Antibacterial functionalized nano silicon dioxide modified polyurethane coating and preparation method thereof

Abstract

The invention relates to the technical field of new materials, and discloses an antibacterial functionalized nano silicon dioxide modified polyurethane coating which is prepared by the following steps: by taking antibacterial functionalized nano silicon dioxide as a filler, synthesizing a polyurethane solution in situ to obtain a modified polyurethane coating; the carboxyl group on the surface of the functionalized nano silicon dioxide and the polyurethane polymer easily form a hydrogen bond pedicle effect, so that the functionalized nano silicon dioxide and the polyurethane coating have good compatibility, and the agglomeration of the nano silicon dioxide is improved; the uniformly dispersed nano silicon dioxide obviously enhances the tensile strength, elongation at break and other mechanical properties of the polyurethane coating, and the N-Cl bond modified on the surface of the nano silicon dioxide has excellent antibacterial property and has strong killing effect on escherichia coli, microorganisms and the like, so that the modified polyurethane coating has excellent antibacterial property and can be used for preparing the antibacterial polyurethane coating. Therefore, the practical application and industrial development of the polyurethane coating are expanded.

Description

Technical Field

[0001] The invention relates to the technical field of new materials, in particular to an antibacterial functionalized nano-silicon dioxide modified polyurethane coating and a preparation method thereof. Background Art

[0002] As a polymer material, polyurethane has excellent strength, elasticity, heat insulation, sound insulation and other advantages, which makes polyurethane can be used as coatings, adhesives, foams and other materials. It is widely used in building materials, shoemaking industry, medical field and other industries. In order to promote the practical application and industrial development of polyurethane materials, functional modification of polyurethane has become a research hotspot in recent years, such as enhancing the mechanical properties and antibacterial properties of polyurethane.

[0003] CN107189585A "A silica-loaded nanosilver water-based antibacterial coating and its preparation method" discloses a composite of nanosilicon dioxide and nanosilver to improve the antibacterial properties of polyurethane coatings. Nanosilicon dioxide, as a nanofiller with excellent performance, is widely available, cheap and easy to obtain. It is very important in polymer materials such as polyurethane and polystyrene. However, nanosilicon dioxide has a large specific surface area and high surface energy, which makes it very easy to agglomerate. In addition, nanosilicon dioxide and polyurethane have poor compatibility, resulting in difficulty in effectively exerting its enhancement effect when nanosilicon dioxide is used as a filler.

[0004] 1. Technical issues to be resolved In view of the deficiencies of the prior art, the present invention provides an antibacterial functionalized nano-silicon dioxide modified polyurethane coating and a preparation method thereof, which significantly enhances the mechanical properties of the polyurethane coating film and imparts the polyurethane film with unique antibacterial properties.

[0005] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: an antibacterial functionalized nano-silicon dioxide modified polyurethane coating, and the preparation method of the antibacterial functionalized nano-silicon dioxide modified polyurethane coating is as follows: (1) Preparation of amino-modified nano-silica: Add 0.1-5 g of nano-silica to 5-200 mL of ethanol, perform ultrasonication until uniform dispersion, then add 0.02-1.5 g of γ-aminopropyltrimethoxysilane, react at 40-60 °C for 2-8 h, centrifuge, wash with ethanol and deionized water, and dry to obtain amino-modified nano-silica.

[0006] (2) Preparation of carboxylated nano-silica: Add amino nano-silica and citric acid to ethanol and deionized water, and perform ultrasonication until the dispersion is uniform. Pour the solution into a hydrothermal reactor to react, and then use ethanol and deionized water for centrifugal washing and drying to obtain carboxylated nano-silica.

[0007] (3) Preparation of piperidinamine-carboxylated nano-silica: carboxylated nano-silica and tetramethylpiperidinamine were added to deionized water, and ultrasonicated until uniformly dispersed. The solution was poured into a hydrothermal reactor to react, and then centrifuged and washed with ethanol and deionized water and dried to obtain piperidinamine-carboxylated nano-silica.

[0008] (4) Preparation of antibacterial functionalized nano-silica: piperidinamine-carboxylated nano-silica was added to an aqueous solution of sodium hypochlorite, and the mixture was ultrasonically dispersed until uniformly dispersed. The mixture was reacted at 20-35 °C for 3-8 h, and then washed by centrifugation with deionized water and dried to obtain antibacterial functionalized nano-silica.

