A self-repairable silicone bio-antibacterial coating and a preparation method and application thereof

Abstract

This invention relates to the field of antibacterial coating technology, specifically to a self-healing organosilicon bio-antibacterial coating, its preparation method, and its application. The self-healing organosilicon bio-antibacterial coating of this invention comprises, by mass percentage: 78%–84.5% side-amino polysiloxane; 15%–20% biomass polyacid; and 0.5%–2% antibacterial metal ions. The organosilicon bio-antibacterial coating of this invention utilizes the amino groups in the side-amino polysiloxane to form a dynamic multi-linked network with the carboxyl groups of the biomass polyacid, while simultaneously combining with antibacterial metal ions to form coordination bonds within this dynamic multi-linked network. This results in the organosilicon bio-antibacterial coating not only possessing rapid self-healing properties but also exhibiting good mechanical properties after repair. Furthermore, the combined action of the biomass polyacid and the antibacterial metal ions endows the organosilicon bio-antibacterial coating with excellent antibacterial properties.

Description

Technical Field

[0001] This invention relates to the field of antibacterial technology, and more specifically, to a self-healing organosilicon bio-antibacterial coating, its preparation method, and its application. Background Technology

[0002] Antibacterial coatings are protective layers that can inhibit or kill bacteria and microorganisms. By applying antibacterial coatings to the surface of a substrate, an antibacterial coating is formed, which not only protects the substrate surface from bacterial contamination but also improves surface properties such as wear resistance, scratch resistance, and corrosion resistance. Furthermore, antibacterial coatings have the advantage of adjustable thickness and can load specific antibacterial agents, making them widely used in the medical field. However, existing antibacterial coatings are easily damaged and peel off, resulting in poor sustained antibacterial effect and low durability.

[0003] To address the aforementioned issues, existing technologies disclose a strawberry-shaped silver-supported polysilsesquioxane nanohybrid antibacterial material and its preparation method. PCMSQ nanospheres are prepared by emulsion polymerization of hydrophobic methylsilane and reactive monomeric carboxysilane in an aqueous system. The numerous hydrophobic methyl groups on the surface can reduce bacterial adhesion behavior, while the -COOH groups on the surface can react with Ag... + Complexation and as a reactive group can enhance the chemical bonding force of the antibacterial coating to prevent it from falling off, thereby improving the continuous antibacterial effect of the antibacterial coating; however, cracks or damage caused by external forces during actual use of the antibacterial coating cannot be repaired, resulting in poor antibacterial effect. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing antibacterial coatings, which cannot self-repair after being damaged by external forces, resulting in poor continuous antibacterial effects. This invention provides a self-healing organosilicon bio-antibacterial coating. It utilizes the amino groups in the side-amino polysiloxane to form a dynamic multi-linked network with the carboxyl groups of biomass polyacids, while simultaneously combining with antibacterial metal ions to form coordination bonds within this dynamic multi-linked network. This results in the organosilicon bio-antibacterial coating not only possessing rapid self-healing properties but also exhibiting good mechanical properties after repair. Furthermore, the combined action of biomass polyacids and antibacterial metal ions endows the organosilicon bio-antibacterial coating with excellent antibacterial performance.

[0005] Another object of the present invention is to provide a method for preparing a self-healing organosilicon bio-antibacterial coating.

[0006] Another object of the present invention is to provide the application of the above-mentioned self-healing organosilicon bio-antibacterial coating in biomedical materials.

[0007] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0008] This invention protects a self-healing organosilicon bio-antibacterial coating, comprising the following components by weight percentage:

[0009] 78%–84.5% side-amino polysiloxane;

[0010] 15%–20% biomass polyacids;

[0011] 0.5% to 2% antibacterial metal ions.

[0012] The organosilicon bio-antibacterial coating of the present invention utilizes the amino groups in the side-amino polysiloxane and the carboxyl groups of the biomass polyacids to form a dynamic multi-crosslinked network, while combining with antibacterial metal ions to form coordination bonds in the dynamic multi-crosslinked network. This makes the organosilicon bio-antibacterial coating not only have rapid self-healing properties, but also have good mechanical properties after repair. Moreover, the combined action of biomass polyacids and antibacterial metal ions endows the organosilicon bio-antibacterial coating with excellent antibacterial properties.

