Perfluoropolyether-graphene film as well as preparation method and application thereof
By doping silver into the graphene material and carboxylation modification, and reacting with perfluoropolyether to form a perfluoropolyether-graphene film, the problem of graphene material pollution is solved, the efficient antibacterial effect of the material is achieved, and the risk to patients is reduced.
Patent Information
- Application Number
- CN202510239026.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-03
- Publication Date
- 2025-05-06
AI Technical Summary
Graphene materials often have pollution problems in the field of biomedicine, especially for open wounds, which increases the cost and life safety threats of patients. How to control the cleanliness of graphene materials has become an urgent problem to be solved.
By mixing the graphene solution, silver nitrate solution and hydrazine hydrate, silver doped graphene material is obtained, then reacted with nitric acid solution for carboxylation modification, and finally mixed with perfluoropolyether alcohol and N,N-dimethylformamide to form a perfluoropolyether-graphene film, and the solvent is removed to obtain a clean film.
This method not only avoids the agglomeration of graphene, but also introduces fluorine-containing segments, which significantly improves the antibacterial properties of the material and provides a clean and pollution-free graphene material, reducing the risk to patients.
Smart Images
Figure BDA0005293517060000062
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of graphene, and in particular to a perfluoropolyether-graphene film and a preparation method and application thereof. Background Art
[0002] Graphene is a two-dimensional carbon nanomaterial with a honeycomb structure. Since it was isolated, it has been widely used. At present, it has been studied in depth in materials science, micro-nano processing, biomedicine and drug delivery. Although the research on graphene in the biomedical field has only been carried out in recent years, it has developed rapidly and played an important role. The main application scenarios are biological components, microbial detection, disease diagnosis, drug transportation, etc., which brings great benefits to patients. With the progress of application, it is found that graphene materials have common pollution problems in biomedicine. This pollution is a fatal risk for open wounds, which greatly increases the cost of patients and threatens their life safety. Therefore, how to control the cleanliness of graphene materials and provide a clean and pollution-free graphene material has become an urgent problem to be solved. Summary of the invention
[0003] The purpose of the present invention is to overcome the defects in the prior art and provide a perfluoropolyether-graphene film and a preparation method and application thereof.
[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0005] The present invention provides a method for preparing a perfluoropolyether-graphene film, comprising the following steps:
[0006] (1) mixing a graphene solution, a silver nitrate solution, and hydrazine hydrate and reacting them to obtain a silver-doped graphene material;
[0007] (2) mixing a silver-doped graphene material and a nitric acid solution to react to obtain a carboxylated graphene material;
[0008] (3) Mixing the carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide to obtain a solution; and removing the solvent to obtain the perfluoropolyether-graphene film.
[0009] Preferably, in step (1), the mass ratio of graphene to water in the graphene solution is 1:50-100; the concentration of the silver nitrate solution is 0.1-0.3 mol / L;
[0010] The mass ratio of the graphene solution, the nitrate solution and the hydrazine hydrate is 8-12:0.5-1.5:3-5.
[0011] Preferably, the pH after mixing in step (1) is 10-11; the reaction temperature in step (1) is 60-80° C., and the reaction time is 8-10 h.
[0012] Preferably, the mass ratio of the silver-doped graphene material to the nitric acid solution in step (2) is 1:60-80.
[0013] Preferably, the reaction time in step (2) is 2 to 3 hours, and the rotation speed is 400 to 600 rpm.
[0014] Preferably, in step (3), the mass ratio of the carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide is 8-12:3-4:80-100.
[0015] Preferably, the reaction temperature in step (3) is 40-60° C., the reaction time is 4-6 h, and the reaction speed is 200-400 rpm.
[0016] Preferably, the removal of the solvent in step (3) is performed sequentially by drying and annealing;
[0017] The drying temperature is 100-120°C;
[0018] The annealing temperature is 80-90° C. and the annealing time is 3-5 hours.
[0019] The present invention also provides a perfluoropolyether-graphene film prepared by the preparation method of the perfluoropolyether-graphene film.
