Hydrophobic antibacterial polymer, preparation method and application in hydrophobic antibacterial coating

Abstract

The invention discloses a hydrophobic antibacterial polymer, a preparation method and application in a hydrophobic antibacterial coating, and belongs to the technical field of high polymer materials, and the preparation method comprises the following steps: mixing a component A with a first organic solvent to obtain a solution 1, and mixing a component B with a second organic solvent to obtain a solution 2; blending the solution 1 and the solution 2, adding a component C and an initiator, and reacting to obtain a hydrophobic antibacterial polymer; dissolving the hydrophobic antibacterial polymer in a third organic solvent to obtain a solute solution; and coating the surfaces of fabrics, silicon wafers, steel and wood with the dissolved matter solution through spraying, dispensing and dipping, and curing to obtain the self-healing high-durability hydrophobic antibacterial coating capable of being freely coated. The preparation method disclosed by the invention is simple in process and low in cost, the obtained coating has excellent hydrophobicity, antibacterial property and environmental stability and also has self-repairing property and free coating property, and the service life and the use convenience of the coating are remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials. More specifically, the present invention relates to a hydrophobic antibacterial polymer, a preparation method thereof, and an application in a hydrophobic antibacterial coating. Background Art

[0002] With the rapid development of fields such as wearable smart fabrics, medical implant devices, and ocean engineering equipment, the demand for hydrophobic antibacterial properties on the surface of functional materials has become increasingly prominent. Low surface energy coatings are widely used due to their hydrophobic and anti-adhesion properties. Currently, the mainstream technical routes of low surface energy coating technology include 1) superhydrophobic coatings based on micro-nano structures and 2) hydrophobic coatings based on low surface energy components. Among them, on the surface of the micro-nano hierarchical structure constructed based on the Cassie-Baxter model, superhydrophobic characteristics with a contact angle > 150° can be achieved. However, the mechanical durability of this surface is insufficient, and the micro-nano structure is prone to structural collapse under external forces such as shear force and impact load, resulting in a sharp decline in hydrophobicity; at the same time, the Mie scattering effect caused by surface roughness will seriously reduce the light transmittance, making it difficult to meet the optical performance requirements.

[0003] By introducing low surface energy components such as fluorocarbon chains or polysiloxanes to prepare coatings, hydrophobic properties can be achieved while maintaining high transparency, and it has substrate universality. Compared with the superhydrophobic coatings with multi-level micro-nano rough surfaces, the technical difficulty of this coating is lower. However, it still faces the problem of poor durability, and the mechanical stability and chemical stability still need to be improved.

[0004] In addition, the antibacterial mechanism of existing hydrophobic coatings mainly relies on the low surface energy characteristics to reduce the initial adhesion rate of microorganisms. However, this mechanism lacks the ability to actively kill the attached bacteria (such as Staphylococcus aureus, Escherichia coli, etc.). And the current technical routes for improving antibacterial performance have the following problems: Although metal components such as copper and silver can achieve contact sterilization by slow release, the persistence is limited, and there are biosafety risks. The accumulation of heavy metals may cause cytotoxicity and affect the ecological environment. Organic quaternary ammonium salt antibacterial agents are widely used due to their long-lasting antibacterial properties and environmental friendliness. However, they are prone to migration loss under mechanical friction or solvent erosion, resulting in a shortened antibacterial life of the coating. Existing research combines quaternary ammonium salt groups with low surface energy components through chemical bonding, and theoretically, the antibacterial-hydrophobic bifunctional synergistic effect can be achieved. However, the long-term durability (including mechanical strength, chemical stability, and functional persistence) of this composite system in complex usage environments still needs to be further broken through. Summary of the Invention

[0005] An object of the present invention is to solve at least the above problems and / or defects and provide at least the advantages described hereinafter.

[0006] To achieve these and other advantages in accordance with the present invention, a hydrophobic antibacterial polymer is provided, and its structural formula is as follows:

[0007]

[0008] Wherein, x:y = 0.5 to 8.5:100; R1 is selected from one of the following structures:

[0009]

[0010] R2 is selected from one of the following structures:

[0011]

[0012] R3 is selected from one of the following structures:

[0013]

[0014] A method for preparing a hydrophobic antibacterial polymer, comprising: mixing component A with a first organic solvent mixture to obtain solution 1, and mixing component B with a second organic solvent to obtain solution 2; mixing solution 1 and solution 2, adding component C and an initiator, mixing evenly in a stirrer, heating to 65 - 80 °C and reacting for 2 - 20 h, and obtaining the hydrophobic antibacterial polymer after purification treatment after the reaction ends.

