CN109627864B - Graphene anticorrosive paint and preparation method thereof - Google Patents
Graphene anticorrosive paint and preparation method thereof Download PDFInfo
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- 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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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The graphene anticorrosive paint is characterized in that: comprises fluorocarbon resin particles, an excessive amount of an emulsifier SE-10N, water, ammonium persulfate, PVA and graphene oxide micro-sheets with the average radial dimension higher than 5 um. Also provides a preparation method of the graphene anticorrosive paint, which comprises the following steps: the preparation method comprises the steps of preparing graphene nanoplatelets, preparing fluorocarbon emulsion and preparing graphene modified paint.
Description
Technical Field
The invention relates to the field of graphene anticorrosive paint, in particular to graphene anticorrosive paint and a preparation method thereof.
Background
The coating technology has been developed for hundreds of years, from the earliest coatings mainly comprising organic solvents to the current coatings mainly comprising energy-saving and environment-friendly coatings, the organic solvents play a great role in the preparation of the early coatings, but the organic coatings have a tiny formula due to environmental pollution, toxic waste materials and substandard discharge, and the current coatings mainly comprise water-based inorganic coatings, and the materials can be subjected to anticorrosion and protection effects on the surfaces of the materials without corrosion or pollution by adding fillers of granular or lamellar materials, so that the advanced development trend is realized.
Fluorocarbon materials are the main raw materials of typical water-based coatings, and have the advantages mentioned above, but fluorocarbon materials also have the advantages and disadvantages. Fluorocarbon resin materials have extremely high resistance to corrosive substances, but in exterior wall applications, the requirements on construction conditions and supporting materials are high, and if the requirements cannot be met, the uniformity and the improvement degree of the materials are directly influenced. The fluorocarbon particles have strong adhesiveness, and can show high decoration and high gloss on some hard surfaces, especially metal surfaces, due to the performance of strong adhesiveness. And the large amount of C-F bonds in the coating exist, so that the material has extremely strong chemical stability.
The disadvantages of the fluorocarbon material are obvious, and firstly, the fluorocarbon material is a water-based coating with dispersed particles, and how to ensure the uniformity of the dispersed particles during brushing is a great problem; secondly, the coating formed by the pure fluorocarbon material has insufficient viscoelasticity, and is easy to crack after expansion with heat and contraction with cold although the coating is chemically stable; thirdly, as a water-based paint, the paint is easy to harden, loses luster and has poor appearance.
In the prior art, the application research of graphene modified fluorocarbon resin proposes that graphene is added into fluorocarbon resin, but the adding mode is very general, and the adding amount is low and is only 1%. However, in the prior art, how to add graphene and in what manner, performance can be really improved, and further research and analysis are needed. At present, the application ratio of graphene is low, and graphene is not selected/selected, so that the promotion effect of graphene on the structure is not reflected.
Disclosure of Invention
The invention aims to provide a graphene/fluorocarbon anticorrosive coating to solve the problems of weak directivity and insufficient performance of fluorocarbon added graphene in the prior art. The invention actually further improves the corrosion resistance through the great improvement of the method and tests, and the uniformity of the material performance is also greatly improved. The toughness and the like of the coating are greatly improved.
In order to achieve the purpose, the invention provides the following technical scheme: the graphene anticorrosive paint is characterized in that: the composite material comprises fluorocarbon resin particles, an excessive amount of emulsifier SE-10N, water, ammonium persulfate, PVA and graphene oxide micro-sheets with the average radial size higher than 5 um; wherein the weight ratio of the fluorocarbon resin to the graphene oxide micro-sheets is between about 2.2-5.4: 1.
Further, the solid content of the graphene anticorrosive paint is 40-65%; the pH value of the graphene anticorrosive paint is 7.5-8; the thickness of a single-layer film brushed by the graphene anticorrosive paint with a common paint is between 20 and 60 mu m.