[0020] The present invention also provides application of the perfluoropolyether-graphene film in antibacterial materials.
[0021] The present invention provides a method for preparing a perfluoropolyether-graphene film, comprising the following steps: mixing a graphene solution, a silver nitrate solution, and a hydrazine hydrate solution and reacting to obtain a silver-doped graphene material; mixing a silver-doped graphene material and a nitric acid solution and reacting to obtain a carboxylated graphene material; mixing a carboxylated graphene material, a perfluoropolyether alcohol, and N,N-dimethylformamide to obtain a solution; and removing the solvent to obtain the perfluoropolyether-graphene film. The present invention first uses silver nitrate and graphene to mix, and nanosilver is doped in the interlayer of the graphene through a reduction reaction to achieve a preliminary antibacterial and sterilization effect. Then, the composite material is carboxylated to make the oxygen-containing functional groups on the surface of the graphene more abundant, and then an esterification reaction is carried out with the perfluoropolyether alcohol to graft the graphene and the perfluoropolyether together; not only does it avoid the agglomeration of graphene, but also introduces fluorine-containing segments into the material, thereby improving the antibacterial property of the material. DETAILED DESCRIPTION
[0022] The present invention provides a method for preparing a perfluoropolyether-graphene film, comprising the following steps:
[0023] (1) mixing a graphene solution, a silver nitrate solution, and hydrazine hydrate and reacting them to obtain a silver-doped graphene material;
[0024] (2) mixing a silver-doped graphene material and a nitric acid solution to react to obtain a carboxylated graphene material;
[0025] (3) Mixing the carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide to obtain a solution; and removing the solvent to obtain the perfluoropolyether-graphene film.
[0026] In the present invention, the mass ratio of graphene to water in the graphene solution in step (1) is preferably 1:50-100, more preferably 1:60-90, and more preferably 1:70-80; the concentration of the silver nitrate solution is preferably 0.1-0.3 mol / L, more preferably 0.15-0.25 mol / L, and more preferably 0.18-0.23 mol / L.
[0027] In the present invention, the mass ratio of the graphene solution, the nitrate solution and the hydrazine hydrate is preferably 8-12: 0.5-1.5: 3-5, more preferably 9-11: 0.6-1.4: 3.5-4.5, and more preferably 9.5-10.5: 0.8-1.2: 3.8-4.2.
[0028] In the present invention, the pH after mixing in step (1) is preferably 10-11, and is adjusted using sodium hydroxide. The reaction temperature in step (1) is preferably 60-80°C, more preferably 65-75°C, and more preferably 68-72°C; the reaction time is preferably 8-10h, more preferably 8.5-9.5h, and more preferably 8.8-9.2h.
[0029] In the present invention, after the reaction in step (1) is completed, the product is washed to neutrality and then dried to constant weight.
[0030] In the present invention, the mass ratio of the silver-doped graphene material and the nitric acid solution in step (2) is preferably 1:60-80, more preferably 1:65-75, and more preferably 1:68-72; the concentration of the nitric acid solution is preferably 50-60%, more preferably 52-58%, and more preferably 54-56%.
[0031] In the present invention, the reaction time in step (2) is preferably 2 to 3 hours, more preferably 2.2 to 2.8 hours, and more preferably 2.4 to 2.6 hours; the rotation speed is preferably 400 to 600 rpm, more preferably 450 to 550 rpm, and more preferably 480 to 520 rpm.
[0032] In the present invention, after the reaction in step (2) is completed, the product is washed to neutrality and dried to constant weight.
[0033] In the present invention, the mass ratio of the carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide in step (3) is preferably 8-12:3-4:80-100, more preferably 9-11:3.2-3.8:85-95, and more preferably 9.5-10.5:3.4-3.6:88-92.
[0034] In the present invention, the reaction temperature in step (3) is preferably 40-60°C, more preferably 45-55°C, more preferably 48-52°C; the reaction time is preferably 4-6h, more preferably 4.5-5.5h, more preferably 4.8-5.2h; the rotation speed is preferably 200-400rpm, more preferably 250-350rpm, more preferably 280-320rpm.
