Nano flower-shaped titanium dioxide modified polyurethane antibacterial dressing and preparation method thereof
By covalently grafting nanoflower-like titanium dioxide in polyurethane materials to form modified antibacterial dressings, the problems of poor antibacterial performance and poor absorption of exudate are solved, and efficient antibacterial and exudate management is achieved to promote wound healing.
Patent Information
- Application Number
- CN202411785353.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-06
- Publication Date
- 2025-02-25
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Traditional dressings have poor antibacterial properties and poor absorption of exudate, making it difficult to meet the high requirements of modern medical treatment for in vitro hemostasis dressings.
An antibacterial dressing of nanoflower-like titanium dioxide modified polyurethane is formed by preparing nanoflower-like titanium dioxide and covalently grafting with the polyurethane material. This method improves the dispersion and stability of nanotitanium dioxide in the polyurethane matrix through ultrasonic dispersion, hydrothermal reaction and covalent grafting.
It significantly improves the antibacterial properties and exudate absorption capacity of antibacterial dressings, can effectively kill microorganisms such as E. coli, improve the wound environment, and promote healing.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of dressings, in particular to an antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane and a preparation method thereof. Background Art
[0002] Dressings are temporary substitutes for skin after skin injury. They can cover the wound to protect it, thereby preventing it from being injured again. At the same time, they can also provide a favorable environment for the wound to accelerate wound healing. With the development of science and technology in my country, people have also put forward higher requirements for extracorporeal hemostatic dressings. Not only do they need to have basic functions and good mechanical properties, but they also need to not increase the patient's pain during use and avoid causing secondary injuries. Traditional dressings generally include gauze, cotton, etc. Although they can also protect the wound and stop bleeding, they have poor antibacterial properties against microorganisms such as Escherichia coli, and poor absorption of wound exudate.
[0003] Compared with traditional dressings, the unique sponge-like porous layered structure of polyurethane foam makes it have better absorption performance for liquids, and gases such as carbon dioxide and oxygen can basically pass through it completely, which is beneficial for the wound to discharge secretions, thereby accelerating wound healing. In addition, polyurethane foam feels more comfortable to use. When used as a wound dressing, it has a good protective effect on the wound. However, the antibacterial performance of polyurethane foam itself against microorganisms such as Escherichia coli is very poor, and it needs to be chemically modified. Nano-titanium dioxide has the advantages of excellent optical properties and large specific surface area, and can be used to modify polyurethane foam materials, significantly improving the performance of polyurethane foam materials, but its dispersibility in the polyurethane matrix is poor, which greatly affects the modification effect.
[0004] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides an antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane and a preparation method thereof, which solves the problems of poor antibacterial performance and poor exudate absorption effect of traditional dressings.
[0005] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: an antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane, and the preparation method of the antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane is as follows: (1) Preparation of nano-flower-like titanium dioxide: Add acetic acid solvent and tetrabutyl titanate to a reactor in a mass ratio of 200-300:10, disperse them uniformly by ultrasonication, place them in a reactor, perform hydrothermal reaction at 140-180 °C for 8-12 h, cool to room temperature, centrifuge, wash with anhydrous ethanol and dry, place the product in an annealing furnace, anneal at 300-380 °C for 2-4 h, cool to room temperature, and obtain nano-flower-like titanium dioxide; (2) Preparation of epoxy functionalized titanium dioxide: adding anhydrous ethanol solvent and nano-flower-like titanium dioxide to a reactor, uniformly dispersing by ultrasonication, adding γ-glycidyloxypropyltrimethoxysilane, uniformly dispersing by ultrasonication, reacting, cooling to room temperature, centrifuging, washing with anhydrous ethanol and drying to obtain epoxy functionalized titanium dioxide; (3) Preparation of hydroxylated titanium dioxide: Add acetone solvent and epoxy functionalized titanium dioxide into a reactor, disperse them uniformly by ultrasonication, add diethanolamine, disperse them uniformly by ultrasonication, react, cool to room temperature, centrifuge, wash with acetone and dry to obtain hydroxylated titanium dioxide; (4) Preparing a solution containing titanium dioxide grafted polyurethane prepolymer: adding polyethylene glycol to a reactor, heating to a molten state, adding a crosslinking agent propylene glycol, a catalyst stannous octoate, hydroxylated titanium dioxide, and toluene diisocyanate, and uniformly dispersing by ultrasonication, reacting at 70-90°C for 6-10 hours, and cooling to room temperature to obtain a solution containing titanium dioxide grafted polyurethane prepolymer; (5) Preparation of antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide: Add a solution of polyurethane prepolymer grafted with titanium dioxide and polyether diol into a reactor, disperse them evenly by ultrasonication, add a catalyst stannous octoate, a foam stabilizer polysiloxane, and a pore-opening agent polybutadiene, disperse them evenly by ultrasonication, add toluene diisocyanate and deionized water, disperse them evenly by ultrasonication, pour into a mold for foaming, and mature at room temperature to obtain an antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide.
