Preparation method and application of nano-aluminum antibacterial material
By combining nano-aluminum with quaternary ammonium fibers and modified phosphorus bromide, nano-aluminum antibacterial materials were prepared, which solved the problem that nano-aluminum does not have significant antibacterial properties, and achieved broad-spectrum long-acting antibacterial and flame retardant effects.
Patent Information
- Application Number
- CN202510377369.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-28
- Publication Date
- 2025-07-04
AI Technical Summary
Nanoaluminum itself does not have significant antibacterial properties, which limits its application in the field of antibacterial.
By combining nano-aluminum with quaternary ammonium fibers and modified phosphorus bromide, nano-aluminum antibacterial materials were prepared, and the antibacterial effect of quaternary phosphorus salts and the flame retardant effect of the dense protective layer generated by modified phosphorus bromide during combustion.
It has achieved the broad-spectrum long-term antibacterial ability of nano-aluminum antibacterial materials in public health and safety, personal belongings and household use, and has good flame retardant properties.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of antibacterial materials, and specifically to a preparation method and application of a nano-aluminum antibacterial material. Background Art
[0002] With the wide application of antibacterial materials in fields such as medical treatment, food packaging, and daily necessities, the development of efficient, safe, and low-cost antibacterial materials has become a research hotspot. Nano-aluminum, due to its high specific surface area and unique physical and chemical properties, however, does not possess significant antibacterial properties itself, which limits its application in the antibacterial field. Therefore, how to avoid this phenomenon is the key to solving the problem. The preparation method of the nano-aluminum antibacterial material provided by the present invention uses base materials that are friendly and harmless to the human body and have broad-spectrum and long-lasting antibacterial ability. In addition to fully playing a role in public health safety, it is also very suitable for personal carry-on items or household use, antibacterial coatings, and antibacterial textiles to effectively kill live bacteria. Summary of the Invention
[0003] (I) Technical Problems to be Solved In view of the deficiencies of the prior art, the present invention provides a preparation method and application of a nano-aluminum antibacterial material, which have good antibacterial and flame-retardant effects.
[0004] (II) Technical Solutions To achieve the above object, the present invention provides the following technical solutions: A nano-aluminum antibacterial material, comprising the following weight components: 2-5 parts by weight of a nano-aluminum antibacterial agent, 3-4 parts by weight of quaternized fiber, and 1-3 parts by weight of modified phosphorus bromide.
[0005] Further, the preparation method of the quaternized fiber is as follows: S1. Add 8-10 mL of N,N-dimethylpropane-1,3-diamine, 5-6 mL of distilled water, and 0.5-0.51 g of dry acrylic fiber to a reactor, react at 75-80 °C for 5-6 h, and after completion, wash and dry the fiber to obtain a tertiary amine group fiber; S2. Add 5-7 mL of bromobutane and 0.45-0.5 g of the tertiary amine group fiber to 20-25 mL of an ethanol solvent, stir and mix, stir and reflux at 60-70 °C for 4-6 h, and after completion, wash and dry to obtain the quaternized fiber.
[0006] Further, the preparation method of the modified phosphorus bromide is as follows: (1) Add 2.14 - 2.19 g of 3 - bromopropylamine hydrobromide and 2.61 - 2.63 g of triphenylphosphine to 25 - 30 mL of acetonitrile solvent for reaction. After completion, filter and collect the precipitated solid, then dissolve it in water and adjust the pH value to 11 with saturated potassium carbonate aqueous solution, and extract the organic phase with dichloromethane. Rotate and evaporate to remove the solvent to obtain (3 - aminopropyl) triphenylphosphonium bromide; (2) Add guanidine acetic acid to thionyl chloride, stir evenly, and react at 65 - 75 °C for 10 - 14 h. After the reaction, filter by suction, wash, and dry to obtain the intermediate; (3) Add the intermediate and (3 - aminopropyl) triphenylphosphonium bromide to 30 - 40 mL of N,N - dimethylformamide solvent, stir to dissolve, continue to add triethylamine catalyst thereto, and react at 76 - 85 °C for 4 - 7 h. After completion, perform vacuum distillation, wash, and dry to obtain the modified phosphonium bromide.
[0007] Further, the reaction temperature in (1) is 70 - 80 °C.
[0008] Further, the reaction time in (1) is 6 - 8 h.
