CN111454525A - High-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material and preparation method thereof - Google Patents
High-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polyvinyl alcohol materials, and discloses a high-conductivity polyaniline-polyvinyl alcohol copolymerThe anticorrosive material comprises the following formula raw materials and components: nano-silver modified aminated carbon nanotube, epoxidized polyvinyl alcohol, aniline and oxidant. The highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material comprises amino and Ag in carbon nano tube+The generated nano silver is uniformly dispersed on the surface of the carbon nano tube and is tightly combined, the epoxidized polyvinyl alcohol reacts with aniline, and the amino group of the carbon nano tube and the aniline are cross-linked and polymerized to form a terpolymer of the polyvinyl alcohol-polyaniline-aminated carbon nano tube.
Description
Technical Field
The invention relates to the technical field of polyvinyl alcohol materials, in particular to a polyaniline-polyvinyl alcohol copolymer anticorrosive material with high conductivity and a preparation method thereof.
Background
The corrosion is a process of generating loss and damage of metal and nonmetal materials under the action of surrounding media such as water, air, acid, alkali and the like, and generally can be divided into chemical corrosion, electrochemical corrosion and microbial corrosion, generally, compounds generated by corrosion are unstable, are easy to dissolve and are not firmly combined with the materials, corrosion products fall off from the surfaces of the materials to cause the materials to be damaged and damaged, conductive materials can be divided into good conductor materials and high-resistance materials and can be used for conveying and conducting current, such as conductive plastics and conductive rubber, and conductive particles such as silver plating on glass, silver plating on aluminum, silver plating on silver and the like can be uniformly distributed in a silicon rubber material to play a role in the conduction of the rubber material.
Polyvinyl alcohol is a biodegradable vinyl polymer high molecular material, is produced in a non-petroleum route in a large scale, has low price, excellent oil resistance and solvent resistance and good gas barrier property, can be used for manufacturing materials such as polyvinyl acetal, vinylon synthetic fiber, gasoline resistant pipelines, paper coatings, adhesives and the like, and has wide application in the fields of food packaging, medicine packaging and the like, but the polyvinyl alcohol has higher intrinsic resistivity, larger internal resistance and poor conductivity, so that the application of the polyvinyl alcohol material is limited, and the polyvinyl alcohol is easily corroded by microorganisms such as bacteria and the like to cause the loss and decomposition of a material matrix.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a polyaniline-polyvinyl alcohol copolymer anticorrosive material with high conductivity and a preparation method thereof, and solves the problems of poor conductivity and poor anticorrosive performance of a polyvinyl alcohol material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material comprises the following formula raw materials in parts by weight: 2-5 parts of nano-silver modified aminated carbon nanotube, 38-50 parts of epoxidized polyvinyl alcohol, 28-32 parts of aniline and 20-25 parts of oxidant, wherein the oxidant is any one of potassium persulfate or ammonium persulfate.
Preferably, the preparation method of the nano-silver modified aminated carbon nanotube comprises the following steps:
(1) introducing nitrogen into a reaction bottle, adding a mixed solvent of ethylene glycol and oleylamine, wherein the volume ratio of the ethylene glycol to the oleylamine is 1:1.5-2.5, adding an aminated carbon nano tube, placing the aminated carbon nano tube into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 40-60 ℃ for 30-60min, wherein the ultrasonic frequency is 25-35KHz, adding silver acetylacetonate and dispersant polyvinylpyrrolidone, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50-80 ℃, uniformly stirring for 10-15h, cooling to 30-40 ℃, adding sodium borohydride serving as a reducing agent, uniformly stirring for reaction for 3-6h, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the nano-silver modified aminated carbon nano tube.
Preferably, the mass ratio of the aminated carbon nanotube to the silver acetylacetonate to the polyvinylpyrrolidone to the sodium borohydride is 1:1.5-2:3-6: 2.5-4.