[0013] When the mass percentage of the amino-containing polysiloxane is too low, the mechanical properties and antibacterial effect of the antibacterial coating after film formation will be poor; when the mass percentage is too high, subsequent processing and coating will be difficult. Biomass polyacids are the antibacterial component in the system and also act as crosslinking agents. When the mass percentage of biomass polyacids is too low, it will affect the antibacterial effect of the antibacterial coating after film formation; when the mass percentage is too high, it will lead to dense crosslinking points, causing the crosslinking network to form too quickly, making subsequent processing and coating difficult. Similarly, when the mass percentage of antibacterial metal ions is too low, it will affect the antibacterial effect of the antibacterial coating after film formation; when the mass percentage is too high, it will affect subsequent processing and coating.

[0014] Optionally, the mass percentages of the above components are as follows: 80%–82% side-amino polysiloxane, 17%–19% citric acid and 0.8%–1.2% antibacterial metal ions; specifically, 81% side-amino polysiloxane, 18% citric acid and 1% antibacterial metal ions.

[0015] Specifically, the biomass polyacid is one or more of citric acid, gallic acid, caffeic acid, proanthocyanidins, and quercetin; preferably, the biomass polyacid is citric acid.

[0016] Specifically, the antibacterial metal ion is silver ion and / or zinc ion; preferably, the antibacterial metal ion is silver ion.

[0017] The side-amino polysiloxane is prepared by the following method:

[0018] Using hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane, octamethylcyclotetrasiloxane, and water as the reaction medium, and in an inert gas atmosphere, a hydrolysis-condensation reaction was carried out at 80–100 °C for 9–15 h, followed by purification to obtain the side-amino polysiloxane. The specific reaction equation is as follows:

[0019]

[0020] Too low a reaction temperature or too short a reaction time will result in insufficient hydrolysis and condensation, leading to poor grafting of the amino group; too high a reaction temperature or too long a reaction time will result in an overly vigorous reaction, easily causing gelation. A reaction at 80–100°C for 9–15 hours can produce a side-amino polysiloxane with sufficient hydrolysis and condensation and good amino grafting. In a specific embodiment, the hydrolysis and condensation reaction temperature can be 85–95°C, and the time can be 11–13 hours; more specifically, the hydrolysis and condensation reaction temperature is 90°C, and the time is 12 hours.

[0021] The above hydrolysis-condensation reaction needs to be carried out under an inert atmosphere, preferably nitrogen. The prepared side-amino polysiloxane needs to be purified. The specific purification steps are as follows: first, remove water and some low-boiling substances by vacuum distillation at 90°C, then raise the temperature to 150°C and hold for 0.5 h to decompose the catalyst while removing the remaining low-boiling substances by vacuum distillation, and finally lower to room temperature to obtain side-amino polysiloxane.

[0022] The above hydrolysis-condensation reaction can also be accelerated by adding a catalyst. The amount of catalyst added is 0.5% to 2% of the total weight of the raw materials (hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane and octamethylcyclotetrasiloxane), specifically 0.5%.

[0023] Preferably, the molar ratio of hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane, and octamethylcyclotetrasiloxane is (1-3):(10-40):100. More preferably, the molar ratio of hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane, and octamethylcyclotetrasiloxane is (1-2):(20-30):100.

[0024] The molar ratio of hexamethyldisiloxane as a capping agent affects the molecular weight of the polymer; γ-diethylenetriaminepropylmethyldimethoxysilane is used to graft side amino groups, affecting the amine value of the side amino polysiloxane. When the molar ratio of hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane, and octamethylcyclotetrasiloxane is (1-2):(20-30):100, the grafting effect of the side amino polysiloxane is better.