The preparation method of the graphene anticorrosive paint is used for preparing the graphene anticorrosive paint, and is characterized by comprising the following steps: 1) the preparation method of the graphene nanoplatelets comprises the following steps: taking a large number of prefabricated expanded graphite sheets as raw materials, and ultrasonically stripping the raw materials in absolute ethyl alcohol for more than 1-2h to generate graphene microchip dispersion liquid; taking out the upper-layer dispersion liquid through low-frequency ultrasound, and leaving the graphite which is not stripped in the container; the process of abandoning: supplementing the solvent absolute ethyl alcohol of the upper layer dispersion liquid to more than 200-300ml, carrying out high-intensity ultrasonic oscillation for 3-5min, standing for 5-10s, immediately discarding the upper half of the dispersion liquid, and supplementing the absolute ethyl alcohol to the volume of more than 200-300 ml; repeating the winnowing process for at least 10-20 times until the average radial size of the graphene nanoplatelets is higher than 5um by AFM or SEM; and (3) evaporating most of the solvent in a spinning mode, and drying at normal temperature under the condition of discontinuously using weak nitrogen for blowing so as to obtain the graphene oxide micro-sheets with large radial sizes.
2) The preparation method of the fluorocarbon emulsion comprises the following steps: mixing 10-15 parts by weight of fluorine-containing liquid monomer TFEMA, 0.8-1.2 parts by weight of emulsifier SE-10N and 48-54 parts by weight of double distilled water in a large wide-mouth container according to a certain proportion, adding a polytetrafluoroethylene magnetic rotor, and stirring at high speed for 30-90min at normal temperature to obtain a pre-emulsion; cleaning and airing a large reaction kettle, adding pre-emulsion, slowly adding 0.8-1.2 parts by weight of finely ground powder of ammonium persulfate serving as an initiator, adding 18-22 parts by weight of double distilled water, reacting the mixture in the reaction kettle under stirring and heating conditions, keeping the stirring speed at 3-10 r/s and the reaction temperature at 65-75 ℃, and reacting for 4-6h to obtain the prefabricated fluorocarbon emulsion.
3) The preparation method of the graphene modified coating comprises the following steps: keeping the stirring speed of the pre-prepared fluorocarbon emulsion at 3-10 r/s and the reaction temperature at 65-75 ℃, taking 0.05-0.1 part by weight of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60 mu m, and slowly and completely sieving the PVA ultrafine powder by using a micro-porous sieve barrel; preparing dispersion liquid by using double distilled water and absolute ethyl alcohol in a weight ratio of 3-5:1, and very slowly sieving 3-5 parts by weight of graphene oxide micro-tablets into 10-12 parts by weight of dispersion liquid heated and stirred at 35-45 ℃ by using a sieve barrel, wherein the stirring speed of the dispersion liquid is 3-10 r/s, so as to obtain the sieved dispersion liquid; on the premise of keeping the stirring speed at 3-10 r/s, a dropper is used for slowly dripping the screened dispersion liquid into the emulsion which keeps the stirring speed at 3-10 r/s in the large reaction kettle; and (3) cooling to 25-30 ℃, continuously stirring at the speed of 3-10 r/s, adjusting the pH value of the emulsion to 7.5-8 by using extremely dilute NaOH and extremely dilute acrylic acid, and stirring the natural volatile solvent substances until the solid content is 40-65%, thereby obtaining the graphene modified anticorrosive paint.
