Bio-based antibacterial mask and preparation method thereof

Abstract

The invention discloses a bio-based antibacterial mask and a preparation method thereof, and relates to the technical field of masks. When the bio-based antibacterial mask is prepared, firstly, chitosan is grafted with gallic acid to obtain modified chitosan, secondly, magnesium-based porphyrin, 5, 15-(aminophenyl)-10, 20-phenylporphyrin and 2, 5-diaminobenzene sulfonic acid react to prepare functional polyimide, and then the functional polyimide reacts with thionyl chloride to prepare modified polyimide; finally, the modified chitosan, hyaluronic acid and gelatin are mixed and subjected to an electrostatic spinning process, a functional film is prepared, modified polyimide and ethidene diamine are mixed and spun on the functional film through the electrostatic spinning process, and the bio-based antibacterial mask is prepared. The bio-based antibacterial mask prepared by the invention has good moisture retention, antibacterial property and oxidation resistance.

Description

Technical Field

[0001] The invention relates to the technical field of facial masks, and in particular to a bio-based antibacterial facial mask and a preparation method thereof. Background Art

[0002] Facial mask is a category of skin care products and a carrier of beauty care products. It is applied on the face to achieve beauty functions, such as hydration, whitening, anti-aging and oil balance. There are many types of facial masks on the market, which can be mainly divided into two categories according to the way of use, namely smear-type and patch-type. Smear-type facial masks are applied evenly on the face and washed off after a period of time, which is more troublesome to use; while patch-type facial masks are easy to use and easy to carry. They are usually composed of non-woven fabric substrates and liquid active ingredients, and mainly use spunlace non-woven fabrics as the substrate.

[0003] In the rapid development of the facial mask market, adding natural and mild bio-based materials has become a hot topic. Bio-based masks use bio-based materials as the main ingredient, and have the advantages of being natural, safe, mild, moisturizing, repairing skin and alleviating skin sensitivity. In daily life, our facial skin is easily exposed to various bacteria, dirt and pollutants. These harmful substances breed and multiply on the surface of the skin. Antibacterial masks can effectively inhibit the reproduction of facial bacteria and prevent bacterial infection and inflammation. Essence is the main ingredient for the mask to exert its effect. Due to the insufficient water absorption and water retention of the mask cloth, the essence is easy to drip and cannot be fully and effectively absorbed by the skin. Therefore, a natural and mild mask with good moisturizing and antibacterial properties is needed. Summary of the invention

[0004] The object of the present invention is to provide a bio-based antibacterial facial mask and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: A bio-based antibacterial facial mask is prepared by firstly mixing modified chitosan, hyaluronic acid and gelatin to prepare a functional membrane through an electrostatic spinning process, and then mixing modified polyimide and ethylenediamine to prepare the functional membrane through an electrostatic spinning process.

[0006] As an optimization, the modified chitosan is obtained by grafting chitosan with gallic acid.

[0007] As an optimization, the modified polyimide is a functionalized polyimide obtained by reacting magnesium-based porphyrin, 5,15-(aminophenyl)-10,20-phenylporphyrin and 2,5-diaminobenzenesulfonic acid, and then reacting with thionyl chloride to obtain the functionalized polyimide.

