CN111534052A - Polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin and preparation method thereof - Google Patents
Polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin and preparation method thereof Download PDFInfo
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- CN111534052A CN111534052A CN202010496472.6A CN202010496472A CN111534052A CN 111534052 A CN111534052 A CN 111534052A CN 202010496472 A CN202010496472 A CN 202010496472A CN 111534052 A CN111534052 A CN 111534052A
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Abstract
The invention relates to the technical field of epoxy resin, and discloses polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin which comprises the following formula raw materials and components: polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol, epoxy resin, curing agent and accelerator. According to the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin, aniline is subjected to in-situ polymerization in epoxidized polyvinyl alcohol, the phenylenediamine functionalized carbon nanotube further participates in polymerization reaction, and an anhydride curing agent reacts with an epoxy group of the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol in the ring-opening cross-linking curing process of epoxy resin, so that the carbon nanotube enhances the barrier property of the epoxy resin to corrosive media such as oxygen, water and the like, improves the chemical corrosion resistance of the epoxy resin, has excellent conductivity with polyaniline, and enhances the electrochemical corrosion resistance of the epoxy resin to iron-based metal materials.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin and a preparation method thereof.
Background
The corrosion widely exists in daily life of people, the damage to metal materials is large, and the corrosion can be divided into chemical corrosion and electrochemical corrosion, the corrosion caused by chemical action of the metal materials in dry gas and non-electrolyte solution is called as chemical corrosion, the product of the chemical corrosion exists on the surface of the material, no current is generated in the corrosion process, the electrochemical corrosion refers to corrosion damage caused by electrochemical action generated between the metal and the electrolyte solution, and the current is generated in the corrosion process.
The epoxy resin is a thermosetting resin, contains two or more than two epoxy groups, can be subjected to ring-opening crosslinking curing with active hydrogen-containing compounds such as acid anhydride, amines and the like, has excellent mechanical properties, school, insulation, mold resistance and anticorrosion functions, mainly comprises structural adhesive, high-temperature-resistant adhesive, special adhesive, latent curing adhesive and the like, is widely applied to the fields of civil construction, electronic appliances, sports goods and the like, but the traditional epoxy resin does not have the effect of preventing electrochemical corrosion, the anticorrosion performance cannot meet the requirements of people for production and life, and in order to further improve the comprehensive performances of anticorrosion and the like of the epoxy resin material, methods such as curing agent modification, reaction diluent modification, filler modification and the like can be adopted.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin and a preparation method thereof, and solves the problems that the traditional epoxy resin does not have the effect of preventing electrochemical corrosion and has limited anti-corrosion performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin comprises the following raw materials and components: the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol, the epoxy resin, the curing agent and the accelerator are mixed according to the mass ratio of 2-10:100:40-60: 2-6.
Preferably, the curing agent is an acid anhydride curing agent, and the accelerator is any one of 2,4, 6-tris (dimethylaminomethyl) phenol or N-methyldiethanolamine.
Preferably, the preparation method of the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin comprises the following steps:
(1) adding anhydrous N, N-dimethylformamide and a carboxylated carbon nanotube into a reaction bottle, adding thionyl chloride after uniform ultrasonic dispersion, placing the mixture into an atmosphere reaction device, heating the mixture to 70-90 ℃ under the nitrogen atmosphere, stirring at a constant speed for reflux reaction for 18-36h, distilling the solution under reduced pressure to remove unreacted thionyl chloride, adding p-phenylenediamine, heating the mixture to 120-150 ℃ under the nitrogen atmosphere, stirring at a constant speed for reaction for 48-96h, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the p-phenylenediamine functionalized carbon nanotube.
(2) Adding a distilled water solvent and polyvinyl alcohol into a reaction bottle, heating to 75-95 ℃, stirring for dissolving, adding sodium hydroxide for adjusting the pH of the solution to 10-11, slowly dropwise adding epoxy chloropropane, stirring at a constant speed for reacting for 3-6h, drying the solution in vacuum for removing the solvent, washing the solid product with ethanol and distilled water until the solid product is neutral, and drying to prepare the epoxidized polyvinyl alcohol.
