CN111253778A - Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet - Google Patents
Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet Download PDFInfo
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Abstract
the preparation method comprises the steps of dissolving pyrrole and a surfactant in an organic solvent, carrying out ultrasonic stirring, adding the boron nitride nanosheet after the ultrasonic stirring, then carrying out ultrasonic stirring again to obtain a mixed solution, adding an oxidant into the mixed solution under an ice bath condition, then carrying out stirring reaction, filtering, collecting a solid obtained by filtering, washing the collected solid by using the organic solvent to remove the unreacted oxidant, then carrying out vacuum drying, and finally obtaining the modified boron nitride nanosheet.
Description
Technical Field
The disclosure relates to the technical field of anticorrosive coatings, in particular to a preparation method of a modified boron nitride nanosheet and application of the modified boron nitride nanosheet.
Background
Graphene has a monoatomic layer structure and molecular impermeability, has received increasing attention in the field of corrosion protection in recent years, and is considered to be the thinnest protective material. However, graphene is a conductive carbon material and has strong corrosion-promoting activity, damage of the graphene/polymer composite anticorrosive layer can cause micro-couple corrosion between graphene and a metal substrate, so that the corrosion of the metal substrate is aggravated, and the application of graphene in corrosion prevention is greatly limited. Patent CN109593391A discloses a method for preparing graphene anticorrosive paint, which uses thermosetting acrylic resin as a matrix, and adds fillers such as graphene, styrene, liquid paraffin, stearic acid, aluminum isopropoxide, and processing aids to obtain the graphene anticorrosive paint, but the anticorrosive material will further corrode protected metal in a long-term anticorrosive process due to the conductivity of graphene.
Boron Nitride (BN), called "white graphene", is a structurally similar graphite electron donor. Single-or multi-layered Boron Nitride Nanoplatelets (BNNS) have many excellent properties similar to graphene, such as hydrophobicity, oxygen barrier, excellent chemical and thermal stability, and higher mechanical strength. Different from graphene, BNNS avoids the conductive limitation of graphene and has unique application value in the field of metal corrosion protection. But the compatibility of BN powder is poor, sometimes even the mechanical property of the composite material is reduced, and the phase separation of the polymer and the filler causes that the h-BN doped coating is difficult to obtain better performance in a longer time. Therefore, improving the dispersibility of BNNS in organic solvents is a key to solving this problem.
Patent CN107324296A discloses a method for preparing hydroxyl modified hexagonal boron nitride, which comprises pretreating hexagonal boron nitride powder in nitric acid, dispersing the pretreated boron nitride in a mixed aqueous solution of formic acid and sulfuric acid, and then performing gamma-ray irradiation treatment to obtain hydroxyl modified boron nitride.
Disclosure of Invention
The purpose of the disclosure is to provide a preparation method of a modified boron nitride nanosheet and application of the modified boron nitride nanosheet so as to achieve the purpose of improving the dispersibility of the boron nitride nanosheet.
In order to realize the purpose, the technical scheme is as follows:
a preparation method of a modified boron nitride nanosheet comprises the following steps: dissolving pyrrole and a surfactant in an organic solvent, carrying out ultrasonic stirring, adding a boron nitride nanosheet after ultrasonic stirring, then carrying out ultrasonic stirring again to obtain a uniform mixed solution, adding an oxidant into the mixed solution under an ice bath condition, then carrying out stirring reaction, filtering, collecting a solid obtained by filtering, washing the collected solid by using the organic solvent to remove the unreacted oxidant, then carrying out vacuum drying, and finally obtaining the modified boron nitride (BNNS @ Ppy, BP) nanosheet.
The ultrasonic power in the ultrasonic stirring is 240W, and the ultrasonic stirring time is 0.5-1.5 h; preferably the temperature of the ice bath is 0 ℃; preferably, the concentration of the organic solvent is 50%, and the organic solvent is ethanol, isopropanol or N-methylpyrrolidone.
The surfactant is Sodium Dodecyl Benzene Sulfonate (SDBS), octadecylamine or sodium lauroyl glutamate; preferably the oxidant is ammonium persulfate or ferric chloride.