Preferably, the top swing joint that supersound dispersion appearance includes instrument main part, instrument main part has the apron, the both sides of apron are provided with the bolt, the surface of apron is provided with the reaction bottle via hole, reaction bottle via hole swing joint has the governing valve, governing valve and regulating block swing joint, the middle part of regulating block is provided with the thread groove with governing valve looks adaptation, the inside fixedly connected with heat preservation inner bag of instrument main part, heat preservation inner bag and heating collar fixed connection, the internal surface fixed connection of heat preservation inner bag has ultrasonic transmitter, the below of instrument main part is provided with the outlet pipe, outlet pipe and outlet valve swing joint.
Preferably, the preparation method of the epoxidized polyvinyl alcohol comprises the following steps:
(1) adding distilled water and polyvinyl alcohol into a reaction bottle, stirring and dissolving, adding potassium hydroxide to adjust the pH value of the solution to 11-12, adding epoxy chloropropane, placing the reaction bottle into a constant-temperature water bath kettle, heating to 75-85 ℃, stirring at a constant speed for reaction for 2-6h, adding dilute hydrochloric acid into the reaction bottle to adjust the pH value of the solution to be neutral, removing the solvent from the solution, washing a solid product with ethanol, and fully drying to prepare the epoxidized polyvinyl alcohol.
Preferably, the mass ratio of the polyvinyl alcohol to the epichlorohydrin is 1: 0.2-0.5.
Preferably, the preparation method of the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material comprises the following steps:
(1) adding distilled water solvent, 38-50 parts of epoxidized polyvinyl alcohol and 28-32 parts of aniline into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 75-90 ℃, uniformly stirring for reaction for 2-5h, then adding 2-5 parts of nano-silver modified aminated carbon nano-tube, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1-2h at 40-60 ℃, wherein the ultrasonic frequency is 25-35KHz, placing the solution in a low-temperature constant-temperature instrument, adding hydrochloric acid at 0-5 ℃ to adjust the pH of the solution to 1-2, adding 20-25 parts of oxidant, uniformly stirring for reaction for 25-35h, performing vacuum drying on the solution to remove the solvent, washing a solid product with ether, fully drying, pouring the solid product into a film forming mold after dissolving, casting to form a film and fully drying, and preparing the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material uses polyvinylpyrrolidone as a dispersing agent to aminate amino in a carbon nano tube and Ag in silver acetylacetonate+Complexing to form Ag+Uniformly adsorbing and dispersing the nano silver on the huge specific surface area of the aminated carbon nanotube, and then using sodium borohydride and a reducing agent to prepare the nano silver modified aminated carbon nanotube, wherein the nano silver modified aminated carbon nanotube and the sodium borohydride are tightly combined, and the nano silver is uniformly dispersed on the surface of the carbon nanotube.
The high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material is prepared by reacting hydroxyl in polyvinyl alcohol with epichlorohydrin to generate epoxidized polyvinyl alcohol, carrying out ring-opening reaction on the epoxy group and amino of aniline to graft the aniline to polyvinyl alcohol, carrying out in-situ polymerization, uses nano silver modified aminated carbon nano tube as polymerization neutrality, and makes amino group of carbon nano tube and aniline implement cross-linking polymerization to form polyvinyl alcohol-polyaniline-aminated carbon nano tube terpolymer, the three components are organically combined by a chemical bond combination method, so that the dispersibility and compatibility of the carbon nano tube and the nano silver in the polyvinyl alcohol-polyaniline copolymer are greatly improved, the carbon nano tube and the nano silver have very high conductivity, and polyaniline also belongs to a conductive polymer, and endows the polyvinyl alcohol material with excellent conductivity.
According to the highly-conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material, the carbon nano tubes have a nano-size effect, the uniformly-dispersed carbon nano tubes are added into pores of a polymer matrix, oxygen and water molecules can be blocked, chemical corrosion of the material is effectively inhibited, meanwhile, the nano silver has a strong function of inhibiting and killing bacteria and microorganisms, and the polyvinyl alcohol material is endowed with good antibacterial performance and a function of preventing microbial corrosion.
Drawings
FIG. 1 is a schematic front view of an instrument body;
FIG. 2 is a schematic front view of the cover plate;
FIG. 3 is a plan view of the cover plate;
FIG. 4 is a schematic top view of a reactor vial via;
fig. 5 is a schematic view of the adjustment block adjustment.