(3) Adding a distilled water solvent and epoxidized polyvinyl alcohol into a reaction bottle, heating to 75-95 ℃ to dissolve, adding aniline, stirring at a constant speed to react for 2-4h, cooling in an ice water bath, adding hydrochloric acid to adjust the pH value of the solution to 1-2, adding an initiator ammonium persulfate, stirring at a constant speed to react for 5-10h, adding a p-phenylenediamine functionalized carbon nanotube, stirring at a constant speed to react for 15-25h, carrying out centrifugal separation on the solution, dialyzing to remove impurities and drying to obtain the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol.
(4) Adding an acetone solvent, epoxy resin and polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol into a reaction bottle, performing a high-speed emulsification process, adding an epoxy resin curing agent and an accelerator, uniformly stirring, pouring the emulsion into a film forming mold, drying, curing and forming a film, and preparing the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin anticorrosive material.
Preferably, the carboxyl content of the carboxylated carbon nanotubes in the step (1) is 2.58-3.86%, and the mass ratio of the carboxylated carbon nanotubes, the thionyl chloride and the p-phenylenediamine is 1:100-160: 30-60.
Preferably, the atmosphere reaction device in the step (1) comprises an air pump, an air pump movably connected with an air inlet pipe, an air inlet pipe surface is provided with air holes, an air inlet pipe fixedly connected with atmosphere reaction chamber is provided with an oil bath pot inside, a base is arranged below an oil bath groove, a reaction bottle is arranged above the base, an adjusting valve is movably connected with the upper surface of the base, an adjusting rod is fixedly connected with the adjusting valve, a rotating ball is movably connected with the adjusting rod, and a supporting rod is movably connected with the rotating ball.
Preferably, the mass ratio of the polyvinyl alcohol to the epichlorohydrin in the step (2) is 10: 15-25.
Preferably, the mass ratio of the epoxidized polyvinyl alcohol, the aniline, the ammonium persulfate and the p-phenylenediamine functionalized carbon nanotube in the step (3) is 100:40-80:100-200: 0.5-3.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin is prepared by acylating chlorination of a carboxyl carbon nanotube by thionyl chloride, further reacting with p-phenylenediamine to obtain a p-phenylenediamine functionalized carbon nanotube, reacting chlorine atoms of epichlorohydrin with hydroxyl groups of polyvinyl alcohol under the action of strong alkali, performing ring-opening reaction on partial epoxy groups of epoxidized polyvinyl alcohol with aniline, initiating in-situ polymerization of aniline in epoxidized polyvinyl alcohol under the action of ammonium persulfate, adding the p-phenylenediamine functionalized carbon nanotube during polymerization, further participating in polymerization reaction of the p-phenylenediamine, grafting and bridging the epoxidized polyvinyl alcohol and the carbon nanotube through polyaniline molecules, taking polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol as a filler, and simultaneously reacting an anhydride curing agent with unreacted epoxy groups in the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol during ring-opening cross-linking curing process, the epoxy polyvinyl alcohol is used as a coupling agent, and the polyaniline and the carbon nano tubes are chemically and covalently grafted into a matrix of the epoxy resin, so that the dispersibility and compatibility of the polyaniline and the carbon nano tubes with the epoxy resin are improved, and the phenomena of agglomeration and sedimentation caused by strong van der Waals force among particles of the carbon nano tubes with huge specific surface area are avoided.
The polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin has the advantages that the blocking performance of the epoxy resin to corrosive media such as oxygen, water and the like is enhanced in gaps of the epoxy resin material filled with the carbon nanotubes which are uniformly dispersed, so that the chemical corrosion resistance of the epoxy resin is improved, the carbon nanotubes and the polyaniline have excellent conductivity, and the electrochemical corrosion resistance of the epoxy resin to iron-based metal materials can be enhanced.