[0009] (5) Preparation of antibacterial functional nano-silica modified polyurethane coating: Add antibacterial functional nano-silica to acetone solvent, ultrasonicate until uniformly dispersed, add isophorone diisocyanate and polyester diol, stir to dissolve, add catalyst dibutyltin dilaurate, react at 75-85 ℃ for 2-3 h, then cool to 50-60 ℃, add dihydroxymethylpropionic acid, react for 1-2 h, then add 1,4-butanediol and react for 30-60 min, finally add acetone solvent and triethylamine for neutralization, add deionized water for emulsification, and obtain antibacterial functional nano-silica modified polyurethane coating.

[0010] Preferably, in step (2), the dosage ratio of ethanol, deionized water, amino-modified nano-silica and citric acid is 2-40 mL: 2-60 mL: 0.3-8 g: 0.05-1.5 g.

[0011] Preferably, the reaction in step (2) is carried out at 100-130° C. for 2-8 h.

[0012] Preferably, in step (3), the usage ratio of deionized water, carboxylated nano-silica and tetramethylpiperidinamine is 5-120 mL: 0.15-30 g: 0.012-3 g.

[0013] Preferably, the reaction in step (3) is carried out at 160-185° C. for 2-6 h. Preferably, the ratio of the sodium hypochlorite aqueous solution to piperidinamine-carboxylated nano-silica in step (4) is 5-1000 mL: 0.2-50 g.

[0014] Preferably, in step (5), the dosage ratio of antibacterial functionalized nano-silica, isophorone diisocyanate, polyester diol, dibutyltin dilaurate, dihydroxymethylpropionic acid, and 1,4-butanediol is 0.02-0.15 g: 3.5-5 g: 10 g: 0.2-0.6 g: 0.4-0.8 g: 0.12-0.3 g.

[0015] 3. Beneficial technical effects Compared with the prior art, the present invention has the following beneficial technical effects: The invention discloses an antibacterial functionalized nano-silica modified polyurethane coating. The nano-silica is modified by γ-aminopropyltrimethoxysilane. The amino functional groups introduced on the surface react with the carboxyl groups of citric acid in a hydrothermal system to undergo an amidation reaction to obtain carboxylated nano-silica. Abundant carboxyl groups are introduced, and then part of the carboxyl groups react with the imino groups of tetramethylpiperidinamine to obtain piperidinamine-carboxylated nano-silica. The active imino groups of the introduced piperidinamine react with halogenation in sodium hypochlorite to generate N-Cl bonds with high antibacterial activity from -NH bonds, thereby obtaining functionalized nano-silica with hydrophilic carboxyl groups and antibacterial N-Cl bonds on the surface.

[0016] The antibacterial functionalized nano-silica modified polyurethane coating uses antibacterial functionalized nano-silica as a filler, synthesizes a polyurethane solution in situ, and obtains a modified polyurethane coating. The carboxyl groups on the surface of the functionalized nano-silica easily form hydrogen bonds with the polyurethane polymer, so that the functionalized nano-silica has good compatibility with the polyurethane coating, improves the agglomeration of the nano-silica, and the uniformly dispersed nano-silica significantly enhances the mechanical properties of the polyurethane coating, such as tensile strength and elongation at break. In addition, the N-Cl bonds modified on the surface of the nano-silica have excellent antibacterial properties and have a strong killing effect on Escherichia coli, microorganisms, etc., so that the modified polyurethane coating has excellent antibacterial properties, thereby expanding the practical application and industrial development of the polyurethane coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is the structural formula of carboxylated nano-silica; Figure 2 It is the structural formula of piperidinamine-carboxylated nanosilica; Figure 3 It is the structural formula of antibacterial functionalized nano-silica. DETAILED DESCRIPTION

[0018] To achieve the above object, the present invention provides the following specific implementation methods and examples: A method for preparing an antibacterial functionalized nano-silicon dioxide modified polyurethane coating is as follows: (1) Add 0.1-5 g of nano-silica to 5-200 mL of ethanol, perform ultrasonication until uniform dispersion, then add 0.02-1.5 g of γ-aminopropyltrimethoxysilane, react at 40-60 °C for 2-8 h, centrifuge, wash with ethanol and deionized water, and dry to obtain amino-modified nano-silica.