1. An instrument body; 2. a cover plate; 3. a bolt; 4. a reaction bottle is provided with a hole; 5. adjusting a valve; 6. an adjusting block; 7. a thread groove; 8. a heat preservation liner; 9. heating a ring; 10. an ultrasonic transmitter; 11. a water outlet pipe; 12. and (4) a water outlet valve.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material comprises the following formula raw materials in parts by weight: 2-5 parts of nano-silver modified aminated carbon nanotube, 38-50 parts of epoxidized polyvinyl alcohol, 28-32 parts of aniline and 20-25 parts of oxidant, wherein the oxidant is any one of potassium persulfate or ammonium persulfate
The preparation method of the nano-silver modified aminated carbon nanotube comprises the following steps:
(1) introducing nitrogen into a reaction bottle, adding a mixed solvent of ethylene glycol and oleylamine, wherein the volume ratio of the ethylene glycol to the oleylamine is 1:1.5-2.5, adding an aminated carbon nano tube, and placing the aminated carbon nano tube into an ultrasonic dispersion instrument, wherein the ultrasonic dispersion instrument comprises an instrument main body, a cover plate is movably connected above the instrument main body, bolts are arranged on two sides of the cover plate, a reaction bottle through hole is arranged on the surface of the cover plate, a regulating valve is movably connected with the reaction bottle through hole, the regulating valve is movably connected with a regulating block, a thread groove matched with the regulating valve is arranged in the middle of the regulating block, a heat-insulating inner container is fixedly connected inside the instrument main body, the heat-insulating inner container is fixedly connected with a heating ring, an ultrasonic emitter is fixedly connected with the inner surface of the heat-insulating inner container, a water outlet pipe and a water outlet, the ultrasonic frequency is 25-35KHz, silver acetylacetonate and a dispersant polyvinylpyrrolidone are added, the reaction bottle is placed in a constant-temperature water bath kettle, the reaction bottle is heated to 50-80 ℃, the reaction bottle is stirred at a constant speed for 10-15 hours, the temperature is reduced to 30-40 ℃, a reducing agent sodium borohydride is added, the mass ratio of the aminated carbon nanotube to the silver acetylacetonate to the polyvinylpyrrolidone to the sodium borohydride is 1:1.5-2:3-6:2.5-4, the reaction is carried out at a constant speed for 3-6 hours, the solution is filtered to remove the solvent, distilled water and ethanol are used for washing a solid product, and the solid product is fully dried to prepare the nano-silver modified aminated carbon nanotube.
The preparation method of the epoxidized polyvinyl alcohol comprises the following steps:
(1) adding distilled water and polyvinyl alcohol into a reaction bottle, stirring and dissolving, adding potassium hydroxide to adjust the pH value of the solution to 11-12, adding epoxy chloropropane, wherein the mass ratio of polyvinyl alcohol to epoxy chloropropane is 1:0.2-0.5, placing the reaction bottle into a constant-temperature water bath, heating to 75-85 ℃, uniformly stirring and reacting for 2-6 hours, adding dilute hydrochloric acid into the reaction bottle to adjust the pH value of the solution to be neutral, removing the solvent from the solution, washing a solid product by using ethanol, and fully drying to prepare the epoxidized polyvinyl alcohol.
The preparation method of the polyaniline-polyvinyl alcohol copolymer anticorrosive material with high conductivity comprises the following steps:
(1) adding distilled water solvent, 38-50 parts of epoxidized polyvinyl alcohol and 28-32 parts of aniline into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 75-90 ℃, uniformly stirring for reaction for 2-5h, then adding 2-5 parts of nano-silver modified aminated carbon nano-tube, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1-2h at 40-60 ℃, wherein the ultrasonic frequency is 25-35KHz, placing the solution in a low-temperature constant-temperature instrument, adding hydrochloric acid at 0-5 ℃ to adjust the pH of the solution to 1-2, adding 20-25 parts of oxidant, uniformly stirring for reaction for 25-35h, performing vacuum drying on the solution to remove the solvent, washing a solid product with ether, fully drying, pouring the solid product into a film forming mold after dissolving, casting to form a film and fully drying, and preparing the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material.
