Hydrophobic hexagonal boron nitride chlorinated rubber composite coating and preparation method thereof

Abstract

The present application relates to a kind of hydrophobic hexagonal boron nitride chlorinated rubber composite coating and its preparation method.First, ammonium borate and urea are used to carry out temperature-programmed hydrothermal synthesis, after atmosphere protection and acid washing process, obtain hexagonal boron nitride precursor;Second, the cell of hexagonal boron nitride precursor is crushed and ultrasonic stripping is carried out, and by controlling the stripping time, obtain the powder of no surface defect structure hexagonal boron nitride two-dimensional nanometer material and the powder of rich surface defect structure hexagonal boron nitride two-dimensional nanometer material;Finally, the prepared hexagonal boron nitride two-dimensional nanometer material powder is used as filler, and chlorinated rubber resin, hydroxymethyl acrylamide, ethyl acrylate, dispersing agent, plasticizer, thickener, stabilizer, defoaming agent, solvent are compounded according to preset ratio, respectively, to prepare composite coating component one and component two, component one and component two are mixed evenly, film forming treatment is carried out, and then normal temperature curing is carried out, to obtain hydrophobic hexagonal boron nitride chlorinated rubber composite coating.The coating of the embodiment has good hydrophobic property.

Description

Technical Field

[0001] This invention relates to the field of chemical coatings technology, and in particular to a hydrophobic hexagonal boron nitride chlorinated rubber composite coating and its preparation method. Background Technology

[0002] Chlorinated rubber is a chlorinated polymer obtained by chlorinating natural or synthetic rubber. It possesses excellent film-forming properties, adhesion, and corrosion resistance, and is widely used in the manufacture of marine paints, chemical anti-corrosion paints, and architectural coatings. It is one of the promising chlorinated fine chemical products. Traditional chlorinated rubber resin production processes use CCl4 solvent, which is an ozone-depleting substance that pollutes the atmosphere and is subject to environmental restrictions in various countries. To avoid pollution, a green production method for anhydrous chlorinated rubber without carbon tetrachloride needs to be developed. Currently, there is a method using chloroform as a solvent to produce chlorinated rubber through liquid-phase chlorination. This method eliminates the need for CCl4 solvent, making it reliable and environmentally friendly. However, in practical applications, the hydrophobicity of the chlorinated rubber coating prepared by this method still needs improvement.

[0003] Two-dimensional nanomaterials possess excellent surface energy modulation properties, and their application as modified hydrophobic materials in the preparation of hydrophobic coatings holds great potential. Hexagonal boron nitride (BN) two-dimensional nanomaterials are layered materials composed of covalently bonded boron (B) and nitrogen (N) stacked through weak van der Waals forces, exhibiting high hydrophobicity, oxidation resistance, and high chemical stability. Currently, some methods for preparing hydrophobic BN nanosheets achieve a one-pot process of exfoliation and hydrophobic modification, simultaneously achieving high yields of hydrophobic BN nanosheets. However, the dispersibility of hydrophobic BN nanosheets in polymers is poor, hindering their use as fillers in coatings. Meanwhile, some methods for large-scale preparation of hydrophobic BN nanosheets offer advantages such as simple processes, low raw material costs, high yields, and ease of mass production. While these methods produce uniformly dispersed BN nanosheets in polymers, their overall surface energy modulation after composite with coatings is insufficient, failing to fully realize the potential of hydrophobic BN nanosheets.

[0004] Therefore, it is urgently necessary to develop a hydrophobic hexagonal boron nitride chlorinated rubber composite coating that can fully utilize the surface energy regulation capability of hexagonal boron nitride and comprehensively improve the hydrophobic properties of chlorinated rubber coating. Summary of the Invention

[0005] (a) Technical problems to be solved

[0006] The technical problem to be solved by this invention is to address the issue that existing hexagonal boron nitride chlorinated rubber composite coatings do not fully utilize the surface energy regulation capability of hexagonal boron nitride, resulting in poor hydrophobic properties of the coating.

[0007] (II) Technical Solution

[0008] To address the aforementioned technical problems, this invention provides a hydrophobic hexagonal boron nitride chlorinated rubber composite coating. The raw materials for preparation include: chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials, hydroxymethylacrylamide, ethyl acrylate, dispersant, plasticizer, thickener, stabilizer, defoamer, and solvent. The mass ratio of the chlorinated rubber resin, the hexagonal boron nitride two-dimensional nanomaterials, the hydroxymethylacrylamide, the ethyl acrylate, the dispersant, the plasticizer, the thickener, the stabilizer, the defoamer, and the solvent is (80–100):(6–24):(20–40):(20–40):(20–60):(10–60):(20–50):(10–30):(10–50):(100–500).

[0009] In one embodiment, the mass ratio of the chlorinated rubber resin, the hexagonal boron nitride two-dimensional nanomaterial, the hydroxymethyl acrylamide, the ethyl acrylate, the dispersant, the plasticizer, the thickener, the stabilizer, the defoamer, and the solvent is 100:12:30:30:50:40:30:20:20:200, or 100:6:30:30:50:40:30:20:20:200, or 100:12:20:20:30:30:20:10:10:100, or 100:18:40:40:60:50:40:30:30:300, or 100:24:30:30:50:40:30:20:20:200.

[0010] In one embodiment, the chlorinated rubber resin is a chlorinated rubber resin with a chlorine mass fraction between 66% and 68%, and the average relative molecular weight of the chlorinated rubber resin is between 10,000 and 20,000; the dispersant is any one of polyethylene glycol 200 or polyethylene glycol 400 or a mixture thereof; the plasticizer is any one of dioctyl phthalate or dibutyl phthalate or a mixture thereof; the thickener is a mixture of methyl hydroxypropyl cellulose and bentonite; the stabilizer is any one of dibutyltin dilaurate or methyltin mercaptan or a mixture thereof; the defoamer is any one of polyether defoamers or silicone defoamers; and the solvent is any one of acetone, xylene, and ethyl acetate or a mixture of two or more of them.

[0011] In one embodiment, the chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass, and the average relative molecular weight of the chlorinated rubber resin is 12,000; the dispersant is composed of polyethylene glycol 200 and polyethylene glycol 400 in a mass ratio of 1:2; the plasticizer is composed of dioctyl phthalate and dibutyl phthalate in a mass ratio of 1:1; the thickener is composed of methyl hydroxypropyl cellulose and bentonite in a mass ratio of 1:1; the stabilizer is composed of dibutyltin dilaurate and methyltin mercaptan in a mass ratio of 1:2; the defoamer is a polyether defoamer; and the solvent is a mixture of acetone, xylene, and ethyl acetate in a mass ratio of 3:2:3.