[0019] (2) Add 0.3-8 g of amino-modified nano-silica and 0.05-1.5 g of citric acid to 2-40 mL of ethanol and 2-60 mL of deionized water, and perform ultrasonic treatment until the dispersion is uniform. Pour the solution into a hydrothermal reactor, react at 100-130 °C for 2-8 h, and then wash by centrifugation with ethanol and deionized water and dry to obtain carboxylated nano-silica.

[0020] (3) Add 0.15-30 g of carboxylated nano-silica and 0.012-3 g of tetramethylpiperidinamine to 5-120 mL of deionized water, and perform ultrasonic treatment until the dispersion is uniform. Pour the solution into a hydrothermal reactor, react at 160-185 °C for 2-6 h, and then wash by centrifugation with ethanol and deionized water and dry to obtain piperidineamine-carboxylated nano-silica.

[0021] (4) Add 0.2-50 g of piperidinamine-carboxylated nano-silica to 5-1000 mL of an aqueous solution of sodium hypochlorite, perform ultrasonic treatment until the mixture is uniformly dispersed, react at 20-35 °C for 3-8 h, and then wash the mixture by centrifugation with deionized water and dry it to obtain antibacterial functionalized nano-silica.

[0022] (5) Add 0.02-0.15 g of antibacterial functionalized nano-silica to acetone solvent, ultrasonicate until uniformly dispersed, add 3.5-5 g of isophorone diisocyanate and 10 g of polyester diol, stir to dissolve, add 0.2-0.6 g of catalyst dibutyltin dilaurate, react at 75-85 °C for 2-3 h, then cool to 50-60 °C, add 0.4-0.8 g of dihydroxymethylpropionic acid, react for 1-2 h, then add 0.12-0.3 g of 1,4-butanediol, react for 30-60 min, finally add acetone solvent and triethylamine for neutralization, add deionized water for emulsification, and obtain an antibacterial functionalized nano-silica modified polyurethane coating.

[0023] Example 1

[0024] (1) Add 0.1 g of nano-silica to 5 mL of ethanol and perform ultrasonication until the mixture is uniformly dispersed. Then, add 0.02 g of γ-aminopropyltrimethoxysilane and react at 40 °C for 2 h. The mixture is centrifuged, washed with ethanol and deionized water, and dried to obtain amino-modified nano-silica.

[0025] (2) Add 0.3 g of amino-modified nano-silica and 0.05 g of citric acid to 2 mL of ethanol and 2 mL of deionized water, and perform ultrasonic treatment until the mixture is uniformly dispersed. Pour the solution into a hydrothermal reactor and react at 100 °C for 2 h. Then, wash the mixture by centrifugation with ethanol and deionized water and dry it to obtain carboxylated nano-silica.

[0026] (3) Add 0.15 g of carboxylated nano-silica and 0.012 g of tetramethylpiperidinamine to 5 mL of deionized water, and perform ultrasonic treatment until the dispersion is uniform. Pour the solution into a hydrothermal reactor and react at 160 °C for 2 h. Then, wash the mixture by centrifugation with ethanol and deionized water and dry it to obtain piperidineamine-carboxylated nano-silica.

[0027] (4) Add 0.2 g of piperidinamine-carboxylated nano-silica to 5 mL of sodium hypochlorite aqueous solution, ultrasonicate until uniformly dispersed, react at 20 °C for 3 h, then wash with deionized water by centrifugation and dry to obtain antibacterial functionalized nano-silica.

[0028] (5) Add 0.02 g of antibacterial functionalized nano-silica to acetone solvent, ultrasonicate until uniformly dispersed, add 3.5 g of isophorone diisocyanate and 10 g of polyester diol, stir to dissolve, add 0.2 g of catalyst dibutyltin dilaurate, react at 75 °C for 2 h, then cool to 50 °C, add 0.4 g of dihydroxymethylpropionic acid, react for 1 h, then add 0.12 g of 1,4-butanediol and react for 30 min, finally add acetone solvent and triethylamine for neutralization, add deionized water for emulsification, and obtain antibacterial functionalized nano-silica modified polyurethane coating.

[0029] Example 2

[0030] (1) Add 1 g of nano-silica to 50 mL of ethanol and perform ultrasonication until the mixture is uniformly dispersed. Then, add 0.3 g of γ-aminopropyltrimethoxysilane and react at 40 °C for 4 h. The mixture is centrifuged, washed with ethanol and deionized water, and dried to obtain amino-modified nano-silica.