[0008] A method for preparing a bio-based antibacterial facial mask comprises the following preparation steps: (1) Chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide were weighed in a mass ratio of 1:(3.0-3.2):(0.18-0.2):(0.1-0.13); chitosan and 70wt% ethanol were mixed in a mass ratio of 1:(200-300) to obtain a chitosan dispersion; gallic acid and 70wt% ethanol were mixed in a mass ratio of 1:(20-300) at 0°C. 30) mixed, then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and mixed for 50-60 min to obtain a gallic acid solution, and the gallic acid solution was added dropwise to the chitosan dispersion at a dropping speed of 1 mL / min, stirred at 0°C for 30 min, heated to room temperature and continued to react for 24 h. After the reaction was completed, the lower precipitate was removed by centrifugation, washed with ethanol, and freeze-dried to obtain modified chitosan; (2) Mix magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol in a mass ratio of 1: (0.5-0.7): (1.1-1.2): (20-30), heat to 50-60°C under nitrogen protection, react for 4-5 hours, then add isoquinoline 10 times the mass of magnesium-based porphyrin, heat to 190°C, react for 10-12 hours, add methanol 10-12 times the volume of m-cresol after the reaction, cool to 5°C, filter, wash with pure water 3-4 times, and dry at 70-80°C for 12 hours to obtain functionalized polyimide; (3) functionalized polyimide, thionyl chloride and N,N-dimethylformamide are mixed in a mass ratio of 1:(0.8-1.0):(20-30), heated to 30-40°C for reaction for 3-4 hours, and after the reaction, ethyl acetate in an amount 3-4 times the volume of N,N-dimethylformamide is added, filtered and washed with pure water for 3-4 times, and dried at 70-80°C for 12 hours to obtain modified polyimide; (4) Weighing modified chitosan, hyaluronic acid, and gelatin in a mass ratio of 1:(0.5-0.7):(10-12), mixing the modified chitosan and 70wt% acetic acid solution in a mass ratio of 1:(25-30) to obtain a chitosan solution, mixing hyaluronic acid and pure water in a mass ratio of 1:(10-15) to obtain a hyaluronic acid solution, mixing gelatin and hexafluoroisopropanol in a mass ratio of 1:(3-4) to obtain a gelatin solution, mixing the modified chitosan solution, the hyaluronic acid solution, and the gelatin solution to obtain a functional membrane by an electrospinning process; (5) Modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol are mixed in a mass ratio of 1:(1.1-1.5):(1.1-1.2):(8-10) at 40-50°C for 3-5 minutes, and then spun onto a functional membrane through an electrospinning process. After spinning, the electrospun membrane is peeled off and vacuum dried at room temperature for 5-6 hours to obtain a bio-based antibacterial facial mask.

[0009] As an optimization, the chitosan deacetylation degree in step (1) is ≥90%.

[0010] As an optimization, the preparation method of the magnesium-based porphyrin in step (2) is as follows: under nitrogen protection, 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride and chloroform are mixed in a mass ratio of 1:(8-10):(30-40), and reacted at room temperature for 2-3 hours. After the reaction, pure water 2-3 times the volume of chloroform is added, and chloroform is used for extraction, the lower organic solution is retained, and the organic solution is subjected to rotary evaporation and drying to obtain magnesium-based porphyrin.

[0011] As an optimization, the molecular weight of the hyaluronic acid in step (4) is 1×105Da.

[0012] As an optimization, the electrospinning process parameters of step (4) are as follows: voltage of 20 kV, propulsion speed of 3 mL / h, receiving distance of 17 cm, receiving rod speed of 220 r / min, receiving rod diameter of 7.5 cm, length of 25 cm, and a layer of silicone oil paper wrapped on the receiving rod; the functional film surface density is 1.2 mg / cm 2 .

[0013] As an optimization, the electrospinning process parameters of step (5) are as follows: electrospinning voltage is 12 kV, propulsion speed is 2 mL / h, receiving distance is 10 cm, receiving roller rotation speed is 220 r / min, and spinning time is 24 min.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing the bio-based antibacterial facial mask, the present invention firstly grafts gallic acid onto chitosan to obtain modified chitosan, then reacts magnesium-based porphyrin, 5,15-(aminophenyl)-10,20-phenylporphyrin, and 2,5-diaminobenzenesulfonic acid to obtain functionalized polyimide, which is then reacted with thionyl chloride to obtain modified polyimide; finally, the modified chitosan, hyaluronic acid, and gelatin are mixed to obtain a functional membrane through an electrospinning process, and the modified polyimide and ethylenediamine are mixed and spun on the functional membrane through an electrospinning process to obtain the bio-based antibacterial facial mask.