Drawings
FIG. 1 is a schematic front view of an atmospheric reaction chamber;
FIG. 2 is a schematic view of an adjustment lever;
fig. 3 is a schematic view of adjustment lever adjustment.
1-an air pump; 2, an air inlet pipe; 3-air holes; 4-atmosphere reaction chamber; 5-oil bath pan; 6-a base; 7-reaction flask; 8-adjusting valve; 9-adjusting the rod; 10-a rolling ball; 11-support bar.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin comprises the following raw materials and components: the polyaniline-carbon nano tube grafted epoxidized polyvinyl alcohol, the epoxy resin, the curing agent and the accelerator are in a mass ratio of 2-10:100:40-60:2-6, wherein the curing agent is an anhydride curing agent, and the accelerator is any one of 2,4, 6-tris (dimethylaminomethyl) phenol or N-methyldiethanolamine.
The preparation method of the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin comprises the following steps:
(1) adding anhydrous N, N-dimethylformamide and carboxylated carbon nanotubes into a reaction bottle, adding thionyl chloride after ultrasonic dispersion is uniform, placing the mixture into an atmosphere reaction device, wherein the atmosphere reaction device comprises an air pump, the air pump is movably connected with an air inlet pipe, the surface of the air inlet pipe is provided with air holes, the air inlet pipe is fixedly connected with an atmosphere reaction chamber, an oil bath pot is arranged inside the atmosphere reaction chamber, a base is arranged below an oil bath groove, the reaction bottle is arranged above the base, the upper surface of the base is movably connected with an adjusting valve, the adjusting valve is fixedly connected with an adjusting rod, the adjusting rod is movably connected with a rotating ball, the rotating ball is movably connected with a supporting rod, heating is carried out to 70-90 ℃ under the nitrogen atmosphere, stirring at constant speed and refluxing for 18-36 hours, carrying out reduced pressure distillation on the solution to remove unreacted thionyl chloride, and then adding, the mass ratio of the carboxylated carbon nano tube to the thionyl chloride to the p-phenylenediamine is 1:100-160:30-60, the mixture is heated to 120-150 ℃ in the nitrogen atmosphere, the mixture is stirred at a constant speed for reaction for 48-96h, the solution is centrifugally separated to remove the solvent, and the solid product is washed by distilled water and ethanol and dried to prepare the p-phenylenediamine functionalized carbon nano tube.
(2) Adding a distilled water solvent and polyvinyl alcohol into a reaction bottle, heating to 75-95 ℃, stirring for dissolving, adding sodium hydroxide for adjusting the pH of the solution to 10-11, slowly dropwise adding epoxy chloropropane, wherein the mass ratio of epoxy chloropropane to polyvinyl alcohol is 15-25:10, stirring at a constant speed for reacting for 3-6h, carrying out vacuum drying on the solution for removing the solvent, washing a solid product with ethanol and distilled water until the solid product is neutral, and drying to prepare the epoxidized polyvinyl alcohol.
(3) Adding a distilled water solvent and epoxidized polyvinyl alcohol into a reaction bottle, heating to 75-95 ℃ for dissolution, adding aniline, uniformly stirring for reaction for 2-4h, placing the reaction bottle in an ice-water bath for cooling, adding hydrochloric acid for regulating the pH value of the solution to 1-2, adding an initiator ammonium persulfate, uniformly stirring for reaction for 5-10h, adding a p-phenylenediamine functionalized carbon nanotube, wherein the mass ratio of the epoxidized polyvinyl alcohol to the aniline to the ammonium persulfate to the p-phenylenediamine functionalized carbon nanotube is 100:40-80:100 and 200:0.5-3, uniformly stirring for reaction for 15-25h, carrying out centrifugal separation on the solution, dialyzing for impurity removal and drying to prepare the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol.
