CN115197627B

CN115197627B - Preparation method and application of BPCT nano hybrid material and anticorrosive paint

Info

Publication number: CN115197627B
Application number: CN202210344799.0A
Authority: CN
Inventors: 肖国清; 邹瑞; 陈春林; 陈春燕; 钟菲; 羊正伟; 王明坦; 李媛媛; 李蕊利
Original assignee: Southwest Petroleum University
Current assignee: Southwest Petroleum University
Priority date: 2022-08-05
Filing date: 2022-08-05
Publication date: 2023-04-18
Anticipated expiration: 2042-08-05
Also published as: CN115197627A

Abstract

In order to improve the passive barrier property and the active self-healing property of the waterborne epoxy resin anticorrosive paint, the embodiment of the invention provides a preparation method and application of a BPCT nano hybrid material and anticorrosive paint, wherein the preparation method comprises the following steps: reacting h-BN @ PDA material with CD (BTA) @ TEOS material to obtain the BPCT nano hybrid material; uniformly mixing a base material and the BPCT nano hybrid material to obtain the anticorrosive paint; according to the embodiment of the invention, the anticorrosive coating obtained by uniformly mixing the base material and the BPCT nano hybrid material can realize high barrier performance and lasting self-healing performance in a corrosion process, so that the anticorrosive performance is greatly improved, and the passive barrier property and the active self-healing property of the water-based epoxy resin anticorrosive coating are improved.

Description

Preparation method and application of BPCT (boron nitride-titanium-cobalt-titanium) nano hybrid material and anticorrosive paint

Technical Field

The invention relates to a preparation method and application of a BPCT nano hybrid material and an anticorrosive coating.

Background

In petrochemical industry, agriculture, paper making industry and other industries, the phenomena of equipment damage and harmful substance leakage caused by corrosion of metal materials sometimes occur, the surrounding environment is seriously polluted, and the health of people is threatened. The use of polymeric coatings to protect metals is one of the most common corrosion protection measures, providing a barrier between the metal and the environment.

Common polymer coatings are largely divided into solvent-borne, aqueous and powder-based coatings. Among them, the water-based paint has a large market share due to its environmental friendliness and low emission of volatile organic compounds (volatile organic compounds). However, during the formation and use of waterborne coatings, micro-porosity and micro-cracks can occur, which can lead to increased corrosion, decreased service life, and thus safety hazards.

It has been reported that passive barrier properties of coatings can be improved by adding a two-dimensional layered material to an aqueous coating matrix to improve the passive barrier effect of the coating. In practical applications, however, cracks in the coating inevitably occur due to the influence of the external environment, resulting in a gradual loss of the corrosion resistance of the coating having only passive barrier properties. To overcome these limitations, the concept of self-healing was introduced into the material and intelligent anti-corrosive coatings were designed and manufactured. Hexagonal boron nitride (h-BN) is a two-dimensional layered nano material which has a layered structure, and B and N atoms are combined together in sp2 non-uniformity, so that the hexagonal boron nitride (h-BN) has good dimensional stability and ideal corrosion resistance and oxidation resistance. Therefore, the passive barrier property of the composite coating can be improved by improving the dispersion degree of the h-BN in the resin system.

Dopamine (DA) is a mussel-inspired biogel that readily adheres to any surface by autopolymerization to form a Polydopamine (PDA) layer. Recent studies have shown that the outer layer of PDA can be used to enhance the dispersion of two-dimensional layered materials in aqueous coatings. In addition, another report indicates that catechol in a compromised PDA polymer network can be coordinated to Fe via coordination bonds ³⁺ Reconnect, thereby creating a self-healing feature. On the basis, the PDA coating can enhance the passive barrier effect and certain active self-healing effect of the h-BN water-based composite coating. The capsule-based self-healing material has the advantages of low cost, simple preparation and convenient application, and is a suitable additive material for improving the active self-healing performance of the composite coating. The Cyclodextrin (CD) material has a hydrophilic outer hydrophobic inner cavity, so that the supramolecular microcapsule has good sealing property and permeability resistance. The released Benzotriazole (BTA) inhibitor forms an adsorption layer on the surface of the metal, and is extremely largeAnd the penetration of corrosive substances around the scratch and the corrosion expansion are hindered.

