CN112126314A - Preparation process of water-based antibacterial anticorrosive paint - Google Patents
Preparation process of water-based antibacterial anticorrosive paint Download PDFInfo
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- CN112126314A CN112126314A CN202011017724.9A CN202011017724A CN112126314A CN 112126314 A CN112126314 A CN 112126314A CN 202011017724 A CN202011017724 A CN 202011017724A CN 112126314 A CN112126314 A CN 112126314A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a preparation process of a water-based antibacterial anticorrosive paint, which comprises the following steps: firstly, preparing an anticorrosive composite filler; secondly, preparing an antibacterial agent; dispersing the anticorrosive composite filler in deionized water, performing magnetic stirring for 20min, performing ultrasonic treatment for 2h, adding the mixture into the aqueous epoxy resin emulsion after the ultrasonic treatment is finished, sequentially adding the defoaming agent and the dispersing agent, stirring for 1h, adding the antibacterial agent, and continuing stirring for 1h to prepare the aqueous antibacterial anticorrosive coating; mixing chitosan, acetic acid and deionized water to prepare the treated chitosan, wherein the surface of the chitosan has a large amount of amino groups and excellent antibacterial performance, and mixing the treated chitosan and the treated bentonite according to the weight ratio of 1: 1 to form the antibacterial agent, so that the antibacterial agent has excellent stability and antibacterial performance.
Description
Technical Field
The invention belongs to the technical field of water-based paint preparation, and particularly relates to a preparation process of a water-based antibacterial anticorrosive paint.
Background
The traditional anticorrosive paint is an anticorrosive paint containing heavy metals and a zinc-rich anticorrosive paint, wherein the heavy metal anticorrosive organic paint containing chromium, lead and molybdenum compounds is relatively effective, but can release a large amount of toxic and harmful heavy metal ions of chromium, lead and molybdenum in the using process, so that the environment is seriously polluted, particularly the scratch resistance of the paint is poor, and once the paint is slightly scratched, the anticorrosive effect is greatly reduced; the zinc-rich organic or inorganic anticorrosive paint has no national strategy for sustainable development along with the gradual exhaustion of global zinc ore resources. In recent years, the environment-friendly polyaniline anticorrosive paint containing no heavy metal and zinc powder has attracted general attention of people, and the paint gradually becomes the development direction of the anticorrosive field due to excellent corrosion resistance and scratch resistance.
The invention discloses a Chinese patent CN103865359A, and relates to an oil-stain-resistant polyaniline anticorrosive paint and a preparation method thereof, belonging to the technical field of metal anticorrosive paints. The problem of poor stain resistance of the conventional polyaniline anticorrosive coating is solved; the anticorrosive coating comprises a component A, by weight, 13-28 parts of epoxy resin, 8-13 parts of organic silicon resin, 0.5-2 parts of eigenstate polyaniline, 27-53 parts of pigment, 3-22 parts of filler, 1.8-7.5 parts of anti-fouling additive, 24-38 parts of diluent, 0.3-2.5 parts of flatting agent, 0.5-3.2 parts of dispersing agent and 0.3-1.5 parts of fumed silica; and B component: 6-17 parts of a curing agent.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a preparation process of a water-based antibacterial anticorrosive paint.
The graphene has super van der Waals force and conjugate acting force, a three-dimensional structure is easily formed, and the dispersibility of the graphene in an organic phase and an aqueous phase solvent is poor, and the polyaniline can form a layer of passivation film on the surface of a base material, so that the base material can be protected, and the anti-corrosion performance of the polyaniline is improved.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of a water-based antibacterial anticorrosive paint comprises the following steps:
firstly, preparing an anticorrosive composite filler;
secondly, preparing an antibacterial agent;
and thirdly, dispersing 35-50 parts by weight of the anticorrosive composite filler in 550-700 parts by weight of deionized water, magnetically stirring at the rotating speed of 120r/min for 20min, then performing ultrasonic treatment for 2h, adding the mixture into 55-70 parts by weight of aqueous epoxy resin emulsion after the ultrasonic treatment is finished, sequentially adding 3-5 parts by weight of a defoaming agent and 5-8 parts by weight of a dispersing agent, stirring at the rotating speed of 1000r/min for 1h, adding 1-3 parts by weight of an antibacterial agent, and continuously stirring for 1h to prepare the aqueous antibacterial anticorrosive coating.
Further, the dispersing agent is one or two of sodium tripolyphosphate and sodium hexametaphosphate which are mixed according to any proportion, and the defoaming agent is one or two of trialkyl melamine and dimethyl siloxane which are mixed according to any proportion.
