Preparation method of antibacterial material stable at high temperature

Abstract

The invention discloses a preparation method of a high-temperature stable antibacterial material, a g-C3N4 nano material is obtained by adopting a roasting method, then polyhexamethylene biguanide is used for modification, the dispersibility of polyhexamethylene biguanide can be ensured, and because polyhexamethylene biguanide is easy to deliquesce when encountering water, the polyhexamethylene biguanide is easy to deliquesce when encountering water, so that the high-temperature stable antibacterial material is prepared. And growing a 3-5nm inert material protective layer on the surface of the powder by atomic layer deposition, so that on one hand, the protective layer can prevent moisture in the air from contacting with a sample to prevent deliquescence, and on the other hand, the antibacterial property of the material is not influenced. The method provided by the invention is relatively simple and easy to operate, and can be used for batch production. The antibacterial material prepared by the method can be used in various fields, is particularly used for preparing antibacterial master batches, and is good in high-temperature stability and excellent in antibacterial performance.

Description

Technical Field

[0001] The invention relates to the field of antibacterial materials, and in particular to a method for preparing a high-temperature stable antibacterial material. Background Art

[0002] The existence of pathogenic microorganisms such as various bacteria and viruses seriously threatens human health. The development of antibacterial functional materials can inhibit the growth and reproduction of microorganisms, which is of great significance for ensuring the health of people and the environment.

[0003] Biguanide materials have a high antibacterial rate and their decomposition products are safe. They can be added to plastics to prepare plastic products with antibacterial functions, or added to fibers after treatment to develop fabrics with antibacterial functions. They can also be added to products such as hydrogels to increase their antibacterial activity, especially when compounded with biomaterials such as polylactic acid, which can solve the problem of being damaged by common sterilization methods and expand their application areas. However, although biguanide products such as polyhexamethylene biguanide have excellent antibacterial properties, they easily absorb water and deliquesce in the air. Although it does not affect its antibacterial and antibacterial properties, its processability is relatively poor.

[0004] The present invention firstly loads polyhexamethylene biguanide uniformly on the surface of g-C3N4 nanomaterial, and then modifies the surface with a stabilizing layer, so that the g-C3N4 nanomaterial can stably exist in the air for a long time without the problem of moisture absorption and hardening. The preparation process is simple and the preparation cost is low, which has practical application value for further promoting the development of antibacterial products. Summary of the invention

[0005] In view of the shortcomings of antibacterial materials that are difficult to simultaneously meet the requirements of high-temperature stability, water deliquesce and antibacterial activity, the present invention aims to provide a method for preparing a high-temperature stable antibacterial material, which can achieve functional improvement of traditional materials.

[0006] The object of the present invention is achieved by the following scheme: a method for preparing a high-temperature stable antibacterial material, wherein a g-C3N4 nanomaterial is obtained by a roasting method, and then modified with polyhexamethylene biguanide to ensure the dispersibility of the polyhexamethylene biguanide. Since the polyhexamethylene biguanide is easily deliquescent when it comes into contact with water, an inert material protective layer of 3 to 5 nm is grown on the surface of the powder by atomic layer deposition, comprising the following steps: Step 1: Place urea in a covered crucible and calcine it in a muffle furnace. When the temperature drops to room temperature, take out the sample and bombard it with plasma to obtain g-C3N4 nanomaterials with surface defects. Step 2: prepare a polyhexamethylene biguanide aqueous solution with a mass concentration of 30-50%; immerse the g-C3N4 nanomaterial sample with surface defects obtained in step 1 in the polyhexamethylene biguanide aqueous solution at a mass ratio of sample to polyhexamethylene biguanide of 50:20-30, and then dry it at -80°C by freeze drying, grind the dried sample, this is one cycle, repeat the cycle 5-10 times, and obtain a g-C3N4 nanomaterial sample modified with metformin; Step 3: After grinding and dispersing the sample obtained in step 2, an atomic layer deposition system is used to grow a 3-5 nm inert material protective coating to obtain a high-temperature stable antibacterial material.

[0007] Furthermore, the inert material protective layer uses atomic layer deposition technology to grow at least one of TiO2, ZnO, and Al2O3 nanolayers with a thickness of 3 to 5 nm on the material surface.

[0008] The present invention adopts a roasting method to obtain a g-C3N4 nanomaterial, and then uses polyhexamethylene biguanide to modify it, so as to ensure the dispersibility of the polyhexamethylene biguanide. Since the polyhexamethylene biguanide is easily deliquescent when it comes into contact with water, atomic layer deposition is then used to grow a 3-5 nm inert material protective layer on the surface of the powder. On the one hand, the protective layer can prevent water vapor in the air from contacting with the sample to prevent deliquesce, and on the other hand, it does not affect the antibacterial property of the material.