[0012] In another aspect, the present invention provides a method for preparing the hydrophobic hexagonal boron nitride chlorinated rubber composite coating described above. The method involves using hexagonal boron nitride two-dimensional nanomaterial powder as a filler, and combining it with chlorinated rubber resin, hydroxymethyl acrylamide, ethyl acrylate, dispersant, plasticizer, thickener, stabilizer, defoamer, and solvent in a preset ratio to prepare composite coating component one and component two. Component one and component two are then mixed uniformly, subjected to film-forming treatment, and cured at room temperature to obtain the hydrophobic hexagonal boron nitride chlorinated rubber composite coating.

[0013] In one embodiment, the method involves using hexagonal boron nitride two-dimensional nanomaterial powder as a filler, and compounding it with chlorinated rubber resin, hydroxymethylacrylamide, ethyl acrylate, dispersant, plasticizer, thickener, stabilizer, defoamer, and solvent according to a preset ratio to prepare composite coating component one and component two. Component one and component two are then mixed uniformly, subjected to film-forming treatment, and cured at room temperature to obtain a hydrophobic hexagonal boron nitride chlorinated rubber composite coating. This includes: grinding, high-speed dispersing, and filtering chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterial, hydroxymethylacrylamide, ethyl acrylate, and dispersant to obtain hexagonal boron nitride chlorinated rubber composite coating component one; grinding, high-speed dispersing, and filtering plasticizer, thickener, stabilizer, defoamer, and solvent to obtain hexagonal boron nitride chlorinated rubber composite coating component two; and mixing the obtained hexagonal boron nitride chlorinated rubber composite coating components one and two uniformly, subjected to film-forming treatment, and cured at room temperature to obtain the hexagonal boron nitride chlorinated rubber composite coating.

[0014] In one embodiment, the preparation process of the hexagonal boron nitride two-dimensional nanomaterial powder is as follows: hydrothermal synthesis using ammonium borate and urea with programmed temperature rise, followed by atmospheric protection and acid washing process to obtain a hexagonal boron nitride precursor; the hexagonal boron nitride precursor is subjected to cell disruption and ultrasonic exfoliation, and the surface defect-free hexagonal boron nitride two-dimensional nanomaterial powder and the surface defect-rich hexagonal boron nitride two-dimensional nanomaterial powder are obtained by controlling the exfoliation time.

[0015] In one embodiment, the hydrothermal synthesis using ammonium borate and urea with programmed temperature rise, after atmospheric protection and acid washing process to obtain a hexagonal boron nitride precursor, includes: mixing ammonium borate and urea, stirring evenly, placing in a stainless steel reactor, heating to 80-100°C, holding at that temperature for 1-2 hours, then heating to 120-150°C, holding at that temperature for 1-2 hours, heating to 160-180°C, introducing nitrogen gas, and washing the reaction product with hydrochloric acid to obtain the hexagonal boron nitride precursor.

[0016] In one embodiment, the mass ratio of the ammonium borate to the urea is 2:3.

[0017] In one embodiment, the process of cell disruption and ultrasonic exfoliation of the hexagonal boron nitride precursor to obtain hexagonal boron nitride two-dimensional nanomaterial powders with and without surface defects, by controlling the exfoliation time, includes: weighing the hexagonal boron nitride precursor and adding it to a beaker, then adding deionized water and isopropanol, stirring with a stirrer to mix evenly, sealing the beaker mouth, and placing it in an ultrasonic cleaner for 1-2 hours to fully disperse the hexagonal boron nitride precursor powder. The beaker containing the evenly mixed hexagonal boron nitride precursor dispersion is placed in a cell disruptor, and the total exfoliation time is 4-18 hours. The dispersion obtained by disruption and exfoliation is centrifuged at 5000 r / min, and the supernatant is collected to obtain a hexagonal boron nitride two-dimensional nanosheet dispersion. After filtration and drying, the hexagonal boron nitride two-dimensional nanomaterial powder is obtained.

[0018] In one embodiment, the mass ratio of the hexagonal boron nitride precursor, the deionized water, and the isopropanol is 1:(2-3):(2-3).

[0019] In one embodiment, when the exfoliation time is controlled to be 6 hours or less, a two-dimensional hexagonal boron nitride nanomaterial powder with no surface defects is obtained; when the exfoliation time is controlled to be greater than 6 hours, a two-dimensional hexagonal boron nitride nanomaterial powder with rich surface defects is obtained.

[0020] (III) Beneficial Effects

[0021] The above-described technical solution of the present invention has the following advantages:

[0022] This embodiment adds a specific ratio of dispersant, plasticizer, thickener, and stabilizer during the preparation of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating. This makes the mixing of the raw materials of the composite coating faster and more uniform, which is beneficial to improving the performance stability of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating. The defoamer reduces the generation of bubbles during the mixing of raw materials, avoiding the problem of internal voids caused by bubbles in the prepared hydrophobic hexagonal boron nitride chlorinated rubber composite coating, which is beneficial to improving the corrosion resistance of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating.

[0023] In this embodiment, during the preparation of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating, the exfoliation time of the hexagonal boron nitride two-dimensional nanomaterial preparation step is controlled. By using chemical means, nanoscale surface defect structures are constructed on the surface of hexagonal boron nitride, achieving the effect of surface functionalization. These defect structures can regulate the surface energy of the hexagonal boron nitride two-dimensional nanomaterial, thereby improving the hydrophobicity of the hexagonal boron nitride chlorinated rubber composite coating. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the morphology of the hydrophobic hexagonal boron nitride two-dimensional nanomaterial according to an embodiment of the present invention;

[0025] Figure 2 This is an example diagram showing the elemental distribution of hydrophobic hexagonal boron nitride according to an embodiment of the present invention;

[0026] Figure 3 This is a schematic diagram comparing the microstructures of hexagonal boron nitride with no surface defects and hexagonal boron nitride with rich surface defects according to an embodiment of the present invention.

[0027] Figure 4 This is a schematic diagram of the contact angles in various embodiments of the present invention. Detailed Implementation

[0028] To better understand the above-mentioned objectives, features, and advantages of the present invention, the solutions of the present invention will be further described below. It should be noted that, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.

[0029] Many specific details are set forth in the following description in order to provide a full understanding of the invention, but the invention may also be practiced in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of the invention, and not all embodiments.

[0030] The embodiments of the present invention will be further described in detail below with reference to the accompanying drawings and examples. The following detailed description of the embodiments and the accompanying drawings are used to illustrate the principles of the present invention by way of example, but should not be used to limit the scope of the present invention, that is, the present invention is not limited to the described embodiments.