[0009] Further, the mass ratio of guanidine acetic acid to thionyl chloride in (2) is 1.2 - 1.5 g: 2.31 - 2.82 g.
[0010] Further, the mass ratio of the intermediate, (3 - aminopropyl) triphenylphosphonium bromide, and triethylamine catalyst in (3) is 1 - 2 g: 1.35 - 2.6 g: 0.01 - 0.02 g.
[0011] Further, the preparation method of the nano - aluminum antibacterial material is: Add nano - aluminum antibacterial agent, quaternized fiber, and modified phosphonium bromide to a stirrer, stir for 5 - 8 min, and dry after completion to obtain the nano - aluminum antibacterial material.
[0012] Further, the applications include the following aspects: applications in antibacterial coatings and antibacterial textiles.
[0013] (III) Beneficial technical effects In the present invention, a nano - aluminum antibacterial material is obtained by adding a nano - aluminum antibacterial agent, quaternized fiber, and modified phosphonium bromide to a stirrer, stirring, and drying after completion.
[0014] The bromine in 3-bromopropylamine hydrobromide reacts with the phosphorus atom in triphenylphosphine to form a quaternary phosphonium salt, and at the same time an amino group is introduced, thus obtaining (3-aminopropyl) triphenylphosphonium bromide; the carboxyl group in guanidine acetate reacts with thionyl chloride to form an acyl chloride group, thus obtaining an intermediate; the acyl chloride in the intermediate and the amino group in (3-aminopropyl) triphenylphosphonium bromide undergo an amidation reaction, thus obtaining a modified phosphorus bromide. The phosphorus element in the modified phosphorus bromide can generate polyphosphoric acid and metaphosphoric acid with strong dehydration ability during combustion. Since polyphosphoric acid and metaphosphoric acid are not volatile, they can form a dense protective layer on the surface of the coating, thus achieving a flame retardant effect; the quaternary phosphonium salt contained therein has a good antibacterial effect. The quaternary ammonium salt in the quaternized fiber also has a good antibacterial effect. Detailed implementation mode
[0015] S1. Place 3 parts by weight of aluminum material in caustic soda with a concentration of 40 g / L and a temperature of 40 °C for cleaning for 3 min, and then clean it with tap water; S2. Place the material cleaned in S1 in the electrolyte, connect the positive electrode to the workpiece, connect the negative electrode to the electrolyte with an aluminum plate as the medium, apply a DC power supply of 550 mA / dm^2, electrolyze for 30 min, and then clean it with deionized water; S3. Place the material cleaned in S2 in 5 parts by weight of hydrated antibacterial solution at a temperature of 70 °C for 8 min. The components of the hydrated antibacterial solution are: 185 unit amounts of hydrated molecules, 10 unit amounts of nano-silica powder filler, and 2 unit amounts of copper-based antibacterial agent; S4: Place the material soaked in S3 in pure water at room temperature, clean it, and then place it in an oven at 60 - 0 °C to bake dry the surface moisture, and passivate it naturally for 24 h to obtain a nano-aluminum antibacterial agent. Description of the drawings
[0016] Figure 1 is the electron microscope image of the nano-aluminum antibacterial agent.