[0025] Preferably, the molar ratio of γ-diethylenetriaminepropylmethyldimethoxysilane to water is 1:1 to 2. Specifically, the molar ratio of γ-diethylenetriaminepropylmethyldimethoxysilane to water is 1:2. Water, as the reaction medium, mainly affects the degree of hydrolysis-condensation reaction. When the molar ratio of water to γ-diethylenetriaminepropylmethyldimethoxysilane is small, insufficient hydrolysis of octamethylcyclotetrasiloxane is likely to occur, resulting in a low yield of side-amino polysiloxane; when the molar ratio is large, gelation is likely to occur.

[0026] Preferably, the ammonia value of the side-amino polysiloxane is 1-3 mmol / g. The ammonia value of the side-amino polysiloxane is determined according to the People's Republic of China Chemical Industry Standard HG / T 4260-2011.

[0027] An appropriate ammonia value can help the coating bond better with the substrate and maintain long-term antibacterial properties.

[0028] This invention also protects a method for preparing the aforementioned self-healing organosilicon bio-antibacterial coating. The method involves mixing side-amino polysiloxane, biomass polyacid, and antibacterial metal ions in an organic solvent until homogeneous, followed by coating to obtain the self-healing organosilicon bio-antibacterial coating. The organic solvent serves to achieve a suitable viscosity to facilitate coating and forming the desired thickness of the self-healing organosilicon bio-antibacterial coating.

[0029] Preferably, the organic solvent is anhydrous ethanol, and the amount used is 10% to 30% of the total mass of the amino polysiloxane, biomass polyacid and antibacterial metal ions.

[0030] The application of a self-healing organosilicon bio-antibacterial coating in biomedical materials is also within the scope of protection of this invention.

[0031] The present invention has the following beneficial effects:

[0032] The organosilicon bio-antibacterial coating of the present invention utilizes the amino groups in the side-amino polysiloxane and the carboxyl groups of the biomass polyacids to form a dynamic multi-crosslinked network, while combining with antibacterial metal ions to form coordination bonds in the dynamic multi-crosslinked network. This makes the organosilicon bio-antibacterial coating not only have rapid self-healing properties, but also have good mechanical properties after repair. Moreover, the combined action of biomass polyacids and antibacterial metal ions endows the organosilicon bio-antibacterial coating with excellent antibacterial properties. Attached Figure Description

[0033] Figure 1 The infrared spectrum of the side-amino polysiloxane and the self-healing organosilicon bio-antibacterial coating in Example 1 is shown.

[0034] Figure 2 The images show the antibacterial effect of the self-healing organosilicon bio-antibacterial coatings in Examples 1-3 against Escherichia coli.

[0035] Figure 3 The images show the antibacterial effect of the self-healing organosilicon bio-antibacterial coatings in Examples 1-3 against Staphylococcus aureus.

[0036] Figure 4 This is a photograph of the self-healing silicone bio-antibacterial coating applied to the substrate in Example 1.

[0037] Figure 5 This is a diagram showing the recovery effect of the self-healing organosilicon bio-antibacterial coating applied to mouse wounds in Example 1. Detailed Implementation

[0038] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0039] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0040] Example 1

[0041] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0042] 78% side-amino polysiloxane, 20% citric acid and 2% antibacterial silver ions.

[0043] The aforementioned side-amino polysiloxane can be prepared by the following method:

[0044] In a 500 mL four-necked flask equipped with a thermometer, a stirrer, and a condenser, 1.14 g (0.007 mol) of hexamethyldisiloxane, 18.18 g (0.073 mol) of γ-diethylenetriaminepropylmethyldimethoxysilane, and 207.63 g (0.700 mol) of octamethylcyclotetrasiloxane were added in a molar ratio of 1:10.4:100. Then, 1.10 g of tetramethylammonium hydroxide and 2.63 g (0.146 mol) of water were added. The mixture was stirred at 90 °C for 12 h under a nitrogen atmosphere. Subsequently, some low-boiling substances were removed by vacuum distillation at 90 °C. Then, the temperature was raised to 150 °C and held for 0.5 h to decompose the catalyst while removing the remaining low-boiling substances by vacuum distillation. Finally, the temperature was lowered to room temperature to obtain a tert-aminopolysiloxane.