Example 1
(1) Preparing a nano-silver modified aminated carbon nanotube component 1: introducing nitrogen into a reaction bottle, adding a mixed solvent of ethylene glycol and oleylamine with the volume ratio of 1:1.5, adding an aminated carbon nano tube, and placing the aminated carbon nano tube into an ultrasonic dispersion instrument, wherein the ultrasonic dispersion instrument comprises an instrument main body, a cover plate is movably connected above the instrument main body, bolts are arranged on two sides of the cover plate, a reaction bottle through hole is arranged on the surface of the cover plate, a regulating valve is movably connected with the reaction bottle through hole and is movably connected with a regulating valve, the regulating valve is movably connected with a regulating block, a thread groove matched with the regulating valve is arranged in the middle of the regulating block, a heat-insulating inner container is fixedly connected inside the instrument main body and is fixedly connected with a heating ring, an ultrasonic emitter is fixedly connected with the inner surface of the heat-insulating inner container, a water outlet pipe is arranged below the instrument main body and is movably connected with the water outlet valve, ultrasonic, And (2) placing a reaction bottle in a constant-temperature water bath, heating to 50 ℃, uniformly stirring for 10h, cooling to 30 ℃, adding a reducing agent sodium borohydride, stirring at a uniform speed for 3h, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the nano-silver modified aminated carbon nanotube component 1, wherein the mass ratio of the aminated carbon nanotube to the silver acetylacetonate to the polyvinylpyrrolidone to the sodium borohydride is 1:1.5:3: 2.5.
(2) Preparation of epoxidized polyvinyl alcohol component 1: adding distilled water and polyvinyl alcohol into a reaction bottle, stirring and dissolving, adding potassium hydroxide to adjust the pH value of the solution to 11, adding epoxy chloropropane, wherein the mass ratio of polyvinyl alcohol to epoxy chloropropane is 1:0.2, placing the reaction bottle into a constant-temperature water bath kettle, heating to 75 ℃, stirring at a constant speed for reaction for 2 hours, adding dilute hydrochloric acid into the reaction bottle to adjust the pH value of the solution to be neutral, removing the solvent from the solution, washing a solid product with ethanol, and fully drying to obtain an epoxidized polyvinyl alcohol component 1.
(3) Preparing a high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 1: adding a distilled water solvent, 50 parts of epoxidized polyvinyl alcohol component 1 and 28 parts of aniline into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 75-90 ℃, uniformly stirring for reaction for 2 hours, adding 2 parts of nano-silver modified aminated carbon nanotube component 1, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1 hour at 40 ℃, wherein the ultrasonic frequency is 25KHz, placing the solution in a low-temperature thermostat, adding hydrochloric acid to adjust the pH value of the solution to 1 at 5 ℃, adding 20 parts of oxidant, uniformly stirring for reaction for 25 hours, performing vacuum drying on the solution to remove the solvent, washing a solid product with diethyl ether, fully drying, dissolving the solid product, pouring into a film-forming mold, casting into a film, and fully drying to prepare the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 1.
Example 2
(1) Preparing a nano-silver modified aminated carbon nanotube component 2: introducing nitrogen into a reaction bottle, adding a mixed solvent of ethylene glycol and oleylamine with the volume ratio of 1:1.5, adding an aminated carbon nano tube, and placing the aminated carbon nano tube into an ultrasonic dispersion instrument, wherein the ultrasonic dispersion instrument comprises an instrument main body, a cover plate is movably connected above the instrument main body, bolts are arranged on two sides of the cover plate, a reaction bottle through hole is arranged on the surface of the cover plate, a regulating valve is movably connected with the reaction bottle through hole and is movably connected with a regulating valve, the regulating valve is movably connected with a regulating block, a thread groove matched with the regulating valve is arranged in the middle of the regulating block, a heat-insulating inner container is fixedly connected inside the instrument main body and is fixedly connected with a heating ring, an ultrasonic emitter is fixedly connected with the inner surface of the heat-insulating inner container, a water outlet pipe is arranged below the instrument main body and is movably connected with the water outlet valve, ultrasonic, And dispersing agent polyvinylpyrrolidone, wherein the mass ratio of the aminated carbon nanotube to the silver acetylacetonate, the polyvinylpyrrolidone to the sodium borohydride is 1:1.5:6:2.5, placing the reaction bottle in a constant-temperature water bath, heating to 80 ℃, uniformly stirring for 15h, cooling to 40 ℃, adding reducing agent sodium borohydride, uniformly stirring for reaction for 3-6h, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the nano-silver modified aminated carbon nanotube component 2.