The mass ratio of the surfactant to the boron nitride nanosheet is 1: 60, wherein the molar ratio of the oxidant to the pyrrole is 1:1, the mass ratio of the pyrrole to the surfactant is 20: 1, wherein the volume ratio of the pyrrole to the organic solvent is 1: 200.
the application of the modified boron nitride nanosheet prepared by the preparation method of the modified boron nitride nanosheet in an anticorrosive coating is characterized in that the anticorrosive coating comprises the following components: boron nitride nanosheets, polypyrrole (Ppy), BP nanosheets and epoxy resin.
The epoxy resin is E44 or E51.
The preparation method of the anticorrosive paint comprises the following specific operations: adding the BP nanosheet, the boron nitride nanosheet and the polypyrrole into absolute ethyl alcohol, uniformly stirring, performing ultrasonic treatment, adding epoxy resin, uniformly stirring, and finally drying to remove the absolute ethyl alcohol to obtain the anticorrosive coating.
The boron nitride nanosheet: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is (0.01-0.05): (0.01-0.05): (0.01-0.05): (0.8-1.2), preferably the ratio of the epoxy resin to the absolute ethanol is 2: 1 (g/mL).
The preparation method of the boron nitride nanosheet comprises the following steps: and dispersing boron nitride in an organic solvent, carrying out ultrasonic treatment, standing, filtering, washing and drying to obtain the boron nitride nanosheet.
The organic solvent is ethanol, thionyl chloride or isopropanol, the concentration of the organic solvent is 50%, and the size of the boron nitride is 0.2-10 um; the adding proportion of the boron nitride to the organic solvent is 5: 3 (mg/mL); the power of ultrasonic treatment is 240W, the time of ultrasonic treatment is 15h, and the time of standing is 8 h.
The preparation method of the polypyrrole comprises the following steps: dispersing pyrrole and a surfactant in deionized water to obtain a uniform pyrrole mixture, dispersing an oxidant in the deionized water, adding the oxidant into the pyrrole mixture, stirring, filtering and collecting polypyrrole, washing the collected polypyrrole with an ethanol solution, and then drying in vacuum.
The molar ratio of the oxidant to the pyrrole is 1:1, the mass ratio of the pyrrole to the surfactant is 20: 1, wherein the volume ratio of the pyrrole to the organic solvent is 1: 100.
the preparation method of the modified boron nitride nanosheet has the beneficial effects that an oxidant is added under the ice bath condition, so that the pyrrole polymerization speed is reduced, the speed of attaching to BNNS is reduced, a Ppy coating film with more uniform thickness can be obtained, Ppy carries out non-covalent modification on the boron nitride nanosheet BNNS, the BP nanosheet is synthesized through the strong п -BNN interaction between the BNNS and the aromatic pyrrole molecule, the modification amount is up to 23%, the dispersibility of the BNNS in an organic solvent is improved, the organic solvent, the pyrrole and the oxidant used in the preparation process are all green and easily-obtained materials, so that the environmental pollution cannot be caused, Ppy is added as a filler in an anticorrosive coating when the BP prepared by the preparation method of the modified boron nitride nanosheet is applied to the anticorrosive coating, the space between the BP nanosheets is improved, the dispersibility of the BP nanosheet is further improved, the Ppy can also improve the corrosion resistance through passivating a metal oxide film, and the hydrophobicity of the BP nanosheet and the anticorrosive coating prevent water permeation, and the anticorrosive coating prepared by the anticorrosive coating has excellent steric hindrance capability.
Drawings
Fig. 1 is a schematic diagram of a BP nanosheet preparation process.
Fig. 2 is a dispersion performance test chart of BP nanosheet and BNNS prepared in example 1.
FIG. 3 is a graph showing the results of testing the corrosion resistance of the boron nitride anticorrosive coatings prepared in examples 1 to 8.
Figure 4 is a thermal degradation diagram of BNNS and BP nanosheets.
Detailed Description
The following steps are only used for illustrating the technical scheme of the disclosure and are not limited; although the present disclosure has been described in detail with reference to the foregoing steps, those of ordinary skill in the art will understand that: the technical solutions recorded in the foregoing steps may still be modified, or some or all of the technical features may be equivalently replaced; and such modifications or substitutions do not depart from the scope of the respective technical solutions of the steps of the present disclosure.