[0015] Preferably, wherein, component A is one of allyltrimethylammonium bromide, acryloyloxyethyltrimethylammonium chloride, (3 - acrylamidopropyl)trimethylammonium chloride, N-(2-(acryloyloxy)ethyl)-N,N - dimethyl - 1 - hexylamine bromide, N-(2-(acryloyloxy)ethyl)-N,N - dimethyl - 1 - decylamine bromide, N-(2-(methacryloyl)ethyl)-N,N - dimethyl - 1 - dodecylamine bromide, and their respective corresponding structural formulas are:

[0016]

[0017] Preferably, wherein, component B is one of octadecyl acrylate, docosyl acrylate, and their respective corresponding structural formulas are:

[0018]

[0019] Preferably, wherein, component C is one of γ - mercaptopropyltriethoxysilane, γ - mercaptopropyltrimethoxysilane, n - dodecyl mercaptan, and their respective corresponding structural formulas are:

[0020]

[0021] Preferably, the initiator is one of 2,2-azobisisobutyronitrile, benzoyl peroxide, dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylvaleronitrile), and dicumyl peroxide.

[0022] Preferably, the first organic solvent and / or the second organic solvent includes alcohol solvents, ether solvents, aromatic solvents, chlorinated alkane solvents, nitrile solvents, ester solvents, and aliphatic hydrocarbon solvents, specifically including: methanol, ethanol, tetrahydrofuran, 1,4-dioxane, toluene, benzene, dichloromethane, chloroform, 1,2-dichloroethane, acetonitrile, propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, butyl acetate, petroleum ether, n-hexane, and cyclohexane.

[0023] Preferably, the mass ratio of component A to component B is 1:1 to 9; the mass ratio of component B to component C is 1:0.03 to 0.1; the mass ratio of component B to the initiator is 1:0.01 to 0.05; the mass ratio of component A to the first organic solvent is 1:3 to 6, and the mass ratio of component B to the second organic solvent is 1:12 to 40.

[0024] Preferably, the purification treatment specifically includes: after the reaction is terminated, the product is first separated from the reaction solvent by centrifugation; then methanol and petroleum ether are used as washing solvents to perform gradient purification on the crude product; after centrifugal separation, the lower-layer target product is selectively collected; finally, through vacuum drying treatment, a hydrophobic antibacterial polymer is obtained.

[0025] An application of a hydrophobic antibacterial polymer, which is applied to the preparation of a free-coatable self-healing highly durable hydrophobic antibacterial coating. The specific method includes:

[0026] Step 1: Dissolve the hydrophobic antibacterial polymer in a third organic solvent to obtain a dissolved solution; wherein, the mass ratio of the hydrophobic antibacterial polymer to the third organic solvent is 0.5 to 5:100, and the third organic solvent is one or more of methanol, ethanol, tetrahydrofuran, 1,4-dioxane, toluene, benzene, dichloromethane, chloroform, 1,2-dichloroethane, acetonitrile, propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, butyl acetate, petroleum ether, n-hexane, and cyclohexane;

[0027] Step 2: Apply the dissolved solution to the surfaces of fabrics, silicon wafers, steel, and wood by spraying, drop coating, or dipping, and cure to obtain a free-coatable self-healing highly durable hydrophobic antibacterial coating; wherein, the curing temperature is 50 to 100 °C, and the curing time is 10 to 300 min.

[0028] The present invention has at least the following beneficial effects:

[0029] 1. The novel free - coatable self - healing highly durable hydrophobic and antibacterial coating prepared by the present invention has a reprogrammable self - healing property. Utilizing the melting and crystallization characteristics of long - chain alkanes, it endows the coating with a thermally responsive self - repair ability that can be reprogrammed. The morphology of the damaged coating can be restored by heating, significantly extending the service life. The present invention combines the hydrophobicity of fluorine - free long - chain alkanes with the antibacterial property of quaternary ammonium salts, realizing dual functions of anti - microbial contamination and physical protection in a single coating. Adopting low - threshold processes such as dipping / spraying / drop - coating, it supports "custom - made coating at will", adapting to different fabric substrates and scenario requirements. The present invention adjusts the structure to make the crystallization - melting phase transition behavior of the polymer around 45 - 50 °C, enabling the rearrangement of molecular chains under mild heating conditions, and finally achieving the repair of physical and chemical damages, including cracks, scratches, washing, acid and alkali corrosion, etc. The raw materials used in the present invention are cheap and easily available, and the operation is simple, having good prospects for industrial utilization;

[0030] 2. The free - coatable self - healing highly durable hydrophobic and antibacterial coating prepared by the present invention adheres well to the substrate and has good durability.