At present, no relevant report for improving the passive barrier property and the active self-healing property of the waterborne epoxy resin anticorrosive paint exists.

Disclosure of Invention

The embodiment of the invention provides a preparation method and application of a BPCT nano hybrid material and an anticorrosive paint, which are used for improving the passive barrier property and the active self-healing property of a waterborne epoxy resin anticorrosive paint.

The embodiment of the invention is realized by the following technical scheme:

in a first aspect, an embodiment of the present invention provides a method for preparing a BPCT nano hybrid material, including:

the BPCT nano hybrid material is obtained through the reaction of h-BN @ PDA material and CD (BTA) @ TEOS material;

wherein, the mass ratio of the h-BN @ PDA material to the CD (BTA) @ TEOS material is 1-1.5.

Further, the preparation method of the h-BN @ PDA material comprises the following steps:

adding h-BN and buffer solution into water, uniformly mixing, adjusting the pH to be alkaline, adding dopamine hydrochloride, uniformly mixing, reacting until the pH is neutral to obtain the h-BN @ PDA material, wherein the mass ratio of the h-BN, the buffer solution and the dopamine hydrochloride is 4-6:3-5:5-7.

Further, the preparation method of the CD (BTA) @ TEOS material comprises the following steps:

ultrasonically mixing BTA and an ethanol solution uniformly, adding beta-CD, and continuously and ultrasonically mixing uniformly to obtain a mixed solution, wherein the mass ratio of the BTA to the beta-CD is (6-8);

treating the uniformly mixed solution in a rotary evaporator to enable BTA molecules to be uploaded into a cavity of beta-CD to obtain a suspension;

adding pure water and an ammonium solution into the suspension, uniformly mixing, and then dropwise adding tetraethoxysilane, and uniformly mixing to obtain tetraethoxysilane uniform mixing liquid, wherein the mass ratio of tetraethoxysilane to pure water is 1-30;

and (3) uniformly mixing the uniform ethyl orthosilicate solution and a coupling agent, and reacting to obtain the CD (BTA) @ TEOS nano hybrid.

Further, the coupling agent is KH-560; uniformly mixing the uniform solution of tetraethoxysilane and a coupling agent, and reacting to obtain a CD (BTA) @ TEOS nano hybrid; the method comprises the following steps:

stirring the mixed solution of tetraethoxysilane for 10-14h, adding a coupling agent, stirring and mixing uniformly, washing after reaction, and drying to obtain the CD (BTA) @ TEOS nano hybrid.

Further, distilling the uniformly mixed solution in a rotary evaporator to transfer BTA molecules into a cavity of the beta-CD to obtain a suspension; the method comprises the following steps:

and (3) carrying out vacuum treatment on the uniformly mixed solution in a rotary evaporator for 3h, and returning to the atmospheric pressure every hour to enable BTA molecules to be uploaded into a cavity of the beta-CD to obtain a suspension.

Further, adding pure water and an ammonium solution into the suspension, uniformly mixing, and then dropwise adding tetraethoxysilane, and uniformly mixing to obtain a tetraethoxysilane uniform mixing solution; the method comprises the following steps:

adding pure water and an ammonium solution into the suspension, uniformly mixing, then dropwise adding ethyl orthosilicate, and stirring for 1h every time 1ml of ethyl orthosilicate is added until all the ethyl orthosilicate is completely added and stirred, so as to obtain a mixed solution of the ethyl orthosilicate, wherein the ratio of BTA to the ethyl orthosilicate is 6-8g.