[0031] (2) Add 1 g of amino-modified nano-silica and 0.2 g of citric acid to 5 mL of ethanol and 10 mL of deionized water, and perform ultrasonic treatment until the dispersion is uniform. Pour the solution into a hydrothermal reactor and react at 100 °C for 4 h. Then, wash the solution by centrifugation with ethanol and deionized water and dry the solution to obtain carboxylated nano-silica.

[0032] (3) Add 0.5 g of carboxylated nano-silica and 0.05 g of tetramethylpiperidinamine to 20 mL of deionized water, and perform ultrasonic treatment until the dispersion is uniform. Pour the solution into a hydrothermal reactor and react at 185 °C for 2 h. Then, wash the mixture by centrifugation with ethanol and deionized water and dry it to obtain piperidineamine-carboxylated nano-silica.

[0033] (4) Add 1 g of piperidinamine-carboxylated nano-silica to 200 mL of sodium hypochlorite aqueous solution, ultrasonicate until uniformly dispersed, react at 30 °C for 3 h, then wash with deionized water by centrifugation and dry to obtain antibacterial functionalized nano-silica.

[0034] (5) Add 0.05 g of antibacterial functionalized nano-silica to acetone solvent, ultrasonicate until uniformly dispersed, add 4 g of isophorone diisocyanate and 10 g of polyester diol, stir to dissolve, add 0.3 g of catalyst dibutyltin dilaurate, react at 85 °C for 2 h, then cool to 50 °C, add 0.5 g of dihydroxymethylpropionic acid, react for 1 h, then add 0.18 g of 1,4-butanediol and react for 30 min, finally add acetone solvent and triethylamine for neutralization, add deionized water for emulsification, and obtain antibacterial functionalized nano-silica modified polyurethane coating.

[0035] Example 3

[0036] (1) Add 3 g of nano-silica to 120 mL of ethanol and perform ultrasonication until the nano-silica is uniformly dispersed. Then, add 0.8 g of γ-aminopropyltrimethoxysilane and react at 50 °C for 6 h. The mixture is centrifuged, washed with ethanol and deionized water, and dried to obtain amino-modified nano-silica.

[0037] (2) Add 5 g of amino-modified nano-silica and 1 g of citric acid to 25 mL of ethanol and 40 mL of deionized water, and perform ultrasonic treatment until the mixture is uniformly dispersed. Pour the solution into a hydrothermal reactor and react at 120 °C for 4 h. Then, wash the mixture by centrifugation with ethanol and deionized water and dry the mixture to obtain carboxylated nano-silica.

[0038] (3) Add 18 g of carboxylated nano-silica and 2 g of tetramethylpiperidinamine to 80 mL of deionized water, and perform ultrasonic treatment until the dispersion is uniform. Pour the solution into a hydrothermal reactor and react at 180 °C for 4 h. Then, wash the mixture by centrifugation with ethanol and deionized water and dry it to obtain piperidineamine-carboxylated nano-silica.

[0039] (4) Add 35 g of piperidinamine-carboxylated nano-silica to 800 mL of sodium hypochlorite aqueous solution, ultrasonicate until uniformly dispersed, react at 25 °C for 4 h, then wash with deionized water by centrifugation and dry to obtain antibacterial functionalized nano-silica.

[0040] (5) Add 0.1 g of antibacterial functionalized nano-silica to acetone solvent, ultrasonicate until uniformly dispersed, add 4 g of isophorone diisocyanate and 10 g of polyester diol, stir to dissolve, add 0.45 g of catalyst dibutyltin dilaurate, react at 80 °C for 2.5 h, then cool to 55 °C, add 0.65 g of dihydroxymethylpropionic acid, react for 1.5 h, then add 0.23 g of 1,4-butanediol and react for 40 min, finally add acetone solvent and triethylamine for neutralization, add deionized water for emulsification, and obtain antibacterial functionalized nano-silica modified polyurethane coating.

[0041] Example 4

[0042] (1) Add 5 g of nano-silica to 200 mL of ethanol and perform ultrasonication until the mixture is uniformly dispersed. Then, add 1.5 g of γ-aminopropyltrimethoxysilane and react at 60 °C for 8 h. The mixture is centrifuged, washed with ethanol and deionized water, and dried to obtain amino-modified nano-silica.