(2) Preparation of epoxidized polyvinyl alcohol component 2: adding distilled water and polyvinyl alcohol into a reaction bottle, stirring and dissolving, adding potassium hydroxide to adjust the pH value of the solution to 11, adding epoxy chloropropane, wherein the mass ratio of polyvinyl alcohol to epoxy chloropropane is 1:0.2, placing the reaction bottle into a constant-temperature water bath kettle, heating to 75 ℃, stirring at a constant speed for reaction for 6 hours, adding dilute hydrochloric acid into the reaction bottle to adjust the pH value of the solution to be neutral, removing the solvent from the solution, washing a solid product with ethanol, and fully drying to obtain an epoxidized polyvinyl alcohol component 2.
(3) Preparing a high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 2: adding distilled water solvent, 46 parts of epoxidized polyvinyl alcohol component 2 and 29 parts of aniline into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring for reaction for 5 hours, adding 2.5 parts of nano-silver modified aminated carbon nanotube component 2, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 2 hours at 40 ℃, wherein the ultrasonic frequency is 25KHz, placing the solution in a low-temperature thermostat, adding hydrochloric acid to adjust the pH value of the solution to 2 at 5 ℃, adding 21.5 parts of oxidant, uniformly stirring for reaction for 35 hours, performing vacuum drying on the solution to remove the solvent, washing a solid product with diethyl ether, fully drying, dissolving the solid product, pouring into a film-forming mold, casting into a film and fully drying to prepare the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 2.
Example 3
(1) Preparing a nano-silver modified aminated carbon nanotube component 3: introducing nitrogen into a reaction bottle, adding a mixed solvent of ethylene glycol and oleylamine with the volume ratio of 1:1.5, adding an aminated carbon nano tube, and placing the aminated carbon nano tube into an ultrasonic dispersion instrument, wherein the ultrasonic dispersion instrument comprises an instrument main body, a cover plate is movably connected above the instrument main body, bolts are arranged on two sides of the cover plate, a reaction bottle through hole is arranged on the surface of the cover plate, a regulating valve is movably connected with the reaction bottle through hole and is movably connected with a regulating valve, the regulating valve is movably connected with a regulating block, a thread groove matched with the regulating valve is arranged in the middle of the regulating block, a heat-insulating inner container is fixedly connected inside the instrument main body and is fixedly connected with a heating ring, an ultrasonic emitter is fixedly connected with the inner surface of the heat-insulating inner container, a water outlet pipe is arranged below the instrument main body and is movably connected with the water outlet valve, ultrasonic, Dispersing agent polyvinylpyrrolidone, wherein the mass ratio of the aminated carbon nanotube to the silver acetylacetonate, the polyvinylpyrrolidone to the sodium borohydride is 1:1.5:6:2.5, placing a reaction bottle in a constant-temperature water bath, heating to 50-80 ℃, uniformly stirring for 15h, cooling to 30 ℃, adding reducing agent sodium borohydride, uniformly stirring for reaction for 3-6h, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the nano-silver modified aminated carbon nanotube component 3.
(2) Preparation of epoxidized polyvinyl alcohol component 3: adding distilled water and polyvinyl alcohol into a reaction bottle, stirring and dissolving, adding potassium hydroxide to adjust the pH value of the solution to 12, adding epoxy chloropropane, wherein the mass ratio of polyvinyl alcohol to epoxy chloropropane is 1:0.2, placing the reaction bottle into a constant-temperature water bath kettle, heating to 75 ℃, stirring at a constant speed for reaction for 6 hours, adding dilute hydrochloric acid into the reaction bottle to adjust the pH value of the solution to be neutral, removing the solvent from the solution, washing a solid product with ethanol, and fully drying to prepare an epoxidized polyvinyl alcohol component 3.