Further, the anticorrosion composite filler is prepared by the following method:
step S1, adding graphene into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding a hydrogen peroxide aqueous solution with the mass fraction of 10%, continuously reacting for 10min to prepare a graphene oxide solution, then adding ethylene oxide, heating to 30-35 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring for 30-45min at the rotating speed of 120-, preparing treated graphene oxide powder;
step S2, adding the treated graphene oxide powder into a beaker filled with deionized water, stirring at a constant speed for 30min to prepare a dispersion liquid, transferring the dispersion liquid into a three-neck flask, adding aniline and 5-aminosalicylic acid, ultrasonically shaking for 1h, introducing nitrogen, heating to 75-85 ℃, preserving heat at the temperature and reacting for 12h, cooling to 25 ℃ after the reaction is finished, adding a dilute hydrochloric acid solution with the mass fraction of 25% to adjust the pH until the pH is 1-1.5, transferring into an ice water bath, stirring at a constant speed, adding sodium persulfate, stirring at a constant speed and reacting for 20h to prepare a suspension, performing suction filtration, washing a filter cake three times with absolute ethyl alcohol, drying at the temperature of 45-50 ℃ for 20h to prepare an anticorrosive composite filler, controlling the weight ratio of the treated graphene oxide powder, aniline, 5-aminosalicylic acid and sodium persulfate to be 1: 2-3: 0.1-0.3, the weight ratio of the treated graphene oxide powder to the deionized water is 1: 50-75.
The method comprises the following steps that superstrong van der Waals force and conjugate acting force exist among graphene, a three-dimensional structure is easily formed, and the dispersibility of the graphene in an organic phase and a water phase solvent is poor, graphene oxide is prepared from the graphene under the action of potassium chlorate, 10% hydrogen peroxide water solution and the like in step S1, the graphene oxide can be dispersed in water and can also be dispersed in the organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; step S2, modifying graphene oxide by mixing and stirring silicon tetrachloride and graphene oxide at-8 ℃, modifying graphene oxide by silicon tetrachloride, introducing silicon element into graphene oxide in the modification process to enable the graphene oxide to easily form a single-layer structure, forming wrinkles on the surface of the graphene oxide, further increasing the specific surface area of the graphene oxide, and further enhancing the adsorption performance of the graphene oxide, and enabling the structure of the modified graphene to be looser due to the wrinkles on the surface of the modified graphene when the modified graphene is aggregated, so that large-aperture through holes are formed, and the adsorption performance of the modified graphene is enhanced through the large-aperture through holes; polyaniline can form a layer of passive film on the surface of a base material, and can protect the base material and improve the corrosion resistance of the base material, but polyaniline has poor dispersibility in water and is limited in application of water-based paint, 5-aminosalicylic acid has active reactive groups such as amino, hydroxyl, carboxyl and the like, the treated graphene oxide powder, aniline, 5-aminosalicylic acid and the like are mixed in step S2 to prepare the corrosion-resistant composite filler, the treated graphene oxide powder in the filler can play an excellent physical barrier effect, and the added 5-aminosalicylic acid can promote polyaniline dispersion, so that the corrosion-resistant composite filler can be dispersed in the prepared water-based paint.
Further, in the step S1, the weight ratio of the graphene, the sodium nitrate, the potassium chlorate, the ethylene oxide, the silicon tetrachloride and the triethylamine is controlled to be 1: 0.5-0.8: 0.1-0.2: 1-1.2: 0.2-0.25: 0.8-1.0, and the weight ratio of the graphene, the 98% concentrated sulfuric acid and the 10% aqueous hydrogen peroxide solution is 1: 10: 2-3.
Further, the antibacterial agent is prepared by the following method:
step S11, adding an aluminum chloride solution with the mass fraction of 10% into a three-neck flask, carrying out magnetic stirring at the rotating speed of 450-480r/min, heating in a water bath at 40-45 ℃, dropwise adding a sodium hydroxide solution with the mass fraction of 10%, controlling the dropwise adding speed to be 0.5-1mL/min, continuing stirring for 30min after the dropwise adding is finished, then cooling, aging for 1-2 days at 35-40 ℃ to prepare a treatment solution, and controlling the mass ratio of aluminum chloride to sodium hydroxide to be 2.5-3: 1;
s12, adding bentonite into deionized water according to the weight ratio of 1: 100, stirring at a constant speed until slurry is formed, adding the treatment liquid prepared in the step S11, dispersing at the rotating speed of 350-;
step S13, mixing chitosan, acetic acid and deionized water according to the weight ratio of 1: 45-50, heating in water bath at 40 ℃, stirring for 2h at the rotating speed of 120r/min, then preserving heat for 5h at the temperature to prepare a mixed solution, then adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH until the pH is 8.5-9, stirring at a constant speed until no precipitate is separated out, filtering, washing with deionized water for three times to prepare treated chitosan, and then mixing the treated chitosan and the treated bentonite according to the weight ratio of 1: 1 to prepare the antibacterial agent.