[0015] First, chitosan is grafted with gallic acid to obtain modified chitosan. Chitosan has excellent biocompatibility, biodegradability and antibacterial activity, which can give the mask good moisturizing and antibacterial properties. Gallic acid, as one of the abundant plant secondary metabolites in nature, has excellent biological activities such as good antioxidant and antibacterial properties. Using gallic acid to graft chitosan can give the mask good antioxidant properties. Secondly, magnesium-based porphyrin, 5,15-(aminophenyl)-10,20-phenylporphyrin and 2,5-diaminobenzenesulfonic acid are reacted to obtain functionalized polyimide. The magnesium ions in magnesium-based porphyrin can increase the content of hyaluronic acid in the skin by promoting the expression of hyaluronic acid synthase, thereby effectively maintaining the moisture and elasticity of the skin and making the skin more moisturized and smooth. The functionalized polyimide is then reacted with thionyl chloride to convert the sulfonic acid functional group on the functionalized polyimide into sulfonyl chloride. Finally, modified chitosan, hyaluronic acid and gelatin were mixed and subjected to electrospinning process to obtain a functional membrane, and modified polyimide and ethylenediamine were mixed and spun on the functional membrane through electrospinning process to obtain a bio-based antibacterial facial mask. The sulfonyl chloride functional group contained in the side chain of the modified polyimide reacts with ethylenediamine to produce a sulfonamide structure with antibacterial properties, which can not only further improve the antibacterial properties of the facial mask, but also form a certain degree of cross-linking network when the modified polyimide is spun into a film, thereby enhancing the mechanical properties of the modified polyimide. The modified polyimide can be used as the base layer of the functional membrane to improve the convenience of the functional membrane when used. Secondly, the functional membrane with good hydrophilicity is used as the inner functional layer, and the polyimide with certain hydrophobic properties is used as the outer hydrophobic layer, which can also achieve unidirectional moisture conduction of the facial mask; the carboxylic acid functional group on the hyaluronic acid has good complexing ability for metal ions, and can be complexed with the magnesium ions in the polyimide, so that the functional layer and the polyimide layer can be more closely combined. DETAILED DESCRIPTION

[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0017] The chitosan used in the following examples and comparative examples has a deacetylation degree of ≥90%; the molecular weight of hyaluronic acid is 1×10 5 Da.