Example 1
Preparation of BNNS: 500mgBN (size of 1um) was dispersed in 300ml of a mixed solvent of ethanol and distilled water (volume ratio 1:1), subjected to ultrasonic treatment at 240W for 15 hours and left standing for 8 hours, and then the supernatant was filtered with a polytetrafluoroethylene membrane having a diameter of 0.22m, washed and dried to obtain BNNS.
Preparation of Ppy: dispersing 3mL of pyrrole and 5 wt% of SDBS in 300mL of deionized water, stirring for 1 hour by ultrasonic, stirring for 10min to obtain a uniform pyrrole mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture into the pyrrole mixture, stirring for 8 hours, filtering, collecting Ppy, washing with 50% ethanol for three times continuously, removing unreacted oxidant, and then drying in vacuum at 60 ℃ to obtain the Ppy.
Preparing BP nano sheets: dispersing 3mL of pyrrole and 5 wt% of sodium dodecyl benzene sulfonate in a mixed solution of 300mL of deionized water and 300mL of absolute ethyl alcohol, ultrasonically stirring for 1h, adding 1g of BNNS, ultrasonically stirring for 1h to obtain a uniform mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture in an ice bath, stirring for 8h, filtering and collecting BP nanosheets, washing with 50% of ethanol successively for three times to remove unreacted oxidant, and then vacuum-drying at 60 ℃ to obtain the BP nanosheets. The preparation flow chart is shown in figure 1.
Then dissolving the prepared BP nano-sheet and BNNS in ethanol, standing for 24h, and observing the dispersibility of the BP nano-sheet and BNNS in the ethanol, wherein the result is shown in FIG. 2 (BNNS is on the left side, and BP nano-sheet is on the right side), and the BP nano-sheet has good dispersibility and relatively stable dispersibility.
The prepared BP nano-sheet and BNNS are subjected to thermal degradation detection, and the result is shown in FIG. 4, it can be seen that, with the increase of temperature, BNNS molecules have no mass loss at 800 ℃ due to thermal stability, while the BP nano-sheet gradually reduces the mass due to thermal degradation of polypyrrole organic matter modified by the BP nano-sheet, the pyrolysis temperature range of polypyrrole is 250-550 ℃, the later stage tends to be stable, and it can be seen from FIG. 4 that the modification amount of polypyrrole is 23%.
A preparation method of an anticorrosive coating containing modified boron nitride nanosheets comprises the following specific operations: adding 5ml of absolute ethyl alcohol into a beaker, then adding the prepared BNNS, BP nano-sheets and Ppy into the beaker, continuously stirring for 10min, then carrying out ultrasonic treatment for 30min, then adding 10g E44 epoxy resin, stirring for 2h until obtaining a uniform mixture, drying the mixture by a rotary evaporation method, and removing the absolute ethyl alcohol to obtain the boron nitride anticorrosive coating, wherein the boron nitride nano-sheets: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is 0.01: 0.01: 0.01: 0.8.
example 2
Preparation of BNNS: 500mgBN (size of 2um) was dispersed in 300ml of a mixed solvent of isopropyl alcohol and distilled water (volume ratio 1:1), subjected to ultrasonic treatment at 240W for 15 hours and left standing for 8 hours, and then the supernatant was filtered with a polytetrafluoroethylene membrane having a diameter of 0.22m, washed and dried to obtain BNNS.
Preparation of Ppy: dispersing 3mL of pyrrole and 5 wt% of SDBS in 300mL of deionized water, stirring for 1 hour by ultrasonic, stirring for 10min to obtain a uniform pyrrole mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture into the pyrrole mixture, stirring for 8 hours, filtering, collecting Ppy, washing with 50% ethanol for three times continuously, removing unreacted oxidant, and then drying in vacuum at 60 ℃ to obtain the Ppy.
Preparing BP nano sheets: dispersing 3mL of pyrrole and 5 wt% of sodium dodecyl benzene sulfonate in a mixed solution of 300mL of deionized water and 300mL of isopropanol, ultrasonically stirring for 1h, adding 1g of BNNS, ultrasonically stirring for 1h to obtain a uniform mixture, dispersing 987mg of ferric chloride in 100mL of deionized water, adding the mixture in an ice bath, stirring for 8h, filtering and collecting BP nanosheets, washing with 50% of isopropanol for three times to remove unreacted oxidant, and then vacuum-drying at 60 ℃ to obtain the BP nanosheets.