Step S11, dropwise adding a sodium hydroxide solution into an aluminum chloride solution, controlling the dropwise adding speed to be 0.5-1mL/min, so that the generated polymerization reaction is carried out step by step, the phenomenon that the dropwise adding speed is too high, the alkalinity in the aluminum chloride solution is too high, hydroxide precipitation is generated, a treatment solution is prepared, step S12, the treatment solution is added into bentonite, hydroxyl aluminum ions in the treatment solution are polymerized into complex ions, so that the space between bentonite layers is enlarged, micropores can be generated among montmorillonite layers in the bentonite, so that the prepared modified bentonite has larger specific surface area and pore volume, step S13, mixing chitosan, acetic acid and deionized water according to the weight ratio of 1: 45-50, so as to prepare the treated chitosan, wherein the surface of the chitosan has a large amount of amino groups and excellent antibacterial performance, the treated chitosan and the treated bentonite are mixed according to the weight ratio of 1: 1, forming an antibacterial agent, and endowing the antibacterial agent with excellent stability and antibacterial performance.
The invention has the beneficial effects that:
(1) according to the water-based antibacterial and anticorrosive coating, an anticorrosive composite filler and an antibacterial agent are respectively prepared in the preparation process, graphene is prepared into graphene oxide under the action of potassium chlorate, 10% hydrogen peroxide water solution and the like in the step S1 in the preparation process of the anticorrosive composite filler, the graphene oxide can be dispersed in water and can also be dispersed in an organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; step S2, modifying graphene oxide by mixing and stirring silicon tetrachloride and graphene oxide at-8 ℃, modifying graphene oxide by silicon tetrachloride, introducing silicon element into graphene oxide in the modification process to enable the graphene oxide to easily form a single-layer structure, forming wrinkles on the surface of the graphene oxide, further increasing the specific surface area of the graphene oxide, and further enhancing the adsorption performance of the graphene oxide, and enabling the structure of the modified graphene to be looser due to the wrinkles on the surface of the modified graphene when the modified graphene is aggregated, so that large-aperture through holes are formed, and the adsorption performance of the modified graphene is enhanced through the large-aperture through holes; polyaniline can form a layer of passive film on the surface of a base material, and can protect the base material and improve the corrosion resistance of the base material, but polyaniline has poor dispersibility in water and is limited in application of water-based paint, 5-aminosalicylic acid has active reactive groups such as amino, hydroxyl, carboxyl and the like, the treated graphene oxide powder, aniline, 5-aminosalicylic acid and the like are mixed in step S2 to prepare the corrosion-resistant composite filler, the treated graphene oxide powder in the filler can play an excellent physical barrier effect, and the added 5-aminosalicylic acid can promote polyaniline dispersion, so that the corrosion-resistant composite filler can be dispersed in the prepared water-based paint.
(2) In the invention, in the preparation process of the antibacterial agent, in step S11, sodium hydroxide solution is dropwise added into aluminum chloride solution, the dropwise adding speed is controlled to be 0.5-1mL/min, so that the generated polymerization reaction is carried out step by step, the phenomenon that the dropwise adding speed is too high, the alkalinity in the aluminum chloride solution is too high, hydroxide precipitation is generated, treatment liquid is prepared, in step S12, the treatment liquid is added into bentonite, hydroxyl aluminum ions in the treatment liquid are polymerized into complex ions to enlarge the space between bentonite layers, micropores can be generated among montmorillonite layers in the bentonite, so that the prepared modified bentonite has larger specific surface area and pore volume, in step S13, chitosan, acetic acid and deionized water are mixed according to the weight ratio of 1: 45-50 to prepare the treated chitosan, the surface of which has a large amount of amino groups and excellent antibacterial performance, mixing the treated chitosan and the treated bentonite according to the weight ratio of 1: 1 to form the antibacterial agent, and endowing the antibacterial agent with excellent stability and antibacterial performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation process of a water-based antibacterial anticorrosive paint comprises the following steps:
firstly, preparing an anticorrosive composite filler;
secondly, preparing an antibacterial agent;
and thirdly, dispersing 35 parts by weight of anticorrosive composite filler in 550 parts by weight of deionized water, magnetically stirring at the rotating speed of 100r/min for 20min, then performing ultrasonic treatment for 2h, adding the mixture into 55 parts by weight of aqueous epoxy resin emulsion after the ultrasonic treatment is finished, sequentially adding 3 parts by weight of dimethyl siloxane and 5 parts by weight of sodium tripolyphosphate, stirring at the rotating speed of 800r/min for 1h, adding 1 part by weight of antibacterial agent, and continuously stirring for 1h to obtain the aqueous antibacterial anticorrosive coating.