In a second aspect, an embodiment of the present invention provides a method for preparing an anticorrosive paint, including:

uniformly mixing a base material and the BPCT nano hybrid material to obtain the anticorrosive paint;

wherein the base material is obtained by uniformly mixing epoxy resin and a curing agent; wherein, the BPCT nano hybrid material accounts for 1.5-3.5% of the total weight of the anticorrosive paint.

Further, the base material is obtained by uniformly mixing epoxy resin and a curing agent, and comprises:

stirring the epoxy resin and the curing agent in a mass ratio of 1.5-3:1 for 1.5-2.5h at a rotating speed of 250-350r/min, and then stirring for 0.5-1.5h at a rotating speed of 50-70r/min to obtain the uniformly mixed base material.

mixing the components in a mass ratio of 1.5-3:1:0.02-0.06 of epoxy resin, curing agent and defoaming agent, stirring for 1.5-2.5h at the rotating speed of 250-350r/min, and then stirring for 0.5-1.5h at the rotating speed of 50-70r/min to obtain the uniformly mixed base material.

In a third aspect, the embodiment of the invention provides a use of the BPCT nano hybrid material or the anticorrosive paint for steel structure anticorrosive protection.

Compared with the prior art, the embodiment of the invention has the following advantages and beneficial effects:

according to the preparation method and the application of the BPCT nano hybrid material and the anticorrosive paint, the anticorrosive paint obtained by uniformly mixing the base material and the BPCT nano hybrid material can realize high barrier property and lasting self-healing property in the corrosion process, so that the anticorrosive property is greatly improved, and the passive barrier property and the active self-healing property of the water-based epoxy resin anticorrosive paint are improved.

Drawings

In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and that for those skilled in the art, other related drawings can be obtained from these drawings without inventive effort.

FIG. 1 shows FITR plots of h-BN, h-BN @ PDA, CD (BTA) @ TEOS, and BPCT.

FIG. 2 is a transmission electron micrograph of h-BN, h-BN @ PDA, BPCT, wherein (a) - (b) are h-BN, (c) - (d) are h-BN @ PDA, and (e) - (f) are BPCT.

FIG. 3 is a scanning electron microscope image of the cross section of EP, h-BN/EP, h-BN @ PDA/EP, CD (BTA) @ TEOS/EP, BPCT/EP coatings, wherein (a) - (b) are EP, (c) - (d) are h-BN/EP, (e) - (f) are h-BN @ PDA/EP, (g) - (h) are CD (BTA) @ TEOS/EP, and (i) - (j) are BPCT/EP.

FIG. 4 is a scanning electron microscope image and an EDS test chart of the corrosion morphology of the surface of the coating after the composite coating is soaked in 3.5wt.% sodium chloride solution for 40 days, wherein (a) - (b) are EP, (c) - (d) are h-BN/EP, (e) - (f) are h-BN @ PDA/EP, (g) - (h) are CD (BTA) @ TEOS/EP, and (i) - (j) are BPCT/EP.

Fig. 5 is an EIS spectrum of the composite coating after various soaking times in a 3.5wt.% sodium chloride solution: (a-b) EP, (c-d) h-BN/EP, (e-f) h-BN @ PDA/EP, (g-h) CD (BTA) @ TEOS/EP, and (i-j) BPCT/EP.

FIG. 6 is an image of pure EP (a, b, c), BN/EP (d, e, f), BN @ PDA/EP (g, h, i), CD (BTA) @ TEOS/EP (j, k, l) and BPCT/EP (m, n, o) after 100, 200 and 300h exposure in neutral salt spray experiments.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: it is not necessary to employ these specific details to practice the present invention. In other instances, well-known structures, circuits, materials, or methods have not been described in detail so as not to obscure the present invention.

Throughout the specification, reference to "one embodiment," "an embodiment," "one example," or "an example" means: the particular features, structures, or characteristics described in connection with the embodiment or example are included in at least one embodiment of the invention. Thus, the appearances of the phrase "one embodiment," "an embodiment," "one example" or "an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combination and/or sub-combination in one or more embodiments or examples. Further, those of ordinary skill in the art will appreciate that the illustrations provided herein are for illustrative purposes and are not necessarily drawn to scale. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the description of the present invention, the terms "front", "rear", "left", "right", "upper", "lower", "vertical", "horizontal", "upper", "lower", "inner", "outer", etc. indicate orientations or positional relationships based on those shown in the drawings, merely for convenience of description and simplification of description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and therefore, should not be construed as limiting the scope of the invention.