[0018] Embodiment 1: A method for preparing a bio-based antibacterial facial mask, the method comprising the following preparation steps: (1) Chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide were weighed in a mass ratio of 1:3.0:0.18:0.1; chitosan and 70wt% ethanol were mixed in a mass ratio of 1:200 to obtain a chitosan dispersion; gallic acid and 70wt% ethanol were mixed in a mass ratio of 1:20 at 0°C, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and mixed for 60 min to obtain a gallic acid solution; the gallic acid solution was added dropwise to the chitosan dispersion at a dropping rate of 1 mL / min; the mixture was stirred at 0°C for 30 min, and the mixture was heated to room temperature and the reaction was continued for 24 h. After the reaction was completed, the lower precipitate was removed by centrifugation, washed with ethanol, and freeze-dried to obtain modified chitosan; (2) Under nitrogen protection, 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride and chloroform were mixed in a mass ratio of 1:8:30, and reacted at room temperature for 3 hours. After the reaction, pure water twice the volume of chloroform was added, and chloroform was used for extraction. The lower organic solution was retained, and the organic solution was subjected to rotary evaporation and drying to obtain magnesium-based porphyrin; magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride and meta-cresol were mixed in a mass ratio of 1:0.5:1.1:20, heated to 60°C for reaction for 5 hours under nitrogen protection, and then 10 times the mass of isoquinoline of magnesium-based porphyrin was added, and the temperature was raised to 190°C for reaction for 12 hours. After the reaction, methanol 12 times the volume of meta-cresol was added and the temperature was lowered to 5°C, filtered and washed with pure water 4 times, and dried at 80°C for 12 hours to obtain functionalized polyimide; (3) functionalized polyimide, thionyl chloride and N,N-dimethylformamide were mixed in a mass ratio of 1:0.8:20, heated to 40°C and reacted for 4 hours. After the reaction, ethyl acetate was added in an amount 4 times the volume of N,N-dimethylformamide, filtered and washed with pure water for 4 times, and dried at 80°C for 12 hours to obtain modified polyimide; (4) Modified chitosan, hyaluronic acid and gelatin were weighed in a mass ratio of 1:0.5:10, and the modified chitosan and 70wt% acetic acid solution were mixed in a mass ratio of 1:25 to obtain a chitosan solution, hyaluronic acid and pure water were mixed in a mass ratio of 1:10 to obtain a hyaluronic acid solution, and gelatin and hexafluoroisopropanol were mixed in a mass ratio of 1:3 to obtain a gelatin solution. The modified chitosan solution, hyaluronic acid solution and gelatin solution were mixed and spun by an electrospinning process to obtain a functional membrane; the electrospinning process parameters were as follows: voltage of 20 kV, propulsion speed of 3 mL / h, receiving distance of 17 cm, receiving rod speed of 220 r / min, receiving rod diameter of 7.5 cm, length of 25 cm, and a layer of silicone oil paper was wrapped on the receiving rod; the functional membrane surface density was 1.2 mg / cm 2 ; (5) Modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol were mixed at a mass ratio of 1:1.1:1.1:8 at 50°C for 5 minutes, and then spun onto the functional membrane through an electrospinning process. After spinning, the electrospinning membrane was peeled off and vacuum dried at room temperature for 6 hours to obtain a bio-based antibacterial facial mask; the electrospinning voltage was 12 kV, the propulsion speed was 2 mL / h, the receiving distance was 10 cm, the speed of the receiving roller was 220 r / min, and the spinning time was 24 min.

[0019] Embodiment 2: A method for preparing a bio-based antibacterial facial mask, the method comprising the following preparation steps: (1) Chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide were weighed in a mass ratio of 1:3.1:0.19:0.12; chitosan and 70wt% ethanol were mixed in a mass ratio of 1:250 to obtain a chitosan dispersion; gallic acid and 70wt% ethanol were mixed in a mass ratio of 1:25 at 0°C, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and mixed for 55 min to obtain a gallic acid solution; the gallic acid solution was added dropwise to the chitosan dispersion at a dropping speed of 1 mL / min; the mixture was stirred at 0°C for 30 min, and the mixture was heated to room temperature and the reaction was continued for 24 h. After the reaction was completed, the lower precipitate was removed by centrifugation, washed with ethanol, and freeze-dried to obtain modified chitosan; (2) Under nitrogen protection, 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride and chloroform were mixed in a mass ratio of 1:9:35, and reacted at room temperature for 2.5 hours. After the reaction, pure water 2.5 times the volume of chloroform was added, and chloroform was used for extraction. The lower organic solution was retained, and the organic solution was subjected to rotary evaporation and drying to obtain magnesium-based porphyrin; magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride and meta-cresol were mixed in a mass ratio of 1:0.6:1.15:25, and heated to 55°C for reaction for 4.5 hours under nitrogen protection, and then isoquinoline 10 times the mass of magnesium-based porphyrin was added, and the temperature was raised to 190°C for reaction for 11 hours. After the reaction, methanol 11 times the volume of meta-cresol was added and the temperature was lowered to 5°C, filtered and washed with pure water 3 times, and dried at 75°C for 12 hours to obtain functionalized polyimide; (3) functionalized polyimide, thionyl chloride and N,N-dimethylformamide were mixed in a mass ratio of 1:0.9:25, heated to 35°C and reacted for 3.5 hours. After the reaction, ethyl acetate was added in an amount 3 times the volume of N,N-dimethylformamide, filtered and washed with pure water for 3 times, and dried at 75°C for 12 hours to obtain modified polyimide; (4) Modified chitosan, hyaluronic acid and gelatin were weighed in a mass ratio of 1:0.6:11, and the modified chitosan and 70wt% acetic acid solution were mixed in a mass ratio of 1:27 to obtain a chitosan solution, hyaluronic acid and pure water were mixed in a mass ratio of 1:12 to obtain a hyaluronic acid solution, and gelatin and hexafluoroisopropanol were mixed in a mass ratio of 1:3.5 to obtain a gelatin solution. The modified chitosan solution, hyaluronic acid solution and gelatin solution were mixed and spun by an electrospinning process to obtain a functional membrane; the electrospinning process parameters were as follows: voltage of 20 kV, propulsion speed of 3 mL / h, receiving distance of 17 cm, receiving rod speed of 220 r / min, receiving rod diameter of 7.5 cm, length of 25 cm, and a layer of silicone oil paper was wrapped on the receiving rod; the functional membrane surface density was 1.2 mg / cm 2 ; (5) Modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol were mixed at a mass ratio of 1:1.3:1.15:9 at 45°C for 4 minutes, and then spun onto the functional membrane through an electrospinning process. After spinning, the electrospinning membrane was peeled off and vacuum dried at room temperature for 5.5 hours to obtain a bio-based antibacterial facial mask; the electrospinning voltage was 12 kV, the propulsion speed was 2 mL / h, the receiving distance was 10 cm, the speed of the receiving rod was 220 r / min, and the spinning time was 24 minutes.

