is fixedly connected with a base, the right side of the base is fixedly connected with a refrigerating device, the right side of the refrigerating device is fixedly connected with a magnetic device, the right side of the magnetic device is fixedly connected with a damping device, the bottom of the inner wall of the ultrasonic groove is movably connected with a container, the bottom of the inner wall of the container is movably linked with a rotor, the right side of the inner wall of the ultrasonic groove is fixedly connected with an ultrasonic device, the right side of the outer wall of the ultrasonic groove is fixedly connected with a water outlet, the inside of the water outlet is movably linked with a first water stop valve, a water level sensor is fixedly connected above the water outlet, the left side of the outer wall of the ultrasonic groove is fixedly, performing ultrasonic dispersion and dispersion for 0.5-h, taking azobisisobutyronitrile as an initiator, wherein the mass ratio of the azobisisobutyronitrile to the graphene oxide is 1:20, reacting for 6h at 60 ℃, filtering and washing a product, drying to obtain cyano-modified graphene oxide, adding sodium hydroxide and the cyano-modified graphene oxide with the mass ratio of 10:10 into an ethanol solvent, stirring and reacting for 30h at 70 ℃, adjusting the pH of the solution to 2, filtering, washing with distilled water, and drying to obtain carboxylated graphene with high carboxyl content;
(2) adding thionyl chloride and carboxylated graphene into a flask, wherein the mass ratio of the thionyl chloride to the carboxylated graphene is 120:1, ultrasonically dispersing for 0.5h, carrying out reflux reaction for 20h in a nitrogen atmosphere at the temperature of 80 ℃, adding toluene, carrying out reduced pressure distillation, removing redundant thionyl chloride, and preparing the acyl chlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion for 0.5h, adding 4- (BOC-amino) phenol, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol is 15:100, performing reflux reaction for 10h in a nitrogen atmosphere at 60 ℃, adding excessive trifluoroacetic acid and dichloromethane, stirring for 0.5h, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene;
(4) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethanol solvent, wherein the mass ratio of the nano silicon dioxide to the isocyanatopropyl triethoxysilane to the chitosan is 15:100:300, adding glacial acetic acid until the chitosan is dissolved, stirring and reacting for 20 hours at 50 ℃, condensing and refluxing, washing and drying to prepare silicon dioxide-chitosan;
(5) adding perfluoro-heptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into a 2% acetic acid solution, wherein the mass ratio of the perfluoro-heptanoic acid to the ammonium persulfate to the aniline to the silica-chitosan to the aminated graphene is 3.5:210:100:8:0.5, stirring for reaction for 0.5h, filtering, washing and drying a product by using an acetone solution, and preparing the silica-graphene oxide modified polyaniline.
Example 2
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic dispersing device comprises an ultrasonic groove, the lower surface of the ultrasonic groove is fixedly connected with a base, the right side of the base is fixedly connected with a refrigerating device, the right side of the refrigerating device is fixedly connected with a magnetic device, the right side of the magnetic device is fixedly connected with a damping device, the bottom of the inner wall of the ultrasonic groove is movably connected with a container, the bottom of the inner wall of the container is movably linked with a rotor, the right side of the inner wall of the ultrasonic groove is fixedly connected with an ultrasonic device, the right side of the outer wall of the ultrasonic groove is fixedly connected with a water outlet, the inside of the water outlet is movably linked with a first water stop valve, a water level sensor is fixedly connected above the water outlet, the left side of the outer wall of the ultrasonic groove is fixedly, performing ultrasonic dispersion and dispersion for 1.5h, taking azobisisobutyronitrile as an initiator, wherein the mass ratio of the azobisisobutyronitrile to the graphene oxide is 1:40, reacting at 80 ℃ for 9h, filtering and washing the product, drying to obtain cyano-modified graphene oxide, adding sodium hydroxide and the cyano-modified graphene oxide into an ethanol solvent at the mass ratio of 10:30, stirring and reacting at 100 ℃ for 40h, adjusting the pH of the solution to 4, filtering, washing with distilled water, and drying to obtain carboxylated graphene with high carboxyl content;
(2) adding thionyl chloride and carboxylated graphene into a flask, wherein the mass ratio of the thionyl chloride to the carboxylated graphene is 200:1, ultrasonically dispersing for 2h, carrying out reflux reaction for 30h in a nitrogen atmosphere at 100 ℃, adding toluene, carrying out reduced pressure distillation, removing redundant thionyl chloride, and preparing acyl chlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion for 1h, adding 4- (BOC-amino) phenol, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol is 30:100, performing reflux reaction for 15h in a nitrogen atmosphere at 80 ℃, adding excessive trifluoroacetic acid and dichloromethane, stirring for 2h, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene;
(4) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethanol solvent, wherein the mass ratio of the nano silicon dioxide to the isocyanatopropyl triethoxysilane to the chitosan is 20:100:600, adding glacial acetic acid until the chitosan is dissolved, stirring and reacting for 30h at 80 ℃, condensing and refluxing, washing and drying to prepare silicon dioxide-chitosan;
(5) adding perfluoroheptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into a 2% acetic acid solution, wherein the mass ratio of the perfluoroheptanoic acid to the ammonium persulfate to the aniline to the silica-chitosan to the aminated graphene is 4.5:230:100:12:2, stirring for reaction for 2 hours, filtering, washing and drying a product by using an acetone solution, and preparing the silica-graphene oxide modified polyaniline.