Examples

In order to improve the passive barrier property and the active self-healing property of the water-based epoxy resin anticorrosive paint. In a first aspect, an embodiment of the present invention provides a method for preparing a BPCT nano hybrid material, including:

Optionally, the buffer solution is Tris buffer.

ultrasonically mixing BTA and an ethanol solution (with certain concentration), adding beta-CD, continuously ultrasonically mixing uniformly to obtain a mixed solution, wherein the mass ratio of the BTA to the beta-CD is 6-8;

optionally, the mass ratio of BTA to beta-CD is 6-8:1.

Further, adding pure water and an ammonium solution into the suspension, uniformly mixing, and then dropwise adding tetraethoxysilane, and uniformly mixing to obtain tetraethoxysilane uniform mixing liquid; the method comprises the following steps:

adding pure water and an ammonium solution into the suspension, uniformly mixing, then dropwise adding ethyl orthosilicate, and stirring 1ml of ethyl orthosilicate for 1h until all the ethyl orthosilicate is completely added and stirred to obtain a mixed solution of ethyl orthosilicate, wherein the ratio of BTA to ethyl orthosilicate is 6-8g.

Therefore, the anticorrosive coating obtained by uniformly mixing the base material and the BPCT nano hybrid material can realize high barrier performance and lasting self-healing performance in the corrosion process, so that the anticorrosive performance is greatly improved, and the passive barrier property and the active self-healing property of the water-based epoxy resin anticorrosive coating are improved.

Optionally, the mass ratio of epoxy resin to curing agent is 2:1.

Example 1

The preparation method of the BPCT nano hybrid material comprises the following steps:

the mass ratio of the components is 1: the h-BN @ PDA material of 1 reacts with the CD (BTA) @ TEOS material to obtain the BPCT nano hybrid material.

The preparation method of the h-BN @ PDA material comprises the following steps:

s1, adding h-BN and a Tris buffer solution into water, uniformly mixing, adjusting the pH value to 8.5, adding dopamine hydrochloride, uniformly mixing, and reacting until the pH value is neutral to obtain an h-BN @ PDA material, wherein the mass ratio of h-BN to the buffer solution to the dopamine hydrochloride is 4.

The preparation method of the CD (BTA) @ TEOS material comprises the following steps:

s1, adding beta-CD (beta-CD) to perform ultrasonic mixing after BTA and an ethanol solution are subjected to ultrasonic mixing to obtain a mixed solution, wherein the mass ratio of BTA to beta-CD is 6.

S2, carrying out vacuum treatment on the uniformly mixed solution in a rotary evaporator for 3h, and returning to the atmospheric pressure every hour to enable BTA molecules to be uploaded into a cavity of the beta-CD to obtain a suspension.

S3, adding pure water and an ammonium solution into the suspension, uniformly mixing, and then dropwise adding tetraethoxysilane, wherein the mass ratio of tetraethoxysilane to pure water is 1.

S4, stirring the mixed solution of tetraethoxysilane for 10 hours, adding KH-560, stirring and mixing uniformly, reacting, washing and drying to obtain the CD (BTA) @ TEOS nano hybrid.

The preparation method of the anticorrosive paint comprises the following steps:

stirring the epoxy resin and the curing agent in a mass ratio of 1.5.

Uniformly mixing a base material and the BPCT nano hybrid material to obtain the anticorrosive paint; wherein the base material is obtained by uniformly mixing epoxy resin and a curing agent; wherein, the BPCT nano hybrid material accounts for 1.5 percent of the total weight of the anticorrosive paint.