[0006] Preferably, in step (2), the mass ratio of anhydrous ethanol, nano-flower-shaped titanium dioxide, and γ-glycidyloxypropyltrimethoxysilane is 80-120:10:0.2-0.6.
[0007] Preferably, the reaction conditions in step (2) are 60-80° C. for 1-3 h.
[0008] Preferably, in step (3), the mass ratio of acetone, epoxy-functionalized titanium dioxide and diethanolamine is 100-180:10:0.4-0.8.
[0009] Preferably, the reaction conditions in step (3) are 40-60° C. for 4-8 h.
[0010] Preferably, in step (4), the mass ratio of polyethylene glycol, glycerol, stannous octoate, hydroxylated titanium dioxide, and toluene diisocyanate is 80-120:2-4:0.4-0.8:2-6:100.
[0011] Preferably, in step (5), the mass ratio of titanium dioxide grafted polyurethane prepolymer, polyether diol, stannous octoate, polysiloxane, polybutadiene, toluene diisocyanate, and deionized water is 100:20-40:0.2-0.6:30-50:4-6:10-20:5-15.
[0012] 3. Beneficial technical effects Compared with the prior art, the present invention has the following beneficial technical effects: The antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane is prepared by using tetrabutyl titanate as raw material, and is subjected to hydrothermal treatment to generate titanium dioxide nanosheets, which are then assembled into titanium dioxide nanoflowers. The unique nano-flower-shaped morphology has an ultra-high specific surface area, which is conducive to exposing more photocatalytic active sites. The nanosheets are further reacted with γ-glycidyloxypropyltrimethoxysilane to obtain epoxy functionalized titanium dioxide, and epoxy groups are introduced. The nanosheets are then subjected to a ring-opening reaction with the imino groups on diethanolamine to obtain hydroxylated titanium dioxide, and two hydroxyl groups are introduced. The nano-flower-shaped titanium dioxide is used as a functional component, and is further reacted with polyethylene glycol, propylene glycol, and toluene diisocyanate to obtain a solution containing titanium dioxide grafted polyurethane prepolymers, and the antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane is further obtained.
[0013] The antibacterial dressing of nano-flower-like titanium dioxide modified polyurethane significantly improves the dispersibility of nano-titanium dioxide in the polyurethane matrix and reduces the agglomeration phenomenon through covalent grafting. Under light, titanium dioxide will generate photogenerated electrons and photogenerated holes. The photogenerated electrons will react with oxygen to generate superoxide free radicals, and the photogenerated holes will react with water to generate hydroxyl free radicals. Both of them have strong oxidizing properties and can directly attack the cell membrane of microorganisms such as Escherichia coli and rupture it, thereby leaking the cell contents and killing microorganisms such as Escherichia coli, so that the antibacterial dressing has excellent antibacterial properties. DETAILED DESCRIPTION
[0014] To achieve the above purpose, the present invention provides the following specific implementation methods and examples: an antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane, and a preparation method of the antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane is as follows: (1) Preparation of nano-flower-like titanium dioxide: Add acetic acid solvent and tetrabutyl titanate to a reactor in a mass ratio of 200-300:10, disperse them uniformly by ultrasonication, place them in a reactor, perform hydrothermal reaction at 140-180 °C for 8-12 h, cool to room temperature, centrifuge, wash with anhydrous ethanol and dry, place the product in an annealing furnace, anneal at 300-380 °C for 2-4 h, cool to room temperature, and obtain nano-flower-like titanium dioxide; (2) Preparation of epoxy functionalized titanium dioxide: adding anhydrous ethanol solvent and nano-flower-like titanium dioxide to a reactor, uniformly dispersing by ultrasonication, adding γ-glycidyloxypropyltrimethoxysilane, wherein the mass ratio of anhydrous ethanol, nano-flower-like titanium dioxide and γ-glycidyloxypropyltrimethoxysilane is 80-120:10:0.2-0.6, uniformly dispersing by ultrasonication, reacting at 