Compared with the prior art, the invention has the following beneficial effects: 1) and is more uniform. In the prior art, because insulating isolated islands of PVA powder are not added to improve the dispersibility of the system, and specific large-size graphene micro-sheets are not selected, the addition of graphene is only simple, and because of the diversity of the particle size of graphene, the uniformity of the obtained coating is not actually guaranteed on the basis of 1% addition of graphene, and once graphene is added in the prior art, the cosmetic state of mixed dispersion of the coating is difficult to maintain. The graphene without the selected size has wide particle size distribution range, can improve the uniformity of the coating to some extent, and is not ensured. We have also found, by duplicating the prior art method, that the roughness of the different coated areas is very different. 2) The corrosion resistance is improved. We compared the prior art coatings with the coatings of the present application, with a single brush thin layer coating, the prior art fluorocarbon/graphene coating had holes at 800h, but this application has not yet appeared. A specific graphene is selected, and due to the addition of a large amount of graphene with large radial dimension, corrosive substances are difficult to penetrate through/permeate the coating layer; the graphene nanoplatelets are mostly arranged in more parallel planes in the spraying process, so that the performances such as corrosion resistance and the like are enhanced, the action is called as a labyrinth effect in the literature, and the labyrinth effect is further enhanced by adopting the selected graphene nanoplatelets. 3) With the increase of the concentration of the graphene, the adhesive force of the coating is improved. We compare the coating of the present application with the prior art and test with a spatula it is evident that the adhesion of the present application is stronger and more difficult to scrape. 4) The use of PVA fine powder is that add a large amount of graphite alkene, obviously be higher than 1% of prior art, and the key that can homodisperse, because it is can to add graphite alkene, but how to guarantee graphite alkene and fluorocarbon particle's homodisperse and adhere to, be very big problem, because reasons such as static, fluorocarbon particle is very easy to reunite, the graphite alkene microchip is also very easy to be stained with together, add PVA fine powder before here, similar play insulating isolated island effect, can greatly strengthen the dispersion degree, make the introduction of a large amount of graphite alkene possible. This prior art does not suggest. The technology is expected to provide better and more even coatings with new performance.
Drawings
FIG. 1 is a schematic diagram of a process for preparing the coating of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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
The graphene anticorrosive paint is characterized in that: the composite material comprises fluorocarbon resin particles, an excessive amount of emulsifier SE-10N, water, ammonium persulfate, PVA and graphene oxide micro-sheets with the average radial size higher than 5 um; wherein the weight ratio of the fluorocarbon resin to the graphene oxide micro-sheets is between about 2.2-5.4: 1. The solid content of the graphene anticorrosive paint is 40-65%; the pH value of the graphene anticorrosive paint is 7.5-8; the thickness of a single-layer film brushed by the graphene anticorrosive paint with a common paint is between 20 and 60 mu m.
Example 2
The preparation method of the graphene anticorrosive paint is used for preparing the graphene anticorrosive paint, and is characterized by comprising the following steps: 1) the preparation method of the graphene nanoplatelets comprises the following steps: taking a large number of prefabricated expanded graphite sheets as raw materials, and ultrasonically stripping the raw materials in absolute ethyl alcohol for more than 1-2h to generate graphene microchip dispersion liquid; taking out the upper-layer dispersion liquid through low-frequency ultrasound, and leaving the graphite which is not stripped in the container; the process of abandoning: supplementing the solvent absolute ethyl alcohol of the upper layer dispersion liquid to more than 200-300ml, carrying out high-intensity ultrasonic oscillation for 3-5min, standing for 5-10s, immediately discarding the upper half of the dispersion liquid, and supplementing the absolute ethyl alcohol to the volume of more than 200-300 ml; repeating the winnowing process for at least 10-20 times until the average radial size of the graphene nanoplatelets is higher than 5um by AFM or SEM; and (3) evaporating most of the solvent in a spinning mode, and drying at normal temperature under the condition of discontinuously using weak nitrogen for blowing so as to obtain the graphene oxide micro-sheets with large radial sizes. The specific selection of graphene with a large radial dimension not only contributes to the uniformity of the system, but also enhances the corrosion resistance, making it extremely difficult for corrosive substances to penetrate the coating.
2) The preparation method of the fluorocarbon emulsion comprises the following steps: mixing 10-15 parts by weight of fluorine-containing liquid monomer TFEMA, 0.8-1.2 parts by weight of emulsifier SE-10N and 48-54 parts by weight of double distilled water in a large wide-mouth container according to a certain proportion, adding a polytetrafluoroethylene magnetic rotor, and stirring at high speed for 30-90min at normal temperature to obtain a pre-emulsion; cleaning and airing a large reaction kettle, adding pre-emulsion, slowly adding 0.8-1.2 parts by weight of finely ground powder of ammonium persulfate serving as an initiator, adding 18-22 parts by weight of double distilled water, reacting the mixture in the reaction kettle under stirring and heating conditions, keeping the stirring speed at 3-10 r/s and the reaction temperature at 65-75 ℃, and reacting for 4-6h to obtain the prefabricated fluorocarbon emulsion. Here ammonium persulfate may be added very slowly using a sieve barrel to allow emulsification to occur in as small a portion as possible to allow the emulsification to be as uniform as possible.