Example 2

the BPCT nano hybrid material is obtained by reacting h-BN @ PDA material and CD (BTA) @ TEOS material with the mass ratio of 1.5.

s1, adding h-BN and a Tris buffer solution into water, uniformly mixing, adjusting the pH value to 8.5, adding dopamine hydrochloride, uniformly mixing, and reacting until the pH value is neutral to obtain an h-BN @ PDA material, wherein the mass ratio of h-BN to the buffer solution to the dopamine hydrochloride is 6.

s1, adding beta-CD (beta-CD) to perform ultrasonic mixing after BTA and an ethanol solution are subjected to ultrasonic mixing to obtain a mixed solution, wherein the mass ratio of BTA to beta-CD is 8.

S4, stirring the mixed solution of tetraethoxysilane for 14 hours, adding KH-560, stirring and mixing uniformly, reacting, washing and drying to obtain the CD (BTA) @ TEOS nano hybrid.

mixing 3:1:0.06 of epoxy resin, a curing agent and a defoaming agent are mixed uniformly, stirred for 2 hours at the rotating speed of 350r/min and then stirred for 1.5 hours at the rotating speed of 70r/min to obtain a uniformly mixed base material.

Uniformly mixing a base material and the BPCT nano hybrid material to obtain the anticorrosive paint; wherein the base material is obtained by uniformly mixing epoxy resin and a curing agent; wherein, the BPCT nano hybrid material accounts for 3.5 percent of the total weight of the anticorrosive paint.

Example 3

the BPCT nano hybrid material is obtained by reacting h-BN @ PDA material and CD (BTA) @ TEOS material with the mass ratio of 1.2.

s1, adding h-BN and a Tris buffer solution into water, uniformly mixing, adjusting the pH value to 8.5, adding dopamine hydrochloride, uniformly mixing, and reacting until the pH value is neutral to obtain an h-BN @ PDA material, wherein the mass ratio of h-BN to the buffer solution to the dopamine hydrochloride is 5.

s1, adding beta-CD (beta-CD) to perform ultrasonic mixing after BTA and an ethanol solution are subjected to ultrasonic mixing to obtain a mixed solution, wherein the mass ratio of BTA to beta-CD is 6.8.

S2, carrying out vacuum treatment on the uniformly mixed solution in a rotary evaporator for 3 hours, and returning to the atmospheric pressure every hour to enable BTA molecules to be uploaded into a cavity of the beta-CD to obtain a suspension.

S4, stirring the mixed solution of tetraethoxysilane for 12 hours, adding KH-560, stirring and mixing uniformly, reacting, washing and drying to obtain the CD (BTA) @ TEOS nano hybrid.

mixing 2:1:0.04 of epoxy resin, curing agent and defoaming agent are mixed evenly, stirred for 1.5 to 2.5 hours at the rotating speed of 300r/min and then stirred for 2 hours at the rotating speed of 60r/min to obtain the evenly mixed base material.

Uniformly mixing a base material and the BPCT nano hybrid material to obtain the anticorrosive paint; wherein the base material is obtained by uniformly mixing epoxy resin and a curing agent; wherein, the BPCT nanometer hybrid material accounts for 3 percent of the total weight of the anticorrosive paint.

Example 4

The preparation method of the anticorrosive material comprises the following steps:

s1: weighing 48.64g of epoxy resin, 24.32g of curing agent and 1g of defoaming agent, mechanically stirring for 2 hours at 300r/min, and then stirring for 1 hour at 60r/min to obtain a uniformly mixed base material; wherein the short-chain aliphatic amine curing agent is Ethylenediamine (EDA), diethylenetriamine (DTA) or Triethylene Tetramine (TTA);