(4) Adding an acetone solvent, epoxy resin and polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol into a reaction bottle, performing a high-speed emulsification process, adding an epoxy resin curing agent and an accelerator, uniformly stirring, pouring the emulsion into a film forming mold, drying, curing and forming a film, and preparing the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin anticorrosive material.
Example 1
(1) Adding anhydrous N, N-dimethylformamide and carboxylated carbon nanotubes into a reaction bottle, adding thionyl chloride after ultrasonic dispersion is uniform, placing the mixture into an atmosphere reaction device, wherein the atmosphere reaction device comprises an air pump, the air pump is movably connected with an air inlet pipe, the surface of the air inlet pipe is provided with air holes, the air inlet pipe is fixedly connected with an atmosphere reaction chamber, an oil bath pot is arranged inside the atmosphere reaction chamber, a base is arranged below an oil bath groove, the reaction bottle is arranged above the base, the upper surface of the base is movably connected with an adjusting valve, the adjusting valve is fixedly connected with an adjusting rod, the adjusting rod is movably connected with a rotating ball, the rotating ball is movably connected with a supporting rod, heating is carried out under the nitrogen atmosphere, stirring at a constant speed and refluxing for 18 hours, carrying out reduced pressure distillation on the solution to remove unreacted thionyl chloride, and then adding p-phenylenediamine, Heating thionyl chloride and p-phenylenediamine to 120 ℃ in a mass ratio of 1:100:30 in a nitrogen atmosphere, stirring at a constant speed for reaction for 48 hours, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the p-phenylenediamine functionalized carbon nanotube.
(2) Adding a distilled water solvent and polyvinyl alcohol into a reaction bottle, heating to 75 ℃, stirring for dissolving, adding sodium hydroxide for adjusting the pH value of the solution to 10, slowly dropwise adding epoxy chloropropane, wherein the mass ratio of epoxy chloropropane to polyvinyl alcohol is 15:10, stirring at a constant speed for reaction for 3 hours, carrying out vacuum drying on the solution for removing the solvent, washing a solid product with ethanol and distilled water until the solid product is neutral, and drying to prepare the epoxidized polyvinyl alcohol.
(3) Adding a distilled water solvent and epoxidized polyvinyl alcohol into a reaction bottle, heating to 75 ℃ to dissolve, adding aniline, stirring at a constant speed to react for 2 hours, cooling in an ice water bath, adding hydrochloric acid to adjust the pH value of the solution to 1, adding an initiator ammonium persulfate, stirring at a constant speed to react for 50 hours, adding a p-phenylenediamine functionalized carbon nanotube, wherein the mass ratio of the epoxidized polyvinyl alcohol to the aniline to the ammonium persulfate to the p-phenylenediamine functionalized carbon nanotube is 100:40:100:0.5, stirring at a constant speed to react for 15 hours, carrying out centrifugal separation on the solution, dialyzing to remove impurities, and drying to prepare the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol.
(4) Adding an acetone solvent, epoxy resin and polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol into a reaction bottle, performing a high-speed emulsification process, adding an anhydride curing agent and an accelerator 2,4, 6-tris (dimethylaminomethyl) phenol in a mass ratio of 100:2:40:2, uniformly stirring, pouring the emulsion into a film forming mold, drying, curing and forming a film, and preparing the anticorrosive material 1 of the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin.
Example 2
(1) Adding anhydrous N, N-dimethylformamide and carboxylated carbon nanotubes into a reaction bottle, adding thionyl chloride after ultrasonic dispersion is uniform, placing the mixture into an atmosphere reaction device, wherein the atmosphere reaction device comprises an air pump, the air pump is movably connected with an air inlet pipe, the surface of the air inlet pipe is provided with air holes, the air inlet pipe is fixedly connected with an atmosphere reaction chamber, an oil bath pot is arranged inside the atmosphere reaction chamber, a base is arranged below an oil bath groove, the reaction bottle is arranged above the base, the upper surface of the base is movably connected with an adjusting valve, the adjusting valve is fixedly connected with an adjusting rod, the adjusting rod is movably connected with a rotating ball, the rotating ball is movably connected with a supporting rod, heating is carried out under the nitrogen atmosphere to 90 ℃, stirring at a constant speed and refluxing for 18 hours, carrying out reduced pressure distillation on the solution to remove unreacted thionyl chloride, and then adding p, Heating thionyl chloride and p-phenylenediamine to 120 ℃ in a mass ratio of 1:120:40 in a nitrogen atmosphere, uniformly stirring to react for 96 hours, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the p-phenylenediamine functionalized carbon nanotube.