[0031] In this invention, unless otherwise specified, the raw materials and equipment used can be purchased from the market or are commonly used in the field. The methods in the embodiments, unless otherwise specified, are conventional methods in the field.

[0032] Before introducing the solution of this embodiment, let's first explain why existing hexagonal boron nitride chlorinated rubber composite coatings have poor hydrophobic properties. Specifically:

[0033] 1. Dispersion problem of hexagonal boron nitride in chlorinated rubber

[0034] Hexagonal boron nitride nanosheets have a large surface area. When added to chlorinated rubber as a functional filler, the surface area tends to decrease due to electrostatic forces, van der Waals forces, and chemical bonds between particles, leading to aggregation. This aggregation of hexagonal boron nitride nanosheets in chlorinated rubber reduces the degree of cross-linking, resulting in defects such as microcracks and pores in the coating, negatively impacting its physical shielding and hydrophobic properties.

[0035] 2. The hydrophobic properties of hexagonal boron nitride are difficult to fully utilize and maintain in composite coatings.

[0036] The mechanism of hydrophobicity is closely related to the specific orientation and arrangement of water molecules at the hydrophobic interface. Because hydrophobic surfaces have little or no ability to form hydrogen bonds, some interfacial water molecules are forced to change their original orientation, forming a certain number of "suspended" hydrogen-oxygen bonds perpendicular to the hydrophobic surface. These fixed-direction dipoles drive the surrounding water molecules to rearrange into a relatively orderly hydration layer through a dynamic hydrogen bond network. The formation of this ordered network of interfacial water molecules leads to a significant decrease in entropy, which is thermodynamically unfavorable. Therefore, hydrophobic substances tend to aggregate in water to reduce the number of interfacial water molecules, increase the system entropy, and lower the system's surface free energy, thus maintaining hydrophobic properties. Unlike graphene oxide, which has many oxygen-containing functional groups (hydroxyl, carboxyl, epoxy, etc.) on its surface, hexagonal boron nitride has almost no functional groups on its surface. When hydrophobic hexagonal boron nitride is combined with chlorinated rubber, it is not conducive to exerting its surface hydrophobic properties in the composite coating system. The polymer backbone in the system is easily affected by external factors (light, water, oxygen and chemicals), which affects the service life of the composite coating.

[0037] To address the aforementioned issues, this embodiment incorporates dispersants, plasticizers, thickeners, and stabilizers in specific proportions during the preparation of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating. This results in faster and more uniform mixing of the raw materials, which improves the performance stability of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating. Furthermore, the use of defoamers reduces bubble formation during raw material mixing, preventing internal voids caused by bubbles in the prepared hydrophobic hexagonal boron nitride chlorinated rubber composite coating and enhancing its corrosion resistance.

[0038] Furthermore, this embodiment modulates the exfoliation time of the hexagonal boron nitride (HNB) two-dimensional nanomaterial preparation step during the preparation of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating. This constructs a special defect structure on the surface of the HNB two-dimensional nanomaterial, achieving surface functionalization and enhancing the hydrophobic properties of HNB. Simultaneously, the HNB two-dimensional nanomaterial powder with its rich surface defect structure fully exerts its hydrophobic effect in the composite coating. The surface defect structure provides abundant dangling bonds on the surface of the HNB two-dimensional nanomaterial, improving its dispersibility and compatibility in the composite coating system. It integrates into the cross-linked network of the entire chlorinated rubber. Simultaneously, the surface defect structure alters the local electronic structure, modulates the local charge density, strengthens the hydrophobic properties of HNB, and improves the overall performance of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating.

[0039] The following will describe the solution in detail.

[0040] General Implementation Examples

[0041] A hydrophobic hexagonal boron nitride chlorinated rubber composite coating is prepared from the following raw materials: chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials, hydroxymethylacrylamide, ethyl acrylate, dispersant, plasticizer, thickener, stabilizer, defoamer and solvent;

[0042] The mass ratio of the chlorinated rubber resin, the hexagonal boron nitride two-dimensional nanomaterial, the hydroxymethyl acrylamide, the ethyl acrylate, the dispersant, the plasticizer, the thickener, the stabilizer, the defoamer, and the solvent is (80-100):(6-24):(20-40):(20-40):(20-60):(10-60):(20-50):(10-30):(10-50):(100-500).

[0043] In practical applications, the mass ratio of the chlorinated rubber resin, the hexagonal boron nitride two-dimensional nanomaterial, the hydroxymethyl acrylamide, the ethyl acrylate, the dispersant, the plasticizer, the thickener, the stabilizer, the defoamer, and the solvent can be specifically selected as 100:12:30:30:50:40:30:20:20:200, or 100:6:30:30:50:40:30:20:20:200, or 100:12:20:20:30:30:20:10:10:100, or 100:18:40:40:60:50:40:30:30:300, or 100:24:30:30:50:40:30:20:20:200.

[0044] In this embodiment, the chlorinated rubber resin can be a chlorinated rubber resin with a chlorine content between 66% and 68% by mass, and the average relative molecular weight of the chlorinated rubber resin can be between 10,000 and 20,000; the dispersant can be any one of polyethylene glycol 200 or polyethylene glycol 400 or a mixture thereof; the plasticizer can be any one of dioctyl phthalate or dibutyl phthalate or a mixture thereof; the thickener can be a mixture of methyl hydroxypropyl cellulose and bentonite; the stabilizer can be any one of dibutyltin dilaurate or methyltin mercaptan or a mixture thereof; the defoamer can be any one of polyether defoamers or silicone defoamers; and the solvent can be any one of acetone, xylene, or ethyl acetate or a mixture of two or more of them.

[0045] In practical applications, the chlorinated rubber resin can specifically be a chlorinated rubber resin with a chlorine content between 66% and 68% by mass, and an average relative molecular weight of 12,000; the dispersant can specifically be a mixture of polyethylene glycol 200 and polyethylene glycol 400 in a mass ratio of 1:2; the plasticizer can specifically be a mixture of dioctyl phthalate and dibutyl phthalate in a mass ratio of 1:1; the thickener can specifically be a mixture of methyl hydroxypropyl cellulose and bentonite in a mass ratio of 1:1; the stabilizer can specifically be a mixture of dibutyltin dilaurate and methyltin mercaptan in a mass ratio of 1:2; the defoamer can specifically be a polyether defoamer; and the solvent can specifically be a mixture of acetone, xylene, and ethyl acetate in a mass ratio of 3:2:3.