s2: preparation of CD (BTA) @ TEOS nano hybrid material: 6.4g of BTA were added to 80ml of ethanol solution and the suspension was sonicated for 20min, then 1g of beta-CD and sonicated for 30min. The mixture was then transferred to a rotary evaporator and evacuated by vacuum pump for 3 hours, returning to atmospheric pressure every 1 hour, allowing BTA molecules to be uploaded into the β -CD cavity. To remove excess BTA adsorbed on the surface of the vessel, the suspension was washed with ethanol. The suspension was transferred to a conical flask. To the suspension was added 20ml of deionized water and 1ml of ammonium solution, followed by dropwise addition of 1ml of TEOS. After the mixture was stirred for 1 hour, the dropping of TEOS was repeated again. Then, stirring the mixture with a magnetic stirrer at a uniform speed for 12 hours, adding 1ml KH560 to the mixture, stirring at room temperature for 15 hours to obtain a white emulsion, washing with an ethanol solution, and drying at 60 ℃ to obtain a CD (BTA) @ TEOS nano hybrid;

s3: preparing a two-dimensional BPCT nano hybrid material: 0.4gh-BN and 0.32g Tris buffer were added to a flask containing 200ml deionized water and sonicated with a probe for 30min. Then, dilute sodium hydroxide solution was gradually added to the above mixture until pH = 8.5. Subsequently, 0.5g dopamine hydrochloride was added to the flask. The mixture was stirred with a magnetic stirrer at a uniform speed for 16 hours. And (3) at the end of the reaction, washing the solution with deionized water until the pH value of the solution becomes neutral, and separating to obtain the h-BN @ PDA nanosheet. Finally, the h-BN @ PDA nano-sheet is put in a vacuum oven at 80 ℃ for drying for 24 hours. 0.5gh-BN @ PDA and 0.5g CD (BTA) @ TEOS nano-hybrid were added to a three necked flask containing 100 ml absolute ethanol and stirred in an oil bath at 70 ℃ for 10 hours. After the reaction, the products are repeatedly washed by absolute ethyl alcohol until the pH value becomes neutral, and then the products are dried for 24 hours to obtain a BPCT nano material;

s4: the preparation of the nano BPCT water-based epoxy resin self-healing anticorrosive paint with high barrier performance comprises the following steps: the steel plate was pretreated with 600, 800, 1200 grade sandpaper, respectively, and then degreased with acetone. Weighing the base material and the BPCT nano material, mixing, mechanically stirring and dispersing for 5 hours to form an even dispersion system, then spraying the even dispersion system on the surface of a rectangular steel sheet, and curing at normal temperature for 7 days after finishing brushing to obtain the nano BPCT self-healing anticorrosive coating with high barrier property.

Respectively mixing h-BN, h-BN @ PDA, CD (BTA) @ TEOS and BPCT with epoxy resin, mechanically stirring and dispersing for 3h to respectively prepare h-BN, h-BN @ PDA, CD (BTA) @ TEOS and BPCT coatings with the content of 1.5wt% of h-BN/EP, h-BN @ PDA/EP, CD (BTA) @ TEOS/EP and BPCT/EP, respectively pretreating steel plates by 600-grade, 800-grade and 1200-grade abrasive papers, degreasing by acetone, spraying the coatings within 1 hour after the sand blasting treatment of the matrix steel sheet is finished, solidifying the steel sheet with the coatings for 7 days at room temperature after the spraying is finished to obtain samples, and taking pure epoxy resin (EP) as a contrast.

(1) The functional groups of h-BN, h-BN @ PDA, CD (BTA) @ TEOS and BPCT were characterized by means of an infrared spectrometer (FITR). The results are shown in FIG. 1. As can be seen from figure 1, after modification, in the FITR spectrogram of the nano BPCT self-healing anticorrosive coating, characteristic diffraction peaks of h-BN, PDA, CD and TEOS can be simultaneously detected, which indicates that the hybrid material is successfully synthesized.