The anticorrosive composite filler is prepared by the following steps:
step S1, adding graphene into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding a hydrogen peroxide aqueous solution with the mass fraction of 10%, continuously reacting for 10min to obtain a graphene oxide solution, then adding ethylene oxide, heating to 30 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring for 30min at the rotating speed of 120r/min, adding triethylamine, heating to 45 ℃, stirring for 10min at the rotating speed of 200r/min, continuously heating and refluxing for 5h, transferring to deionized water, filtering, washing, drying for 8h at the temperature of 80 ℃, grinding to obtain treated graphene oxide powder, and controlling the graphene, the sodium nitrate and the concentrated sulfuric acid to be in the ice bath, and controlling the concentration of the, The weight ratio of sodium nitrate, potassium chlorate, ethylene oxide, silicon tetrachloride and triethylamine is 1: 0.5: 0.1: 1: 0.2: 0.8, and the weight ratio of graphene, 98% concentrated sulfuric acid and 10% aqueous hydrogen peroxide is 1: 10: 2;
step S2, adding the treated graphene oxide powder into a beaker filled with deionized water, stirring at a constant speed for 30min to prepare a dispersion liquid, transferring the dispersion liquid into a three-neck flask, adding aniline and 5-aminosalicylic acid, introducing nitrogen after ultrasonic oscillation for 1h, heating to 75 ℃, keeping the temperature at the temperature, reacting for 12h, cooling to 25 ℃ after the reaction is finished, adding a dilute hydrochloric acid solution with the mass fraction of 25% to adjust the pH until the pH is 1, then transferring to an ice water bath, stirring at a constant speed, adding sodium persulfate, stirring at a constant speed, reacting for 20h to prepare a suspension, performing suction filtration, washing a filter cake with absolute ethyl alcohol for three times, drying at 45 ℃ for 20h to prepare the anticorrosive composite filler, wherein the weight ratio of the treated graphene oxide powder, aniline, 5-aminosalicylic acid and sodium persulfate is controlled to be 1: 2: 0.1, and the weight ratio of the treated graphene oxide powder and deionized water is controlled to be 1: 50.
The antibacterial agent is prepared by the following method:
step S11, adding an aluminum chloride solution with the mass fraction of 10% into a three-neck flask, carrying out magnetic stirring at the rotating speed of 450r/min, heating in a water bath at 40 ℃, dropwise adding a sodium hydroxide solution with the mass fraction of 10%, controlling the dropwise adding speed to be 0.5mL/min, continuing stirring for 30min after dropwise adding, then cooling, aging for 1 day at 35 ℃ to prepare a treatment solution, and controlling the mass ratio of aluminum chloride to sodium hydroxide to be 2.5: 1;
s12, adding bentonite into deionized water according to the weight ratio of 1: 100, stirring at a constant speed until slurry is formed, adding the treatment liquid prepared in the step S11, dispersing for 2 hours at the rotating speed of 350r/min, centrifuging, washing, filtering until the filtrate does not contain chloride ions, and drying to prepare the treated bentonite;
step S13, mixing chitosan, acetic acid and deionized water according to the weight ratio of 1: 45, heating in water bath at 40 ℃, stirring for 2 hours at the rotating speed of 100r/min, then keeping the temperature for 5 hours to prepare a mixed solution, then adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH until the pH is 8.5, stirring at a constant speed until no precipitate is separated out, filtering, washing with deionized water for three times to prepare treated chitosan, and then mixing the treated chitosan and the treated bentonite according to the weight ratio of 1: 1 to prepare the antibacterial agent.
Example 2
A preparation process of a water-based antibacterial anticorrosive paint comprises the following steps:
firstly, preparing an anticorrosive composite filler;
secondly, preparing an antibacterial agent;
and thirdly, dispersing 40 parts by weight of anticorrosive composite filler in 600 parts by weight of deionized water, magnetically stirring at the rotating speed of 100r/min for 20min, then performing ultrasonic treatment for 2h, adding 60 parts by weight of aqueous epoxy resin emulsion after the ultrasonic treatment is finished, sequentially adding 4 parts by weight of dimethyl siloxane and 6 parts by weight of sodium tripolyphosphate, stirring at the rotating speed of 800r/min for 1h, adding 2 parts by weight of antibacterial agent, and continuously stirring for 1h to obtain the aqueous antibacterial anticorrosive coating.