(2) Adding a distilled water solvent and polyvinyl alcohol into a reaction bottle, heating to 85 ℃, stirring for dissolving, adding sodium hydroxide for adjusting the pH value of the solution to 11, slowly dropwise adding epoxy chloropropane, wherein the mass ratio of epoxy chloropropane to polyvinyl alcohol is 18:10, stirring at a constant speed for reaction for 6 hours, carrying out vacuum drying on the solution for removing the solvent, washing a solid product with ethanol and distilled water until the solid product is neutral, and drying to prepare the epoxidized polyvinyl alcohol.
(3) Adding a distilled water solvent and epoxidized polyvinyl alcohol into a reaction bottle, heating to 85 ℃ for dissolution, adding aniline, uniformly stirring for reaction for 3 hours, placing the reaction bottle in an ice water bath for cooling, adding hydrochloric acid for regulating the pH value of the solution to 2, adding an initiator ammonium persulfate, uniformly stirring for reaction for 10 hours, adding a p-phenylenediamine functionalized carbon nanotube, wherein the mass ratio of the epoxidized polyvinyl alcohol to the aniline to the ammonium persulfate to the p-phenylenediamine functionalized carbon nanotube is 100:50:130:1, uniformly stirring for reaction for 25 hours, carrying out centrifugal separation on the solution, dialyzing for removing impurities, and drying to prepare the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol.
(4) Adding an acetone solvent, epoxy resin and polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol into a reaction bottle, performing a high-speed emulsification process, adding an anhydride curing agent and an accelerator N-methyldiethanolamine in a mass ratio of 100:5:46:3, uniformly stirring, pouring the emulsion into a film forming mold, drying, curing and forming a film, and preparing the anticorrosive material 2 of the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin.
Example 3
(1) Adding anhydrous N, N-dimethylformamide and carboxylated carbon nanotubes into a reaction bottle, adding thionyl chloride after ultrasonic dispersion is uniform, placing the mixture into an atmosphere reaction device, wherein the atmosphere reaction device comprises an air pump, the air pump is movably connected with an air inlet pipe, the surface of the air inlet pipe is provided with air holes, the air inlet pipe is fixedly connected with an atmosphere reaction chamber, an oil bath pot is arranged inside the atmosphere reaction chamber, a base is arranged below an oil bath groove, the reaction bottle is arranged above the base, the upper surface of the base is movably connected with an adjusting valve, the adjusting valve is fixedly connected with an adjusting rod, the adjusting rod is movably connected with a rotating ball, the rotating ball is movably connected with a supporting rod, heating is carried out to 80 ℃ under the nitrogen atmosphere, stirring at constant speed and refluxing for 24 hours, carrying out reduced pressure distillation on the solution to remove unreacted thionyl chloride, and then adding p, Heating thionyl chloride and p-phenylenediamine to 130 ℃ in a mass ratio of 1:140:50 in a nitrogen atmosphere, stirring at a constant speed for reaction for 72 hours, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the p-phenylenediamine functionalized carbon nanotube.
(2) Adding a distilled water solvent and polyvinyl alcohol into a reaction bottle, heating to 85 ℃, stirring for dissolving, adding sodium hydroxide for adjusting the pH value of the solution to 11, slowly dropwise adding epoxy chloropropane, wherein the mass ratio of epoxy chloropropane to polyvinyl alcohol is 22:10, stirring at a constant speed for reaction for 4 hours, carrying out vacuum drying on the solution for removing the solvent, washing a solid product with ethanol and distilled water until the solid product is neutral, and drying to prepare the epoxidized polyvinyl alcohol.