(2) The microstructure of the h-BN, h-BN @ PDA and BPCT hybrid material was observed using a JEOLJEM-2100 high resolution transmission electron microscope (HR-TEM), and the results are shown in FIG. 2. As can be seen from FIGS. 2A-B, h-BN exhibits a typical lamellar structure, and an organic layer is uniformly loaded on the h-BN surface after modification of poly-dopamine (FIGS. 2C-D); after binding with CD (BTA) @ TEOS (FIG. 2E-F), CD (BTA) @ TEOS nanocapsules were uniformly and tightly adhered on h-BN @ PDA nanosheets. The successful synthesis of the BPCT hybrid material is demonstrated.

(3) The cross-sectional morphology of each coating was observed using a JSM-7500F scanning electron microscope, and the results are shown in FIG. 3. As can be seen from FIG. 3, the unmodified h-BN (FIGS. 3C-D) showed significant agglomeration in the resin system with voids and cracks; 3E-F and 3G-H, it can be seen that the modified H-BN @ PDA and CD (BTA) @ TEOS have reduced porosity and cracks when added to the coating; it can be seen from FIGS. 3I-J that BPCT disperses well in the resin system and no cross-sectional gaps and cracks are observed.

(4) And observing the corrosion morphology of each coating by adopting a JSM-7500F scanning electron microscope and analyzing and detecting element components in a corrosion area by adopting an EDS energy spectrum to detect the corrosion resistance of the anticorrosive coating. The results are shown in FIG. 4. As can be seen from fig. 4, the anticorrosive coating containing BPCT has the lowest corrosion degree, indicating that the anticorrosive performance is the best, which indicates that the synthesized hybrid material BPCT can effectively improve the passive barrier property of the anticorrosive coating, thereby improving the anticorrosive performance.

(5) The self-healing and barrier properties of the composite coatings in a 3.5wt.% sodium chloride solution were characterized using electrochemical testing performed at an electrochemical workstation (cortest cs350, corrTest instruments ltd, wuhan) and the results are shown in fig. 5. According to Nyquist and Bode diagrams under different soaking times, the addition of the BPCT hybrid material effectively increases the impedance and improves the corrosion resistance, which shows that the BPCT hybrid filler can effectively inhibit and improve the passive barrier characteristic of the coating; as can be seen from the change of impedance under different soaking times, the addition of the BPCT hybrid material effectively reduces the rate of impedance drop and provides the self-healing characteristic, indicating that the BPCT hybrid material has both good passive barrier performance and self-healing performance.

(6) The long-term corrosion resistance of the composite material coating is further evaluated by adopting a neutral salt spray test. Referring to astm b117, a scratch 2mm wide by 4cm long was scratched on the surface of the composite coating and placed in a salt spray chamber (YWX-750). A 5wt% sodium chloride solution was continuously sprayed on the surface of the coated sample at 40 ℃. The surface condition of the coating after different experimental times was recorded and compared and the results are shown in fig. 6. As can be seen from FIG. 6, the scratches of the EP, h-BN/EP, h-BN @ PDA/EP and CD (BTA) @ TEOS/EP coatings all corroded to different degrees after 100 hours of the salt spray test, the BPCT/EP sample showed slight scratches after 200 hours when the BPCT hybrid material was added, and the best corrosion resistance was achieved at each test stage. The modified two-dimensional BPCT nano hybrid material can effectively enhance the passive barrier performance and the self-healing performance of the coating, thereby improving the anti-corrosion performance of the anti-corrosion coating.

Therefore, the anticorrosive material of the embodiment of the invention overcomes the dangerous characteristics of the existing waterborne epoxy resin, such as micropore and microcrack, corrosion enhancement, shortened service life, safety hazard and the like, and the obtained nano anticorrosive coating has both passive barrier property and active self-healing property, so that the anticorrosive property is greatly improved. The invention is mainly used for the anticorrosion protection of the steel structure, can realize high barrier performance and lasting self-healing performance in the corrosion process, and greatly improves the anticorrosion performance. The preparation process of the coating is simple and feasible, the cost is low, the coating is environment-friendly, and the coating is suitable for industrial production.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. A preparation method of a BPCT nano hybrid material is characterized by comprising the following steps:

reacting h-BN @ PDA material with CD (BTA) @ TEOS material to obtain the BPCT nano hybrid material;