Example 3
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic dispersing device comprises an ultrasonic groove, the lower surface of the ultrasonic groove is fixedly connected with a base, the right side of the base is fixedly connected with a refrigerating device, the right side of the refrigerating device is fixedly connected with a magnetic device, the right side of the magnetic device is fixedly connected with a damping device, the bottom of the inner wall of the ultrasonic groove is movably connected with a container, the bottom of the inner wall of the container is movably linked with a rotor, the right side of the inner wall of the ultrasonic groove is fixedly connected with an ultrasonic device, the right side of the outer wall of the ultrasonic groove is fixedly connected with a water outlet, the inside of the water outlet is movably linked with a first water stop valve, a water level sensor is fixedly connected above the water outlet, the left side of the outer wall of the ultrasonic groove is fixedly, performing ultrasonic dispersion and dispersion for 1h, taking azobisisobutyronitrile as an initiator, wherein the mass ratio of the azobisisobutyronitrile to the graphene oxide is 1:30, reacting for 8h at 70 ℃, filtering and washing the product, drying to obtain cyano-modified graphene oxide, adding sodium hydroxide and the cyano-modified graphene oxide into an ethanol solvent at the mass ratio of 10:20, stirring and reacting for 35h at 90 ℃, adjusting the pH of the solution to 3, filtering, washing with distilled water, and drying to obtain carboxylated graphene with high carboxyl content;
(2) adding thionyl chloride and carboxylated graphene into a flask, wherein the mass ratio of the thionyl chloride to the carboxylated graphene is 180:1, ultrasonically dispersing for 1.5h, carrying out reflux reaction for 25h in a nitrogen atmosphere at 90 ℃, adding toluene, carrying out reduced pressure distillation, removing redundant thionyl chloride, and preparing and obtaining acyl chlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion for 0.5h, adding 4- (BOC-amino) phenol, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol is 20:100, performing reflux reaction for 12h in a nitrogen atmosphere at 70 ℃, adding excessive trifluoroacetic acid and dichloromethane, stirring for 1.5h, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene;
(4) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethanol solvent, wherein the mass ratio of the nano silicon dioxide to the isocyanatopropyl triethoxysilane to the chitosan is 17:100:400, adding glacial acetic acid until the chitosan is dissolved, stirring and reacting for 25h at 60 ℃, condensing and refluxing, washing and drying to prepare silicon dioxide-chitosan;
(5) adding perfluoroheptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into a 2% acetic acid solution, wherein the mass ratio of the perfluoroheptanoic acid to the ammonium persulfate to the aniline to the silica-chitosan to the aminated graphene is 4:220:100:10:1.5, stirring for reaction for 1.5h, filtering and washing a product with an acetone solution, and drying to prepare the silica-graphene oxide modified polyaniline.