3) The preparation method of the graphene modified coating comprises the following steps: keeping the stirring speed of the pre-prepared fluorocarbon emulsion at 3-10 r/s and the reaction temperature at 65-75 ℃, taking 0.05-0.1 part by weight of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60 mu m, and slowly and completely sieving the PVA ultrafine powder by using a micro-porous sieve barrel; preparing dispersion liquid by using double distilled water and absolute ethyl alcohol in a weight ratio of 3-5:1, and very slowly sieving 3-5 parts by weight of graphene oxide micro-tablets into 10-12 parts by weight of dispersion liquid heated and stirred at 35-45 ℃ by using a sieve barrel, wherein the stirring speed of the dispersion liquid is 3-10 r/s, so as to obtain the sieved dispersion liquid; on the premise of keeping the stirring speed at 3-10 r/s, a dropper is used for slowly dripping the screened dispersion liquid into the emulsion which keeps the stirring speed at 3-10 r/s in the large reaction kettle; and (3) cooling to 25-30 ℃, continuously stirring at the speed of 3-10 r/s, adjusting the pH value of the emulsion to 7.5-8 by using extremely dilute NaOH and extremely dilute acrylic acid, and stirring the natural volatile solvent substances until the solid content is 40-65%, thereby obtaining the graphene modified anticorrosive paint. Through contrast experiments, the nonuniform condition can be greatly improved by adding PVA fine powder in advance, the uniformity is greatly improved in comparison after the PVA fine powder is added, and the condition that graphene micro-sheets are overlapped together is greatly reduced from an electron microscope photo.
Example 3
As in example 2, in the step (1), graphene microchip dispersion liquid is generated through ultrasonic stripping for more than 1.5h in absolute ethyl alcohol; the process of abandoning: supplementing absolute ethanol as solvent of upper layer dispersion liquid to above 220ml, high intensity ultrasonic oscillating for 4min, standing for 6s, immediately discarding half of upper layer dispersion liquid, and supplementing absolute ethanol to above 220ml volume; the above discarding process was repeated at least 15 times until the average radial dimension of the graphene nanoplatelets was confirmed to be above 5um with AFM or SEM.
In the step (2), 10 parts by weight of fluorine-containing liquid monomer TFEMA, 0.9 part by weight of emulsifier SE-10N and 48 parts by weight of double distilled water are stirred at high speed for 50min at normal temperature, 0.9 part by weight of ammonium persulfate serving as initiator is slowly added to form fine powder, 19 parts by weight of double distilled water is added, the stirring speed is kept at 4 r/s, the reaction temperature is kept between 65 ℃ and 70 ℃, and the reaction is carried out for 5 h.
In the step (3), keeping the stirring speed of the pre-prepared fluorocarbon emulsion at 3-5 r/s and keeping the reaction temperature at 65-70 ℃, and slowly and completely sieving 0.08 weight part of PVA (polyvinyl alcohol) ultrafine powder which is crushed into 60um or less in average particle size by multiple times of freeze-drying powder by using a micro-pore sieve barrel; preparing dispersion liquid by using double distilled water and absolute ethyl alcohol in a weight ratio of 5:1, and slowly sieving 4 parts by weight of graphene oxide micro-tablets by using a sieve barrel at a stirring speed of 3 r/s at 40-45 ℃ while heating, so as to obtain sieved dispersion liquid; on the premise of keeping the stirring speed at 3 revolutions per second, a dropper is used for slowly dripping the screened dispersion liquid into the emulsion which keeps the stirring speed at 3 revolutions per second in the large reaction kettle; and (3) cooling to 26 ℃, continuously stirring at the speed of 3 r/s, adjusting the pH value of the emulsion to 7.5-7.8 by using extremely-dilute NaOH and extremely-dilute acrylic acid, and stirring the naturally-volatilized solvent substances until the solid content is 40-55%, thereby obtaining the graphene modified anticorrosive paint.