[0009] The method provided by the present invention is relatively simple, easy to operate, and can be mass-produced. The prepared antibacterial material can be used in various fields, especially in the preparation of antibacterial masterbatch, has good high temperature stability, and excellent antibacterial performance. DETAILED DESCRIPTION

[0010] Example 1 A high-temperature stable antibacterial material, wherein a g-C3N4 nanomaterial is obtained by a calcination method, and then modified with polyhexamethylene biguanide to ensure the dispersibility of polyhexamethylene biguanide. Since polyhexamethylene biguanide is easily deliquescent when in contact with water, an inert material protective layer of 3 to 5 nm is grown on the surface of the powder by atomic layer deposition, and the preparation is carried out according to the following steps: (1) Urea was placed in a covered crucible and calcined in a muffle furnace at 200°C for 3 h and 550°C for 4 h at a heating rate of 2°C / min. After the temperature dropped to room temperature, the sample was taken out and bombarded with plasma at a power of 150 W in an atmosphere of Ar and H2 to obtain a g-C3N4 nanomaterial sample with surface defects. (2) Weigh g-C3N4 nanomaterials and polyhexamethylene biguanide at a mass ratio of 50:20, immerse the g-C3N4 nanomaterial in an aqueous solution of polyhexamethylene biguanide with a mass concentration of 30%, and then freeze-dry the sample at -80 °C. Grind the dried sample. This is one cycle. Repeat the cycle 7 times to obtain metformin-modified g-C3N4 nanomaterials. (3) After the metformin-modified g-C3N4 nanomaterials were ground and dispersed, a 5 nm TiO2 protective coating was grown using an atomic layer deposition system to obtain a high-temperature stable antibacterial material.

[0011] The obtained high-temperature stable antibacterial material has an antibacterial activity value of greater than 5.0 to Staphylococcus aureus ATCC6538P and an antibacterial activity value of greater than 5.7 to Escherichia coli ATCC8739.

[0012] Example 2 A high temperature stable antibacterial material is prepared in the following steps similar to the steps in the embodiment: (1) Urea was placed in a covered crucible and calcined in a muffle furnace at 250 °C for 3 h and 600 °C for 4 h at a heating rate of 1 °C / min. After the temperature dropped to room temperature, the sample was taken out and bombarded with plasma at a power of 180 W in an atmosphere of Ar and H2 to obtain g-C3N4 nanomaterials with surface defects. (2) Weigh g-C3N4 nanomaterials and polyhexamethylene biguanide at a mass ratio of 50:30, immerse the g-C3N4 nanomaterial in an aqueous solution of polyhexamethylene biguanide with a mass concentration of 50%, and then freeze-dry the sample at -80 °C. Grind the dried sample. This is one cycle. Repeat the cycle 5 times to obtain metformin-modified g-C3N4 nanomaterials. (3) After the metformin-modified g-C3N4 nanomaterials were ground and dispersed, a 3 nm TiO2 protective coating was grown using an atomic layer deposition system to obtain a high-temperature stable antibacterial material.

[0013] The antibacterial activity value of this example against Staphylococcus aureus ATCC6538P is greater than 5.2, and the antibacterial activity value against Escherichia coli ATCC8739 is greater than 5.9.

[0014] Example 3 A high temperature stable antibacterial material is prepared in the following steps similar to the steps in the embodiment: (1) Urea was placed in a covered crucible and calcined in a muffle furnace at 250 °C for 2 h and 550 °C for 2 h, with a heating rate of 1 °C / min. After the temperature dropped to room temperature, the sample was taken out and bombarded with plasma at a power of 180 W in an atmosphere of Ar and H2 to obtain g-C3N4 nanomaterials with surface defects. (2) Weigh g-C3N4 nanomaterials and polyhexamethylene biguanide at a mass ratio of 50:25, immerse the g-C3N4 nanomaterial in an aqueous solution of polyhexamethylene biguanide, the mass concentration of the aqueous solution of polyhexamethylene biguanide being 50%, and then freeze-dry at -80 °C. Grind the dried sample. This is one cycle. Repeat the cycle 5 times to obtain metformin-modified g-C3N4 nanomaterials. (3) After the metformin-modified g-C3N4 nanomaterials were ground and dispersed, a 3 nm ZnO protective coating was grown using an atomic layer deposition system to obtain a high-temperature stable antibacterial material.

[0015] The antibacterial activity value of this example against Staphylococcus aureus ATCC6538P is greater than 5.4, and the antibacterial activity value against Escherichia coli ATCC8739 is greater than 6.1.