Example 4
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic dispersing device comprises an ultrasonic groove, the lower surface of the ultrasonic groove is fixedly connected with a base, the right side of the base is fixedly connected with a refrigerating device, the right side of the refrigerating device is fixedly connected with a magnetic device, the right side of the magnetic device is fixedly connected with a damping device, the bottom of the inner wall of the ultrasonic groove is movably connected with a container, the bottom of the inner wall of the container is movably linked with a rotor, the right side of the inner wall of the ultrasonic groove is fixedly connected with an ultrasonic device, the right side of the outer wall of the ultrasonic groove is fixedly connected with a water outlet, the inside of the water outlet is movably linked with a first water stop valve, a water level sensor is fixedly connected above the water outlet, the left side of the outer wall of the ultrasonic groove is fixedly, performing ultrasonic dispersion and dispersion for 0.5h, taking azobisisobutyronitrile as an initiator, wherein the mass ratio of the azobisisobutyronitrile to the graphene oxide is 1:20, reacting at 70 ℃ for 6h, filtering and washing the product, drying to obtain cyano-modified graphene oxide, adding sodium hydroxide and the cyano-modified graphene oxide into an ethanol solvent at the mass ratio of 10:20, stirring and reacting at 70 ℃ for 40h, adjusting the pH of the solution to 2, filtering, washing with distilled water, and drying to obtain carboxylated graphene with high carboxyl content;
(2) adding thionyl chloride and carboxylated graphene into a flask, wherein the mass ratio of the thionyl chloride to the carboxylated graphene is 200:1, ultrasonically dispersing for 1.5h, carrying out reflux reaction for 20h in a nitrogen atmosphere at the temperature of 80 ℃, adding toluene, carrying out reduced pressure distillation, removing redundant thionyl chloride, and preparing the acyl chlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion for 1h, adding 4- (BOC-amino) phenol, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol is 30:100, performing reflux reaction for 12h in a nitrogen atmosphere at 60 ℃, adding excessive trifluoroacetic acid and dichloromethane, stirring for 2h, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene;
(4) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethyl alcohol solvent, wherein the mass ratio of the nano silicon dioxide to the isocyanatopropyl triethoxysilane to the chitosan is 15:100:300, adding glacial acetic acid until the chitosan is dissolved, stirring and reacting for 20h at 60 ℃, condensing and refluxing, washing and drying to obtain the silicon dioxide-chitosan.
(5) Adding perfluoro-heptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into a 2% acetic acid solution, wherein the mass ratio of the perfluoro-heptanoic acid to the ammonium persulfate to the aniline to the silica-chitosan to the aminated graphene is 4:250:100:8:1, stirring for reaction for 2 hours, filtering, washing and drying a product by using an acetone solution, and thus obtaining the silica-graphene oxide modified polyaniline.
Comparative example 1
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic dispersing device comprises an ultrasonic groove, the lower surface of the ultrasonic groove is fixedly connected with a base, the right side of the base is fixedly connected with a refrigerating device, the right side of the refrigerating device is fixedly connected with a magnetic device, the right side of the magnetic device is fixedly connected with a damping device, the bottom of the inner wall of the ultrasonic groove is movably connected with a container, the bottom of the inner wall of the container is movably linked with a rotor, the right side of the inner wall of the ultrasonic groove is fixedly connected with an ultrasonic device, the right side of the outer wall of the ultrasonic groove is fixedly connected with a water outlet, the inside of the water outlet is movably linked with a first water stop valve, a water level sensor is fixedly connected above the water outlet, the left side of the outer wall of the ultrasonic groove is fixedly, performing ultrasonic dispersion and dispersion for 3 hours, taking azobisisobutyronitrile as an initiator, wherein the mass ratio of the azobisisobutyronitrile to the graphene oxide is 1:10, reacting at 50 ℃ for 5 hours, filtering and washing the product, drying to obtain cyano-modified graphene oxide, adding sodium hydroxide and the cyano-modified graphene oxide into an ethanol solvent at the mass ratio of 10:50, stirring and reacting at 50 ℃ for 20 hours, adjusting the pH of the solution to 1, filtering, washing with distilled water, and drying to obtain carboxylated graphene with high carboxyl content;
(2) adding thionyl chloride and carboxylated graphene into a flask, wherein the mass ratio of the thionyl chloride to the carboxylated graphene is 90:1, ultrasonically dispersing for 4 hours, carrying out reflux reaction for 10 hours in a nitrogen atmosphere at the temperature of 60 ℃, adding toluene, carrying out reduced pressure distillation, removing redundant thionyl chloride, and preparing acyl chlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion for 2 hours, adding 4- (BOC-amino) phenol, wherein the mass ratio of the acylchlorinated graphene to the 4- (BOC-amino) phenol is 10:100, performing reflux reaction for 8 hours in a nitrogen atmosphere at 50 ℃, adding excessive trifluoroacetic acid and dichloromethane, stirring for 2.5 hours, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene;
(4) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethanol solvent, wherein the mass ratio of the nano silicon dioxide to the isocyanatopropyl triethoxysilane to the chitosan is 10:100:200, adding glacial acetic acid until the chitosan is dissolved, stirring and reacting for 50h at 100 ℃, condensing and refluxing, washing and drying to prepare silicon dioxide-chitosan;
(5) adding perfluoro-heptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into a 2% acetic acid solution, wherein the mass ratio of the perfluoro-heptanoic acid to the ammonium persulfate to the aniline to the silica-chitosan to the aminated graphene is 2:150:100:5:3, stirring for reaction for 4 hours, filtering, washing and drying a product by using an acetone solution, and preparing the silica-graphene oxide modified polyaniline.
The corrosion resistance of the silica-graphene oxide modified polyaniline in the examples and the comparative examples was tested using a HT-YW-60 salt spray test chamber, and tested in GB/T37595-2019.