[0017] Figure 2 is the cross-sectional characteristic of the nano-aluminum antibacterial agent. Example 1
[0018] S1. Add 8 mL of N,N-dimethylpropane-1,3-diamine, 5 mL of distilled water, and 0.5 g of dry acrylic fiber to the reactor, react at 75 °C for 5 h, and after completion, wash and dry the fiber to obtain tertiary amino fiber; S2. Add 5 mL of bromobutane and 0.45 g of tertiary amino fiber to 20 mL of ethanol solvent, stir and mix, stir and reflux at 60 °C for 4 h, and after completion, wash and dry to obtain quaternized fiber; S3. Add 2.14 g of 3-bromopropylamine hydrobromide and 2.61 g of triphenylphosphine to 25 mL of acetonitrile solvent, react at 70 °C for 6 h, filter and collect the precipitated solid after completion, then dissolve it in water and adjust the pH value to 11 with saturated potassium carbonate aqueous solution, extract the organic phase with dichloromethane, and rotary evaporate to remove the solvent to obtain (3-aminopropyl)triphenylphosphonium bromide; S4. Add 1.2 g of guanidine acetic acid to 2.31 g of thionyl chloride, stir evenly, react at 65 °C for 10 h, filter, wash and dry after the reaction to obtain the intermediate; S5. Add 1 g of the intermediate and 1.35 g of (3-aminopropyl)triphenylphosphonium bromide to 30 mL of N,N-dimethylformamide solvent, stir to dissolve, continue to add 0.01 g of triethylamine catalyst thereto, react at 76 °C for 4 h, carry out vacuum distillation, wash and dry after completion to obtain modified phosphonium bromide; S6. Add 2 parts by weight of nano-aluminum antibacterial agent, 3 parts by weight of quaternized fiber, and 1 part by weight of modified phosphonium bromide to a stirrer, stir for 5 min, and dry after completion to obtain the nano-aluminum antibacterial material. Example 2
[0019] S1. Add 10 mL of N,N-dimethylpropane-1,3-diamine, 6 mL of distilled water, and 0.51 g of dry acrylic fiber to the reactor, react at 80 °C for 6 h, wash and dry the fiber after completion to obtain tertiary amino fiber; S2. Add 7 mL of bromobutane and 0.5 g of tertiary amino fiber to 25 mL of ethanol solvent, stir and mix, stir and reflux at 70 °C for 6 h, wash and dry after completion to obtain quaternized fiber; S3. Add 2.19 g of 3-bromopropylamine hydrobromide and 2.63 g of triphenylphosphine to 30 mL of acetonitrile solvent, react at 80 °C for 8 h, filter and collect the precipitated solid after completion, then dissolve it in water and adjust the pH value to 11 with saturated potassium carbonate aqueous solution, extract the organic phase with dichloromethane, and rotary evaporate to remove the solvent to obtain (3-aminopropyl)triphenylphosphonium bromide; S4. Add 1.5 g of guanidine acetic acid to 2.82 g of thionyl chloride, stir evenly, react at 75 °C for 14 h, filter, wash and dry after the reaction to obtain the intermediate; S5. Add 2 g of the intermediate and 2.6 g of (3-aminopropyl)triphenylphosphonium bromide to 40 mL of N,N-dimethylformamide solvent, stir to dissolve, continue to add 0.02 g of triethylamine catalyst thereto, react at 85 °C for 7 h, carry out vacuum distillation, wash and dry after completion to obtain modified phosphonium bromide; S6. Add 5 parts by weight of nano-aluminum antibacterial agent, 4 parts by weight of quaternized fiber, and 3 parts by weight of modified phosphonium bromide into a stirrer, stir for 8 min, and then dry to obtain the nano-aluminum antibacterial material. Example 3
[0020] S1. Add 9 mL of N,N-dimethylpropane-1,3-diamine, 5 mL of distilled water, and 0.5 g of dried acrylic fiber into a reactor, react at 78 °C for 6 h, wash and dry the fiber after completion to obtain tertiary amine fiber. S2. Add 6 mL of bromobutane and 0.47 g of tertiary amine fiber into 22 mL of ethanol solvent, stir and mix, stir and reflux at 65 °C for 5 h, wash and dry after completion to obtain quaternized fiber. S3. Add 2.16 g of 3-bromopropylamine hydrobromide and 2.62 g of triphenylphosphine into 27 mL of acetonitrile solvent, react at 75 °C for 7 h, filter and collect the precipitated solid after completion, then dissolve it in water and adjust the pH value to 11 with saturated potassium carbonate aqueous solution, extract the organic phase with dichloromethane, and rotary evaporate to remove the solvent to obtain (3-aminopropyl)triphenylphosphonium bromide. S4. Add 1.3 g of guanidine acetic acid into 2.65 g of thionyl chloride, stir evenly, react at 70 °C for 12 h, filter by suction, wash and dry after reaction to obtain the intermediate. S5. Add 1 g of the intermediate and 2.2 g of (3-aminopropyl)triphenylphosphonium bromide into 35 mL of N,N-dimethylformamide solvent, stir to dissolve, continue to add 0.015 g of triethylamine catalyst thereto, react at 80 °C for 5 h, carry out vacuum distillation, wash and dry after completion to obtain modified phosphonium bromide. S6. Add 3 parts by weight of nano-aluminum antibacterial agent, 4 parts by weight of quaternized fiber, and 2 parts by weight of modified phosphonium bromide into a stirrer, stir for 6 min, and then dry to obtain the nano-aluminum antibacterial material. Example 4