[0045] The preparation method of the above-mentioned self-healing organosilicon bio-antibacterial coating includes the following steps:

[0046] 5.00g of side-amino polysiloxane, 1.28g of citric acid, and 0.20g of silver nitrate (equivalent to 0.13g Ag) were added. +Add 1g of anhydrous ethanol, mix well, and coat to obtain a self-healing organosilicon bio-antibacterial coating.

[0047] Example 2

[0048] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0049] 81% side-amino polysiloxane, 18% citric acid and 1% antibacterial silver ions.

[0050] The preparation method of the above-mentioned side-amino polysiloxane is the same as that in Example 1, and the preparation method of the self-healing organosilicon bio-antibacterial coating is the same as that in Example 1.

[0051] Example 3

[0052] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0053] 84.5% side-amino polysiloxane, 15% citric acid and 0.5% antibacterial silver ions.

[0054] The preparation method of the above-mentioned side-amino polysiloxane is the same as that in Example 1, and the preparation method of the self-healing organosilicon bio-antibacterial coating is the same as that in Example 1.

[0055] Example 4

[0056] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0057] 81% side-amino polysiloxane, 18% citric acid and 1% antibacterial silver ions.

[0058] The aforementioned side-amino polysiloxane can be prepared by the following method:

[0059] In a 500 mL four-necked flask equipped with a thermometer, a stirrer, and a condenser, 1.14 g (0.007 mol) of hexamethyldisiloxane, 18.18 g (0.073 mol) of γ-diethylenetriaminepropylmethyldimethoxysilane, and 207.63 g (0.700 mol) of octamethylcyclotetrasiloxane were added in a molar ratio of 1:10.4:100. Then, 1.10 g of tetramethylammonium hydroxide and 2.63 g (0.146 mmol) of water were added. The mixture was stirred at 80 °C for 9 h under a nitrogen atmosphere. Subsequently, some low-boiling substances were removed by vacuum distillation at 90 °C. Then, the temperature was raised to 150 °C and held for 0.5 h to decompose the catalyst while removing the remaining low-boiling substances by vacuum distillation. Finally, the temperature was lowered to room temperature to obtain a lateral amino polysiloxane.

[0060] The preparation method of the above-mentioned self-healing organosilicon bio-antibacterial coating includes the following steps:

[0061] 5g of side-amino polysiloxane, 1.11g of citric acid, and 0.094g of silver nitrate (equivalent to 0.06g Ag) were added. + Add 1g of anhydrous ethanol, mix well, and coat to obtain a self-healing organosilicon bio-antibacterial coating.

[0062] Example 5

[0063] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0064] 78% side-amino polysiloxane, 20% citric acid and 2% antibacterial silver ions.

[0065] The aforementioned side-amino polysiloxane can be prepared by the following method:

[0066] In a 500 mL four-necked flask equipped with a thermometer, a stirrer, and a condenser, 1.14 g (0.007 mol) of hexamethyldisiloxane, 39.57 g (0.159 mol) of γ-diethylenetriaminepropylmethyldimethoxysilane, and 207.63 g (0.700 mol) of octamethylcyclotetrasiloxane were added in a molar ratio of 1:22.7:100. Then, 1.20 g of tetramethylammonium hydroxide and 5.72 g (0.318 mol) of water were added. The mixture was stirred at 90 °C for 12 h under a nitrogen atmosphere. Subsequently, some low-boiling substances were removed by vacuum distillation at 90 °C. Then, the temperature was raised to 150 °C and held for 0.5 h to decompose the catalyst while removing the remaining low-boiling substances by vacuum distillation. Finally, the temperature was lowered to room temperature to obtain a tert-aminopolysiloxane.

[0067] The preparation method of the above-mentioned self-healing organosilicon bio-antibacterial coating is the same as that in Example 1.

[0068] Example 6

[0069] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0070] 78% side-amino polysiloxane, 20% citric acid and 2% antibacterial silver ions.