[0031] 3. The hydrophobic and antibacterial coating prepared by the present invention can achieve self - healing of physical or chemical damages through the melting - crystallization transition of long - chain alkanes. The hydrophobic property of the coating remains basically unchanged before and after healing, effectively improving the long - term durability of the coating. Based on the dynamic characteristics of melting crystallization, it also endows the coating with excellent re - coatability, and the coating can be repeatedly coated through a simple "mild heating - room temperature cycle".

[0032] 4. The hydrophobic and antibacterial coating provided by the present invention has excellent workability and long - term durability. Its precursor solution has good stability, supporting various coating methods such as spraying, dipping, and drop - coating, and can achieve convenient repair and performance restoration of damaged parts. This coating innovatively combines the intrinsic self - healing characteristics of the material and the advantage of free coating, and effectively maintains its hydrophobic and antibacterial properties through the synergistic effect of dual mechanisms. When the coating is damaged during use, its initial functional characteristics can be almost completely restored through simple re - coating operations. This technological breakthrough provides a reliable solution for fields such as medical devices, ocean engineering, and food packaging that require long - term hydrophobic and antibacterial properties, and has important application value.

[0033] Other advantages, objectives, and features of the present invention will be partially reflected by the following description and partially understood by those skilled in the art through the research and practice of the present invention. Description of the Drawings

[0034] Figure 1 Antibacterial performance tests before and after the self - healing highly durable hydrophobic and antibacterial coating obtained on the aramid fabric surface in Example 12;

[0035] Figure 2 It is a graph showing the change in hydrophobicity of the self-healing, highly durable, hydrophobic and antibacterial coating obtained on the surface of the aramid fabric during the alkali destruction process in Example 12;

[0036] Figure 3 It is a graph showing the change in hydrophobicity of the self-healing, highly durable, hydrophobic and antibacterial coating obtained on the surface of the aramid fabric after alkali destruction-self-healing repair in Example 12;

[0037] Figure 4 It is a scanning electron microscope image of the self-healing, highly durable, hydrophobic and antibacterial coating obtained on the surface of the aramid fabric after alkali destruction and self-healing repair in Example 12;

[0038] Figure 5 It is a graph showing the change in hydrophobicity and the number of washing cycles of the self-healing, highly durable, hydrophobic and antibacterial coating obtained on the surfaces of cotton, polyester, aramid and nylon fabrics in Example 12. Detailed implementation manners

[0039] The following further elaborates on the present invention with reference to the accompanying drawings, so that those skilled in the art can implement it according to the text of the specification.

[0040] It should be understood that terms such as "having", "comprising" and "including" as used herein do not exclude the presence or addition of one or more other elements or their combinations.

[0041] Example 1

[0042] First, the monomer (3-acrylamidopropyl) trimethylammonium chloride and methanol are mixed in a mass ratio of 1:3 to prepare Solution 1. At the same time, the monomer docosyl acrylate and ethyl acetate are mixed in a mass ratio of 1:40 to prepare Solution 2, where the mass ratio of docosyl acrylate to (3-acrylamidopropyl) trimethylammonium chloride is 1:1;

[0043] Solutions 1 and 2 are blended and then γ-mercaptopropyltriethoxysilane equivalent to 5% of the mass of docosyl acrylate and 2,2-azobisisobutyronitrile are added. After mixing evenly, the reaction is carried out at 80 °C and 400 rpm for 10 hours. After the reaction is completed, it is left standing for 48 hours, and then filtered and washed three times with petroleum ether and methanol in sequence. Finally, it is dried at 45 °C and -0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0044] Example 2

[0045] First, mix the monomer (3 - acrylamidopropyl) trimethyl ammonium chloride with methanol at a mass ratio of 1:3 to obtain Solution 1. At the same time, mix the monomer docosyl acrylate with ethyl acetate at a mass ratio of 1:30 to obtain Solution 2, where the mass ratio of docosyl acrylate to (3 - acrylamidopropyl) trimethyl ammonium chloride is 3:1.