(3) Adding a distilled water solvent and epoxidized polyvinyl alcohol into a reaction bottle, heating to 90 ℃ to dissolve, adding aniline, stirring at a constant speed to react for 3 hours, cooling in an ice water bath, adding hydrochloric acid to adjust the pH value of the solution to 2, adding an initiator ammonium persulfate, stirring at a constant speed to react for 6 hours, adding a p-phenylenediamine functionalized carbon nanotube, wherein the mass ratio of the epoxidized polyvinyl alcohol to the aniline to the ammonium persulfate to the p-phenylenediamine functionalized carbon nanotube is 100:65:175:2, stirring at a constant speed to react for 20 hours, carrying out centrifugal separation on the solution, dialyzing to remove impurities, and drying to prepare the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol.
(4) Adding an acetone solvent, epoxy resin and polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol into a reaction bottle, performing a high-speed emulsification process, adding an anhydride curing agent and an accelerator N-methyldiethanolamine at a mass ratio of 100:8:53:5, uniformly stirring, pouring the emulsion into a film forming mold, drying, curing and forming a film, and thus obtaining the anticorrosive material 3 of the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin.
Example 4
(1) Adding anhydrous N, N-dimethylformamide and carboxylated carbon nanotubes into a reaction bottle, adding thionyl chloride after ultrasonic dispersion is uniform, placing the mixture into an atmosphere reaction device, wherein the atmosphere reaction device comprises an air pump, the air pump is movably connected with an air inlet pipe, the surface of the air inlet pipe is provided with air holes, the air inlet pipe is fixedly connected with an atmosphere reaction chamber, an oil bath pot is arranged inside the atmosphere reaction chamber, a base is arranged below an oil bath groove, the reaction bottle is arranged above the base, the upper surface of the base is movably connected with an adjusting valve, the adjusting valve is fixedly connected with an adjusting rod, the adjusting rod is movably connected with a rotating ball, the rotating ball is movably connected with a supporting rod, heating is carried out under the nitrogen atmosphere to 90 ℃, stirring at a constant speed and carrying out reflux reaction for 36 hours, carrying out reduced pressure distillation on the solution to remove the unreacted thionyl chloride, heating thionyl chloride and p-phenylenediamine to 150 ℃ in a mass ratio of 1:160:60 in a nitrogen atmosphere, stirring at a constant speed for reaction for 96 hours, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the p-phenylenediamine functionalized carbon nanotube.
(2) Adding a distilled water solvent and polyvinyl alcohol into a reaction bottle, heating to 95 ℃, stirring for dissolving, adding sodium hydroxide for adjusting the pH value of the solution to 11, slowly dropwise adding epoxy chloropropane, wherein the mass ratio of epoxy chloropropane to polyvinyl alcohol is 25:10, stirring at a constant speed for reaction for 6 hours, carrying out vacuum drying on the solution for removing the solvent, washing a solid product with ethanol and distilled water until the solid product is neutral, and drying to prepare the epoxidized polyvinyl alcohol.
(3) Adding a distilled water solvent and epoxidized polyvinyl alcohol into a reaction bottle, heating to 95 ℃ for dissolution, adding aniline, stirring at a constant speed for reaction for 2 hours, cooling in an ice water bath, adding hydrochloric acid for regulating the pH value of the solution to 1, adding an initiator ammonium persulfate, stirring at a constant speed for reaction for 10 hours, adding a p-phenylenediamine functionalized carbon nanotube, wherein the mass ratio of the epoxidized polyvinyl alcohol to the aniline to the ammonium persulfate to the p-phenylenediamine functionalized carbon nanotube is 100:80:200:3, stirring at a constant speed for reaction for 25 hours, carrying out centrifugal separation on the solution, dialyzing for removing impurities, and drying to prepare the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol.