[0020] Embodiment 3: A method for preparing a bio-based antibacterial facial mask, the method comprising the following preparation steps: (1) Chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide were weighed in a mass ratio of 1:3.2:0.2:0.13; chitosan and 70wt% ethanol were mixed in a mass ratio of 1:300 to obtain a chitosan dispersion; gallic acid and 70wt% ethanol were mixed in a mass ratio of 1:30 at 0°C, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and mixed for 50 min to obtain a gallic acid solution; the gallic acid solution was added dropwise to the chitosan dispersion at a dropping speed of 1 mL / min; the mixture was stirred at 0°C for 30 min, and the mixture was heated to room temperature and the reaction was continued for 24 h. After the reaction was completed, the lower precipitate was removed by centrifugation, washed with ethanol, and freeze-dried to obtain modified chitosan; (2) Under nitrogen protection, 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride and chloroform were mixed in a mass ratio of 1:10:40, and reacted at room temperature for 2 hours. After the reaction, pure water 3 times the volume of chloroform was added, and chloroform was used for extraction. The lower organic solution was retained, and the organic solution was subjected to rotary evaporation and drying to obtain magnesium-based porphyrin; magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride and meta-cresol were mixed in a mass ratio of 1:0.7:1.2:30, heated to 50°C for reaction for 4 hours under nitrogen protection, and then 10 times the mass of isoquinoline of magnesium-based porphyrin was added, and the temperature was raised to 190°C for reaction for 10 hours. After the reaction, methanol 12 times the volume of meta-cresol was added and the temperature was lowered to 5°C, filtered and washed with pure water 3 times, and dried at 70°C for 12 hours to obtain functionalized polyimide; (3) functionalized polyimide, thionyl chloride and N,N-dimethylformamide were mixed in a mass ratio of 1:1.0:30, heated to 30°C for reaction for 3 hours, and after the reaction, ethyl acetate was added in an amount 4 times the volume of N,N-dimethylformamide, filtered and washed with pure water for 3 times, and dried at 70°C for 12 hours to obtain modified polyimide; (4) Modified chitosan, hyaluronic acid and gelatin were weighed in a mass ratio of 1:0.7:12, and the modified chitosan and 70wt% acetic acid solution were mixed in a mass ratio of 1:30 to obtain a chitosan solution, hyaluronic acid and pure water were mixed in a mass ratio of 1:15 to obtain a hyaluronic acid solution, and gelatin and hexafluoroisopropanol were mixed in a mass ratio of 1:4 to obtain a gelatin solution. The modified chitosan solution, hyaluronic acid solution and gelatin solution were mixed and spun by an electrospinning process to obtain a functional membrane; the electrospinning process parameters were as follows: voltage of 20 kV, propulsion speed of 3 mL / h, receiving distance of 17 cm, receiving rod speed of 220 r / min, receiving rod diameter of 7.5 cm, length of 25 cm, and a layer of silicone oil paper was wrapped on the receiving rod; the functional membrane surface density was 1.2 mg / cm 2 ; (5) Modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol were mixed at a mass ratio of 1:1.5:1.2:10 at 40°C for 3 min, and then spun onto the functional membrane through an electrospinning process. After spinning, the electrospun membrane was peeled off and vacuum dried at room temperature for 5 h to obtain a bio-based antibacterial facial mask; the electrospinning voltage was 12 kV, the propulsion speed was 2 mL / h, the receiving distance was 10 cm, the speed of the receiving roller was 220 r / min, and the spinning time was 24 min.