wherein, the mass ratio of the h-BN @ PDA material to the CD (BTA) @ TEOS material is (1-1.5): 1;

adding h-BN and a buffer solution into water, uniformly mixing, adjusting the pH to be alkaline, adding dopamine hydrochloride, uniformly mixing, reacting until the pH is neutral to obtain an h-BN @ PDA material, wherein the mass ratio of the h-BN, the buffer solution and the dopamine hydrochloride is (4-6) to (3-5) to (5-7);

ultrasonically mixing BTA and an ethanol solution, adding beta-CD, continuously and ultrasonically mixing to obtain a mixed solution, wherein the mass ratio of the BTA to the beta-CD is (6-8) to (0.8-1.2);

adding pure water and an ammonium solution into the suspension, uniformly mixing, and then dropwise adding tetraethoxysilane, and uniformly mixing to obtain tetraethoxysilane uniform mixing liquid, wherein the mass ratio of tetraethoxysilane to pure water is 1 (15-30);

uniformly mixing the uniform ethyl orthosilicate solution and a coupling agent, and reacting to obtain a CD (BTA) @ TEOS material; the coupling agent is KH-560.

2. The preparation method of the BPCT nano hybrid material as claimed in claim 1, wherein the uniformly mixed solution of tetraethoxysilane and the coupling agent are uniformly mixed and reacted to obtain a CD (BTA) @ TEOS nano material; the method comprises the following steps:

stirring the mixed solution of tetraethoxysilane for 10-14h, adding a coupling agent, stirring and mixing uniformly, reacting, washing and drying to obtain the CD (BTA) @ TEOS nano material.

3. The method for preparing the BPCT nano hybrid material as claimed in claim 1, wherein the blending solution is distilled in a rotary evaporator so that BTA molecules are transferred to a cavity of beta-CD to obtain a suspension; the method comprises the following steps:

4. The method for preparing BPCT nano hybrid material as claimed in claim 1, wherein, pure water and ammonium solution are added into the suspension to be mixed evenly, and then tetraethoxysilane is added drop by drop to be mixed evenly to obtain tetraethoxysilane mixed liquor; the method comprises the following steps:

adding pure water and an ammonium solution into the suspension, uniformly mixing, then dropwise adding ethyl orthosilicate for 1 hour, and stirring for 1ml of ethyl orthosilicate until all the ethyl orthosilicate is completely added and stirred to obtain a mixed solution of ethyl orthosilicate, wherein the ratio of BTA to ethyl orthosilicate is (6-8 g) to (1-2 ml).

5. A preparation method of an anticorrosive paint is characterized by comprising the following steps:

uniformly mixing a base material and the BPCT nano hybrid material of any one of claims 1 to 4 to obtain the anticorrosive paint;

6. The preparation method of the anticorrosive paint according to claim 5, wherein the base material is obtained by uniformly mixing the epoxy resin and the curing agent, and comprises the following steps:

stirring the epoxy resin and the curing agent in a mass ratio of (1.5-3) to 1 at a rotating speed of 250-350r/min for 1.5-2.5h, and then stirring at a rotating speed of 50-70r/min for 0.5-1.5h to obtain a uniformly mixed base material.

7. The preparation method of the anticorrosive paint according to claim 5, wherein the base material is obtained by uniformly mixing the epoxy resin and the curing agent, and comprises the following steps:

mixing the raw materials in a mass ratio of (1.5-3) to 1: (0.02-0.06), uniformly mixing the epoxy resin, the curing agent and the defoaming agent, stirring at the rotating speed of 250-350r/min for 1.5-2.5h, and then stirring at the rotating speed of 50-70r/min for 0.5-1.5h to obtain the uniformly mixed base material.

8. Use of the BPCT nano-hybrid material according to any of claims 1-4 or the anticorrosive coating obtained by the method for preparing the anticorrosive coating according to any of claims 5-7 for the anticorrosion protection of steel structures.