[0071] The aforementioned side-amino polysiloxane can be prepared by the following method:

[0072] In a 500 mL four-necked flask equipped with a thermometer, a stirrer, and a condenser, 1.14 g (0.007 mol) of hexamethyldisiloxane, 64.06 g (0.257 mol) of γ-diethylenetriaminepropylmethyldimethoxysilane, and 207.63 g (0.700 mol) of octamethylcyclotetrasiloxane were added in a molar ratio of 1:36.7:100. Then, 1.33 g of tetramethylammonium hydroxide and 9.25 g (0.514 mol) of water were added. The mixture was stirred at 90 °C for 12 h under a nitrogen atmosphere. Subsequently, some low-boiling substances were removed by vacuum distillation at 90 °C. Then, the temperature was raised to 150 °C and held for 0.5 h to decompose the catalyst while removing the remaining low-boiling substances by vacuum distillation. Finally, the temperature was lowered to room temperature to obtain a tert-aminopolysiloxane.

[0073] The preparation method of the above-mentioned self-healing organosilicon bio-antibacterial coating is the same as that in Example 1.

[0074] Example 7

[0075] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0076] 78% side-amino polysiloxane, 20% citric acid and 2% antibacterial silver ions.

[0077] The aforementioned side-amino polysiloxane can be prepared by the following method:

[0078] In a 500 mL four-necked flask equipped with a thermometer, a stirrer, and a condenser, 1.14 g (0.007 mol) of hexamethyldisiloxane, 18.18 g (0.073 mol) of γ-diethylenetriaminepropylmethyldimethoxysilane, and 207.63 g (0.700 mol) of octamethylcyclotetrasiloxane were added in a molar ratio of 1:10.4:100. Then, 1.10 g of tetramethylammonium hydroxide and 1.314 g (0.073 mol) of water were added. The mixture was stirred at 90 °C for 12 h under a nitrogen atmosphere. Subsequently, some low-boiling substances were removed by vacuum distillation at 90 °C. Then, the temperature was raised to 150 °C and held for 0.5 h to decompose the catalyst while removing the remaining low-boiling substances by vacuum distillation. Finally, the temperature was lowered to room temperature to obtain a tert-aminopolysiloxane.

[0079] The preparation method of the above-mentioned self-healing organosilicon bio-antibacterial coating is the same as that in Example 1.

[0080] Comparative Example 1

[0081] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0082] 70% amino polysiloxane, 28% citric acid and 2% antibacterial silver ions.

[0083] The preparation method of the above-mentioned side-amino polysiloxane is the same as that in Example 1, and the preparation method of the self-healing organosilicon bio-antibacterial coating is the same as that in Example 1.

[0084] Comparative Example 2

[0085] A self-healing silicone bio-antibacterial coating comprises the following components in weight fractions:

[0086] 88% side-amino polysiloxane, 10% citric acid and 2% antibacterial silver ions.

[0087] The preparation method of the above-mentioned side-amino polysiloxane is the same as that in Example 1, and the preparation method of the self-healing organosilicon bio-antibacterial coating is the same as that in Example 1.

[0088] Performance testing

[0089] (1) Fourier Transform Infrared Spectroscopy Characterization (FTIR)

[0090] The FTIR spectra of the example samples were measured using a Nicoleti S50 Fourier transform infrared spectrometer manufactured by Thermo Fisher Scientific, USA, with the KBr pellet method employed and wavenumbers ranging from 3500 to 900 cm⁻¹. -1 scope; Figure 1 Infrared spectra of the side-amino polysiloxane and the self-healing organosilicon bio-antibacterial coating prepared in Example 1. Figure 1 It can be seen that the characteristic peak of the side-amino polysiloxane is mainly at 3360 cm⁻¹. -1 3290cm -1 1090cm -1 and 1020cm -1 Citric acid is present at 1728 cm⁻¹. -1 There is a distinct stretching vibration peak at 3360 cm⁻¹. -1 3290cm -1 The two peaks are the stretching vibration peaks of the amino group NH on the side chain of the side-amino polysiloxane, at 1090 cm⁻¹. -1 and 1020cm -1 The two peaks represent the stretching vibration peaks of Si-O in the Si-O-Si structure of the side-amino polysiloxane. The prepared self-healing organosilicon bio-antibacterial coating exhibits peaks at 1093 cm⁻¹. -1 and 1023cm -1 There are also two Si-O bond stretching vibration peaks at 3360 cm⁻¹. -1 ~3290cm -1 The stretching vibration peak of amino groups at 1728 cm⁻¹ and at 1728 cm⁻¹ -1The stretching vibration peaks of the carboxyl group have all disappeared, indicating that the amino group in the amino-containing polysiloxane has undergone a cross-linking reaction with the carboxyl group in the citric acid.