[0021] Comparative Example 1: The difference between the preparation method of the bio-based antibacterial mask of Comparative Example 1 and Example 2 is that step (2) is modified as follows: 5,15-(aminophenyl)-10,20-phenylporphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol are mixed in a mass ratio of 1:0.6:1.15:25, heated to 55°C under nitrogen protection for reaction for 4.5 hours, and then 10 times the mass of isoquinoline of magnesium-based porphyrin is added, the temperature is raised to 190°C for reaction for 11 hours, and after the reaction, 11 times the volume of m-cresol is added with methanol and the temperature is lowered to 5°C, filtered and washed with pure water 3 times, and dried at 75°C for 12 hours to obtain functionalized polyimide.

[0022] Comparative Example 2: The preparation method of the bio-based antibacterial facial mask of Comparative Example 2 differs from that of Example 2 in that step (5) is modified as follows: after the modified polyimide and hexafluoroisopropanol are mixed at a mass ratio of 1:9 at 45°C for 4 minutes, the mixture is spun onto the functional membrane through an electrospinning process. After the spinning is completed, the electrospinning membrane is peeled off and vacuum dried at room temperature for 5.5 hours to obtain a bio-based antibacterial facial mask; the electrospinning voltage is 12 kV, the propulsion speed is 2 mL / h, the receiving distance is 10 cm, the rotation speed of the receiving roller is 220 r / min, and the spinning time is 24 minutes.

[0023] Comparative Example 3: The preparation method of the bio-based antibacterial facial mask of Comparative Example 3 differs from that of Example 2 in that step (1) is not included, and step (4) is modified as follows: hyaluronic acid and gelatin are weighed at a mass ratio of 0.6:11, hyaluronic acid and pure water are mixed at a mass ratio of 1:12 to obtain a hyaluronic acid solution, gelatin and hexafluoroisopropanol are mixed at a mass ratio of 1:3.5 to obtain a gelatin solution, the hyaluronic acid solution and the gelatin solution are mixed and spun by an electrospinning process to obtain a functional membrane; the electrospinning process parameters are a voltage of 20 kV, a propulsion speed of 3 mL / h, a receiving distance of 17 cm, a receiving rod rotation speed of 220 r / min, a receiving rod diameter of 7.5 cm, a length of 25 cm, and a layer of silicone oil paper is wrapped on the receiving rod; the functional membrane surface density is 1.2 mg / cm 2 .

[0024] Test Example 1: Mechanical properties test: Test method: Using a fiber tensile tester, the facial masks prepared in the examples and comparative examples were cut into rectangular samples of 5 mm × 30 mm in size. During the experiment, the instrument tensile speed was set to 20 mm / min, the upper and lower clamping distance was 20 mm, and the breaking strength of the samples was tested. The results are shown in Table 1.

