Antibacterial composite non-woven fabric

Abstract

The present invention discloses an antibacterial composite non-woven fabric, which belongs to the technical field of non-woven fabric preparation. The antibacterial composite non-woven fabric comprises a wear-resistant layer, an inner lining layer and an antibacterial layer, wherein the inner lining layer is located between the wear-resistant layer and the antibacterial layer, and each layer is combined by hot pressing. The antibacterial layer material is prepared by a composite antibacterial agent and polyacrylic acid, and the inner lining material is composed of a spunbonded non-woven fabric. The wear-resistant layer material is prepared by 4-aminophenol, 2-chloro-5-nitrotrifluorotoluene, 4-nitrobenzoyl chloride, hydrazine hydrate and 3,4,9,10-perylenetetracarboxylic dianhydride. The antibacterial composite non-woven fabric prepared by the method has excellent antibacterial performance, wear resistance and heat resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of non-woven fabric preparation, and particularly relates to an antibacterial composite non-woven fabric. Background Art

[0002] In recent years, with the significant increase in global health awareness and people's increasing demands for quality of life, the application scope of antimicrobial materials has become increasingly extensive. In particular, the demand for antimicrobial nonwovens in the medical, hygiene, home and industrial fields continues to grow, driving the rapid development of antimicrobial composite nonwoven fabric technology.

[0003] Traditional non-woven fabrics often lack effective antibacterial mechanisms and are difficult to effectively inhibit or kill bacteria, viruses and other microorganisms. This not only affects the service life and performance of non-woven fabrics, but may also pose a potential threat to people's health. In addition, due to their relatively loose fiber structure, traditional composite non-woven fabrics are easily worn or damaged by external forces, thereby reducing the service life and performance of non-woven fabrics. Especially in some fields with high requirements for wear resistance, such as industrial packaging, outdoor products, etc., the wear resistance of traditional composite non-woven fabrics often cannot meet the needs.

[0004] Patent CN105398152A discloses an antibacterial composite non-woven fabric, which includes, from bottom to top, an antibacterial non-woven fabric, an antibacterial mesh cloth layer and a hydrophilic layer; the antibacterial non-woven fabric is made of antibacterial acrylic fiber, which is prepared by modification with nano-titanium dioxide, chitin and copper sulfate; the antibacterial mesh cloth layer is prepared by weaving textile fibers and silver fibers in a mass ratio of 100:1, and then composited to the antibacterial non-woven fabric by a hydroentanglement method, and has antibacterial and hydrophilic properties. However, the antibacterial properties, wear resistance and heat resistance of the non-woven fabric prepared by this method still have room for improvement. Summary of the Invention

[0005] The object of the present invention is to provide an antibacterial composite non-woven fabric to solve the technical problem of poor antibacterial performance, wear resistance and heat resistance of composite non-woven fabrics in the prior art.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention provides an antibacterial composite non-woven fabric, comprising a wear-resistant layer, an inner lining layer and an antibacterial layer, wherein the inner lining layer is located between the wear-resistant layer and the antibacterial layer, and the layers are bonded by hot pressing. The antibacterial layer material is prepared from a composite antibacterial agent and polyacrylic acid, the inner lining layer material is composed of a spunbonded non-woven fabric, and the wear-resistant layer material is prepared from 4-aminophenol, 2-chloro-5-nitrotrifluorotoluene, 4-nitrobenzoyl chloride, hydrazine hydrate and 3,4,9,10-perylenetetracarboxylic dianhydride.

[0008] Preferably, the preparation method of the composite antibacterial agent comprises the following steps:

[0009] Q1: 3-phenyl-2-acryloyl chloride and ethanolamine hydrochloride are added to a container filled with nitrogen and equipped with a condenser, and then hydroquinone is added. The temperature is raised to react, vigorously stirred, then the temperature is lowered to react, cooled, diluted, precipitated, washed, dried, recrystallized, and dried to obtain monomer 1;

[0010] Q2: Monomer 1 and butyl methacrylate are added to a container equipped with a magnetic stirrer, nitrogen is introduced, and then dimethyl sulfoxide is added. The temperature is raised, and azobisisobutyronitrile is dissolved in dimethyl sulfoxide and slowly added dropwise to the container. The reaction is allowed to proceed, precipitated, washed, redissolved, precipitated, washed, and dried to obtain monomer 2.