Claims

1. A method for preparing a high temperature stable antibacterial material, characterized in that: The g-C3N4 nanomaterial is obtained by calcination, and then modified with polyhexamethylene biguanide to ensure the dispersibility of polyhexamethylene biguanide. Since polyhexamethylene biguanide is easily deliquescent when in contact with water, an atomic layer deposition is used to grow a 3-5 nm inert material protective layer on the powder surface, including the following steps: Step 1: Place urea in a covered crucible and calcine it in a muffle furnace. When the temperature drops to room temperature, take out the sample and bombard it with plasma to obtain g-C3N4 nanomaterials with surface defects. Step 2: prepare a polyhexamethylene biguanide aqueous solution with a mass concentration of 30-50%; immerse the g-C3N4 nanomaterial sample with surface defects obtained in step 1 in the polyhexamethylene biguanide aqueous solution at a mass ratio of sample to polyhexamethylene biguanide of 50:20-30, and then dry it at -80°C by freeze drying, grind the dried sample, this is one cycle, repeat the cycle 5-10 times, and obtain a g-C3N4 nanomaterial sample modified with metformin; Step 3: After grinding and dispersing the sample obtained in step 2, an atomic layer deposition system is used to grow a 3-5 nm inert material protective coating to obtain a high-temperature stable antibacterial material.

2. The method for preparing the high temperature stable antibacterial material according to claim 1, characterized in that: In step 1, the calcination temperature is 200-250° C. for 2-3 hours, 500-600° C. for 2-4 hours, and the heating rate is 1-5° C. / min.

3. The method for preparing the high temperature stable antibacterial material according to claim 1, characterized in that: In step 1, the plasma treatment power is 150 W~180 W, and the atmosphere is Ar and H2.

4. The method for preparing the high temperature stable antibacterial material according to claim 1, characterized in that: In step three, the inert material protective layer is formed by growing at least one of TiO2, ZnO, and Al2O3 nanolayers with a thickness of 3 to 5 nm on the surface of the material using atomic layer deposition technology.

5. The method for preparing the high temperature stable antibacterial material according to any one of claims 1 to 4, characterized in that: Prepare as follows: (1) Urea was placed in a covered crucible and calcined in a muffle furnace at 200°C for 3 h and 550°C for 4 h at a heating rate of 2°C / min. After the temperature dropped to room temperature, the sample was taken out and bombarded with plasma at a power of 150 W in an atmosphere of Ar and H2 to obtain a g-C3N4 nanomaterial sample with surface defects. (2) Weigh g-C3N4 nanomaterials and polyhexamethylene biguanide at a mass ratio of 50:20, immerse the g-C3N4 nanomaterial in an aqueous solution of polyhexamethylene biguanide with a mass concentration of 30%, and then freeze-dry the sample at -80 °C. Grind the dried sample. This is one cycle. Repeat the cycle 7 times to obtain metformin-modified g-C3N4 nanomaterials. (3) After the metformin-modified g-C3N4 nanomaterials were ground and dispersed, a 5 nm TiO2 protective coating was grown using an atomic layer deposition system to obtain a high-temperature stable antibacterial material.

6. The method for preparing the high temperature stable antibacterial material according to any one of claims 1 to 4, characterized in that: Prepare as follows: (1) Urea was placed in a covered crucible and calcined in a muffle furnace at 250 °C for 3 h and 600 °C for 4 h at a heating rate of 1 °C / min. After the temperature dropped to room temperature, the sample was taken out and bombarded with plasma at a power of 180 W in an atmosphere of Ar and H2 to obtain g-C3N4 nanomaterials with surface defects. (2) Weigh g-C3N4 nanomaterials and polyhexamethylene biguanide at a mass ratio of 50:30, immerse the g-C3N4 nanomaterial in an aqueous solution of polyhexamethylene biguanide with a mass concentration of 50%, and then freeze-dry the sample at -80 °C. Grind the dried sample. This is one cycle. Repeat the cycle 5 times to obtain metformin-modified g-C3N4 nanomaterials. (3) After the metformin-modified g-C3N4 nanomaterials were ground and dispersed, a 3 nm TiO2 protective coating was grown using an atomic layer deposition system to obtain a high-temperature stable antibacterial material.

7. The method for preparing the high temperature stable antibacterial material according to any one of claims 1 to 4, characterized in that: Prepare as follows: (1) Urea was placed in a covered crucible and calcined in a muffle furnace at 250 °C for 2 h and 550 °C for 2 h, with a heating rate of 1 °C / min. After the temperature dropped to room temperature, the sample was taken out and bombarded with plasma at a power of 180 W in an atmosphere of Ar and H2 to obtain g-C3N4 nanomaterials with surface defects. (2) Weigh g-C3N4 nanomaterials and polyhexamethylene biguanide at a mass ratio of 50:25, immerse the g-C3N4 nanomaterial in an aqueous solution of polyhexamethylene biguanide, the mass concentration of the aqueous solution of polyhexamethylene biguanide being 50%, and then freeze-dry at -80 °C. Grind the dried sample. This is one cycle. Repeat the cycle 5 times to obtain metformin-modified g-C3N4 nanomaterials. (3) After the metformin-modified g-C3N4 nanomaterials were ground and dispersed, a 3 nm ZnO protective coating was grown using an atomic layer deposition system to obtain a high-temperature stable antibacterial material.