Example 4
The method of example 2, in the step (1), graphene microchip dispersion liquid is generated through ultrasonic stripping in absolute ethyl alcohol for more than 2 hours; the process of abandoning: supplementing absolute ethanol as solvent of upper layer dispersion liquid to above 270ml, high intensity ultrasonic oscillating for 5min, standing for 10s, immediately discarding half of upper layer dispersion liquid, and supplementing absolute ethanol to above 270ml volume; the above discarding process was repeated at least 15 times until the average radial dimension of the graphene nanoplatelets was confirmed to be above 5um with AFM or SEM.
In the step (2), 10 parts by weight of fluorine-containing liquid monomer TFEMA, 0.9 part by weight of emulsifier SE-10N and 48 parts by weight of double distilled water are stirred at high speed for 50min at normal temperature, 0.9 part by weight of ammonium persulfate serving as initiator is slowly added to form fine powder, 19 parts by weight of double distilled water is added, the stirring speed is kept at 4 r/s, the reaction temperature is kept between 65 ℃ and 70 ℃, and the reaction is carried out for 5 h.
In the step (3), keeping the stirring speed of the pre-prepared fluorocarbon emulsion at 3-5 r/s and the reaction temperature at 65-70 ℃, and crushing 0.08 weight part of PVA (polyvinyl alcohol) ultrafine powder with the average particle size below 60um by multiple times of freeze-drying powder; preparing dispersion liquid by using double distilled water and absolute ethyl alcohol in a weight ratio of 5:1, and slowly sieving 4 parts by weight of graphene oxide micro-tablets by using a sieve barrel at a stirring speed of 5 revolutions per second at a temperature of 40-45 ℃ to obtain sieved dispersion liquid; on the premise of keeping the stirring speed at 5 revolutions per second, a dropper is used for slowly dripping the screened dispersion liquid into the emulsion which keeps the stirring speed at 5 revolutions per second in the large reaction kettle; and (3) cooling to 26 ℃, continuously stirring at the speed of 5 r/s, adjusting the pH value of the emulsion to 7.8-8 by using extremely-dilute NaOH and extremely-dilute acrylic acid, and stirring the natural volatile solvent substances until the solid content is 40-55%, thereby obtaining the graphene modified anticorrosive paint.
Through tests, more than 1% of graphene is difficult to add into the emulsion in the prior art, repeated tests show that more than 1% of graphene without screening is added, and the emulsion generated as a result is seriously agglomerated during coating and cannot meet the performance requirements of surface corrosion resistance and the like, namely the addition of PVA powder is necessary, so that the emulsion is obviously improved compared with the prior art and has stable performance.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (5)
1. The graphene anticorrosive paint is characterized in that:
the graphene anticorrosive paint formula comprises a prefabricated fluorocarbon emulsion, PVA (polyvinyl alcohol) ultrafine powder, graphene oxide micro-sheets, extremely-dilute NaOH and extremely-dilute acrylic acid;
the graphene anticorrosive paint is prepared by sieving a prefabricated fluorocarbon emulsion into PVA (polyvinyl alcohol) ultrafine powder and graphene oxide micro-tablets and adjusting the pH value of the emulsion by using extremely dilute NaOH and extremely dilute acrylic acid;
the pre-prepared fluorocarbon emulsion is obtained by adding fine powder of ammonium persulfate and double distilled water into pre-emulsion;
mixing and stirring fluorine-containing liquid monomer TFEMA, excessive emulsifier SE-10N and double distilled water to obtain a pre-emulsion;
wherein the average radial dimension of the graphene oxide nanoplatelets is higher than 5 um;
the weight ratio of the fluorocarbon resin to the graphene oxide micro-sheets in the prepared coating is 2.2-5.4: 1.
2. The graphene anticorrosive paint according to claim 1, characterized in that:
the solid content of the graphene anticorrosive paint is 40-65%;
the pH value of the graphene anticorrosive paint is 7.5-8;
the thickness of a single-layer film brushed by the graphene anticorrosive paint with a common paint is between 20 and 60 mu m.