[0046] After mixing Solution 1 and Solution 2, add γ - mercaptopropyltriethoxysilane equivalent to 3% of the mass of docosyl acrylate and 2% of benzoyl peroxide. After mixing evenly, react at 80 °C and 400 rpm for 8 hours. After the reaction is completed, let it stand for 48 hours. After suction filtration, wash it three times with petroleum ether and methanol in sequence. Finally, dry it at 45 °C and - 0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0047] Example 3

[0048] First, mix the monomer allyltrimethylammonium bromide with methanol at a mass ratio of 1:3 to obtain Solution 1. At the same time, mix the monomer docosyl acrylate with ethyl acetate at a mass ratio of 1:20 to obtain Solution 2, where the mass ratio of docosyl acrylate to propyltrimethylammonium bromide is 8:1.

[0049] After mixing Solution 1 and Solution 2, add n - dodecyl mercaptan equivalent to 3% of the mass of docosyl acrylate and 2.5% of 2,2 - azobisisobutyronitrile. After mixing evenly, react at 70 °C and 400 rpm for 4 hours. After the reaction is completed, let it stand for 48 hours. After suction filtration, wash it three times with petroleum ether and methanol in sequence. Finally, dry it at 45 °C and - 0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0050] Example 4

[0051] First, mix the monomer N - (2 - (methacryloyl) ethyl) - N,N - dimethyl - 1 - dodecylamine bromide with methanol at a mass ratio of 1:6 to obtain Solution 1. At the same time, mix the monomer octadecyl acrylate with ethyl acetate at a mass ratio of 1:15 to obtain Solution 2, where the mass ratio of octadecyl acrylate to N - (2 - (methacryloyl) ethyl) - N,N - dimethyl - 1 - dodecylamine bromide is 9:1.

[0052] After mixing Solution 1 and Solution 2, add γ - mercaptopropyltriethoxysilane equivalent to 5% of the mass of octadecyl acrylate and 3% of benzoyl peroxide. After mixing evenly, react at 80 °C and 500 rpm for 16 hours. After the reaction is completed, let it stand for 48 hours. After suction filtration, wash it three times with petroleum ether and methanol in sequence. Finally, dry it at 45 °C and - 0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0053] Example 5

[0054] First, mix the monomer N-(2-(methacryloyl)ethyl)-N,N-dimethyl-1-dodecylamine bromide with methanol in a mass ratio of 1:6 to obtain Solution 1. At the same time, mix the monomer docosyl acrylate with ethyl acetate in a mass ratio of 1:12 to obtain Solution 2, where the mass ratio of docosyl acrylate to N-(2-(methacryloyl)ethyl)-N,N-dimethyl-1-dodecylamine bromide is 9:1.

[0055] After mixing Solution 1 and Solution 2, add γ-mercaptopropyltriethoxysilane equivalent to 5% of the mass of docosyl acrylate and 3% of benzoyl peroxide. After mixing evenly, react at 80 °C and 500 rpm for 15 hours. After the reaction is completed, let it stand for 48 hours. After suction filtration, wash it three times with petroleum ether and methanol in sequence. Finally, dry it at 45 °C and -0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0056] Example 6

[0057] First, mix the monomer N-(2-(acryloyloxy)ethyl)-N,N-dimethyl-1-hexylamine bromide with methanol in a mass ratio of 1:6 to obtain Solution 1. At the same time, mix the monomer octadecyl acrylate with ethyl acetate in a mass ratio of 1:20 to obtain Solution 2, where the mass ratio of octadecyl acrylate to N-(2-(acryloyloxy)ethyl)-N,N-dimethyl-1-hexylamine bromide is 7:1.

[0058] After mixing Solution 1 and Solution 2, add n-dodecyl mercaptan equivalent to 5% of the mass of octadecyl acrylate and 3% of 2,2'-azobisisobutyronitrile. After mixing evenly, react at 80 °C and 400 rpm for 10 hours. After the reaction is completed, let it stand for 48 hours. After suction filtration, wash it three times with petroleum ether and methanol in sequence. Finally, dry it at 45 °C and -0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0059] Example 7

[0060] First, mix the monomer acryloyloxyethyltrimethylammonium chloride with methanol in a mass ratio of 1:3 to obtain Solution 1. At the same time, mix the monomer docosyl acrylate with ethyl acetate in a mass ratio of 1:15 to obtain Solution 1, where the mass ratio of docosyl acrylate to acryloyloxyethyltrimethylammonium chloride is 6:1.