(3) Preparing a high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 3: adding a distilled water solvent, 44 epoxy polyvinyl alcohol component 3 and 30 parts of aniline into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring for reaction for 5 hours, adding 3.5 parts of nano silver modified aminated carbon nanotube component 3, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 2 hours at 40 ℃, wherein the ultrasonic frequency is 25KHz, placing the solution in a low-temperature thermostat, adding hydrochloric acid to adjust the pH value of the solution to 1-2 at 0 ℃, adding 22.5 parts of oxidant, uniformly stirring for reaction for 35 hours, performing vacuum drying on the solution to remove the solvent, washing a solid product with diethyl ether, fully drying, dissolving the solid product, pouring into a film forming mold, casting into a film and fully drying to prepare the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 3.
Example 4
(1) Preparing a nano-silver modified aminated carbon nanotube component 4: introducing nitrogen into a reaction bottle, adding a mixed solvent of ethylene glycol and oleylamine with the volume ratio of 1:2, adding an aminated carbon nano tube, and placing the aminated carbon nano tube into an ultrasonic dispersion instrument, wherein the ultrasonic dispersion instrument comprises an instrument main body, a cover plate is movably connected above the instrument main body, bolts are arranged on two sides of the cover plate, a reaction bottle through hole is arranged on the surface of the cover plate, a regulating valve is movably connected with the reaction bottle through hole and is movably connected with a regulating valve, the regulating valve is movably connected with a regulating block, a thread groove matched with the regulating valve is arranged in the middle of the regulating block, a heat-insulating inner container is fixedly connected inside the instrument main body and is fixedly connected with a heating ring, an ultrasonic emitter is fixedly connected with the inner surface of the heat-insulating inner container, a water outlet pipe is arranged below the instrument main body and is movably connected with a water outlet valve, ultrasonic, And dispersant polyvinylpyrrolidone, wherein the mass ratio of the aminated carbon nanotube to the silver acetylacetonate to the polyvinylpyrrolidone to the sodium borohydride is 1:1.8:4.5:3.2, the reaction bottle is placed in a constant-temperature water bath, the heating is carried out to 65 ℃, the stirring at a constant speed is carried out for 12h, the temperature is reduced to 35 ℃, the reducing agent sodium borohydride is added, the stirring at a constant speed is carried out for reaction for 4h, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol, and the solid product is fully dried, so that the nano-silver modified aminated carbon nanotube component 4 is prepared.
(2) Preparation of epoxidized polyvinyl alcohol component 4: adding distilled water and polyvinyl alcohol into a reaction bottle, stirring and dissolving, adding potassium hydroxide to adjust the pH value of the solution to 12, adding epoxy chloropropane, wherein the mass ratio of polyvinyl alcohol to epoxy chloropropane is 1:0.35, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed for reaction for 4 hours, adding dilute hydrochloric acid into the reaction bottle to adjust the pH value of the solution to be neutral, removing the solvent from the solution, washing a solid product with ethanol, and fully drying to prepare an epoxidized polyvinyl alcohol component 4.
(3) Preparing a high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 4: adding distilled water solvent, 41.5 epoxidized polyvinyl alcohol component 4 and 31 parts of aniline into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 85 ℃, uniformly stirring for reaction for 3 hours, then adding 4 parts of nano-silver modified aminated carbon nanotube component 4, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1.5 hours at 50 ℃, wherein the ultrasonic frequency is 25-35KHz, placing the solution in a low-temperature thermostat, adding hydrochloric acid to adjust the pH value of the solution to 1 at 2 ℃, adding 23.5 parts of oxidant, uniformly stirring for reaction for 30 hours, performing vacuum drying on the solution to remove the solvent, washing a solid product with diethyl ether, fully drying, dissolving the solid product, pouring into a film-forming mold, casting into a film and fully drying to prepare the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 4.