The anticorrosive composite filler is prepared by the following steps:
step S1, adding graphene into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding a hydrogen peroxide aqueous solution with the mass fraction of 10%, continuously reacting for 10min to obtain a graphene oxide solution, then adding ethylene oxide, heating to 30 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring for 30min at the rotating speed of 120r/min, adding triethylamine, heating to 45 ℃, stirring for 10min at the rotating speed of 200r/min, continuously heating and refluxing for 5h, transferring to deionized water, filtering, washing, drying for 8h at the temperature of 80 ℃, grinding to obtain treated graphene oxide powder, and controlling the graphene, the sodium nitrate and the concentrated sulfuric acid to be in the ice bath, and controlling the concentration of the, The weight ratio of sodium nitrate, potassium chlorate, ethylene oxide, silicon tetrachloride and triethylamine is 1: 0.5: 0.1: 1: 0.2: 0.8, and the weight ratio of graphene, 98% concentrated sulfuric acid and 10% aqueous hydrogen peroxide is 1: 10: 2;
step S2, adding the treated graphene oxide powder into a beaker filled with deionized water, stirring at a constant speed for 30min to prepare a dispersion liquid, transferring the dispersion liquid into a three-neck flask, adding aniline and 5-aminosalicylic acid, introducing nitrogen after ultrasonic oscillation for 1h, heating to 75 ℃, keeping the temperature at the temperature, reacting for 12h, cooling to 25 ℃ after the reaction is finished, adding a dilute hydrochloric acid solution with the mass fraction of 25% to adjust the pH until the pH is 1, then transferring to an ice water bath, stirring at a constant speed, adding sodium persulfate, stirring at a constant speed, reacting for 20h to prepare a suspension, performing suction filtration, washing a filter cake with absolute ethyl alcohol for three times, drying at 45 ℃ for 20h to prepare the anticorrosive composite filler, wherein the weight ratio of the treated graphene oxide powder, aniline, 5-aminosalicylic acid and sodium persulfate is controlled to be 1: 2: 0.1, and the weight ratio of the treated graphene oxide powder and deionized water is controlled to be 1: 50.
The antibacterial agent is prepared by the following method:
step S11, adding an aluminum chloride solution with the mass fraction of 10% into a three-neck flask, carrying out magnetic stirring at the rotating speed of 450r/min, heating in a water bath at 40 ℃, dropwise adding a sodium hydroxide solution with the mass fraction of 10%, controlling the dropwise adding speed to be 0.5mL/min, continuing stirring for 30min after dropwise adding, then cooling, aging for 1 day at 35 ℃ to prepare a treatment solution, and controlling the mass ratio of aluminum chloride to sodium hydroxide to be 2.5: 1;
s12, adding bentonite into deionized water according to the weight ratio of 1: 100, stirring at a constant speed until slurry is formed, adding the treatment liquid prepared in the step S11, dispersing for 2 hours at the rotating speed of 350r/min, centrifuging, washing, filtering until the filtrate does not contain chloride ions, and drying to prepare the treated bentonite;
step S13, mixing chitosan, acetic acid and deionized water according to the weight ratio of 1: 45, heating in water bath at 40 ℃, stirring for 2 hours at the rotating speed of 100r/min, then keeping the temperature for 5 hours to prepare a mixed solution, then adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH until the pH is 8.5, stirring at a constant speed until no precipitate is separated out, filtering, washing with deionized water for three times to prepare treated chitosan, and then mixing the treated chitosan and the treated bentonite according to the weight ratio of 1: 1 to prepare the antibacterial agent.
Example 3
A preparation process of a water-based antibacterial anticorrosive paint comprises the following steps:
firstly, preparing an anticorrosive composite filler;
secondly, preparing an antibacterial agent;
and thirdly, dispersing 45 parts by weight of anticorrosive composite filler in 650 parts by weight of deionized water, performing magnetic stirring at the rotating speed of 100r/min for 20min, performing ultrasonic treatment for 2h, adding the mixture into 65 parts by weight of aqueous epoxy resin emulsion after the ultrasonic treatment is finished, sequentially adding 4 parts by weight of dimethyl siloxane and 7 parts by weight of sodium tripolyphosphate, performing stirring at the rotating speed of 800r/min for 1h, adding 2 parts by weight of antibacterial agent, and continuing stirring for 1h to obtain the aqueous antibacterial anticorrosive coating.