[0025] Table 1 From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the bio-based antibacterial facial mask prepared by the present invention has good mechanical properties.

[0026] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Example 2, indicating that the modified chitosan, hyaluronic acid and gelatin are mixed and subjected to an electrospinning process to obtain a functional membrane, and the modified polyimide and ethylenediamine are mixed and spun on the functional membrane through an electrospinning process to obtain a bio-based antibacterial facial mask, and the sulfonyl chloride functional groups contained in the side chains of the modified polyimide react with ethylenediamine to form a certain degree of cross-linking network when the modified polyimide is spun into a film, thereby enhancing the mechanical properties of the modified polyimide.

[0027] Test Example 2: Antibacterial performance test: Test method: The antibacterial properties of the bio-based antibacterial masks prepared in the examples and comparative examples were tested according to the standard GB / T20944.2. The results are shown in Table 2.

[0028] Table 2 From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, it can be found that the bio-based antibacterial mask prepared by the present invention has good antibacterial properties.

[0029] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that the modified chitosan, hyaluronic acid and gelatin are mixed and subjected to an electrospinning process to prepare a functional membrane, and the modified polyimide and ethylenediamine are mixed and spun on the functional membrane through an electrospinning process to prepare a bio-based antibacterial facial mask, and the sulfonyl chloride functional group contained in the side chain of the modified polyimide reacts with ethylenediamine to produce a sulfonamide structure with antibacterial properties, which can further improve the antibacterial properties of the facial mask.

[0030] Test Example 3: Moisturizing performance test: Test method: First, weigh the glass sheet, record it as M0; then cut the mask prepared in the embodiment and comparative example into 2.5cmx2.5cm size, and place it on the glass sheet and weigh it together, record it as M1; then moisten the mask with 20mL of water, and use a dry paper towel to wipe off the moisture on the glass sheet except the mask, and weigh it at this time as M2; wait for 20 minutes and weigh the glass sheet with the wet mask again as M3. This experiment was carried out at a temperature of 25°C and a relative humidity of 30%, and was used to calculate the water retention rate N of the mask, N=(M3-M0) / (M1-M0)*100%. The results are shown in Table 3.

[0031] Table 3 From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 3, it can be found that the bio-based antibacterial facial mask prepared by the present invention has good moisturizing performance.

[0032] The water retention rates of Examples 1 to 3 are greater than that of Comparative Example 3, indicating that chitosan is grafted with gallic acid to obtain modified chitosan, which has excellent biocompatibility, biodegradability and antibacterial activity, and can give the mask good moisturizing properties.

[0033] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A bio-based antibacterial facial mask, characterized in that: The bio-based antibacterial facial mask is prepared by first mixing modified chitosan, hyaluronic acid and gelatin to prepare a functional membrane through an electrostatic spinning process, and then mixing modified polyimide and ethylenediamine to prepare the functional membrane through an electrostatic spinning process; The modified chitosan is obtained by grafting chitosan with gallic acid; The modified polyimide is prepared by reacting magnesium-based porphyrin, 5,15-(aminophenyl)-10,20-phenylporphyrin and 2,5-diaminobenzenesulfonic acid to obtain a functionalized polyimide, and then reacting the functionalized polyimide with thionyl chloride.