Example 5
(1) Preparing a nano-silver modified aminated carbon nanotube component 5: introducing nitrogen into a reaction bottle, adding a mixed solvent of ethylene glycol and oleylamine with the volume ratio of 1:2.5, adding an aminated carbon nano tube, and placing the aminated carbon nano tube into an ultrasonic dispersion instrument, wherein the ultrasonic dispersion instrument comprises an instrument main body, a cover plate is movably connected above the instrument main body, bolts are arranged on two sides of the cover plate, a reaction bottle through hole is arranged on the surface of the cover plate, a regulating valve is movably connected with the reaction bottle through hole and is movably connected with a regulating valve, the regulating valve is movably connected with a regulating block, a thread groove matched with the regulating valve is arranged in the middle of the regulating block, a heat-insulating inner container is fixedly connected inside the instrument main body and is fixedly connected with a heating ring, an ultrasonic emitter is fixedly connected with the inner surface of the heat-insulating inner container, a water outlet pipe is arranged below the instrument main body and is movably connected with the water outlet valve, ultrasonic, And dispersing agent polyvinylpyrrolidone, wherein the mass ratio of the aminated carbon nanotube to the silver acetylacetonate to the polyvinylpyrrolidone to the sodium borohydride is 1:2:6:4, placing the reaction bottle in a constant-temperature water bath, heating to 80 ℃, stirring at a constant speed for 15h, cooling to 40 ℃, adding reducing agent sodium borohydride, stirring at a constant speed for reaction for 6h, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the nano-silver modified aminated carbon nanotube component 5.
(2) Preparation of epoxidized polyvinyl alcohol component 5: adding distilled water and polyvinyl alcohol into a reaction bottle, stirring and dissolving, adding potassium hydroxide to adjust the pH value of the solution to 12, adding epoxy chloropropane, wherein the mass ratio of polyvinyl alcohol to epoxy chloropropane is 1:0.5, placing the reaction bottle into a constant-temperature water bath kettle, heating to 85 ℃, stirring at a constant speed for reaction for 6 hours, adding dilute hydrochloric acid into the reaction bottle to adjust the pH value of the solution to be neutral, removing the solvent from the solution, washing a solid product with ethanol, and fully drying to prepare an epoxidized polyvinyl alcohol component 5.
(3) Preparing a high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 5: adding a distilled water solvent, 38 epoxidized polyvinyl alcohol component 5 and 32 parts of aniline into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring for reaction for 2-5h, adding 5 parts of nano-silver modified aminated carbon nanotube component 5, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 2h at 60 ℃, wherein the ultrasonic frequency is 35KHz, placing the solution in a low-temperature thermostat, adding hydrochloric acid at 0 ℃ to adjust the pH of the solution to 2, adding 25 parts of oxidant, uniformly stirring for reaction for 35h, performing vacuum drying on the solution to remove the solvent, washing a solid product with diethyl ether, fully drying, dissolving the solid product, pouring into a film-forming mold, casting into a film, and fully drying to prepare the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material 5.
In summary, the highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material takes polyvinylpyrrolidone as a dispersant to aminate amino and acetyl in the carbon nanotubeAg in silver acetonate+Complexing to form Ag+Uniformly adsorbing and dispersing the nano silver on the huge specific surface area of the aminated carbon nanotube, and then using sodium borohydride and a reducing agent to prepare the nano silver modified aminated carbon nanotube, wherein the nano silver modified aminated carbon nanotube and the sodium borohydride are tightly combined, and the nano silver is uniformly dispersed on the surface of the carbon nanotube.
The method comprises the steps of reacting hydroxyl in polyvinyl alcohol with epichlorohydrin to generate epoxidized polyvinyl alcohol, carrying out ring-opening reaction on epoxy groups and amino of aniline to graft the aniline onto the polyvinyl alcohol, carrying out in-situ polymerization to obtain a polymer of a polyvinyl alcohol-polyaniline-aminated carbon nanotube by using a nano-silver modified aminated carbon nanotube as polymerization neutrality and carrying out cross-linking polymerization on amino of the carbon nanotube and aniline to form a terpolymer of the polyvinyl alcohol-polyaniline-aminated carbon nanotube, and organically combining the three through a chemical bond combination method to greatly improve the dispersibility and compatibility of the carbon nanotube and nano-silver in the polyvinyl alcohol-polyaniline copolymer, wherein the carbon nanotube and the nano-silver have very high conductivity, and the polyaniline also belongs to a conductive polymer and endows the polyvinyl alcohol material with excellent conductivity.