The anticorrosive composite filler is prepared by the following steps:
step S1, adding graphene into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding a hydrogen peroxide aqueous solution with the mass fraction of 10%, continuously reacting for 10min to obtain a graphene oxide solution, then adding ethylene oxide, heating to 30 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring for 30min at the rotating speed of 120r/min, adding triethylamine, heating to 45 ℃, stirring for 10min at the rotating speed of 200r/min, continuously heating and refluxing for 5h, transferring to deionized water, filtering, washing, drying for 8h at the temperature of 80 ℃, grinding to obtain treated graphene oxide powder, and controlling the graphene, the sodium nitrate and the concentrated sulfuric acid to be in the ice bath, and controlling the concentration of the, The weight ratio of sodium nitrate, potassium chlorate, ethylene oxide, silicon tetrachloride and triethylamine is 1: 0.5: 0.1: 1: 0.2: 0.8, and the weight ratio of graphene, 98% concentrated sulfuric acid and 10% aqueous hydrogen peroxide is 1: 10: 2;
step S2, adding the treated graphene oxide powder into a beaker filled with deionized water, stirring at a constant speed for 30min to prepare a dispersion liquid, transferring the dispersion liquid into a three-neck flask, adding aniline and 5-aminosalicylic acid, introducing nitrogen after ultrasonic oscillation for 1h, heating to 75 ℃, keeping the temperature at the temperature, reacting for 12h, cooling to 25 ℃ after the reaction is finished, adding a dilute hydrochloric acid solution with the mass fraction of 25% to adjust the pH until the pH is 1, then transferring to an ice water bath, stirring at a constant speed, adding sodium persulfate, stirring at a constant speed, reacting for 20h to prepare a suspension, performing suction filtration, washing a filter cake with absolute ethyl alcohol for three times, drying at 45 ℃ for 20h to prepare the anticorrosive composite filler, wherein the weight ratio of the treated graphene oxide powder, aniline, 5-aminosalicylic acid and sodium persulfate is controlled to be 1: 2: 0.1, and the weight ratio of the treated graphene oxide powder and deionized water is controlled to be 1: 50.
The antibacterial agent is prepared by the following method:
step S11, adding an aluminum chloride solution with the mass fraction of 10% into a three-neck flask, carrying out magnetic stirring at the rotating speed of 450r/min, heating in a water bath at 40 ℃, dropwise adding a sodium hydroxide solution with the mass fraction of 10%, controlling the dropwise adding speed to be 0.5mL/min, continuing stirring for 30min after dropwise adding, then cooling, aging for 1 day at 35 ℃ to prepare a treatment solution, and controlling the mass ratio of aluminum chloride to sodium hydroxide to be 2.5: 1;
s12, adding bentonite into deionized water according to the weight ratio of 1: 100, stirring at a constant speed until slurry is formed, adding the treatment liquid prepared in the step S11, dispersing for 2 hours at the rotating speed of 350r/min, centrifuging, washing, filtering until the filtrate does not contain chloride ions, and drying to prepare the treated bentonite;
step S13, mixing chitosan, acetic acid and deionized water according to the weight ratio of 1: 45, heating in water bath at 40 ℃, stirring for 2 hours at the rotating speed of 100r/min, then keeping the temperature for 5 hours to prepare a mixed solution, then adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH until the pH is 8.5, stirring at a constant speed until no precipitate is separated out, filtering, washing with deionized water for three times to prepare treated chitosan, and then mixing the treated chitosan and the treated bentonite according to the weight ratio of 1: 1 to prepare the antibacterial agent.
Example 4
A preparation process of a water-based antibacterial anticorrosive paint comprises the following steps:
firstly, preparing an anticorrosive composite filler;
secondly, preparing an antibacterial agent;
and thirdly, dispersing 50 parts by weight of anticorrosive composite filler in 700 parts by weight of deionized water, performing magnetic stirring at the rotating speed of 100r/min for 20min, performing ultrasonic treatment for 2h, adding the mixture into 70 parts by weight of aqueous epoxy resin emulsion after the ultrasonic treatment is finished, sequentially adding 5 parts by weight of dimethyl siloxane and 8 parts by weight of sodium tripolyphosphate, performing stirring at the rotating speed of 800r/min for 1h, adding 3 parts by weight of antibacterial agent, and continuing stirring for 1h to obtain the aqueous antibacterial anticorrosive coating.