60-80 °C for 1-3 h, cooling to room temperature, centrifuging, washing with anhydrous ethanol and drying to obtain epoxy functionalized titanium dioxide; (3) Preparation of hydroxylated titanium dioxide: Add acetone solvent and epoxy functionalized titanium dioxide to a reactor, disperse them uniformly by ultrasonication, add diethanolamine, wherein the mass ratio of acetone, epoxy functionalized titanium dioxide and diethanolamine is 100-180:10:0.4-0.8, disperse them uniformly by ultrasonication, react at 40-60 °C for 4-8 h, cool to room temperature, centrifuge, wash with acetone and dry to obtain hydroxylated titanium dioxide; (4) Preparing a solution containing titanium dioxide grafted polyurethane prepolymer: adding polyethylene glycol to a reactor, heating to a molten state, adding a crosslinking agent propylene glycol, a catalyst stannous octoate, hydroxylated titanium dioxide, and toluene diisocyanate, wherein the mass ratio of polyethylene glycol, propylene glycol, stannous octoate, hydroxylated titanium dioxide, and toluene diisocyanate is 80-120:2-4:0.4-0.8:2-6:100, ultrasonically dispersing the mixture uniformly, reacting at 70-90°C for 6-10 h, and cooling to room temperature to obtain a solution containing titanium dioxide grafted polyurethane prepolymer; (5) Preparation of antibacterial dressing of polyurethane modified with titanium dioxide in a nano-flower shape: Add a solution of polyurethane prepolymer grafted with titanium dioxide and polyether diol into a reactor, disperse them evenly by ultrasonication, add a catalyst stannous octoate, a foam stabilizer polysiloxane, and a pore-opening agent polybutadiene, disperse them evenly by ultrasonication, add toluene diisocyanate and deionized water, wherein the mass ratio of polyurethane prepolymer grafted with titanium dioxide, polyether diol, stannous octoate, polysiloxane, polybutadiene, toluene diisocyanate and deionized water is 100:20-40:0.2-0.6:30-50:4-6:10-20:5-15, disperse them evenly by ultrasonication, pour them into a mold for foaming, and mature them at room temperature to obtain an antibacterial dressing of polyurethane modified with titanium dioxide in a nano-flower shape. Example
[0015] (1) Preparation of nano-flower-like titanium dioxide: 200 mL of acetic acid solvent and 10 g of tetrabutyl titanate were added to the reactor, ultrasonically dispersed, placed in a reactor, hydrothermally reacted at 140 °C for 8 h, cooled to room temperature, centrifuged, washed with anhydrous ethanol and dried, placed in an annealing furnace, annealed at 300 °C for 2 h, cooled to room temperature, and obtained nano-flower-like titanium dioxide; (2) Preparation of epoxy functionalized titanium dioxide: Add 110 mL of anhydrous ethanol solvent and 10 g of nano-flower-like titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.2 g of γ-glycidyloxypropyltrimethoxysilane, disperse them evenly by ultrasonication, react at 60 °C for 1 h, cool to room temperature, centrifuge, wash with anhydrous ethanol and dry to obtain epoxy functionalized titanium dioxide; (3) Preparation of hydroxylated titanium dioxide: add 130 mL of acetone solvent and 10 g of epoxy functionalized titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.4 g of diethanolamine, disperse them evenly by ultrasonication, react at 40 °C for 4 h, cool to room temperature, centrifuge, wash with acetone and dry to obtain hydroxylated titanium dioxide; (4) Preparation of a solution containing titanium dioxide grafted polyurethane prepolymer: Add 80 g of polyethylene glycol to a reactor, heat to a molten state, add 2 g of crosslinking agent propylene glycol, 0.4 g of catalyst stannous octoate, 2 g of hydroxylated titanium dioxide, and 100 g of toluene diisocyanate, disperse uniformly by ultrasonication, react at 70 °C for 6 h, and cool to room temperature to obtain a solution containing titanium dioxide grafted polyurethane prepolymer; (5) Preparation of antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide: Add a solution containing 100 g of titanium dioxide grafted polyurethane prepolymer and 20 g of polyether diol into a reactor and disperse them evenly by ultrasonication. Add 0.2 g of stannous octoate as a catalyst, 30 g of polysiloxane as a foam stabilizer, and 4 g of polybutadiene as a pore opener and disperse them evenly by ultrasonication. Add 10 g of toluene diisocyanate and 5 g of deionized water and disperse them evenly by ultrasonication. Pour the mixture into a mold for foaming and mature it at room temperature to obtain an antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide. Example