A preparation method of an anticorrosive coating containing modified boron nitride nanosheets comprises the following specific operations: adding 5ml of absolute ethyl alcohol into a beaker, then adding the prepared BNNS, BP nano-sheets and Ppy into the beaker, continuously stirring for 10min, then carrying out ultrasonic treatment for 30min, then adding 10g E44 epoxy resin, stirring for 2h until obtaining a uniform mixture, drying the mixture by a rotary evaporation method, and removing the absolute ethyl alcohol to obtain the boron nitride anticorrosive coating, wherein the boron nitride nano-sheets: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is 0.05: 0.05: 0.05: 1.2.
example 3
Preparation of BNNS: 500mgBN (size of 0.2um) was dispersed in 300ml of a mixed solvent of ethanol and distilled water (volume ratio 1:1), subjected to ultrasonic treatment at 240W for 15 hours and left standing for 8 hours, and then the supernatant was filtered with a polytetrafluoroethylene membrane having a diameter of 0.22m, washed and dried to obtain BNNS.
Preparation of Ppy: dispersing 3mL of pyrrole and 5 wt% of SDBS in 300mL of deionized water, stirring for 1 hour by ultrasonic, stirring for 10min to obtain a uniform pyrrole mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture into the pyrrole mixture, stirring for 8 hours, filtering, collecting Ppy, washing with 50% ethanol for three times continuously, removing unreacted oxidant, and then drying in vacuum at 60 ℃ to obtain the Ppy.
Preparing BP nano sheets: dispersing 3mL of pyrrole and 5 wt% of sodium dodecyl benzene sulfonate in a mixed solution of 300mL of deionized water and 300mL of N-methyl pyrrolidone, ultrasonically stirring for 1h, adding 1g of BNNS, ultrasonically stirring for 1h to obtain a uniform mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture in an ice bath, stirring for 8h, filtering and collecting BP nanosheets, washing with 50% of N-methyl pyrrolidone for three times in sequence, removing unreacted oxidant, and then vacuum drying at 60 ℃ to obtain the BP nanosheets.
A preparation method of an anticorrosive coating containing modified boron nitride nanosheets comprises the following specific operations: adding 5ml of absolute ethyl alcohol into a beaker, then adding the prepared BNNS, BP nano-sheets and Ppy into the beaker, continuously stirring for 10min, then carrying out ultrasonic treatment for 30min, then adding 10g E44 epoxy resin, stirring for 2h until obtaining a uniform mixture, drying the mixture by a rotary evaporation method, and removing the absolute ethyl alcohol to obtain the boron nitride anticorrosive coating, wherein the boron nitride nano-sheets: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is 0.02: 0.02: 0.02: 0.9.
example 4
Preparation of BNNS: 500mgBN (size of 2um) was dispersed in 300ml of a mixed solvent of isopropyl alcohol and distilled water (volume ratio 1:1), subjected to ultrasonic treatment at 240W for 15 hours and left standing for 8 hours, and then the supernatant was filtered with a polytetrafluoroethylene membrane having a diameter of 0.22m, washed and dried to obtain BNNS.
Preparation of Ppy: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in 300mL of deionized water, ultrasonically stirring for 1h, and then stirring for 10min to obtain a uniform pyrrole mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture into the pyrrole mixture, stirring for 8h, filtering to collect Ppy, continuously washing with 50% ethanol for three times to remove unreacted oxidants, and then vacuum-drying at 60 ℃ to obtain Ppy.
Preparing BP nano sheets: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in a mixed solution of 300mL of deionized water and 300mL of absolute ethyl alcohol, ultrasonically stirring for 1h, adding 1g of BNNS, ultrasonically stirring for 1h to obtain a uniform mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture in an ice bath, stirring for 8h, filtering and collecting BP nanosheets, washing with 50% of ethanol successively for three times, removing unreacted oxidant, and then vacuum drying at 60 ℃ to obtain the BP nanosheets.