The anticorrosive composite filler is prepared by the following steps:
step S1, adding graphene into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding a hydrogen peroxide aqueous solution with the mass fraction of 10%, continuously reacting for 10min to obtain a graphene oxide solution, then adding ethylene oxide, heating to 30 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring for 30min at the rotating speed of 120r/min, adding triethylamine, heating to 45 ℃, stirring for 10min at the rotating speed of 200r/min, continuously heating and refluxing for 5h, transferring to deionized water, filtering, washing, drying for 8h at the temperature of 80 ℃, grinding to obtain treated graphene oxide powder, and controlling the graphene, the sodium nitrate and the concentrated sulfuric acid to be in the ice bath, and controlling the concentration of the, The weight ratio of sodium nitrate, potassium chlorate, ethylene oxide, silicon tetrachloride and triethylamine is 1: 0.5: 0.1: 1: 0.2: 0.8, and the weight ratio of graphene, 98% concentrated sulfuric acid and 10% aqueous hydrogen peroxide is 1: 10: 2;
step S2, adding the treated graphene oxide powder into a beaker filled with deionized water, stirring at a constant speed for 30min to prepare a dispersion liquid, transferring the dispersion liquid into a three-neck flask, adding aniline and 5-aminosalicylic acid, introducing nitrogen after ultrasonic oscillation for 1h, heating to 75 ℃, keeping the temperature at the temperature, reacting for 12h, cooling to 25 ℃ after the reaction is finished, adding a dilute hydrochloric acid solution with the mass fraction of 25% to adjust the pH until the pH is 1, then transferring to an ice water bath, stirring at a constant speed, adding sodium persulfate, stirring at a constant speed, reacting for 20h to prepare a suspension, performing suction filtration, washing a filter cake with absolute ethyl alcohol for three times, drying at 45 ℃ for 20h to prepare the anticorrosive composite filler, wherein the weight ratio of the treated graphene oxide powder, aniline, 5-aminosalicylic acid and sodium persulfate is controlled to be 1: 2: 0.1, and the weight ratio of the treated graphene oxide powder and deionized water is controlled to be 1: 50.
The antibacterial agent is prepared by the following method:
step S11, adding an aluminum chloride solution with the mass fraction of 10% into a three-neck flask, carrying out magnetic stirring at the rotating speed of 450r/min, heating in a water bath at 40 ℃, dropwise adding a sodium hydroxide solution with the mass fraction of 10%, controlling the dropwise adding speed to be 0.5mL/min, continuing stirring for 30min after dropwise adding, then cooling, aging for 1 day at 35 ℃ to prepare a treatment solution, and controlling the mass ratio of aluminum chloride to sodium hydroxide to be 2.5: 1;
s12, adding bentonite into deionized water according to the weight ratio of 1: 100, stirring at a constant speed until slurry is formed, adding the treatment liquid prepared in the step S11, dispersing for 2 hours at the rotating speed of 350r/min, centrifuging, washing, filtering until the filtrate does not contain chloride ions, and drying to prepare the treated bentonite;
step S13, mixing chitosan, acetic acid and deionized water according to the weight ratio of 1: 45, heating in water bath at 40 ℃, stirring for 2 hours at the rotating speed of 100r/min, then keeping the temperature for 5 hours to prepare a mixed solution, then adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH until the pH is 8.5, stirring at a constant speed until no precipitate is separated out, filtering, washing with deionized water for three times to prepare treated chitosan, and then mixing the treated chitosan and the treated bentonite according to the weight ratio of 1: 1 to prepare the antibacterial agent.
Comparative example 1
Compared with example 1, the comparative example does not add the anticorrosion composite filler.
Comparative example 2
This comparative example compared to example 1, replacing the antimicrobial with chitosan.
Comparative example 3
The comparative example is a water-based antibacterial anticorrosive paint in the market.
The antibacterial properties and abrasion resistance of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;
it can be seen from the above table that the bacteriostatic ratio of the examples 1-4 to escherichia coli is 99.8-99.9%, the bacteriostatic ratio to staphylococcus aureus is 99.2-99.6%, no change is found in the abrasion resistance test, the bacteriostatic ratio of the comparative examples 1-3 to escherichia coli is 93.2-96.5%, the bacteriostatic ratio to staphylococcus aureus is 94.8-95.3%, the transparency of the coatings of the comparative examples 1 and 3 is obviously reduced in the abrasion resistance test, and the transparency of the coating of the comparative example 2 is slightly reduced; therefore, in the step S2, the treated graphene oxide powder, aniline, 5-aminosalicylic acid and the like are mixed to prepare the anticorrosive composite filler, the treated graphene oxide powder in the filler can play an excellent physical barrier effect, and the added 5-aminosalicylic acid can promote polyaniline dispersion, so that the anticorrosive composite filler can be dispersed in the prepared water-based paint.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (5)
1. A preparation process of a water-based antibacterial anticorrosive paint is characterized by comprising the following steps:
firstly, preparing an anticorrosive composite filler;
secondly, preparing an antibacterial agent;
and thirdly, dispersing 35-50 parts by weight of the anticorrosive composite filler in 550-700 parts by weight of deionized water, magnetically stirring at the rotating speed of 120r/min for 20min, then performing ultrasonic treatment for 2h, adding the mixture into 55-70 parts by weight of aqueous epoxy resin emulsion after the ultrasonic treatment is finished, sequentially adding 3-5 parts by weight of a defoaming agent and 5-8 parts by weight of a dispersing agent, stirring at the rotating speed of 1000r/min for 1h, adding 1-3 parts by weight of an antibacterial agent, and continuously stirring for 1h to prepare the aqueous antibacterial anticorrosive coating.