[0016] (1) Preparation of nano-flower-like titanium dioxide: 220 mL of acetic acid solvent and 10 g of tetrabutyl titanate were added to the reactor, ultrasonically dispersed uniformly, placed in a reactor, hydrothermally reacted at 150 °C for 9 h, cooled to room temperature, centrifuged, washed with anhydrous ethanol and dried, placed in an annealing furnace, annealed at 320 °C for 2.5 h, and cooled to room temperature to obtain nano-flower-like titanium dioxide; (2) Preparation of epoxy functionalized titanium dioxide: Add 120 mL of anhydrous ethanol solvent and 10 g of nano-flower-like titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.3 g of γ-glycidyloxypropyltrimethoxysilane, disperse them evenly by ultrasonication, react at 65 °C for 1.5 h, cool to room temperature, centrifuge, wash with anhydrous ethanol and dry to obtain epoxy functionalized titanium dioxide; (3) Preparation of hydroxylated titanium dioxide: add 150 mL of acetone solvent and 10 g of epoxy functionalized titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.5 g of diethanolamine, disperse them evenly by ultrasonication, react at 45 °C for 5 h, cool to room temperature, centrifuge, wash with acetone and dry to obtain hydroxylated titanium dioxide; (4) Preparation of a solution containing titanium dioxide grafted polyurethane prepolymer: Add 90 g of polyethylene glycol to a reactor, heat to a molten state, add 2.5 g of crosslinking agent propylene glycol, 0.5 g of catalyst stannous octoate, 3 g of hydroxylated titanium dioxide, and 100 g of toluene diisocyanate, disperse uniformly by ultrasonication, react at 75 °C for 9 h, and cool to room temperature to obtain a solution containing titanium dioxide grafted polyurethane prepolymer; (5) Preparation of antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide: Add a solution containing 100 g of titanium dioxide grafted polyurethane prepolymer and 25 g of polyether diol into a reactor and disperse them evenly by ultrasonication. Add 0.3 g of catalyst stannous octoate, 35 g of foam stabilizer polysiloxane and 4.5 g of pore-opening agent polybutadiene and disperse them evenly by ultrasonication. Add 12.5 g of toluene diisocyanate and 7.5 g of deionized water and disperse them evenly by ultrasonication. Pour the mixture into a mold for foaming and mature at room temperature to obtain an antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide. Example
[0017] (1) Preparation of nano-flower-like titanium dioxide: 240 mL of acetic acid solvent and 10 g of tetrabutyl titanate were added to the reactor, ultrasonically dispersed uniformly, placed in a reactor, hydrothermally reacted at 160 °C for 10 h, cooled to room temperature, centrifuged, washed with anhydrous ethanol and dried, placed in an annealing furnace, annealed at 340 °C for 3 h, and cooled to room temperature to obtain nano-flower-like titanium dioxide; (2) Preparation of epoxy functionalized titanium dioxide: Add 130 mL of anhydrous ethanol solvent and 10 g of nano-flower-like titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.4 g of γ-glycidyloxypropyltrimethoxysilane, disperse them evenly by ultrasonication, react at 70 °C for 2 h, cool to room temperature, centrifuge, wash with anhydrous ethanol and dry to obtain epoxy functionalized titanium dioxide; (3) Preparation of hydroxylated titanium dioxide: Add 170 mL of acetone solvent and 10 g of epoxy functionalized titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.6 g of diethanolamine, disperse them evenly by ultrasonication, react at 50 °C for 6 h, cool to room temperature, centrifuge, wash with acetone and dry to obtain hydroxylated titanium dioxide; (4) Preparation of a solution containing titanium dioxide grafted polyurethane prepolymer: Add 100 g of polyethylene