[0046] This embodiment adds a specific ratio of dispersant, plasticizer, thickener, and stabilizer during the preparation of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating. This makes the mixing of the raw materials of the composite coating faster and more uniform, which is beneficial to improving the performance stability of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating. The defoamer reduces the generation of bubbles during the mixing of raw materials, avoiding the problem of internal voids caused by bubbles in the prepared hydrophobic hexagonal boron nitride chlorinated rubber composite coating, which is beneficial to improving the corrosion resistance of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating.

[0047] Furthermore, in this embodiment, the preparation method of any of the above-mentioned hydrophobic hexagonal boron nitride chlorinated rubber composite coatings is as follows:

[0048] Hexagonal boron nitride precursors were obtained through hydrothermal synthesis using ammonium borate and urea at a programmed temperature, followed by atmosphere protection and acid washing. The precursors were then subjected to cell disruption and ultrasonic exfoliation. By controlling the exfoliation time, two-dimensional hexagonal boron nitride nanomaterial powders with and without surface defects were obtained, along with powders rich in surface defects. Using these prepared hexagonal boron nitride nanomaterial powders as fillers, they were compounded with chlorinated rubber resin, hydroxymethylacrylamide, ethyl acrylate, dispersant, plasticizer, thickener, stabilizer, defoamer, and solvent in specific proportions to prepare composite coating components one and two, respectively. Components one and two were then mixed uniformly, subjected to film-forming treatment, and cured at room temperature to obtain the desired coating.

[0049] The specific technical solution mainly includes 5 steps:

[0050] 1. Mix 2 parts ammonium borate and 3 parts urea, stir well, and place in a stainless steel reactor. Heat to 80-100℃ and hold for 1-2 hours, then heat to 120-150℃ and hold for 1-2 hours. Next, heat to 160-180℃ and purge with nitrogen. Wash the reaction product with hydrochloric acid to obtain a hexagonal boron nitride precursor. Weigh 1 part of the hexagonal boron nitride precursor and add it to a beaker, then add 2-3 parts deionized water and 2-3 parts isopropanol. Stir with a stirrer until well mixed. Seal the beaker and place it in an ultrasonic cleaner for 1-2 hours to fully disperse the hexagonal boron nitride precursor powder. A beaker containing a uniformly mixed hexagonal boron nitride precursor dispersion was placed in a cell disruptor. The total exfoliation time was 4–18 h. The dispersion obtained by crushing and exfoliation was centrifuged at 5000 r / min, and the supernatant was collected to obtain a hexagonal boron nitride two-dimensional nanosheet dispersion. After filtration and drying, hexagonal boron nitride two-dimensional nanomaterial powder was obtained.

[0051] 2. Prepare the following raw materials in parts by weight: 80-100 parts chlorinated rubber resin; 6-24 parts hexagonal boron nitride two-dimensional nanomaterials; 20-40 parts hydroxymethyl acrylamide; 20-40 parts ethyl acrylate; 20-60 parts dispersant; 10-60 parts plasticizer; 20-50 parts thickener; 10-30 parts stabilizer; 10-50 parts defoamer; and 100-500 parts solvent. The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass and an average relative molecular weight of 10,000 to 20,000; the dispersant is any one of polyethylene glycol 200 or polyethylene glycol 400 or a mixture thereof; the plasticizer is any one of dioctyl phthalate or dibutyl phthalate or a mixture thereof; the thickener is a mixture of methyl hydroxypropyl cellulose and bentonite; the stabilizer is any one of dibutyltin dilaurate or methyltin mercaptan or a mixture thereof; the defoamer is any one of polyether defoamers or silicone defoamers; and the solvent is any one of acetone, xylene, and ethyl acetate or a mixture of two or more of them.

[0052] 3. Prepare chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials, hydroxymethylacrylamide, ethyl acrylate, and dispersant according to the formula. After grinding, high-speed dispersion, and filtration, obtain component one of the hexagonal boron nitride chlorinated rubber composite coating.

[0053] 4. Prepare plasticizer, thickener, stabilizer, defoamer and solvent according to the ratio, and obtain component two of the hexagonal boron nitride chlorinated rubber composite coating by grinding, high-speed dispersion and filtration.

[0054] 5. Mix the obtained hexagonal boron nitride chlorinated rubber composite coating components one and two evenly, perform film formation treatment, and then cure at room temperature to obtain the hexagonal boron nitride chlorinated rubber composite coating.

[0055] Here, when the exfoliation time is controlled to be 6 hours or less, hexagonal boron nitride two-dimensional nanomaterial powder with no surface defects can be obtained; when the exfoliation time is controlled to be greater than 6 hours, hexagonal boron nitride two-dimensional nanomaterial powder with rich surface defects can be obtained.

[0056] When implementing the application, it is recommended to control the peeling time to more than 6 hours to obtain hexagonal boron nitride two-dimensional nanomaterial powder with rich surface defect structure. Using the hexagonal boron nitride two-dimensional nanomaterial powder with rich surface defect structure to prepare hexagonal boron nitride chlorinated rubber composite coating can improve the hydrophobic properties of the hexagonal boron nitride chlorinated rubber composite coating.

[0057] This embodiment modulates the exfoliation time of the hexagonal boron nitride (HNB) two-dimensional nanomaterial preparation step during the preparation of the hydrophobic hexagonal boron nitride (HNB) chlorinated rubber composite coating. This constructs a special defect structure on the surface of the HNB two-dimensional nanomaterial, achieving surface functionalization and enhancing the hydrophobic properties of HNB. Simultaneously, the HNB two-dimensional nanomaterial powder with its rich surface defect structure fully exerts its hydrophobic effect in the composite coating. The surface defect structure provides abundant dangling bonds on the surface of the HNB two-dimensional nanomaterial, improving its dispersibility and compatibility in the composite coating system. It integrates into the cross-linked network of the entire chlorinated rubber. Furthermore, the surface defect structure alters the local electronic structure, regulating the local charge density and strengthening the hydrophobic properties of HNB, thus improving the overall performance of the hydrophobic hexagonal boron nitride (HNB) chlorinated rubber composite coating.