[0021] S1. Add 8 mL of N,N-dimethylpropane-1,3-diamine, 5 mL of distilled water, and 0.5 g of dried acrylic fiber into a reactor, react at 75 °C for 5 h, wash and dry the fiber after completion to obtain tertiary amine fiber. S2. Add 5 mL of bromobutane and 0.45 g of tertiary amine fiber into 20 mL of ethanol solvent, stir and mix, stir and reflux at 60 °C for 4 h, wash and dry after completion to obtain quaternized fiber. S3. Add 2.19 g of 3-bromopropylamine hydrobromide and 2.63 g of triphenylphosphine to 30 mL of acetonitrile solvent, react at 80 °C for 8 h, filter and collect the precipitated solid after completion, then dissolve it in water and adjust the pH value to 11 with saturated potassium carbonate aqueous solution, extract the organic phase with dichloromethane, and rotary evaporate to remove the solvent to obtain (3-aminopropyl)triphenylphosphonium bromide; S4. Add 1.5 g of guanidine acetic acid to 2.82 g of thionyl chloride, stir evenly, react at 75 °C for 14 h, filter, wash and dry after the reaction to obtain the intermediate; S5. Add 1 g of the intermediate and 2.2 g of (3-aminopropyl)triphenylphosphonium bromide to 35 mL of N,N-dimethylformamide solvent, stir to dissolve, continue to add 0.015 g of triethylamine catalyst thereto, react at 80 °C for 5 h, carry out vacuum distillation, wash and dry after completion to obtain modified phosphonium bromide; S6. Add 3 parts by weight of nano-aluminum antibacterial agent, 4 parts by weight of quaternized fiber, and 2 parts by weight of modified phosphonium bromide to a stirrer, stir for 6 min, and dry after completion to obtain nano-aluminum antibacterial material. Example 5
[0022] S1. Add 10 mL of N,N-dimethylpropane-1,3-diamine, 6 mL of distilled water, and 0.51 g of dry acrylic fiber to the reactor, react at 80 °C for 6 h, wash and dry the fiber after completion to obtain tertiary amino fiber; S2. Add 7 mL of bromobutane and 0.5 g of tertiary amino fiber to 25 mL of ethanol solvent, stir and mix, stir and reflux at 70 °C for 6 h, wash and dry after completion to obtain quaternized fiber; S3. Add 2.16 g of 3-bromopropylamine hydrobromide and 2.62 g of triphenylphosphine to 27 mL of acetonitrile solvent, react at 75 °C for 7 h, filter and collect the precipitated solid after completion, then dissolve it in water and adjust the pH value to 11 with saturated potassium carbonate aqueous solution, extract the organic phase with dichloromethane, and rotary evaporate to remove the solvent to obtain (3-aminopropyl)triphenylphosphonium bromide; S4. Add 1.3 g of guanidine acetic acid to 2.65 g of thionyl chloride, stir evenly, react at 70 °C for 12 h, filter, wash and dry after the reaction to obtain the intermediate; S5. Add 1 g of the intermediate and 1.35 g of (3-aminopropyl)triphenylphosphonium bromide to 30 mL of N,N-dimethylformamide solvent, stir to dissolve, continue to add 0.01 g of triethylamine catalyst thereto, react at 76 °C for 4 h, carry out vacuum distillation, wash and dry after completion to obtain modified phosphonium bromide; S6. Add 2 parts by weight of nano-aluminum antibacterial agent, 3 parts by weight of quaternized fiber, and 1 part by weight of modified phosphorus bromide into a stirrer, stir for 5 min, and then dry to obtain the nano-aluminum antibacterial material.
[0023] Comparative Example 1 Compared with Example 5, the difference in this comparative example is that tertiary amine fiber is used instead of quaternized fiber.
[0024] Comparative Example 2 Compared with Example 5, the difference in this comparative example is that (3-aminopropyl) triphenylphosphonium bromide is used instead of modified phosphorus bromide.
[0025] Add the Staphylococcus aureus bacterial solution with a concentration of 2×108 CFU / mL as the test strain into a sterilized petri dish, then add and melt the solid agar medium, and then cool it to 45 °C, and then pour it into the petri dish. Pour 20 mL into each petri dish with an inner diameter of 10 cm. Then place the antibacterial materials (with a diameter of 3 cm and a thickness of 1 mm) of the examples and comparative examples of the present invention on the culture medium plate, and culture them in a constant temperature incubator for 12 h at a temperature of 37 °C. After culturing, measure the diameter of the inhibition zone. The test results are shown in Table 1.