glycol to a reactor, heat to a molten state, add 3 g of crosslinking agent propylene glycol, 0.6 g of catalyst stannous octoate, 4 g of hydroxylated titanium dioxide, and 100 g of toluene diisocyanate, disperse uniformly by ultrasonication, react at 80 °C for 8 h, and cool to room temperature to obtain a solution containing titanium dioxide grafted polyurethane prepolymer; (5) Preparation of antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide: Add a solution containing 100 g of titanium dioxide grafted polyurethane prepolymer and 30 g of polyether diol into a reactor and disperse them evenly by ultrasonication. Add 0.4 g of catalyst stannous octoate, 40 g of foam stabilizer polysiloxane and 5 g of pore-opening agent polybutadiene and disperse them evenly by ultrasonication. Add 15 g of toluene diisocyanate and 10 g of deionized water and disperse them evenly by ultrasonication. Pour the mixture into a mold for foaming and mature at room temperature to obtain an antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide. Example
[0018] (1) Preparation of nano-flower-like titanium dioxide: 260 mL of acetic acid solvent and 10 g of tetrabutyl titanate were added to the reactor, ultrasonically dispersed uniformly, placed in a reactor, hydrothermally reacted at 170 °C for 11 h, cooled to room temperature, centrifuged, washed with anhydrous ethanol and dried, placed in an annealing furnace, annealed at 360 °C for 3.5 h, cooled to room temperature, and obtained nano-flower-like titanium dioxide; (2) Preparation of epoxy functionalized titanium dioxide: 140 mL of anhydrous ethanol solvent and 10 g of nano-flower-like titanium dioxide were added to the reactor, and ultrasonic dispersion was performed uniformly. 0.5 g of γ-glycidyloxypropyltrimethoxysilane was added, and ultrasonic dispersion was performed uniformly. The mixture was reacted at 75 °C for 2.5 h, cooled to room temperature, centrifuged, washed with anhydrous ethanol and dried to obtain epoxy functionalized titanium dioxide. (3) Preparation of hydroxylated titanium dioxide: Add 190 mL of acetone solvent and 10 g of epoxy functionalized titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.7 g of diethanolamine, disperse them evenly by ultrasonication, react at 55 °C for 7 h, cool to room temperature, centrifuge, wash with acetone and dry to obtain hydroxylated titanium dioxide; (4) Preparation of a solution containing titanium dioxide grafted polyurethane prepolymer: Add 110 g of polyethylene glycol to a reactor, heat to a molten state, add 3.5 g of crosslinking agent propylene glycol, 0.7 g of catalyst stannous octoate, 5 g of hydroxylated titanium dioxide, and 100 g of toluene diisocyanate, disperse uniformly by ultrasonication, react at 85 °C for 9 h, and cool to room temperature to obtain a solution containing titanium dioxide grafted polyurethane prepolymer; (5) Preparation of antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide: Add a solution containing 100 g of titanium dioxide grafted polyurethane prepolymer and 35 g of polyether diol into a reactor and disperse them evenly by ultrasonication. Add 0.5 g of catalyst stannous octoate, 45 g of foam stabilizer polysiloxane, and 5.5 g of pore-opening agent polybutadiene and disperse them evenly by ultrasonication. Add 17.5 g of toluene diisocyanate and 12.5 g of deionized water and disperse them evenly by ultrasonication. Pour the mixture into a mold for foaming and mature at room temperature to obtain an antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide. Example
[0019] (1) Preparation of nano-flower-like titanium dioxide: 280 mL of acetic acid solvent and 10 g of tetrabutyl titanate were added to the reactor, ultrasonically dispersed uniformly, placed in a reactor, hydrothermally reacted at 180 °C for 12 h, cooled to room temperature, centrifuged, washed with anhydrous ethanol and dried, placed in an annealing furnace, annealed at 380 °C for 4 h, cooled to room temperature, and obtained nano-flower-like titanium dioxide; (2) Preparation of epoxy functionalized titanium dioxide: Add 150 mL of anhydrous ethanol solvent and 10 g of nano-flower-like titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.6 