[0058] Example 1:

[0059] 1. Prepare the following raw materials in parts by weight: 100 parts chlorinated rubber resin; 30 parts hydroxymethylacrylamide; 30 parts ethyl acrylate; 50 parts dispersant; 40 parts plasticizer; 30 parts thickener; 20 parts stabilizer; 20 parts defoamer; and 200 parts solvent. The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by weight and an average relative molecular weight of 12,000. The dispersant is composed of polyethylene glycol 200 and polyethylene glycol 400 in a 1:1 mass ratio; the plasticizer is composed of dioctyl phthalate and dibutyl phthalate in a 2:1 mass ratio; the thickener is composed of methyl hydroxypropyl cellulose and bentonite in a 2:1 mass ratio; the stabilizer is composed of dibutyltin dilaurate and methyltin mercaptan in a 1:1 mass ratio; the defoamer is a polyether defoamer; and the solvent is a mixture of acetone, xylene, and ethyl acetate in a 1:2:1 mass ratio.

[0060] 2. Prepare chlorinated rubber resin, hydroxymethylacrylamide, ethyl acrylate, and dispersant according to the specified ratio. Grind, disperse at high speed, and filter to obtain component one of the chlorinated rubber coating.

[0061] 3. Prepare plasticizer, thickener, stabilizer, defoamer and solvent according to the ratio, and obtain chlorinated rubber coating component two by grinding, high-speed dispersion and filtration.

[0062] 4. Mix the obtained chlorinated rubber coating components one and two evenly, perform film formation treatment, and then cure at room temperature to obtain the chlorinated rubber coating.

[0063] Example 2:

[0064] 1. Mix 2 parts ammonium borate and 3 parts urea, stir well, place in a stainless steel reactor, heat to 80℃, hold for 1 hour, then heat to 120℃, hold for 1 hour, then heat to 160℃, and purge with nitrogen. Wash the reaction product with hydrochloric acid to obtain a hexagonal boron nitride precursor. Weigh 1 part of the hexagonal boron nitride precursor and add it to a beaker, then add 2 parts deionized water and 2 parts isopropanol. Stir with a stirrer to mix evenly, seal the beaker, and place in an ultrasonic cleaner for 1 hour to fully disperse the hexagonal boron nitride precursor powder. Place the beaker containing the evenly mixed hexagonal boron nitride precursor dispersion in a cell disruptor, and exfoliate for a total time of 6 hours. Centrifuge the dispersion obtained by crushing and exfoliation at 5000 r / min, and collect the supernatant to obtain a hexagonal boron nitride two-dimensional nanosheet dispersion. Filter and dry to obtain a hexagonal boron nitride two-dimensional nanomaterial powder with a surface defect-free structure.

[0065] 2. Prepare the following raw materials in parts by weight: 100 parts chlorinated rubber resin; 12 parts hexagonal boron nitride two-dimensional nanomaterials with no surface defects; 30 parts hydroxymethyl acrylamide; 30 parts ethyl acrylate; 50 parts dispersant; 40 parts plasticizer; 30 parts thickener; 20 parts stabilizer; 20 parts defoamer; and 200 parts solvent. The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass and an average relative molecular weight of 12,000; the dispersant is composed of polyethylene glycol 200 and polyethylene glycol 400 in a mass ratio of 1:1; the plasticizer is composed of dioctyl phthalate and dibutyl phthalate in a mass ratio of 2:1; the thickener is composed of methyl hydroxypropyl cellulose and bentonite in a mass ratio of 2:1; the stabilizer is composed of dibutyltin dilaurate and methyltin mercaptan in a mass ratio of 1:1; the defoamer is a polyether defoamer; and the solvent is a mixture of acetone, xylene, and ethyl acetate in a mass ratio of 1:2:1.

[0066] 3. Prepare chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials with no surface defects, hydroxymethylacrylamide, ethyl acrylate, and dispersant according to the formula. After grinding, high-speed dispersion, and filtration, obtain component one of the hexagonal boron nitride chlorinated rubber composite coating with no surface defects.

[0067] 4. Prepare plasticizer, thickener, stabilizer, defoamer and solvent according to the ratio, and obtain component two of the hexagonal boron nitride chlorinated rubber composite coating with no surface defects by grinding, high-speed dispersion and filtration.

[0068] 5. Mix component one and component two of the obtained hexagonal boron nitride chlorinated rubber composite coating without surface defects evenly, perform film formation treatment, and then cure at room temperature to obtain a hexagonal boron nitride chlorinated rubber composite coating without surface defects.

[0069] Example 3:

[0070] 1. Mix 2 parts ammonium borate and 3 parts urea, stir well, place in a stainless steel reactor, heat to 80℃, hold for 1 hour, then heat to 120℃, hold for 1 hour, then heat to 160℃, introduce nitrogen gas, and wash the reaction product with hydrochloric acid to obtain hexagonal boron nitride precursor. Weigh 1 part of hexagonal boron nitride precursor and add it to a beaker, then add 2 parts deionized water and 2 parts isopropanol, stir with a stirrer to mix evenly, seal the beaker and place in an ultrasonic cleaner for 1 hour to fully disperse the hexagonal boron nitride precursor powder. Place the beaker containing the evenly mixed hexagonal boron nitride precursor dispersion in a cell disruptor, and exfoliate for a total time of 12 hours. Centrifuge the dispersion obtained by crushing and exfoliation at 5000 r / min, and collect the supernatant to obtain a hexagonal boron nitride two-dimensional nanosheet dispersion. Filter and dry to obtain hexagonal boron nitride two-dimensional nanomaterial powder with a surface defect-rich structure.

[0071] 2. Prepare the following raw materials in parts by weight: 100 parts chlorinated rubber resin; 6 parts hexagonal boron nitride two-dimensional nanomaterials with rich surface defect structure; 30 parts hydroxymethyl acrylamide; 30 parts ethyl acrylate; 50 parts dispersant; 40 parts plasticizer; 30 parts thickener; 20 parts stabilizer; 20 parts defoamer; and 200 parts solvent. The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass and an average relative molecular weight of 12,000; the dispersant is composed of polyethylene glycol 200 and polyethylene glycol 400 in a mass ratio of 1:1; the plasticizer is composed of dioctyl phthalate and dibutyl phthalate in a mass ratio of 2:1; the thickener is composed of methyl hydroxypropyl cellulose and bentonite in a mass ratio of 2:1; the stabilizer is composed of dibutyltin dilaurate and methyltin mercaptan in a mass ratio of 1:1; the defoamer is a polyether defoamer; and the solvent is a mixture of acetone, xylene, and ethyl acetate in a mass ratio of 1:2:1.

[0072] 3. Prepare chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials with rich surface defect structure, hydroxymethyl acrylamide, ethyl acrylate, and dispersant according to the formula. After grinding, high-speed dispersion, and filtration, obtain component one of the chlorinated rubber composite coating with rich surface defect structure hexagonal boron nitride.