[0043] (2) Add 8 g of amino-modified nano-silica and 1.5 g of citric acid to 40 mL of ethanol and 60 mL of deionized water, and perform ultrasonic treatment until the mixture is uniformly dispersed. Pour the solution into a hydrothermal reactor and react at 130 °C for 8 h. Then, wash the mixture by centrifugation with ethanol and deionized water and dry the mixture to obtain carboxylated nano-silica.

[0044] (3) Add 30 g of carboxylated nano-silica and 3 g of tetramethylpiperidinamine to 120 mL of deionized water, and perform ultrasonic treatment until the dispersion is uniform. Pour the solution into a hydrothermal reactor and react at 185 °C for 6 h. Then, wash the mixture by centrifugation with ethanol and deionized water and dry it to obtain piperidineamine-carboxylated nano-silica.

[0045] (4) Add 50 g of piperidinamine-carboxylated nano-silica to 1000 mL of sodium hypochlorite aqueous solution, ultrasonicate until uniform dispersion, react at 35 °C for 8 h, then wash with deionized water by centrifugation and dry to obtain antibacterial functionalized nano-silica.

[0046] (5) Add 0.15 g of antibacterial functionalized nano-silica to acetone solvent, ultrasonicate until uniformly dispersed, add 5 g of isophorone diisocyanate and 10 g of polyester diol, stir to dissolve, add 0.6 g of catalyst dibutyltin dilaurate, react at 85 °C for 3 h, then cool to 60 °C, add 0.8 g of dihydroxymethylpropionic acid, react for 2 h, then add 0.3 g of 1,4-butanediol and react for 60 min, finally add acetone solvent and triethylamine for neutralization, add deionized water for emulsification, and obtain antibacterial functionalized nano-silica modified polyurethane coating.

[0047] Comparative Example 1 (1) Add 1 g of nano-silica to 30 mL of ethanol and perform ultrasonication until the mixture is uniformly dispersed. Then, add 0.3 g of γ-aminopropyltrimethoxysilane and react at 60 °C for 2 h. The mixture is centrifuged, washed with ethanol and deionized water, and dried to obtain amino-modified nano-silica.

[0048] (2) Add 3 g of amino-modified nano-silica and 0.4 g of citric acid to 25 mL of ethanol and 40 mL of deionized water, and perform ultrasonic treatment until the dispersion is uniform. Pour the solution into a hydrothermal reactor and react at 100 °C for 8 h. Then, wash the solution by centrifugation with ethanol and deionized water and dry it to obtain carboxylated nano-silica.

[0049] (3) Add 0.1 g of carboxylated nano-silica to acetone solvent, ultrasonicate until uniformly dispersed, add 4 g of isophorone diisocyanate and 10 g of polyester diol, stir to dissolve, add 0.35 g of catalyst dibutyltin dilaurate, react at 85 °C for 2 h, then cool to 60 °C, add 0.6 g of dihydroxymethylpropionic acid, react for 1.5 h, then add 0.18 g of 1,4-butanediol and react for 40 min, finally add acetone solvent and triethylamine for neutralization, add deionized water for emulsification, and obtain nano-silica modified polyurethane coating.

[0050] Comparative Example 2 (1) Add 0.12 g of nano-silica to acetone solvent, and ultrasonicate until it is uniformly dispersed. Add 4.5 g of isophorone diisocyanate and 10 g of polyester diol, stir to dissolve, then add 0.4 g of catalyst dibutyltin dilaurate, react at 75 °C for 2.5 h, then cool to 40 °C, add 0.65 g of dihydroxymethylpropionic acid, react for 1.5 h, then add 0.25 g of 1,4-butanediol, and react for 60 min. Finally, add acetone solvent and triethylamine for neutralization, and add deionized water for emulsification to obtain nano-silica modified polyurethane coating.

[0051] The antibacterial functionalized nano-silica modified polyurethane coating and the nano-silica modified polyurethane coating prepared in the embodiment and the comparative example were poured into a mold, naturally cast, heated and dried, and vacuum degassed to form a film. The tensile properties and elongation at break of the film were tested using a CMT4104 universal testing machine in accordance with GB / T 1040.1-2018.