3. The preparation method of the graphene anticorrosive paint, which is used for preparing the graphene anticorrosive paint according to claim 2, is characterized by comprising the following steps:
1) the preparation method of the graphene nanoplatelets comprises the following steps: taking a large number of prefabricated expanded graphite sheet layers as raw materials, and ultrasonically stripping in absolute ethyl alcohol for more than 1h to generate graphene microchip dispersion liquid; taking out the upper-layer dispersion liquid through low-frequency ultrasound, and leaving the graphite which is not stripped in the container; the process of abandoning: supplementing the solvent absolute ethyl alcohol of the upper layer dispersion liquid to more than 200mL, carrying out high-intensity ultrasonic oscillation for 3-5min, standing for 5-10s, immediately discarding the upper half dispersion liquid, and supplementing the absolute ethyl alcohol to the volume of more than 200 mL; repeating the winnowing process for at least 10 times until the average radial size of the graphene nanoplatelets is higher than 5um by AFM or SEM; most of the solvent is removed by rotary evaporation, and the graphene oxide micro-sheets with large radial sizes are obtained by drying at normal temperature under intermittent weak nitrogen purging;
2) the preparation method of the fluorocarbon emulsion comprises the following steps:
mixing 10-15 parts by weight of fluorine-containing liquid monomer TFEMA, 0.8-1.2 parts by weight of emulsifier SE-10N and 48-54 parts by weight of double distilled water in a large wide-mouth container in proportion, adding a polytetrafluoroethylene magnetic rotor, and stirring at high speed for 30-90min at normal temperature to obtain a pre-emulsion; cleaning and airing a large reaction kettle, adding pre-emulsion, slowly adding 0.8-1.2 parts by weight of ammonium persulfate serving as ground powder of an initiator, adding 18-22 parts by weight of double distilled water, reacting the mixture in the reaction kettle under stirring and heating conditions, keeping the stirring speed at 3-10 r/s and the reaction temperature at 65-75 ℃, and reacting for 4-6h to obtain prefabricated fluorocarbon emulsion;
3) the preparation method of the graphene modified coating comprises the following steps:
keeping the stirring speed of the pre-prepared fluorocarbon emulsion at 3-10 r/s and the reaction temperature at 65-75 ℃, taking 0.05-0.1 part by weight of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60 mu m, and slowly and completely sieving the PVA ultrafine powder by using a micro-porous sieve barrel; preparing dispersion liquid by using double distilled water and absolute ethyl alcohol in a weight ratio of 3-5:1, and very slowly sieving 3-5 parts by weight of graphene oxide micro-tablets into 10-12 parts by weight of dispersion liquid heated and stirred at 35-45 ℃ by using a sieve barrel, wherein the stirring speed of the dispersion liquid is 3-10 r/s, so as to obtain the sieved dispersion liquid; on the premise of keeping the stirring speed at 3-10 r/s, a dropper is used for slowly dripping the screened dispersion liquid into the emulsion which keeps the stirring speed at 3-10 r/s in the large reaction kettle;
and (3) cooling to 25-30 ℃, continuously stirring at the speed of 3-10 r/s, adjusting the pH value of the emulsion to 7.5-8 by using extremely dilute NaOH and extremely dilute acrylic acid, and stirring the natural volatile solvent substances until the solid content is 40-65%, thereby obtaining the graphene modified anticorrosive paint.