[0073] 4. Prepare plasticizer, thickener, stabilizer, defoamer and solvent according to the ratio, and obtain component two of the hexagonal boron nitride chlorinated rubber composite coating with rich surface defect structure by grinding, high-speed dispersion and filtration.

[0074] 5. Mix component one and component two of the obtained hexagonal boron nitride chlorinated rubber composite coating with rich surface defects evenly, perform film formation treatment, and then cure at room temperature to obtain the hexagonal boron nitride chlorinated rubber composite coating with rich surface defects.

[0075] Example 4:

[0076] 1. Mix 2 parts ammonium borate and 3 parts urea, stir well, place in a stainless steel reactor, heat to 80℃, hold for 1 hour, then heat to 120℃, hold for 1 hour, then heat to 160℃, introduce nitrogen gas, and wash the reaction product with hydrochloric acid to obtain hexagonal boron nitride precursor. Weigh 1 part of hexagonal boron nitride precursor and add it to a beaker, then add 2 parts deionized water and 2 parts isopropanol, stir with a stirrer to mix evenly, seal the beaker and place in an ultrasonic cleaner for 1 hour to fully disperse the hexagonal boron nitride precursor powder. Place the beaker containing the evenly mixed hexagonal boron nitride precursor dispersion in a cell disruptor, and exfoliate for a total time of 12 hours. Centrifuge the dispersion obtained by crushing and exfoliation at 5000 r / min, and collect the supernatant to obtain a hexagonal boron nitride two-dimensional nanosheet dispersion. Filter and dry to obtain hexagonal boron nitride two-dimensional nanomaterial powder with a surface defect-rich structure.

[0077] 2. Prepare the following raw materials in parts by weight: 100 parts chlorinated rubber resin; 12 parts hexagonal boron nitride two-dimensional nanomaterials with rich surface defect structure; 20 parts hydroxymethyl acrylamide; 20 parts ethyl acrylate; 30 parts dispersant; 30 parts plasticizer; 20 parts thickener; 10 parts stabilizer; 10 parts defoamer; and 100 parts solvent. The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass and an average relative molecular weight of 12,000; the dispersant is composed of polyethylene glycol 200 and polyethylene glycol 400 in a mass ratio of 1:1; the plasticizer is composed of dioctyl phthalate and dibutyl phthalate in a mass ratio of 2:1; the thickener is composed of methyl hydroxypropyl cellulose and bentonite in a mass ratio of 2:1; the stabilizer is composed of dibutyltin dilaurate and methyltin mercaptan in a mass ratio of 1:1; the defoamer is a polyether defoamer; and the solvent is a mixture of acetone, xylene, and ethyl acetate in a mass ratio of 1:2:1.

[0078] 3. Prepare chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials with rich surface defect structure, hydroxymethyl acrylamide, ethyl acrylate, and dispersant according to the formula. After grinding, high-speed dispersion, and filtration, obtain component one of the chlorinated rubber composite coating with rich surface defect structure hexagonal boron nitride.

[0079] 4. Prepare plasticizer, thickener, stabilizer, defoamer and solvent according to the ratio, and obtain component two of the hexagonal boron nitride chlorinated rubber composite coating with rich surface defect structure by grinding, high-speed dispersion and filtration.

[0080] 5. Mix component one and component two of the obtained hexagonal boron nitride chlorinated rubber composite coating with rich surface defects evenly, perform film formation treatment, and then cure at room temperature to obtain the hexagonal boron nitride chlorinated rubber composite coating with rich surface defects.

[0081] Example 5:

[0082] 1. Mix 2 parts ammonium borate and 3 parts urea, stir well, place in a stainless steel reactor, heat to 80℃, hold for 1 hour, then heat to 120℃, hold for 1 hour, then heat to 160℃, introduce nitrogen gas, and wash the reaction product with hydrochloric acid to obtain hexagonal boron nitride precursor. Weigh 1 part of hexagonal boron nitride precursor and add it to a beaker, then add 2 parts deionized water and 2 parts isopropanol, stir with a stirrer to mix evenly, seal the beaker and place in an ultrasonic cleaner for 1 hour to fully disperse the hexagonal boron nitride precursor powder. Place the beaker containing the evenly mixed hexagonal boron nitride precursor dispersion in a cell disruptor, and exfoliate for a total time of 12 hours. Centrifuge the dispersion obtained by crushing and exfoliation at 5000 r / min, and collect the supernatant to obtain a hexagonal boron nitride two-dimensional nanosheet dispersion. Filter and dry to obtain hexagonal boron nitride two-dimensional nanomaterial powder with a surface defect-rich structure.

[0083] 2. Prepare the following raw materials in parts by weight: 100 parts chlorinated rubber resin; 18 parts hexagonal boron nitride two-dimensional nanomaterials with rich surface defect structure; 40 parts hydroxymethyl acrylamide; 40 parts ethyl acrylate; 60 parts dispersant; 50 parts plasticizer; 40 parts thickener; 30 parts stabilizer; 30 parts defoamer; and 300 parts solvent. The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass and an average relative molecular weight of 12,000; the dispersant is composed of polyethylene glycol 200 and polyethylene glycol 400 in a mass ratio of 1:1; the plasticizer is composed of dioctyl phthalate and dibutyl phthalate in a mass ratio of 2:1; the thickener is composed of methyl hydroxypropyl cellulose and bentonite in a mass ratio of 2:1; the stabilizer is composed of dibutyltin dilaurate and methyltin mercaptan in a mass ratio of 1:1; the defoamer is a polyether defoamer; and the solvent is a mixture of acetone, xylene, and ethyl acetate in a mass ratio of 1:2:1.

[0084] 3. Prepare chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials with rich surface defect structure, hydroxymethyl acrylamide, ethyl acrylate, and dispersant according to the formula. After grinding, high-speed dispersion, and filtration, obtain component one of the chlorinated rubber composite coating with rich surface defect structure hexagonal boron nitride.

[0085] 4. Prepare plasticizer, thickener, stabilizer, defoamer and solvent according to the ratio, and obtain component two of the hexagonal boron nitride chlorinated rubber composite coating with rich surface defect structure by grinding, high-speed dispersion and filtration.

[0086] 5. Mix component one and component two of the obtained hexagonal boron nitride chlorinated rubber composite coating with rich surface defects evenly, perform film formation treatment, and then cure at room temperature to obtain the hexagonal boron nitride chlorinated rubber composite coating with rich surface defects.