[0061] After mixing Solution 1 and Solution 2, add n-dodecyl mercaptan equivalent to 5% of the mass of docosyl acrylate and 3% of 2,2'-azobisisobutyronitrile. After mixing evenly, react at 70 °C and 500 rpm for 9 hours. After the reaction is completed, let it stand for 48 hours. After suction filtration, wash it three times with petroleum ether and methanol in sequence. Finally, dry it at 45 °C and -0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0062] Example 8

[0063] First, the monomer N-(2-(acryloyloxy)ethyl)-N,N-dimethyl-1-decanaminium bromide and methanol were mixed at a mass ratio of 1:6 to prepare Solution 1. At the same time, the monomer octadecyl acrylate and ethyl acetate were mixed at a mass ratio of 1:15 to prepare Solution 2, where the mass ratio of octadecyl acrylate to N-(2-(acryloyloxy)ethyl)-N,N-dimethyl-1-decanaminium bromide was 8:1;

[0064] After mixing Solution 1 and Solution 2, dodecyl mercaptan equivalent to 3% of the mass of octadecyl acrylate and 4% of 2,2'-azobis(2-methylpropionitrile) were added. After mixing evenly, the reaction was carried out at 70 °C and 500 rpm for 15 hours. After the reaction was completed, it was allowed to stand for 48 hours. After suction filtration, it was washed three times with petroleum ether and methanol in sequence, and finally dried at 45 °C and -0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0065] Example 9

[0066] First, the monomer N-(2-(acryloyloxy)ethyl)-N,N-dimethyl-1-decanaminium bromide and methanol were mixed at a mass ratio of 1:6 to prepare Solution 1. At the same time, the monomer docosyl acrylate and ethyl acetate were mixed at a mass ratio of 1:12 to prepare Solution 2, where the mass ratio of docosyl acrylate to N-(2-(acryloyloxy)ethyl)-N,N-dimethyl-1-decanaminium bromide was 7:1;

[0067] After mixing Solution 1 and Solution 2, dodecyl mercaptan equivalent to 3% of the mass of docosyl acrylate and 4% of 2,2'-azobis(2-methylpropionitrile) were added. After mixing evenly, the reaction was carried out at 70 °C and 500 rpm for 15 hours. After the reaction was completed, it was allowed to stand for 48 hours. After suction filtration, it was washed three times with petroleum ether and methanol in sequence, and finally dried at 45 °C and -0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0068] Example 10

[0069] First, the monomer N-(2-(acryloyloxy)ethyl)-N,N-dimethyl-1-hexanaminium bromide and methanol were mixed at a mass ratio of 1:6 to prepare Solution 1. At the same time, the monomer docosyl acrylate and ethyl acetate were mixed at a mass ratio of 1:18 to prepare Solution 2, where the mass ratio of docosyl acrylate to N-(2-(acryloyloxy)ethyl)-N,N-dimethyl-1-hexanaminium bromide was 6:1;

[0070] After mixing Solution 1 and Solution 2, add γ-mercaptopropyltriethoxysilane equivalent to 5% of the mass of docosyl acrylate and 3% of 2,2-azobisisobutyronitrile. After mixing evenly, react at 80 °C and 500 rpm for 7.5 hours. After the reaction is completed, let it stand for 48 hours. After suction filtration, wash it three times with petroleum ether and methanol in sequence. Finally, dry it at 45 °C and -0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0071] Example 11

[0072] First, mix the monomer acryloyloxyethyltrimethylammonium chloride and methanol in a mass ratio of 1:3 to prepare Solution 2. At the same time, mix the monomer octadecyl acrylate and ethyl acetate in a mass ratio of 1:20 to prepare Solution 1, where the mass ratio of octadecyl acrylate to acryloyloxyethyltrimethylammonium chloride is 4:1;

[0073] After mixing Solution 1 and Solution 2, add n-dodecyl mercaptan equivalent to 5% of the mass of octadecyl acrylate and 3% of 2,2-azobisisobutyronitrile. After mixing evenly, use a magnetic stirrer to react at 80 °C and 400 rpm for 7 hours. After the reaction is completed, let it stand for 48 hours. After suction filtration, wash it three times with petroleum ether and methanol in sequence. Finally, dry it at 45 °C and -0.9 bar for 30 hours to obtain the hydrophobic antibacterial polymer material.