Claims (6)
1. A silicon dioxide-graphene oxide modified polyaniline anticorrosive material is characterized in that: the preparation method of the silicon dioxide-graphene oxide modified polyaniline anticorrosive material comprises the following steps:
(1) adding graphene oxide into a toluene solvent in a nitrogen atmosphere, performing ultrasonic dispersion and dispersion for 0.5-1.5h by using an ultrasonic device, taking azobisisobutyronitrile as an initiator, wherein the mass ratio of the azobisisobutyronitrile to the graphene oxide is 1:20-40, reacting for 6-9h at 60-80 ℃, filtering and washing a product, drying to obtain cyano-modified graphene oxide, adding sodium hydroxide and the cyano-modified graphene oxide at the mass ratio of 10:10-30 into an ethanol solvent, stirring and reacting for 30-40h at 70-100 ℃, adjusting the pH of the solution to 2-4, filtering, washing with distilled water, and drying to obtain carboxylated graphene with high carboxyl content;
(2) adding thionyl chloride and carboxylated graphene into a flask, performing ultrasonic dispersion for 0.5-2h, performing reflux reaction for 20-30h in a nitrogen atmosphere at the temperature of 80-100 ℃, adding toluene, performing reduced pressure distillation, and removing redundant thionyl chloride to prepare the acyl chlorinated graphene;
(3) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, performing ultrasonic dispersion for 0.5-1h, adding 4- (BOC-amino) phenol, performing reflux reaction for 10-15h at the temperature of 60-80 ℃ in a nitrogen atmosphere, adding excessive trifluoroacetic acid and dichloromethane, stirring for 0.5-2h, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene;
(4) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethanol solvent, adding glacial acetic acid until the chitosan is dissolved, stirring and reacting for 20-30h at 50-80 ℃, condensing and refluxing, washing and drying to prepare silicon dioxide-chitosan;
(5) adding perfluoroheptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into a 2% acetic acid solution, stirring for reaction for 0.5-2h, filtering, washing and drying a product by using an acetone solution, and preparing the polyaniline modified by the silica-graphene oxide.
2. The silica-graphene oxide modified polyaniline corrosion-resistant material according to claim 1, which is characterized in that: the ultrasonic dispersion device in the step (1) comprises an ultrasonic groove, the lower surface of the ultrasonic groove is fixedly connected with a base, the right side of the base is fixedly connected with a refrigerating device, the right side of the refrigerating device is fixedly connected with a magnetic device, the right side of the magnetic device is fixedly connected with a damping device, the bottom of the inner wall of the ultrasonic groove is movably connected with a container, the bottom of the inner wall of the container is movably connected with a rotor, the right side of the inner wall of the ultrasonic groove is fixedly connected with an ultrasonic device, the right side of the outer wall of the ultrasonic groove is fixedly connected with a water outlet, the inside of the water outlet is movably connected with a first water stop valve, a water level sensor is fixedly connected above the water outlet, a temperature sensor is fixedly connected on the left side of the outer wall of the ultrasonic groove, and a water inlet is fixedly connected above the temperature sensor, and a water stop valve II is movably connected inside the water inlet.
3. The silica-graphene oxide modified polyaniline corrosion-resistant material according to claim 1, which is characterized in that: the mass ratio of the thionyl chloride to the carboxylated graphene in the step (2) is 120-200: 1.
4. The silica-graphene oxide modified polyaniline corrosion-resistant material according to claim 1, which is characterized in that: the mass ratio of the acyl chloride graphene to the 4- (BOC-amino) phenol in the step (3) is 15-30: 100.
5. The silica-graphene oxide modified polyaniline corrosion-resistant material according to claim 1, which is characterized in that: the mass ratio of the nano silicon dioxide, the isocyanatopropyl triethoxysilane and the chitosan in the step (4) is 15-20:100: 300-600.
6. The silica-graphene oxide modified polyaniline corrosion-resistant material according to claim 1, which is characterized in that: the mass ratio of the perfluoroheptanoic acid, the ammonium persulfate, the aniline, the silica-chitosan and the aminated graphene in the step (5) is 3.5-4.5:210-230:100:8-12: 0.5-2.
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| CN115821420A (en) * | 2022-11-24 | 2023-03-21 | 江苏江山红化纤有限责任公司 | Graphene modified polyamide 6 composite fiber and preparation method thereof |
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| CN114409950A (en) * | 2021-12-14 | 2022-04-29 | 徐州飞云泡沫制品有限责任公司 | High-conductivity graphene modified polystyrene foam board and preparation method thereof |
| CN115821420A (en) * | 2022-11-24 | 2023-03-21 | 江苏江山红化纤有限责任公司 | Graphene modified polyamide 6 composite fiber and preparation method thereof |
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