[0035] In the present invention, the solution in step (3) is cast into a thin film, and the solvent is subsequently removed.
[0036] In the present invention, the removal of the solvent in step (3) is performed sequentially by drying and annealing.
[0037] In the present invention, the drying temperature is 100-120° C., more preferably 105-115° C., more preferably 108-112° C.; the drying time is preferably 1-2 h, more preferably 1.2-1.8 h, more preferably 1.4-1.6 h.
[0038] In the present invention, the annealing temperature is preferably 80-90° C., more preferably 82-88° C., more preferably 84-86° C.; the annealing time is preferably 3-5 h, more preferably 3.5-4.5 h, more preferably 3.8-4.2 h.
[0039] The present invention also provides a perfluoropolyether-graphene film prepared by the preparation method of the perfluoropolyether-graphene film.
[0040] The present invention also provides application of the perfluoropolyether-graphene film in antibacterial materials.
[0041] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0042] Example 1
[0043] Graphene and water are prepared into a graphene solution in a mass ratio of 1:60. The graphene solution, silver nitrate solution (0.2 mol / L) and hydrazine hydrate are mixed in a mass ratio of 10:1:4. The pH is adjusted to 10 with sodium hydroxide, and then the mixture is reacted at 70°C for 9 hours. After the reaction, the mixture is washed to neutrality and dried to constant weight to obtain a silver-doped graphene material.
[0044] The silver-doped graphene material and nitric acid solution (55%) were mixed in a mass ratio of 1:70, and the reaction was carried out at a speed of 500 rpm for 3 hours. After the reaction was completed, the mixture was filtered, washed to neutrality and dried to constant weight to obtain a carboxylated graphene material.
[0045] The carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide were mixed in a mass ratio of 10:3:90, and reacted at 50°C and 300rpm for 5 hours to obtain a solution; the solution was then cast into a film, dried at 110°C for 1 hour, and then annealed at 85°C for 4 hours to completely remove the solvent to obtain a perfluoropolyether-graphene film.
[0046] Example 2
[0047] Graphene and water are prepared into a graphene solution in a mass ratio of 1:55. The graphene solution, silver nitrate solution (0.3 mol / L) and hydrazine hydrate are mixed in a mass ratio of 9:1.3:3.2. The pH is adjusted to 11 with sodium hydroxide, and then reacted at 65°C for 8.5h. After the reaction is completed, the mixture is washed to neutrality and dried to constant weight to obtain a silver-doped graphene material.
[0048] The silver-doped graphene material and nitric acid solution (60%) were mixed in a mass ratio of 1:65, and the reaction was carried out at a speed of 600 rpm for 2.5 hours. After the reaction was completed, the mixture was filtered, washed to neutrality and dried to constant weight to obtain a carboxylated graphene material.
[0049] The carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide were mixed in a mass ratio of 11:4:86, and reacted at 45°C and 400rpm for 6 hours to obtain a solution; the solution was then cast into a film, dried at 100°C for 2 hours, and then annealed at 80°C for 5 hours to completely remove the solvent to obtain a perfluoropolyether-graphene film.
[0050] Example 3
[0051] Graphene and water are prepared into a graphene solution in a mass ratio of 1:875. The graphene solution, silver nitrate solution (0.23 mol / L) and hydrazine hydrate are mixed in a mass ratio of 11:0.6:4.5. The pH is adjusted to 10 with sodium hydroxide, and then the mixture is reacted at 80°C for 9.6 hours. After the reaction, the mixture is washed to neutrality and dried to constant weight to obtain a silver-doped graphene material.
[0052] The silver-doped graphene material and nitric acid solution (52%) were mixed in a mass ratio of 1:78, and the reaction was carried out at a speed of 500 rpm for 3 hours. After the reaction was completed, the mixture was filtered, washed to neutrality and dried to constant weight to obtain a carboxylated graphene material.
[0053] The carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide were mixed in a mass ratio of 8:3:97, and reacted at 50°C and 270rpm for 4 hours to obtain a solution; the solution was then cast into a film, dried at 118°C for 1.4 hours, and then annealed at 88°C for 3.5 hours to completely remove the solvent to obtain a perfluoropolyether-graphene film.