[0074] Example 12

[0075] Dissolve the hydrophobic antibacterial polymer prepared in Example 11 in ethyl acetate at a ratio of 1 g:100 mL to obtain a coating solution. Spray it on glass slides, steel plates, aluminum plates, polyoxymethylene, silicon wafers, cardboard, polyester, cotton fabrics, nylon fabrics, and aramid fabrics respectively under a pressure of 3 bar using a spray gun. After curing at 50 °C for 0.5 h, the free-coatable self-healing high-durability hydrophobic antibacterial coating is obtained.

[0076] The hydrophobic performance of the hydrophobic antibacterial coating PAA obtained in Example 12 was tested. The results are shown in Table 1, and the hydrophobic performance of various substrates before and after coating was significantly improved.

[0077] Table 1 Changes in hydrophobicity of each sample before and after coating in Example 12

[0078] Sample Contact angle before coating (°) Contact angle after coating (°) Glass slide 44.3±0.9 97.4±1.8 Steel plate 60.3±1.3 99.6±1.9 Aluminum plate 84.1±2.7 94±2.1 Polyoxymethylene 74.8±1.6 97.9±2.1 Silicon wafer 74.3±1.0 98.6±2.0 Cardboard 92.5±4.5 114.5±2.5 Polyester 0 154.9±2.7 Nylon 0 144.2±4.9 Cotton fabric 0 155.0±1.5 Aramid 0 152.5±3.9

[0079] According to the standard GB / T 20944.3-2008, the antibacterial performance of the aramid fabric obtained in Example 12 was tested. As Figure 1 shown, the antibacterial rate of the aramid fabric against Staphylococcus aureus after coating can reach 99.99%.

[0080] The aramid fabric coating obtained in Example 12 was subjected to a self-healing test. The test method was as follows: The aramid fabric coating was immersed in a sodium hydroxide solution with pH = 14 and left at room temperature for 5 days. Then the fabric was washed with deionized water and air-dried at room temperature. Subsequently, the fabric was placed at 50 °C, and the self-healing behavior of the coating was evaluated by a Prox scanning electron microscope and a DSA25E contact angle measuring instrument. As Figure 2 shown, obvious peeling and falling off occurred on the fiber surface coating, and the contact angle decreased accordingly. However, in an environment of 50 °C, the coating only needed about 4 h to repair the damage. As Figure 3 and Figure 4 shown, it can be seen that the coating has excellent self-healing ability. Among them, Figure 4 (a) in it is the scanning electron microscope image of the coating after alkali damage, and (b) is the scanning electron microscope image of the coating after self-healing repair.

[0081] The wash resistance of the cotton, polyester, aramid, and nylon coated fabrics obtained in Example 12 was characterized. The washing process was carried out in accordance with AATCC 61-2013. As Figure 5 shown, after 50 washing cycles, the hydrophobicity of the cotton fabric (Cotton), polyester (Polyester), nylon (Nylon), and aramid fabric (Aramid) decreased to a certain extent. However, after free coating at will (CAW), their hydrophobicity basically recovered to the initial level.

[0082] The hydrophobic properties of the aramid-coated fabric PAA obtained in Example 12 before and after abrasion were characterized. The abrasion test was carried out using 600-mesh sandpaper. A 100-g weight was placed on the sandpaper, and moving back and forth 10 cm was regarded as one abrasion cycle. As shown in Table 2, after 100 abrasion cycles, the hydrophobicity of the three fabrics decreased to a certain extent. After gentle heating, only the hydrophobicity of the PAA-coated fabric recovered to ~148°. Among them, the commercial coated fabric 1 was purchased from Suzhou Jiubang Chemical Co., Ltd., and the commercial coated fabric 2 was purchased from Dongguan Jinda Textile Auxiliary Co., Ltd.

[0083] Table 2 Comparison of the hydrophobic properties of the sample fabric coatings and commercial fabric coatings before and after abrasion

[0084]

[0085] The equipment quantities and processing scales described here are used to simplify the description of the present invention. Applications, modifications, and variations of the present invention will be obvious to those skilled in the art.

[0086] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the embodiments. It can be fully applied to various fields suitable for the present invention. For those skilled in the art, additional modifications can be easily achieved. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and the examples shown and described herein.