A preparation method of an anticorrosive coating containing modified boron nitride nanosheets comprises the following specific operations: adding 5ml of absolute ethyl alcohol into a beaker, then adding the prepared BNNS, BP nano-sheets and Ppy into the beaker, continuously stirring for 10min, then carrying out ultrasonic treatment for 30min, then adding 10g E44 epoxy resin, stirring for 2h until obtaining a uniform mixture, drying the mixture by a rotary evaporation method, and removing the absolute ethyl alcohol to obtain the boron nitride anticorrosive coating, wherein the boron nitride nano-sheets: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is 0.03: 0.03: 0.03: 0.9.
example 5
Preparation of BNNS: 500mgBN (size of 10um) was dispersed in 300ml of a mixed solvent of isopropyl alcohol and distilled water (volume ratio 1:1), subjected to ultrasonic treatment at 240W for 15 hours and left standing for 8 hours, and then the supernatant was filtered with a polytetrafluoroethylene membrane having a diameter of 0.22m, washed and dried to obtain BNNS.
Preparation of Ppy: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in 300mL of deionized water, ultrasonically stirring for 1h, and then stirring for 10min to obtain a uniform pyrrole mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture into the pyrrole mixture, stirring for 8h, filtering to collect Ppy, continuously washing with 50% ethanol for three times to remove unreacted oxidants, and then vacuum-drying at 60 ℃ to obtain Ppy.
Preparing BP nano sheets: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in a mixed solution of 300mL of deionized water and 300mL of absolute ethyl alcohol, ultrasonically stirring for 1h, adding 1g of BNNS, ultrasonically stirring for 1h to obtain a uniform mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture in an ice bath, stirring for 8h, filtering and collecting BP nanosheets, washing with 50% of ethanol successively for three times, removing unreacted oxidant, and then vacuum drying at 60 ℃ to obtain the BP nanosheets.
A preparation method of an anticorrosive coating containing modified boron nitride nanosheets comprises the following specific operations: adding 5ml of absolute ethyl alcohol into a beaker, then adding the prepared BNNS, BP nano-sheets and Ppy into the beaker, continuously stirring for 10min, then carrying out ultrasonic treatment for 30min, then adding 10g E44 epoxy resin, stirring for 2h until obtaining a uniform mixture, drying the mixture by a rotary evaporation method, and removing the absolute ethyl alcohol to obtain the boron nitride anticorrosive coating, wherein the boron nitride nano-sheets: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is 0.05: 0.03: 0.05: 0.9.
example 6
Preparation of BNNS: 500mgBN (size of 2um) was dispersed in 300ml of a mixed solvent of isopropyl alcohol and distilled water (volume ratio 1:1), subjected to ultrasonic treatment at 240W for 15 hours and left standing for 8 hours, and then the supernatant was filtered with a polytetrafluoroethylene membrane having a diameter of 0.22m, washed and dried to obtain BNNS.
Preparation of Ppy: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in 300mL of deionized water, ultrasonically stirring for 1h, and then stirring for 10min to obtain a uniform pyrrole mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture into the pyrrole mixture, stirring for 8h, filtering to collect Ppy, continuously washing with 50% ethanol for three times to remove unreacted oxidants, and then vacuum-drying at 60 ℃ to obtain Ppy.
Preparing BP nano sheets: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in a mixed solution of 300mL of deionized water and 300mL of absolute ethyl alcohol, ultrasonically stirring for 1h, adding 1g of BNNS, ultrasonically stirring for 1h to obtain a uniform mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture in an ice bath, stirring for 8h, filtering and collecting BP nanosheets, washing with 50% of ethanol successively for three times, removing unreacted oxidant, and then vacuum drying at 60 ℃ to obtain the BP nanosheets.
A preparation method of an anticorrosive coating containing modified boron nitride nanosheets comprises the following specific operations: adding 5ml of absolute ethyl alcohol into a beaker, then adding the prepared BNNS, BP nano-sheets and Ppy into the beaker, continuously stirring for 10min, then carrying out ultrasonic treatment for 30min, then adding 10g E44 epoxy resin, stirring for 2h until obtaining a uniform mixture, drying the mixture by a rotary evaporation method, and removing the absolute ethyl alcohol to obtain the boron nitride anticorrosive coating, wherein the boron nitride nano-sheets: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is 0.05: 0.03: 0.03: 1.
example 7
Preparation of BNNS: 500mgBN (size of 2um) was dispersed in 300ml of a mixed solvent of isopropyl alcohol and distilled water (volume ratio 1:1), subjected to ultrasonic treatment at 240W for 15 hours and left standing for 8 hours, and then the supernatant was filtered with a polytetrafluoroethylene membrane having a diameter of 0.22m, washed and dried to obtain BNNS.