2. The preparation process of the water-based antibacterial and anticorrosive coating according to claim 1, wherein the dispersant is one or two of sodium tripolyphosphate and sodium hexametaphosphate mixed according to any proportion, and the defoamer is one or two of trialkyl melamine and dimethyl siloxane mixed according to any proportion.
3. The preparation process of the water-based bacteriostatic and anticorrosive coating according to claim 1, characterized in that the anticorrosive composite filler is prepared by the following method:
step S1, adding graphene into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding a hydrogen peroxide aqueous solution with the mass fraction of 10%, continuously reacting for 10min to prepare a graphene oxide solution, then adding ethylene oxide, heating to 30-35 ℃, carrying out ultrasonic treatment for 30min at the temperature, then cooling to-8 ℃, adding silicon tetrachloride, stirring for 30-45min at the rotating speed of 120-, grinding to obtain treated graphene oxide powder;
step S2, adding the treated graphene oxide powder into a beaker filled with deionized water, stirring at a constant speed for 30min to prepare a dispersion liquid, transferring the dispersion liquid into a three-neck flask, adding aniline and 5-aminosalicylic acid, ultrasonically shaking for 1h, introducing nitrogen, heating to 75-85 ℃, preserving heat at the temperature and reacting for 12h, cooling to 25 ℃ after the reaction is finished, adding a dilute hydrochloric acid solution with the mass fraction of 25% to adjust the pH until the pH is 1-1.5, transferring into an ice water bath, stirring at a constant speed, adding sodium persulfate, stirring at a constant speed and reacting for 20h to prepare a suspension, performing suction filtration, washing a filter cake three times with absolute ethyl alcohol, drying at the temperature of 45-50 ℃ for 20h to prepare an anticorrosive composite filler, controlling the weight ratio of the treated graphene oxide powder, aniline, 5-aminosalicylic acid and sodium persulfate to be 1: 2-3: 0.1-0.3, the weight ratio of the treated graphene oxide powder to the deionized water is 1: 50-75.
4. The preparation process of the water-based antibacterial and anticorrosive paint according to claim 3, wherein in step S1, the weight ratio of graphene, sodium nitrate, potassium chlorate, ethylene oxide, silicon tetrachloride and triethylamine is controlled to be 1: 0.5-0.8: 0.1-0.2: 1-1.2: 0.2-0.25: 0.8-1.0, and the weight ratio of graphene, 98% concentrated sulfuric acid and 10% aqueous hydrogen peroxide solution is 1: 10: 2-3.
5. The preparation process of the water-based antibacterial and anticorrosive paint according to claim 1, wherein the antibacterial agent is prepared by the following method:
step S11, adding an aluminum chloride solution with the mass fraction of 10% into a three-neck flask, carrying out magnetic stirring at the rotating speed of 450-480r/min, heating in a water bath at 40-45 ℃, dropwise adding a sodium hydroxide solution with the mass fraction of 10%, controlling the dropwise adding speed to be 0.5-1mL/min, continuing stirring for 30min after the dropwise adding is finished, then cooling, aging for 1-2 days at 35-40 ℃ to prepare a treatment solution, and controlling the mass ratio of aluminum chloride to sodium hydroxide to be 2.5-3: 1;
s12, adding bentonite into deionized water according to the weight ratio of 1: 100, stirring at a constant speed until slurry is formed, adding the treatment liquid prepared in the step S11, dispersing at the rotating speed of 350-;
step S13, mixing chitosan, acetic acid and deionized water according to the weight ratio of 1: 45-50, heating in water bath at 40 ℃, stirring for 2h at the rotating speed of 120r/min, then preserving heat for 5h at the temperature to prepare a mixed solution, then adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH until the pH is 8.5-9, stirring at a constant speed until no precipitate is separated out, filtering, washing with deionized water for three times to prepare treated chitosan, and then mixing the treated chitosan and the treated bentonite according to the weight ratio of 1: 1 to prepare the antibacterial agent.
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