[0091] (2) Tensile strength test

[0092] Tensile strength was determined using a CMT4204 electronic universal testing machine from Mates Industrial Systems (China) Co., Ltd., according to ASTM D412 standard. The specimen size was 50 mm × 4 mm × 2 mm, and the tensile rate was 50 mm·min. -1 The self-healing silicone bio-antibacterial coating prepared in Example 1 was cut into 50mm × 4mm × 2mm pieces, then cut and reassembled using a utility knife. The tensile strength before and after repair was tested at 37℃ for 4 hours. The ratio of the tensile strength before and after repair was used as the repair efficiency to characterize the material's self-healing ability. The test results are shown in Table 1. Table 1 shows that the self-healing silicone bio-antibacterial coating of Example 1 achieved a repair efficiency of 51.4% within 2 hours, indicating a rapid repair rate. After 4 hours, the repair efficiency reached 80.5%, and the tensile strength recovered to 1.77 MPa, demonstrating good mechanical properties after repair.

[0093] The tensile strength of the self-healing silicone bio-antibacterial coatings prepared in all examples and comparative examples after self-healing for 4 hours at 37°C was tested using the same method. The test results are shown in Table 2. Examples 1-3 show that as the content of side-amino polysiloxane in the self-healing silicone bio-antibacterial coating increases, the original tensile strength of the coating increases accordingly; however, the repair efficiency decreases. This is because side-amino polysiloxane, as the main material of the coating, has excellent tensile strength; as its content increases, the tensile strength of the coating naturally increases. With the increase of side-amino polysiloxane content, the content of citric acid decreases accordingly, resulting in fewer dynamic multi-linked networks between the two, thus reducing the self-healing performance of the prepared coating.

[0094] Examples 1 and 4 show that lowering the dehydration condensation temperature and reducing the reaction time during the preparation of the side-amino polysiloxane resulted in a decrease in the initial tensile strength of the prepared self-healing organosilicon bio-antibacterial coating, but the repair efficiency remained largely unchanged. Examples 1 and 5-7 show that changing the molar ratio of hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane, and octamethylcyclotetrasiloxane, or the molar ratio of water to γ-diethylenetriaminepropylmethyldimethoxysilane, resulted in antibacterial coatings with good initial tensile strength and a repair efficiency of approximately 80% after 4 hours. Comparing the data from Examples 1 and Comparative Examples 1-2 reveals that a higher citric acid content (28%) resulted in a higher initial tensile strength of the prepared antibacterial coating due to the formation of more dynamic multi-crosslinked networks. However, the excessively dense crosslinking points caused the crosslinking network to form too quickly, affecting subsequent coating film formation. A lower citric acid content (12%) resulted in fewer dynamic multi-crosslinked networks, thus reducing the repair rate.

[0095] Table 1. Tensile strength test of self-healing silicone bio-antibacterial coating in Example 1

[0096] Repair time (h) Original tensile strength (MPa) Tensile strength after repair (MPa) Repair efficiency (%) 0.5 2.2 0.50 22.7 1 2.2 0.64 29.1 2 2.2 1.13 51.4 3 2.2 1.46 66.4 4 2.2 1.77 80.5

[0097] Table 2 Comparison of tensile strength and repair efficiency of different self-healing silicone bio-antibacterial coatings after 4 hours of repair.