(4) Adding an acetone solvent, epoxy resin and polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol into a reaction bottle, performing a high-speed emulsification process, adding an anhydride curing agent and an accelerator 2,4, 6-tris (dimethylaminomethyl) phenol in a mass ratio of 100:10:60:6, uniformly stirring, pouring the emulsion into a film forming mold, drying, curing and forming a film, and preparing the anticorrosive material 4 of the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin.
Comparative example 1
(1) Adding anhydrous N, N-dimethylformamide and carboxylated carbon nanotubes into a reaction bottle, adding thionyl chloride after ultrasonic dispersion is uniform, placing the mixture into an atmosphere reaction device, wherein the atmosphere reaction device comprises an air pump, the air pump is movably connected with an air inlet pipe, the surface of the air inlet pipe is provided with air holes, the air inlet pipe is fixedly connected with an atmosphere reaction chamber, an oil bath pot is arranged inside the atmosphere reaction chamber, a base is arranged below an oil bath groove, the reaction bottle is arranged above the base, the upper surface of the base is movably connected with an adjusting valve, the adjusting valve is fixedly connected with an adjusting rod, the adjusting rod is movably connected with a rotating ball, the rotating ball is movably connected with a supporting rod, heating is carried out under the nitrogen atmosphere to 90 ℃, stirring at a constant speed and carrying out reflux reaction for 36 hours, carrying out reduced pressure distillation on the solution to remove the unreacted thionyl chloride, heating thionyl chloride and p-phenylenediamine to 150 ℃ in a mass ratio of 1:80:100 in a nitrogen atmosphere, stirring at a constant speed for reaction for 36 hours, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the p-phenylenediamine functionalized carbon nanotube.
(2) Adding a distilled water solvent and polyvinyl alcohol into a reaction bottle, heating to 95 ℃, stirring for dissolving, adding sodium hydroxide for adjusting the pH value of the solution to 11, slowly dropwise adding epoxy chloropropane, wherein the mass ratio of epoxy chloropropane to polyvinyl alcohol is 30:10, stirring at a constant speed for reaction for 5 hours, carrying out vacuum drying on the solution for removing the solvent, washing a solid product with ethanol and distilled water until the solid product is neutral, and drying to prepare the epoxidized polyvinyl alcohol.
(3) Adding a distilled water solvent and epoxidized polyvinyl alcohol into a reaction bottle, heating to 95 ℃ for dissolution, adding aniline, stirring at a constant speed for reaction for 2 hours, cooling in an ice water bath, adding hydrochloric acid for adjusting the pH value of the solution to 2, adding an initiator ammonium persulfate, stirring at a constant speed for reaction for 10 hours, adding a p-phenylenediamine functionalized carbon nanotube, wherein the mass ratio of the epoxidized polyvinyl alcohol to the aniline to the ammonium persulfate to the p-phenylenediamine functionalized carbon nanotube is 100:30:80:0.2, stirring at a constant speed for reaction for 25 hours, carrying out centrifugal separation on the solution, dialyzing for impurity removal, and drying to prepare the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol.
(4) Adding an acetone solvent, epoxy resin and polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol into a reaction bottle, performing a high-speed emulsification process, adding an anhydride curing agent and an accelerator 2,4, 6-tris (dimethylaminomethyl) phenol in a mass ratio of 100:1:35:1.5, uniformly stirring, pouring the emulsion into a film forming mold, drying, curing and forming a film, and preparing the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin comparison material 1.
The salt spray resistance of the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin in the examples and the comparative examples is tested by using a HYW-250 salt spray corrosion test box, and the test standard GB/T10125-.
Claims (7)
1. A polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin comprises the following raw materials and components, and is characterized in that: the polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol, the epoxy resin, the curing agent and the accelerator are mixed according to the mass ratio of 2-10:100:40-60: 2-6.
2. The polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin as claimed in claim 1, wherein: the curing agent is an anhydride curing agent, and the accelerator is any one of 2,4, 6-tris (dimethylaminomethyl) phenol or N-methyldiethanolamine.