[0087] Example 6:

[0088] 1. Mix 2 parts ammonium borate and 3 parts urea, stir well, place in a stainless steel reactor, heat to 80℃, hold for 1 hour, then heat to 120℃, hold for 1 hour, then heat to 160℃, introduce nitrogen gas, and wash the reaction product with hydrochloric acid to obtain a hexagonal boron nitride precursor. Weigh 1 part of the hexagonal boron nitride precursor and add it to a beaker, then add 2 parts deionized water and 2 parts isopropanol, stir with a stirrer to mix evenly, seal the beaker and place in an ultrasonic cleaner for 1 hour to fully disperse the hexagonal boron nitride precursor powder. Place the beaker containing the evenly mixed hexagonal boron nitride precursor dispersion in a cell disruptor, and exfoliate for a total time of 18 hours. Centrifuge the dispersion obtained by crushing and exfoliation at 5000 r / min, and collect the supernatant to obtain a hexagonal boron nitride two-dimensional nanosheet dispersion. Filter and dry to obtain a hexagonal boron nitride two-dimensional nanomaterial powder with a surface defect-rich structure.

[0089] 2. Prepare the following raw materials in parts by weight: 100 parts chlorinated rubber resin; 24 parts hexagonal boron nitride two-dimensional nanomaterials with rich surface defect structure; 30 parts hydroxymethyl acrylamide; 30 parts ethyl acrylate; 50 parts dispersant; 40 parts plasticizer; 30 parts thickener; 20 parts stabilizer; 20 parts defoamer; and 200 parts solvent. The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass and an average relative molecular weight of 12,000; the dispersant is composed of polyethylene glycol 200 and polyethylene glycol 400 in a mass ratio of 1:2; the plasticizer is composed of dioctyl phthalate and dibutyl phthalate in a mass ratio of 1:1; the thickener is composed of methyl hydroxypropyl cellulose and bentonite in a mass ratio of 1:1; the stabilizer is composed of dibutyltin dilaurate and methyltin mercaptan in a mass ratio of 1:2; the defoamer is a polyether defoamer; and the solvent is a mixture of acetone, xylene, and ethyl acetate in a mass ratio of 3:2:3.

[0090] 3. Prepare chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials with rich surface defect structure, hydroxymethyl acrylamide, ethyl acrylate, and dispersant according to the formula. After grinding, high-speed dispersion, and filtration, obtain component one of the chlorinated rubber composite coating with rich surface defect structure hexagonal boron nitride.

[0091] 4. Prepare plasticizer, thickener, stabilizer, defoamer and solvent according to the ratio, and obtain component two of the hexagonal boron nitride chlorinated rubber composite coating with rich surface defect structure by grinding, high-speed dispersion and filtration.

[0092] 5. Mix component one and component two of the obtained hexagonal boron nitride chlorinated rubber composite coating with rich surface defects evenly, perform film formation treatment, and then cure at room temperature to obtain the hexagonal boron nitride chlorinated rubber composite coating with rich surface defects.

[0093] The chlorinated rubber coatings, the hexagonal boron nitride chlorinated rubber composite coatings without surface defects, and the hexagonal boron nitride chlorinated rubber composite coatings rich in surface defects prepared in Examples 1 to 6 were subjected to comprehensive performance testing. The testing methods were in accordance with GB / T 13452.2-2008 Determination of film thickness of paints and varnishes; GJB 150.11A-2009 Salt spray test for laboratory environmental testing of military equipment; and GB / T 9286-2021 Cross-cut test for paints and varnishes. The results are shown in Table 1.

[0094] Table 1 Test Results

[0095] Example 1 94 No bubbling, no peeling ≤1 54.1 Example 2 96 No bubbling, no peeling ≤1 80.7 Example 3 98 No bubbling, no peeling ≤1 100.7 Example 4 95 No bubbling, no peeling ≤1 102.6 Example 5 102 No bubbling, no peeling ≤1 99.7 Example 6 100 No bubbling, no peeling ≤1 97.1

[0096] Example 1 above is a chlorinated rubber coating without the addition of hexagonal boron nitride two-dimensional nanomaterials, serving as a blank control example. Example 2 is a chlorinated rubber coating with the addition of hexagonal boron nitride two-dimensional nanomaterials without surface defects. Examples 3 to 6 are chlorinated rubber coatings with the addition of hexagonal boron nitride two-dimensional nanomaterials rich in surface defects. The water contact angle in Table 1 reflects the hydrophobic properties of the chlorinated rubber coating. A larger water contact angle indicates better hydrophobic properties, while a smaller water contact angle indicates worse hydrophobic properties. The data in Table 1 shows that, compared to Example 1, Examples 2 to 6 have significantly larger water contact angles, indicating better hydrophobic properties of the chlorinated rubber coating with the addition of hexagonal boron nitride two-dimensional nanomaterials according to this embodiment. Furthermore, compared to Example 2, Examples 3 to 6 have significantly larger water contact angles, indicating that the hydrophobic properties of the chlorinated rubber coating with the addition of hexagonal boron nitride two-dimensional nanomaterials rich in surface defects are better than those with the addition of hexagonal boron nitride two-dimensional nanomaterials without surface defects.

[0097] Additionally, see also Figure 1 This is a schematic diagram of the morphology of a hydrophobic hexagonal boron nitride two-dimensional nanomaterial. Figure 2 This is a schematic diagram of the elemental distribution in hydrophobic hexagonal boron nitride. The diagram shows the distribution of nitrogen and boron elements in the hexagonal boron nitride material sample. Figure 3 A comparison of the microstructures of hexagonal boron nitride with no surface defects and hexagonal boron nitride with abundant surface defects is shown. Figure 3 The left image shows a hexagonal boron nitride structure without surface defects. Figure 3 The right image shows hexagonal boron nitride with a surface defect-rich structure. Hexagonal boron nitride with a surface defect-rich structure exhibits better hydrophobicity in chlorinated rubber coatings. Figure 4 These are schematic diagrams of the contact angles in embodiments one through six described above. Figure 4 (a) The water contact angle in Example 1 is 54.1°. Figure 4(b) The water contact angle for Example 2 is 80.7°. Figure 4 (c) The water contact angle in Example 3 is 100.7°. Figure 4 (d) shows that the water contact angle in Example 4 is 102.6°. Figure 4 (e) The water contact angle in Example 5 is 99.7°. Figure 4 (f) The water contact angle of Example 6 is 97.1°.

[0098] It should be clarified that this invention is not limited to the specific steps and structures described above. Furthermore, for the sake of brevity, detailed descriptions of known methods and techniques are omitted here.