The carbon nano tube has a nano size effect, the uniformly dispersed carbon nano tube is added into pores of the polymer matrix, oxygen and water molecules can be blocked, the chemical corrosion of the material is effectively inhibited, meanwhile, the nano silver has very strong functions of inhibiting and killing bacteria and microorganisms, and the polyvinyl alcohol material is endowed with good antibacterial performance and a function of preventing microbial corrosion.
Claims (8)
1. The high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material comprises the following formula raw materials in parts by weight: 2-5 parts of nano-silver modified aminated carbon nanotube, 38-50 parts of epoxidized polyvinyl alcohol, 28-32 parts of aniline and 20-25 parts of oxidant.
2. The highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material according to claim 1, characterized in that: the oxidant is any one of potassium persulfate or ammonium persulfate.
3. The highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material according to claim 1, characterized in that: the preparation method of the nano-silver modified aminated carbon nanotube comprises the following steps:
(1) introducing nitrogen into a reaction bottle, adding a mixed solvent of ethylene glycol and oleylamine and an aminated carbon nano tube in a volume ratio of 1:1.5-2.5, placing the mixture into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 40-60 ℃ for 30-60min, wherein the ultrasonic frequency is 25-35KHz, adding silver acetylacetonate and dispersant polyvinylpyrrolidone, heating to 50-80 ℃, uniformly stirring for 10-15h, reducing the temperature to 30-40 ℃, adding a reducing agent sodium borohydride, reacting for 3-6h, filtering, washing and drying to obtain the nano-silver modified aminated carbon nano tube.
4. The highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material according to claim 3, characterized in that: the mass ratio of the aminated carbon nanotube to the silver acetylacetonate to the polyvinylpyrrolidone to the sodium borohydride is 1:1.5-2:3-6: 2.5-4.
5. The highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material according to claim 3, characterized in that: ultrasonic dispersion appearance includes the instrument main part, the top swing joint of instrument main part has the apron, the both sides of apron are provided with the bolt, the surface of apron is provided with the reaction bottle via hole, reaction bottle via hole swing joint has the governing valve, governing valve and regulating block swing joint, the middle part of regulating block is provided with the thread groove with governing valve looks adaptation, the inside fixedly connected with heat preservation inner bag of instrument main part, heat preservation inner bag and heating collar fixed connection, the internal surface fixedly connected with ultrasonic transmitter of heat preservation inner bag, the below of instrument main part is provided with the outlet pipe, outlet pipe and outlet valve swing joint.
6. The highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material according to claim 1, characterized in that: the preparation method of the epoxidized polyvinyl alcohol comprises the following steps:
(1) adding polyvinyl alcohol into distilled water, adding potassium hydroxide to adjust the pH value of the solution to 11-12, adding epichlorohydrin, heating the solution to 75-85 ℃, reacting for 2-6h, adding dilute hydrochloric acid to adjust the pH value of the solution to be neutral, removing the solvent from the solution, washing and drying to prepare the epoxidized polyvinyl alcohol.
7. The highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material according to claim 6, characterized in that: the mass ratio of the polyvinyl alcohol to the epichlorohydrin is 1: 0.2-0.5.
8. The highly conductive polyaniline-polyvinyl alcohol copolymer anticorrosive material according to claim 1, characterized in that: the preparation method of the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material comprises the following steps:
(1) adding 38-50 parts of epoxidized polyvinyl alcohol and 28-32 parts of aniline into distilled water solvent, heating to 75-90 ℃, reacting for 2-5h, adding 2-5 parts of nano silver modified aminated carbon nano tube, carrying out ultrasonic dispersion treatment on the solution in an ultrasonic dispersion instrument at 40-60 ℃ for 1-2h with the ultrasonic frequency of 25-35KHz, placing the solution in a low-temperature thermostat, adding hydrochloric acid at 0-5 ℃ to adjust the pH value of the solution to 1-2, adding 20-25 parts of oxidant, reacting for 25-35h, removing the solvent from the solution, washing and drying, pouring the dissolved solid product into a film forming mold to be casted into a film and fully dried, and preparing the high-conductivity polyaniline-polyvinyl alcohol copolymer anticorrosive material.
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