3. The polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin as claimed in claim 1, wherein: the preparation method of the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin comprises the following steps:
(1) adding a carboxylated carbon nano tube into anhydrous N, N-dimethylformamide, adding thionyl chloride after uniform ultrasonic dispersion, placing the mixture into an atmosphere reaction device, heating the mixture to 70-90 ℃ in the nitrogen atmosphere, carrying out reflux reaction for 18-36h, carrying out reduced pressure distillation to remove unreacted thionyl chloride, adding p-phenylenediamine, heating the mixture to 120-150 ℃ in the nitrogen atmosphere, reacting for 48-96h, carrying out centrifugal separation, washing and drying to prepare the p-phenylenediamine functionalized carbon nano tube;
(2) adding polyvinyl alcohol into a distilled water solvent, heating to 75-95 ℃, stirring for dissolving, adding sodium hydroxide to adjust the pH of the solution to 10-11, dropwise adding epoxy chloropropane, reacting for 3-6h, removing the solvent, washing and drying to prepare epoxidized polyvinyl alcohol;
(3) adding epoxidized polyvinyl alcohol into a distilled water solvent, heating to 75-95 ℃ to dissolve, adding aniline to react for 2-4h, placing the mixture in an ice water bath to cool, adding hydrochloric acid to adjust the pH value of the solution to 1-2, adding an initiator ammonium persulfate to react for 5-10h, adding a p-phenylenediamine functionalized carbon nanotube to react for 15-25h, carrying out centrifugal separation, dialysis to remove impurities and drying to prepare polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol;
(4) adding epoxy resin and polyaniline-carbon nanotube grafted epoxidized polyvinyl alcohol into an acetone solvent, performing a high-speed emulsification process, adding an epoxy resin curing agent and an accelerator, uniformly stirring, pouring the emulsion into a film forming mold, drying, curing and forming a film, and preparing the polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin anticorrosive material.
4. The polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin as claimed in claim 3, wherein: the carboxyl content of the carboxylated carbon nanotube in the step (1) is 2.58-3.86%, and the mass ratio of the carboxylated carbon nanotube, the thionyl chloride and the p-phenylenediamine is 1:100-160: 30-60.
5. The polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin as claimed in claim 3, wherein: the atmosphere reaction device in the step (1) comprises an air pump, an air pump movably connected with an air inlet pipe, air holes are formed in the surface of the air inlet pipe, an atmosphere reaction chamber fixedly connected with the air inlet pipe is internally provided with an oil bath pot, a base is arranged below an oil bath groove, a reaction bottle is arranged above the base, an adjusting valve is movably connected to the upper surface of the base, an adjusting rod is fixedly connected with the adjusting valve, a rotating ball is movably connected to the adjusting rod, and a supporting rod is movably connected to the rotating ball.
6. The polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin as claimed in claim 3, wherein: the mass ratio of the polyvinyl alcohol to the epichlorohydrin in the step (2) is 10: 15-25.
7. The polyaniline-carbon nanotube grafted polyvinyl alcohol modified epoxy resin as claimed in claim 3, wherein: the mass ratio of the epoxidized polyvinyl alcohol, the aniline, the ammonium persulfate and the p-phenylenediamine functionalized carbon nanotube in the step (3) is 100:40-80:100-200: 0.5-3.
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| CN113593926A (en) * | 2021-07-19 | 2021-11-02 | 常州大学 | Preparation method of conductive polymer modified carbon nanotube-based flexible self-supporting energy storage device electrode material |
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| CN113593926A (en) * | 2021-07-19 | 2021-11-02 | 常州大学 | Preparation method of conductive polymer modified carbon nanotube-based flexible self-supporting energy storage device electrode material |
| CN113593926B (en) * | 2021-07-19 | 2023-01-17 | 常州大学 | Preparation method of conductive polymer modified carbon nanotube-based flexible self-supporting energy storage device electrode material |
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