2. A method for preparing a bio-based antibacterial facial mask, characterized in that: The method comprises the following preparation steps: (1) Chitosan, gallic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide were weighed in a mass ratio of 1:(3.0-3.2):(0.18-0.2):(0.1-0.13); chitosan and 70wt% ethanol were mixed in a mass ratio of 1:(200-300) to obtain a chitosan dispersion; gallic acid and 70wt% ethanol were mixed in a mass ratio of 1:(20-300) at 0°C. 30) mixed, then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and mixed for 50-60 min to obtain a gallic acid solution, and the gallic acid solution was added dropwise to the chitosan dispersion at a dropping speed of 1 mL / min, stirred at 0°C for 30 min, heated to room temperature and continued to react for 24 h. After the reaction was completed, the lower precipitate was removed by centrifugation, washed with ethanol, and freeze-dried to obtain modified chitosan; (2) Mix magnesium-based porphyrin, 2,5-diaminobenzenesulfonic acid, butanetetracarboxylic dianhydride, and m-cresol in a mass ratio of 1: (0.5-0.7): (1.1-1.2): (20-30), heat to 50-60°C under nitrogen protection, react for 4-5 hours, then add isoquinoline 10 times the mass of magnesium-based porphyrin, heat to 190°C, react for 10-12 hours, add methanol 10-12 times the volume of m-cresol after the reaction, cool to 5°C, filter, wash with pure water 3-4 times, and dry at 70-80°C for 12 hours to obtain functionalized polyimide; (3) functionalized polyimide, thionyl chloride and N,N-dimethylformamide are mixed in a mass ratio of 1:(0.8-1.0):(20-30), heated to 30-40°C for reaction for 3-4 hours, and after the reaction, ethyl acetate in an amount 3-4 times the volume of N,N-dimethylformamide is added, filtered and washed with pure water for 3-4 times, and dried at 70-80°C for 12 hours to obtain modified polyimide; (4) Weighing modified chitosan, hyaluronic acid, and gelatin in a mass ratio of 1:(0.5-0.7):(10-12), mixing the modified chitosan and 70wt% acetic acid solution in a mass ratio of 1:(25-30) to obtain a chitosan solution, mixing hyaluronic acid and pure water in a mass ratio of 1:(10-15) to obtain a hyaluronic acid solution, mixing gelatin and hexafluoroisopropanol in a mass ratio of 1:(3-4) to obtain a gelatin solution, mixing the modified chitosan solution, the hyaluronic acid solution, and the gelatin solution to obtain a functional membrane by an electrospinning process; (5) Modified polyimide, ethylenediamine, potassium carbonate, and hexafluoroisopropanol are mixed in a mass ratio of 1:(1.1-1.5):(1.1-1.2):(8-10) at 40-50°C for 3-5 minutes, and then spun onto a functional membrane through an electrospinning process. After spinning, the electrospun membrane is peeled off and vacuum dried at room temperature for 5-6 hours to obtain a bio-based antibacterial facial mask.

3. The method for preparing a bio-based antibacterial facial mask according to claim 2, characterized in that: The chitosan deacetylation degree in step (1) is ≥90%.

4. The method for preparing a bio-based antibacterial facial mask according to claim 2, characterized in that: The preparation method of the magnesium-based porphyrin in step (2) is as follows: under nitrogen protection, 5,15-(aminophenyl)-10,20-phenylporphyrin, magnesium chloride and chloroform are mixed in a mass ratio of 1:(8-10):(30-40), reacted at room temperature for 2-3 hours, and after the reaction, pure water 2-3 times the volume of chloroform is added, and chloroform is used for extraction, the lower organic solution is retained, and the organic solution is subjected to rotary evaporation and drying to obtain magnesium-based porphyrin.

5. The method for preparing a bio-based antibacterial facial mask according to claim 2, characterized in that: The molecular weight of the hyaluronic acid in step (4) is 1×10 5 Da.

6. The method for preparing a bio-based antibacterial facial mask according to claim 2, characterized in that: The electrospinning process parameters of step (4) are as follows: voltage of 20 kV, propulsion speed of 3 mL / h, receiving distance of 17 cm, receiving rod speed of 220 r / min, receiving rod diameter of 7.5 cm, length of 25 cm, and a layer of silicone oil paper wrapped on the receiving rod; the functional film surface density is 1.2 mg / cm 2 .

7. The method for preparing a bio-based antibacterial facial mask according to claim 2, characterized in that: The electrospinning process parameters of step (5) are as follows: electrospinning voltage is 12 kV, propulsion speed is 2 mL / h, receiving distance is 10 cm, receiving roller rotation speed is 220 r / min, and spinning time is 24 min.

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