g of γ-glycidyloxypropyltrimethoxysilane, disperse them evenly by ultrasonication, react at 80 °C for 3 h, cool to room temperature, centrifuge, wash with anhydrous ethanol and dry to obtain epoxy functionalized titanium dioxide; (3) Preparation of hydroxylated titanium dioxide: Add 210 mL of acetone solvent and 10 g of epoxy functionalized titanium dioxide into the reactor, disperse them evenly by ultrasonication, add 0.8 g of diethanolamine, disperse them evenly by ultrasonication, react at 60 °C for 8 h, cool to room temperature, centrifuge, wash with acetone and dry to obtain hydroxylated titanium dioxide; (4) Preparation of a solution containing titanium dioxide grafted polyurethane prepolymer: Add 120 g of polyethylene glycol to a reactor, heat to a molten state, add 4 g of crosslinking agent propylene glycol, 0.8 g of catalyst stannous octoate, 6 g of hydroxylated titanium dioxide, and 100 g of toluene diisocyanate, disperse uniformly by ultrasonication, react at 90 °C for 10 h, and cool to room temperature to obtain a solution containing titanium dioxide grafted polyurethane prepolymer; (5) Preparation of antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide: Add a solution containing 100 g of titanium dioxide grafted polyurethane prepolymer and 40 g of polyether diol into a reactor and disperse them evenly by ultrasonication. Add 0.6 g of stannous octoate as a catalyst, 50 g of polysiloxane as a foam stabilizer, and 6 g of polybutadiene as a pore opener and disperse them evenly by ultrasonication. Add 20 g of toluene diisocyanate and 15 g of deionized water and disperse them evenly by ultrasonication. Pour the mixture into a mold for foaming and mature it at room temperature to obtain an antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide.
[0020] Comparative Example 1 (1) Preparation of nano-flower-like titanium dioxide: 240 mL of acetic acid solvent and 10 g of tetrabutyl titanate were added to the reactor, ultrasonically dispersed uniformly, placed in a reactor, hydrothermally reacted at 160 °C for 10 h, cooled to room temperature, centrifuged, washed with anhydrous ethanol and dried, placed in an annealing furnace, annealed at 340 °C for 3 h, and cooled to room temperature to obtain nano-flower-like titanium dioxide; (2) Preparation of a solution containing titanium dioxide modified polyurethane prepolymer: Add 100 g of polyethylene glycol to a reactor, heat to a molten state, add 3 g of crosslinking agent propylene glycol, 0.6 g of catalyst stannous octoate, 4 g of nanoflower-like titanium dioxide, and 100 g of toluene diisocyanate, disperse uniformly by ultrasonication, react at 80 °C for 8 h, and cool to room temperature to obtain a solution containing titanium dioxide modified polyurethane prepolymer; (3) Preparation of antibacterial dressing of nano-flower-like titanium dioxide blended modified polyurethane: add a solution containing 100 g of titanium dioxide modified polyurethane prepolymer and 30 g of polyether diol into the reactor, and disperse them evenly by ultrasonication. Add 0.4 g of catalyst stannous octoate, 40 g of foam stabilizer polysiloxane, and 5 g of pore opener polybutadiene, and disperse them evenly by ultrasonication. Add 15 g of toluene diisocyanate and 10 g of deionized water, and disperse them evenly by ultrasonication. Pour the mixture into a mold for foaming and mature it at room temperature to obtain an antibacterial dressing of nano-flower-like titanium dioxide blended modified polyurethane.
[0021] The composite antibacterial dressings obtained in the examples and comparative examples were irradiated with ultraviolet light for 24 h, and then inoculated with the diluted Staphylococcus aureus test bacterial solution and cultured at a constant temperature for 1 h. The bacteria on the surface of the antibacterial dressings were then eluted with physiological saline and the eluted bacteria were diluted with 1:10 7 Dilute it with physiological saline in a certain ratio, then take an appropriate amount of bacterial solution to culture on solid culture medium, observe and calculate its concentration under a microscope, and calculate the antibacterial rate.