[0052]

[0053] The polyurethane films prepared in the examples and comparative examples were cut into discs with a radius of 0.5 cm, placed in a culture dish, and peptone medium and buffer solution were added, followed by the activated Escherichia coli suspension. After being shaken evenly, they were placed in an incubator and cultured at 37°C for 10 h. After the culture, the diameter of the inhibition zone was tested, and the antibacterial properties of the polyurethane films were detected according to the inhibition zone method.

[0054]

Claims

1. An antibacterial functionalized nano-silicon dioxide modified polyurethane coating, characterized in that: The preparation method of the antibacterial functionalized nano-silicon dioxide modified polyurethane coating is as follows: (1) Preparation of amino-modified nano-silica: add 0.1-5 g of nano-silica to 5-200 mL of ethanol, perform ultrasonication until uniform dispersion, then add 0.02-1.5 g of γ-aminopropyltrimethoxysilane, react at 40-60 °C for 2-8 h, centrifuge, wash with ethanol and deionized water, and dry to obtain amino-modified nano-silica; (2) Preparation of carboxylated nano-silica: adding amino-containing nano-silica and citric acid to ethanol and deionized water, ultrasonicating until uniform dispersion, pouring the solution into a hydrothermal reactor to react, and then washing by centrifugation with ethanol and deionized water and drying to obtain carboxylated nano-silica; (3) Preparation of piperidinamine-carboxylated nano-silica: adding carboxylated nano-silica and tetramethylpiperidinamine to deionized water, ultrasonicating until uniform dispersion, pouring the solution into a hydrothermal reactor to react, and then washing by centrifugation with ethanol and deionized water and drying to obtain piperidinamine-carboxylated nano-silica; (4) Preparation of antibacterial functionalized nano-silica: piperidinamine-carboxylated nano-silica was added to an aqueous solution of sodium hypochlorite, and the mixture was subjected to ultrasonication until uniform dispersion, and the mixture was reacted at 20-35°C for 3-8 h, and then centrifuged and washed with deionized water and dried to obtain antibacterial functionalized nano-silica; (5) Preparation of antibacterial functional nano-silica modified polyurethane coating: Add antibacterial functional nano-silica to acetone solvent, ultrasonicate until uniformly dispersed, add isophorone diisocyanate and polyester diol, stir to dissolve, add catalyst dibutyltin dilaurate, react at 75-85 ℃ for 2-3 h, then cool to 50-60 ℃, add dihydroxymethylpropionic acid, react for 1-2 h, then add 1,4-butanediol and react for 30-60 min, finally add acetone solvent and triethylamine for neutralization, add deionized water for emulsification, and obtain antibacterial functional nano-silica modified polyurethane coating.

2. The antibacterial functionalized nano-silicon dioxide modified polyurethane coating according to claim 1, characterized in that: In the step (2), the dosage ratio of ethanol, deionized water, amino-modified nano-silica and citric acid is 2-40 mL: 2-60 mL: 0.3-8 g: 0.05-1.5 g.

3. The antibacterial functionalized nano-silicon dioxide modified polyurethane coating according to claim 1, characterized in that: In the step (2), the reaction is carried out at 100-130° C. for 2-8 h.

4. The antibacterial functionalized nano-silicon dioxide modified polyurethane coating according to claim 1, characterized in that: In the step (3), the dosage ratio of deionized water, carboxylated nano-silica and tetramethylpiperidinamine is 5-120 mL: 0.15-30 g: 0.012-3 g.

5. The antibacterial functionalized nano-silicon dioxide modified polyurethane coating according to claim 1, characterized in that: The reaction in step (3) is carried out at 160-185° C. for 2-6 h.

6. The antibacterial functionalized nano-silicon dioxide modified polyurethane coating according to claim 1, characterized in that: In the step (4), the dosage ratio of the sodium hypochlorite aqueous solution to the piperidinamine-carboxylated nano-silica is 5-1000 mL: 0.2-50 g.

7. The antibacterial functionalized nano-silicon dioxide modified polyurethane coating according to claim 1, characterized in that: In the step (5), the dosage ratio of antibacterial functionalized nano-silica, isophorone diisocyanate, polyester diol, dibutyltin dilaurate, dihydroxymethylpropionic acid, and 1,4-butanediol is 0.02-0.15 g: 3.5-5 g: 10 g: 0.2-0.6 g: 0.4-0.8 g: 0.12-0.3 g.

8. An antibacterial functionalized nano-silicon dioxide modified polyurethane coating prepared by the preparation method according to claims 1-7.

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