Preparation of Ppy: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in 300mL of deionized water, ultrasonically stirring for 1h, and then stirring for 10min to obtain a uniform pyrrole mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture into the pyrrole mixture, stirring for 8h, filtering to collect Ppy, continuously washing with 50% ethanol for three times to remove unreacted oxidants, and then vacuum-drying at 60 ℃ to obtain Ppy.
Preparing BP nano sheets: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in a mixed solution of 300mL of deionized water and 300mL of absolute ethyl alcohol, ultrasonically stirring for 1h, adding 1g of BNNS, ultrasonically stirring for 1h to obtain a uniform mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture in an ice bath, stirring for 8h, filtering and collecting BP nanosheets, washing with 50% of ethanol successively for three times, removing unreacted oxidant, and then vacuum drying at 60 ℃ to obtain the BP nanosheets.
A preparation method of an anticorrosive coating containing modified boron nitride nanosheets comprises the following specific operations: adding 5ml of absolute ethyl alcohol into a beaker, then adding the prepared BNNS, BP nano-sheets and Ppy into the beaker, continuously stirring for 10min, then carrying out ultrasonic treatment for 30min, then adding 10g E51 epoxy resin, stirring for 2h until obtaining a uniform mixture, drying the mixture by a rotary evaporation method, and removing the absolute ethyl alcohol to obtain the boron nitride anticorrosive coating, wherein the boron nitride nano-sheets: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is 0.03: 0.03: 0.03: 0.9.
example 8
Preparation of BNNS: 500mgBN (size of 2um) was dispersed in 300ml of a mixed solvent of isopropyl alcohol and distilled water (volume ratio 1:1), subjected to ultrasonic treatment at 240W for 15 hours and left standing for 8 hours, and then the supernatant was filtered with a polytetrafluoroethylene membrane having a diameter of 0.22m, washed and dried to obtain BNNS.
Preparation of Ppy: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in 300mL of deionized water, ultrasonically stirring for 1h, and then stirring for 10min to obtain a uniform pyrrole mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture into the pyrrole mixture, stirring for 8h, filtering to collect Ppy, continuously washing with 50% ethanol for three times to remove unreacted oxidants, and then vacuum-drying at 60 ℃ to obtain Ppy.
Preparing BP nano sheets: dispersing 3mL of pyrrole and 5 wt% of octadecylamine in a mixed solution of 300mL of deionized water and 300mL of absolute ethyl alcohol, ultrasonically stirring for 1h, adding 1g of BNNS, ultrasonically stirring for 1h to obtain a uniform mixture, dispersing 987mg of ammonium persulfate in 100mL of deionized water, adding the mixture in an ice bath, stirring for 8h, filtering and collecting BP nanosheets, washing with 50% of ethanol successively for three times, removing unreacted oxidant, and then vacuum-drying at 60 ℃ to obtain the BP nanosheets.
A preparation method of an anticorrosive coating containing modified boron nitride nanosheets comprises the following specific operations: adding 5ml of absolute ethyl alcohol into a beaker, then adding the prepared BNNS, BP nano-sheets and Ppy into the beaker, continuously stirring for 10min, then carrying out ultrasonic treatment for 30min, then adding 10g E44 epoxy resin, stirring for 2h until obtaining a uniform mixture, drying the mixture by a rotary evaporation method, and removing the absolute ethyl alcohol to obtain the boron nitride anticorrosive coating, wherein the boron nitride nano-sheets: BP nanosheet: polypyrrole: the addition ratio of the epoxy resin is 0.03: 0.03: 0.03: 0.9.
example 9
Respectively adding 2ml of diethylenetriamine curing agent into 10g of the modified boron nitride-containing anticorrosive paint prepared in the examples 1 to 8, stirring for 10min, respectively and uniformly coating the boron nitride anticorrosive paint on a stainless steel plate by a spin coater at the speed of 800r/min for 1min, horizontally placing the coated steel, drying for 3h at room temperature, then drying in an oven at 60 ℃ for 3h, and forming a film.