[0022]
[0023] The composite antibacterial dressings obtained in the examples and comparative examples were irradiated with ultraviolet light for 24 h, and then inoculated with the diluted Escherichia coli test solution and cultured at a constant temperature for 1 h. The bacteria on the surface of the antibacterial dressings were then eluted with physiological saline and the eluted bacteria were diluted with 1:10 7 Dilute it with physiological saline in a certain ratio, then take an appropriate amount of bacterial solution to culture on solid culture medium, observe and calculate its concentration under a microscope, and calculate the antibacterial rate.
[0024]
Claims
1. An antibacterial dressing of nano-flower-like titanium dioxide modified polyurethane, characterized in that: The preparation method of the antibacterial dressing of the nano-flower-shaped titanium dioxide modified polyurethane is as follows: (1) Preparation of nano-flower-like titanium dioxide: tetrabutyl titanate is added to acetic acid solvent in a mass ratio of 200-300:10, and the mixture is uniformly dispersed by ultrasonication. The mixture is placed in a reactor and subjected to hydrothermal reaction at 140-180 °C for 8-12 h, cooled, centrifuged, washed and dried, and the product is placed in an annealing furnace and annealed at 300-380 °C for 2-4 h, and cooled to obtain nano-flower-like titanium dioxide. (2) Preparation of epoxy functionalized titanium dioxide: adding nano-flower-like titanium dioxide to anhydrous ethanol solvent, uniformly dispersing by ultrasonication, adding γ-glycidyloxypropyltrimethoxysilane, uniformly dispersing by ultrasonication, reacting, cooling, centrifuging, washing and drying to obtain epoxy functionalized titanium dioxide; (3) Preparation of hydroxylated titanium dioxide: adding epoxy functionalized titanium dioxide to acetone solvent, uniformly dispersing by ultrasonication, adding diethanolamine, uniformly dispersing by ultrasonication, reacting, cooling, centrifuging, washing and drying to obtain hydroxylated titanium dioxide; (4) Preparing a solution containing titanium dioxide grafted polyurethane prepolymer: adding polyethylene glycol to a reactor, heating to a molten state, adding a crosslinking agent propylene glycol, a catalyst stannous octoate, hydroxylated titanium dioxide, and toluene diisocyanate, and uniformly dispersing by ultrasonication, reacting at 70-90 °C for 6-10 h, and cooling to obtain a solution containing titanium dioxide grafted polyurethane prepolymer; (5) Preparation of antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide: Add polyether diol to the solution of titanium dioxide grafted polyurethane prepolymer, disperse it evenly by ultrasonic, add catalyst stannous octoate, foam stabilizer polysiloxane, pore opener polybutadiene, disperse it evenly by ultrasonic, add toluene diisocyanate and deionized water, disperse it evenly by ultrasonic, pour it into a mold for foaming, and mature it at room temperature to obtain antibacterial dressing of polyurethane modified with nano-flower-like titanium dioxide.
2. The antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane according to claim 1, characterized in that: In the step (2), the mass ratio of anhydrous ethanol, nano-flower-shaped titanium dioxide and γ-glycidyloxypropyltrimethoxysilane is 80-120:10:0.2-0.
6.
3. The antibacterial dressing of nano-flower-like titanium dioxide modified polyurethane according to claim 1, characterized in that: The reaction conditions in step (2) are 60-80°C for 1-3 h.
4. The antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane according to claim 1, characterized in that: In the step (3), the mass ratio of acetone, epoxy-functionalized titanium dioxide and diethanolamine is 100-180:10:0.4-0.
8.
5. The antibacterial dressing of nano-flower-shaped titanium dioxide modified polyurethane according to claim 1, characterized in that: The reaction conditions in step (3) are 40-60° C. for 4-8 h.
6. The antibacterial dressing of nano-flower-like titanium dioxide modified polyurethane according to claim 1, characterized in that: In the step (4), the mass ratio of polyethylene glycol, glycerol, stannous octoate, hydroxylated titanium dioxide and toluene diisocyanate is 80-120:2-4:0.4-0.8:2-6:
100.
7. The antibacterial dressing of nano-flower-like titanium dioxide modified polyurethane according to claim 1, characterized in that: In the step (5), the mass ratio of titanium dioxide grafted polyurethane prepolymer, polyether diol, stannous octoate, polysiloxane, polybutadiene, toluene diisocyanate, and deionized water is 100:20-40:0.2-0.6:30-50:4-6:10-20:5-15.