Claims

1. A hydrophobic antibacterial polymer, characterized in that, The structural formula of the hydrophobic antibacterial polymer is as follows: where x:y = 0.5 - 8.5:100; R1 is selected from one of the following structures: R2 is selected from one of the following structures: R3 is selected from one of the following structures:

2. A method for preparing the hydrophobic antibacterial polymer according to claim 1, characterized in that, It includes: Mix component A with the first organic solvent mixture to obtain solution 1, and mix component B with the second organic solvent to obtain solution 2; mix solution 1 and solution 2, then add component C and an initiator, mix well in a stirrer, heat up to 65 - 80 °C and react for 2 - 20 h. After the reaction is completed, the hydrophobic antibacterial polymer is obtained through purification treatment.

3. The preparation method of the hydrophobic antibacterial polymer according to claim 2, characterized in that, Component A is one of allyltrimethylammonium bromide, acryloyloxyethyltrimethylammonium chloride, (3 - acrylamidopropyl)trimethylammonium chloride, N-(2-(acryloyloxy)ethyl)-N,N - dimethyl - 1 - hexylamine bromide, N-(2-(acryloyloxy)ethyl)-N,N - dimethyl - 1 - decylamine bromide, N-(2-(methacryloyl)ethyl)-N,N - dimethyl - 1 - dodecylamine bromide.

4. The preparation method of the hydrophobic antibacterial polymer according to claim 2, wherein Component B is one of octadecyl acrylate, docosyl acrylate.

5. The preparation method of the hydrophobic antibacterial polymer according to claim 2, wherein, Component C is one of γ - mercaptopropyltriethoxysilane, γ - mercaptopropyltrimethoxysilane, n - dodecyl mercaptan.

6. The preparation method of the hydrophobic antibacterial polymer according to claim 2, characterized in that, The initiator is one of 2,2 - azobisisobutyronitrile, benzoyl peroxide, dimethyl 2,2 - azobis(isobutyrate), 2,2 - azobis(2 - methylbutyronitrile), diisopropylbenzene peroxide.

7. The preparation method of the hydrophobic antibacterial polymer according to claim 2, wherein The first organic solvent and / or the second organic solvent includes alcohol solvents, ether solvents, aromatic solvents, chloroalkane solvents, nitrile solvents, ester solvents, aliphatic hydrocarbon solvents, specifically including: methanol, ethanol, tetrahydrofuran, 1,4 - dioxane, toluene, benzene, dichloromethane, chloroform, 1,2 - dichloroethane, acetonitrile, propionitrile, N,N - dimethylformamide, N,N - dimethylacetamide, ethyl acetate, butyl acetate, petroleum ether, n - hexane, cyclohexane.

8. The preparation method of the hydrophobic antibacterial polymer according to claim 2, wherein, The mass ratio of component A to component B is 1:1 - 9; the mass ratio of component B to component C is 1:0.03 - 0.1; the mass ratio of component B to the initiator is 1:0.01 - 0.05; the mass ratio of component A to the first organic solvent is 1:3 - 6, and the mass ratio of component B to the second organic solvent is 1:12 - 40.

9. The preparation method of the hydrophobic antibacterial polymer according to claim 2, wherein, The purification treatment specifically includes: after the reaction is terminated, first separate the product from the reaction solvent by centrifugation; then use methanol and petroleum ether as washing solvents to perform gradient purification on the crude product; after centrifugal separation, selectively collect the lower - layer target product; finally, obtain the hydrophobic antibacterial polymer through vacuum drying treatment.

10. Use of the hydrophobic antibacterial polymer according to claim 1, characterized in that, The hydrophobic antibacterial polymer is applied to the preparation of a freely - coatable self - healing highly durable hydrophobic antibacterial coating, specifically including: Step 1: Dissolve the hydrophobic antibacterial polymer in a third organic solvent to obtain a dissolved solution; wherein, the mass ratio of the hydrophobic antibacterial polymer to the third organic solvent is 0.5-5:100, and the third organic solvent is one or more of methanol, ethanol, tetrahydrofuran, 1,4-dioxane, toluene, benzene, dichloromethane, chloroform, 1,2-dichloroethane, acetonitrile, propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, butyl acetate, petroleum ether, n-hexane, cyclohexane; Step 2: Apply the dissolved solution onto the surfaces of fabrics, silicon wafers, steel, and wood by spraying, drop coating, or dip coating, and cure to obtain a self-healing highly durable hydrophobic antibacterial coating that can be freely coated; wherein, the curing temperature is 50-100°C and the curing time is 10-300 min.

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