[0054] Performance Testing
[0055] To verify the antibacterial activity of the film against E. coli and S. aureus, 10 8 CFU / mL, 10 7 CFU / mL and 10 6 CFU / mL of bacterial solution; put a 10mm×10mm sample film into a culture dish and take 20μL of bacterial solution on the drop film sample, and then cover the sample with a sterile PE sheet (8mm×8mm). Put a bottle cap filled with sterile saline into the culture dish to maintain the humidity of the culture environment. After culturing in a constant temperature (37°C) incubator for a period of time, put each sample into a centrifuge tube filled with 2mL of PBS solution and sonicate for 3 minutes to separate the attached bacteria. Take 50μL of the sonicated bacterial solution for coating, and culture the culture dish in a constant temperature (37°C) incubator. E·coli is cultured for 16h and S·aureus is cultured for 18h. After the culture is completed, count the colonies and calculate the antibacterial rate. For the blank, take 20μL of the diluted bacterial solution in 2mL of PBS solution, and then take 50μL for coating the blank. Three parallel experiments were carried out for each group of experiments, and the results were expressed as the average value. The calculation formula is as follows
[0056] The results are recorded in Table 1.
[0057] Table 1 Antibacterial test results
[0058]
[0059] It can be seen from the above embodiments that the present invention provides an antibacterial graphene film with excellent performance. Under the modification of silver particles and perfluoropolyether, the graphene has excellent antibacterial properties, has significant antibacterial effects on E. coli and S. aureus, and can be used as an antibacterial material.
[0060] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A method for preparing a perfluoropolyether-graphene film, characterized in that: It includes the following steps: (1) mixing a graphene solution, a silver nitrate solution, and hydrazine hydrate and reacting them to obtain a silver-doped graphene material; (2) mixing a silver-doped graphene material and a nitric acid solution to react to obtain a carboxylated graphene material; (3) mixing the carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide to obtain a solution; and removing the solvent to obtain the perfluoropolyether-graphene film.
2. The method for preparing a perfluoropolyether-graphene film according to claim 1, wherein: In step (1), the mass ratio of graphene to water in the graphene solution is 1:50-100; the concentration of the silver nitrate solution is 0.1-0.3 mol / L; The mass ratio of graphene solution, nitrate solution and hydrazine hydrate is 8 to 12: 0.5～1.5：3～5。 3. The method for preparing a perfluoropolyether-graphene film according to claim 1 or 2, characterized in that: The pH after mixing in step (1) is 10-11; the reaction temperature in step (1) is 60-80° C. and the reaction time is 8-10 hours.
4. The method for preparing a perfluoropolyether-graphene film according to claim 3, wherein: The mass ratio of the silver-doped graphene material to the nitric acid solution in step (2) is 1:60-80.
5. The method for preparing a perfluoropolyether-graphene film according to claim 1 or 4, characterized in that: The reaction time in step (2) is 2 to 3 hours, and the rotation speed is 400 to 600 rpm.
6. The method for preparing a perfluoropolyether-graphene film according to claim 5, characterized in that: The mass ratio of the carboxylated graphene material, perfluoropolyether alcohol and N,N-dimethylformamide in step (3) is 8-12:3-4:80-100.
7. The method for preparing a perfluoropolyether-graphene film according to claim 1 or 6, characterized in that: The reaction temperature in step (3) is 40-60° C., the reaction time is 4-6 hours, and the reaction speed is 200-400 rpm.
8. The method for preparing a perfluoropolyether-graphene film according to claim 7, wherein: The solvent removal in step (3) is performed sequentially by drying and annealing; The drying temperature is 100-120°C; The annealing temperature is 80-90° C. and the annealing time is 3-5 hours.
9. The perfluoropolyether-graphene film prepared by the method for preparing a perfluoropolyether-graphene film according to any one of claims 1 to 8.
10. Use of the perfluoropolyether-graphene film according to claim 9 in antibacterial materials.