[0099] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a hydrophobic hexagonal boron nitride chlorinated rubber composite coating, characterized in that: The raw materials for preparing hydrophobic hexagonal boron nitride chlorinated rubber composite coatings include: chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials, hydroxymethyl acrylamide, ethyl acrylate, dispersant, plasticizer, thickener, stabilizer, defoamer, and solvent; The mass ratio of the chlorinated rubber resin, the hexagonal boron nitride two-dimensional nanomaterial, the hydroxymethyl acrylamide, the ethyl acrylate, the dispersant, the plasticizer, the thickener, the stabilizer, the defoamer, and the solvent is (80~100):(6~24):(20~40):(20~40):(20~60):(10~60):(20~50):(10~30):(10~50):(100~500). The method includes the following steps: The first component of the hexagonal boron nitride chlorinated rubber composite coating is obtained by grinding, high-speed dispersion, and filtration of chlorinated rubber resin, hexagonal boron nitride two-dimensional nanomaterials, hydroxymethylacrylamide, ethyl acrylate, and dispersant. The plasticizer, thickener, stabilizer, defoamer, and solvent are ground, dispersed at high speed, and filtered to obtain the second component of the hexagonal boron nitride chlorinated rubber composite coating. The hexagonal boron nitride chlorinated rubber composite coating components one and two were mixed evenly, subjected to film formation treatment, and then cured at room temperature to obtain the hexagonal boron nitride chlorinated rubber composite coating. The preparation process of the hexagonal boron nitride two-dimensional nanomaterial powder is as follows: Hexagonal boron nitride precursor was obtained by hydrothermal synthesis using ammonium borate and urea with programmed temperature rise, followed by atmosphere protection and acid washing process. Hexagonal boron nitride precursors were subjected to cell disruption and ultrasonic exfoliation. By controlling the exfoliation time, two-dimensional nanomaterial powders of hexagonal boron nitride with no surface defects and two-dimensional nanomaterial powders of hexagonal boron nitride with rich surface defects were obtained.

2. The preparation method of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating according to claim 1, characterized in that: The mass ratio of the chlorinated rubber resin, the hexagonal boron nitride two-dimensional nanomaterial, the hydroxymethyl acrylamide, the ethyl acrylate, the dispersant, the plasticizer, the thickener, the stabilizer, the defoamer, and the solvent is 100:12:30:30:50:40:30:20:20:200, or 100:6:30:30:50:40:30:20:20:200, or 100:12:20:20:30:30:20:10:10:100, or 100:18: 40： 40： 60:50:40:30:30:300, or 100:24:30:30:50:40:30:20:20:

200.

3. The preparation method of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating according to claim 1, characterized in that: The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass, and the average relative molecular weight of the chlorinated rubber resin is between 10,000 and 20,000; the dispersant is any one of polyethylene glycol 200 or polyethylene glycol 400 or a mixture thereof; the plasticizer is any one of dioctyl phthalate or dibutyl phthalate or a mixture thereof; the thickener is a mixture of methyl hydroxypropyl cellulose and bentonite; the stabilizer is any one of dibutyltin dilaurate or methyltin mercaptan or a mixture thereof; the defoamer is any one of polyether defoamers or silicone defoamers; the solvent is any one of acetone, xylene, ethyl acetate or a mixture of two or more of them.

4. The preparation method of the hydrophobic hexagonal boron nitride chlorinated rubber composite coating according to claim 3, characterized in that: The chlorinated rubber resin is a chlorinated rubber resin with a chlorine content between 66% and 68% by mass, and the average relative molecular weight of the chlorinated rubber resin is 12,000; the dispersant is composed of polyethylene glycol 200 and polyethylene glycol 400 in a mass ratio of 1:2; the plasticizer is composed of dioctyl phthalate and dibutyl phthalate in a mass ratio of 1:1; the thickener is composed of methyl hydroxypropyl cellulose and bentonite in a mass ratio of 1:1; the stabilizer is composed of dibutyltin dilaurate and methyltin mercaptan in a mass ratio of 1:2; the defoamer is a polyether defoamer; and the solvent is a mixture of acetone, xylene, and ethyl acetate in a mass ratio of 3:2:

3.

5. The method for preparing the hydrophobic hexagonal boron nitride chlorinated rubber composite coating according to claim 1, characterized in that, The hydrothermal synthesis using ammonium borate and urea with programmed temperature rise, followed by atmosphere protection and acid washing processes, yields a hexagonal boron nitride precursor, comprising: Ammonium borate and urea are mixed and stirred evenly. The mixture is placed in a stainless steel reactor and heated to 80-100°C. The temperature is maintained for 1-2 hours, then increased to 120-150°C and maintained for 1-2 hours. The temperature is then increased to 160-180°C, and nitrogen gas is introduced. The reaction product is washed with hydrochloric acid to obtain the hexagonal boron nitride precursor.

6. The method for preparing the hydrophobic hexagonal boron nitride chlorinated rubber composite coating according to claim 5, characterized in that, The mass ratio of ammonium borate to urea is 2:

3.

7. The method for preparing the hydrophobic hexagonal boron nitride chlorinated rubber composite coating according to claim 1, characterized in that, The process of cell disruption and ultrasonic exfoliation of the hexagonal boron nitride precursor, by controlling the exfoliation time, yields two-dimensional hexagonal boron nitride nanomaterial powders with and without surface defects, including: Weigh out the hexagonal boron nitride precursor and add it to a beaker, then add deionized water and isopropanol. Stir with a stirrer until the mixture is homogeneous. Seal the beaker and place it in an ultrasonic cleaner for 1-2 hours to fully disperse the hexagonal boron nitride precursor powder. Place the beaker containing the homogeneous hexagonal boron nitride precursor dispersion in a cell disruptor and exfoliate for a total time of 4-18 hours. Centrifuge the dispersion obtained by crushing and exfoliation at 5000 r / min, and collect the supernatant to obtain a hexagonal boron nitride two-dimensional nanosheet dispersion. Filter and dry to obtain hexagonal boron nitride two-dimensional nanomaterial powder.

8. The method for preparing the hydrophobic hexagonal boron nitride chlorinated rubber composite coating according to claim 7, characterized in that, The mass ratio of the hexagonal boron nitride precursor, the deionized water and the isopropanol is 1:(2~3):(2~3).

9. The method for preparing the hydrophobic hexagonal boron nitride chlorinated rubber composite coating according to claim 1, characterized in that, When the exfoliation time is controlled to be 6 hours or less, a two-dimensional hexagonal boron nitride nanomaterial powder with no surface defects is obtained; when the exfoliation time is controlled to be greater than 6 hours, a two-dimensional hexagonal boron nitride nanomaterial powder with rich surface defects is obtained.

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