4. The preparation method of the graphene anticorrosive paint according to claim 3, which prepares the anticorrosive paint according to claim 1, wherein:
in the step (1), the graphene microchip dispersion liquid is generated through ultrasonic stripping for more than 1.5h in absolute ethyl alcohol; the process of abandoning: supplementing absolute ethyl alcohol serving as a solvent of the upper-layer dispersion liquid to more than 220mL, carrying out high-intensity ultrasonic oscillation for 4min, standing for 6s, immediately discarding half of the upper-layer dispersion liquid, and supplementing absolute ethyl alcohol to the volume of more than 220 mL; repeating the winnowing process at least 15 times until the average radial size of the graphene nanoplatelets is higher than 5um by AFM or SEM confirmation;
in the step (2), 10 parts by weight of fluorine-containing liquid monomer TFEMA, 0.9 part by weight of emulsifier SE-10N and 48 parts by weight of double distilled water are stirred at high speed for 50min at normal temperature, 0.9 part by weight of ammonium persulfate serving as ground powder of an initiator is slowly added, 19 parts by weight of double distilled water is added, the stirring speed is kept at 4 r/s, the reaction temperature is kept between 65 ℃ and 70 ℃, and the reaction is carried out for 5 hours;
in the step (3), keeping the stirring speed of the pre-prepared fluorocarbon emulsion at 3-5 r/s and keeping the reaction temperature at 65-70 ℃, and slowly and completely sieving 0.08 weight part of PVA (polyvinyl alcohol) ultrafine powder which is crushed into 60um or less in average particle size by multiple times of freeze-drying powder by using a micro-pore sieve barrel;
preparing dispersion liquid by using double distilled water and absolute ethyl alcohol in a weight ratio of 5:1, and slowly sieving 4 parts by weight of graphene oxide micro-tablets by using a sieve barrel at a stirring speed of 3 r/s at 40-45 ℃ while heating, so as to obtain sieved dispersion liquid;
on the premise of keeping the stirring speed at 3 revolutions per second, a dropper is used for slowly dripping the screened dispersion liquid into the emulsion which keeps the stirring speed at 3 revolutions per second in the large reaction kettle;
and (3) cooling to 26 ℃, continuously stirring at the speed of 3 r/s, adjusting the pH value of the emulsion to 7.5-7.8 by using extremely-dilute NaOH and extremely-dilute acrylic acid, and stirring the naturally-volatilized solvent substances until the solid content is 40-55%, thereby obtaining the graphene modified anticorrosive paint.
5. The preparation method of the graphene anticorrosive paint according to claim 3, characterized by comprising the following steps:
in the step (1), the graphene microchip dispersion liquid is generated through ultrasonic stripping for more than 2 hours in absolute ethyl alcohol; the process of abandoning: supplementing the solvent absolute ethyl alcohol of the upper layer dispersion liquid to more than 270mL, carrying out high-intensity ultrasonic oscillation for 5min, standing for 10s, immediately discarding the upper half dispersion liquid, and supplementing the absolute ethyl alcohol to the volume of more than 270 mL; repeating the winnowing process at least 15 times until the average radial size of the graphene nanoplatelets is higher than 5um by AFM or SEM confirmation;
in the step (2), 10 parts by weight of fluorine-containing liquid monomer TFEMA, 0.9 part by weight of emulsifier SE-10N and 48 parts by weight of double distilled water are stirred at high speed for 50min at normal temperature, 0.9 part by weight of ammonium persulfate serving as ground powder of an initiator is slowly added, 19 parts by weight of double distilled water is added, the stirring speed is kept at 4 r/s, the reaction temperature is kept between 65 ℃ and 70 ℃, and the reaction is carried out for 5 hours; keeping the stirring speed of the pre-prepared fluorocarbon emulsion at 3-5 r/s and the reaction temperature at 65-70 ℃, and taking 0.08 weight part of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying and crushing to obtain PVA ultrafine powder with the average particle size of below 60 mu m; preparing dispersion liquid by using double distilled water and absolute ethyl alcohol in a weight ratio of 5:1, and slowly sieving 4 parts by weight of graphene oxide micro-tablets by using a sieve barrel at a stirring speed of 5 revolutions per second at a temperature of 40-45 ℃ to obtain sieved dispersion liquid;
on the premise of keeping the stirring speed at 5 revolutions per second, a dropper is used for slowly dripping the screened dispersion liquid into the emulsion which keeps the stirring speed at 5 revolutions per second in the large reaction kettle;
and (3) cooling to 26 ℃, continuously stirring at the speed of 5 r/s, adjusting the pH value of the emulsion to 7.8-8 by using extremely-dilute NaOH and extremely-dilute acrylic acid, and stirring the natural volatile solvent substances until the solid content is 40-55%, thereby obtaining the graphene modified anticorrosive paint.
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