Then, carrying out an anti-corrosion performance test: corrosion Rate V obtained by electrochemical testingcorr(mm/year), derived from the following equation:
Vcorr＝(Aicorr/nρF)×87600(mm/year)
wherein icorr is the corrosion current density of the Q235 electrode; q235 has a weight (A) of 55.85g/mol and a density (. rho.) of 7.85g/cm 3; the valence (n) of Fe is 2; f is the faraday constant (F96485C/mol 26.8 Ah).
As shown in FIG. 3, it can be seen that the corrosion rates of examples 1-8 are all less than 6.76X 10 per year in the corrosion thickness-7m, which shows that the anticorrosive coating containing the modified boron nitride nanosheet has good anticorrosive performance.
Claims (10)
1. A preparation method of a modified boron nitride nanosheet is characterized by comprising the following steps: dissolving pyrrole and a surfactant in an organic solvent, carrying out ultrasonic stirring, adding a boron nitride nanosheet after ultrasonic stirring, then carrying out ultrasonic stirring again to obtain a mixed solution, adding an oxidant into the mixed solution under an ice bath condition, then carrying out stirring reaction, then filtering, collecting a solid obtained by filtering, washing the collected solid by using the organic solvent to remove the unreacted oxidant, then carrying out vacuum drying, and finally obtaining the modified boron nitride nanosheet.
2. A preparation method of modified boron nitride nanosheets as claimed in claim 1, wherein the power of ultrasound in the ultrasonic agitation is 240W, and the time of the ultrasonic agitation is 0.5-1.5 h; preferably the temperature of the ice bath is 0 ℃.
3. A method for producing modified boron nitride nanoplates as described in claim 1, wherein the concentration of the organic solvent is 50%, and the organic solvent is ethanol, isopropanol or N-methylpyrrolidone.
4. A method of preparing modified boron nitride nanoplates as described in claim 1, wherein the surfactant is sodium dodecylbenzenesulfonate, octadecylamine or sodium lauroyl glutamate.
5. A method of preparing modified boron nitride nanoplates as in claim 1, wherein the oxidant is ammonium persulfate or ferric chloride.
6. A method for preparing modified boron nitride nanosheets as recited in claim 1, wherein the surfactant is added to the boron nitride nanosheets in a mass ratio of 1: 60, the molar ratio of the oxidant to the pyrrole addition is 1:1, the mass ratio of pyrrole to surfactant is 20: 1, the volume ratio of the pyrrole to the organic solvent is 1: 200.
7. the use of modified boron nitride nanoplates, prepared by the method of preparing modified boron nitride nanoplates as described in any of claims 1-6, in an anti-corrosive coating, wherein the anti-corrosive coating comprises the components: boron nitride nanosheets, polypyrrole, modified boron nitride nanosheets and epoxy resin.
8. The use of modified boron nitride nanoplates prepared by the method of preparing modified boron nitride nanoplates as described in claim 7 in an anticorrosive coating, wherein the epoxy resin is E44 or E51.
9. The application of the modified boron nitride nanosheet prepared by the method for preparing a modified boron nitride nanosheet according to claim 7 in an anticorrosive coating is characterized in that the method for preparing the anticorrosive coating specifically comprises the following operations: adding the modified boron nitride nanosheets, the boron nitride nanosheets and the polypyrrole into absolute ethyl alcohol, stirring uniformly, performing ultrasonic treatment, adding epoxy resin, stirring uniformly, and finally drying to remove the absolute ethyl alcohol to obtain the anticorrosive coating.
10. The use of a modified boron nitride nanoplate prepared by the method of preparing a modified boron nitride nanoplate according to claim 9 in an anticorrosive coating, wherein the boron nitride nanoplate: modified boron nitride nanosheets: polypyrrole: the addition ratio of the epoxy resin is (0.01-0.05): (0.01-0.05): (0.01-0.05): (0.8-1.2); preferably, the ratio of the epoxy resin to the absolute ethyl alcohol is 2: 1 (g/mL).
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