[0026] Table 1: Antibacterial property test.
[0027]
[0028] As can be seen from Table 1, the diameter of the inhibition zone of the nano-aluminum antibacterial material of the present invention reaches 15.89 - 16.81 mm, indicating that it has a good antibacterial effect.
[0029] Use an oxygen index instrument to test the limiting oxygen index of the modified polyacrylamide material; use a horizontal and vertical burning instrument to test the combustion grade of the nano-aluminum antibacterial material.
[0030] Table 2: Flame retardancy test.
[0031]
[0032] As can be seen from Table 2, the flame retardancy effect of Examples 1 - 5 is better than that of Comparative Examples 1 - 2, indicating that the nano-aluminum antibacterial material prepared by the present invention has a good flame retardancy effect.
[0033] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, according to the content of this specification, many modifications and changes can be made. These embodiments are selected and specifically described in this specification to better explain the principle and practical application of the present invention, so that those skilled in the art can understand and utilize the present invention well.
Claims
1. A nano-aluminum antibacterial material, characterized in that, It includes the following weight components: 2-5 parts by weight of nano-aluminum antibacterial agent, 3-4 parts by weight of quaternized fiber, and 1-3 parts by weight of modified phosphorus bromide.
2. The nano-aluminum antibacterial material according to claim 1, wherein The preparation method of the quaternized fiber is as follows: S1. Add 8-10 mL of N,N-dimethylpropane-1,3-diamine, 5-6 mL of distilled water, and 0.5-0.51 g of dry acrylic fiber into a reactor, react at 75-80 °C for 5-6 h, after completion, wash and dry the fiber to obtain tertiary amino fiber; S2. Add 5-7 mL of bromobutane and 0.45-0.5 g of tertiary amino fiber into 20-25 mL of ethanol solvent, stir and mix, stir and reflux at 60-70 °C for 4-6 h, after completion, wash and dry to obtain quaternized fiber.
3. The nano-aluminum antibacterial material according to claim 1, wherein The preparation method of the modified phosphorus bromide is as follows: (1) Add 2.14-2.19 g of 3-bromopropylamine hydrobromide and 2.61-2.63 g of triphenylphosphine into 25-30 mL of acetonitrile solvent for reaction, after completion, filter and collect the precipitated solid, then dissolve it in water and adjust the pH value to 11 with saturated potassium carbonate aqueous solution, extract the organic phase with dichloromethane, and rotary evaporate to remove the solvent to obtain (3-aminopropyl)triphenylphosphonium bromide; (2) Add guanidine acetic acid into thionyl chloride, stir evenly, react at 65-75 °C for 10-14 h, after reaction, filter by suction, wash and dry to obtain an intermediate; (3) Add the intermediate and (3-aminopropyl)triphenylphosphonium bromide into 30-40 mL of N,N-dimethylformamide solvent, stir to dissolve, continue to add triethylamine catalyst thereto, react at 76-85 °C for 4-7 h, after completion, carry out vacuum distillation, wash and dry to obtain modified phosphorus bromide.
4. The nano-aluminum antibacterial material according to claim 2, characterized in that, The reaction temperature in (1) is 70-80 °C.
5. The nano-aluminum antibacterial material according to claim 2, wherein The reaction time in (1) is 6-8 h.
6. The nano-aluminum antibacterial material according to claim 2, characterized in that, The mass ratio of guanidine acetic acid to thionyl chloride in (2) is 1.2-1.5 g:2.31-2.82 g.
7. The nano-aluminum antibacterial material according to claim 2, characterized in that, The mass ratio of the intermediate, (3-aminopropyl)triphenylphosphonium bromide, and triethylamine catalyst in (3) is 1-2 g:1.35-2.6 g:0.01-0.02 g.
8. A method for preparing the nano-aluminum antibacterial material according to any one of claims 1-7, characterized in that, The preparation method of the nano-aluminum antibacterial material is as follows: Add the nano-aluminum antibacterial agent, quaternized fiber, and modified phosphorus bromide into a stirrer, stir for 5-8 min, after completion, dry to obtain the nano-aluminum antibacterial material.
9. Application of a nano-aluminum antibacterial material, characterized in that, The applications include the following aspects: applications in antibacterial coatings and antibacterial textiles.