[0098]

[0099]

[0100] (3) Antibacterial effect test

[0101] The self-healing organosilicon antibacterial coatings prepared in Examples 1-3 were used to prepare inhibition zone test samples with a diameter of 5 mm and a thickness of 4 mm for testing their antibacterial effects against Staphylococcus aureus and Escherichia coli. Before the test, the test samples were soaked in 75% ethanol solution for 1 min, then rinsed with sterile water, and allowed to air dry. Using sterile forceps, the samples were placed on the surfaces of plates stained with Staphylococcus aureus and Escherichia coli, the plates were covered, and the plates were incubated upright at (37±1)℃ and a relative humidity greater than 90% for 1-2 days. The experimental results are as follows: Figure 2 , Figure 3As shown, the self-healing organosilicon bio-antibacterial coatings prepared in Examples 1, 2, and 3 exhibited inhibition zone diameters of 11.51 mm, 11.12 mm, and 11.05 mm against Staphylococcus aureus, respectively, and 11.76 mm, 11.36 mm, and 11.18 mm against Escherichia coli, respectively. It can be observed that the self-healing organosilicon bio-antibacterial coating prepared in this invention possesses excellent antibacterial properties.

[0102] Figure 4 The image shows the actual product of the self-healing silicone bio-antibacterial coating applied to the substrate in Example 1. The self-healing silicone bio-antibacterial coating prepared in Example 1 was used to coat mouse wounds, and the experimental results are as follows. Figure 5 As shown in the figures, (a) the wound circled in red on the left is coated with the self-healing organosilicon bio-antibacterial coating prepared in Example 1, and the wound on the right is the blank control wound without any treatment; (b) the changes in the wound after 24 hours of coating. It can be seen from the figures that the wound coated with the self-healing organosilicon bio-antibacterial coating showed significant healing after 24 hours, while the blank control wound showed almost no change. This indicates that the self-healing organosilicon bio-antibacterial coating prepared in this invention has excellent antibacterial properties and can be used as a biomedical material.

[0103] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A self-healing organosilicon bio-antibacterial coating, characterized in that, By mass percentage, it includes the following components: 78%~84.5% side-amino polysiloxane; 15%~20% biomass polyacids; 0.5%~2% antibacterial metal ions; The biomass polyacids are one or more of citric acid, gallic acid, or caffeic acid.

2. The self-healing organosilicon bio-antibacterial coating according to claim 1, characterized in that, The antibacterial metal ions are silver ions and / or zinc ions.

3. The self-healing organosilicon bio-antibacterial coating according to claim 1, characterized in that, The side-amino polysiloxane is prepared by the following method: Using hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane, and octamethylcyclotetrasiloxane as raw materials, water as the reaction medium, and an inert gas atmosphere, the side-amino polysiloxane is obtained by hydrolysis and condensation reaction at 80~100℃ for 9~15h and then purified.

4. The self-healing organosilicon bio-antibacterial coating according to claim 3, characterized in that, The molar ratio of hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane to octamethylcyclotetrasiloxane is (1~3):(10~40):

100.

5. The self-healing organosilicon bio-antibacterial coating according to claim 4, characterized in that, The molar ratio of hexamethyldisiloxane, γ-diethylenetriaminepropylmethyldimethoxysilane and octamethylcyclotetrasiloxane is (1~2):(10~30):

100.

6. The self-healing organosilicon bio-antibacterial coating according to claim 3, characterized in that, The molar ratio of γ-diethylenetriaminepropylmethyldimethoxysilane to water is 1:(1~2).

7. The self-healing organosilicon bio-antibacterial coating according to claim 3, characterized in that, The amino group polysiloxane has an amino value of 1~3 mmol / g.

8. A method for preparing a self-healing organosilicon bio-antibacterial coating according to any one of claims 1 to 7, characterized in that, Includes the following steps: A self-healing organosilicon bio-antibacterial coating is obtained by mixing side-amino polysiloxane, biomass polyacids and antibacterial metal ions in an organic solvent, mixing them evenly, and then coating them.

9. The application of the self-healing organosilicon bio-antibacterial coating according to any one of claims 1 to 7 in biomedical materials.

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