[0011] Q3: Monomer 2, trimethylamine and 1H-pyrazole-1-carboxamidine hydrochloride were added to a container containing deionized water, nitrogen was introduced, and the mixture was reacted at room temperature. After the reaction was completed, the mixture was dialyzed, concentrated by rotary evaporation, and freeze-dried to obtain a composite antibacterial agent.

[0012] In the above process, 3-phenyl-2-acryloyl chloride and ethanolamine hydrochloride are first reacted to obtain monomer 1, and then monomer 1 is polymerized with butyl methacrylate to obtain monomer 2. Then, a guanidinyl reaction is performed to obtain a composite antibacterial agent. The synthetic reaction formula of the composite antibacterial agent is as follows:

[0013]

[0014] The results of mass spectrometry analysis of monomer 1 were: m / z: 227.07 (100.0%), 229.07 (32.0%), 228.07 (12.3%), 230.07 (4.0%), 229.08 (1.1%).

[0015] Preferably, in Q1, the molar ratio of 3-phenyl-2-acryloyl chloride and ethanolamine hydrochloride is (3-3.5): (2-2.3), the reaction temperature is 90-95°C, the reaction time is 1-2h, the cooling reaction temperature is 70-75°C, the reaction time is 2-4h, and the reaction is cooled to 25-30°C, diluted with tetrahydrofuran, precipitated with n-pentane, washed with distilled water, and recrystallized with a mixed solution of ethyl acetate and isopropanol in a volume ratio of 7:3.

[0016] Preferably, in Q2, the amount ratio of monomer 1, butyl methacrylate, dimethyl sulfoxide, azobisisobutyronitrile and dimethyl sulfoxide in which azobisisobutyronitrile is dissolved is (1-1.8) g: (2-2.4) g: (15-20) mL: (0.04-0.07) g: (3-5) mL, the heating temperature is 70-75° C., the reaction time is 12-16 h, the mixture is precipitated with acetone, washed, redissolved with dimethyl sulfoxide, precipitated again with acetone, washed, and dried at 40-45° C.; in Q3, the amount ratio of monomer 2, trimethylamine and 1H-pyrazole-1-carboxamidine hydrochloride is (1-1.3) g: (3-3.8) g: (1.5-1.95) g, the reaction time at room temperature is 20-24 h, the molecular weight cutoff of the dialysis bag is 1000, and the dialysis time is 48-56 h.

[0017] Preferably, the method for preparing the wear-resistant layer material comprises the following steps:

[0018] S1: Add 4-aminophenol, 2-chloro-5-nitrotrifluorotoluene, and potassium carbonate to a container containing N,N-dimethylformamide, heat the reaction, cool the temperature, add distilled water, stir, collect the crude product, and recrystallize to obtain intermediate product 1; add 4-nitrobenzoyl chloride to a container containing tetrahydrofuran, stir until completely dissolved, add pyridine dropwise, react, then dissolve intermediate product 1 in tetrahydrofuran and slowly add dropwise to the container, stir in an ice bath, heat the reaction, cool, pour into distilled water, filter, recrystallize, and filter to obtain intermediate product 2;

[0019] S2: Under nitrogen atmosphere, intermediate product 2 was added to a container containing ethanol and stirred. Then, palladium activated carbon was added and the temperature was raised to react. Subsequently, hydrazine hydrate was added dropwise and the temperature was kept under reflux. After the reaction was completed, the filtrate was collected by hot filtration and rotary evaporation to obtain a crude product, which was recrystallized to obtain intermediate 3.

[0020] S3: Add intermediate 3 to a container containing N,N-dimethylacetamide, stir and dissolve, then add 3,4,9,10-perylenetetracarboxylic dianhydride, stir, mix and react at room temperature under nitrogen environment, spread flat, heat, heat and solidify, and cool to obtain a wear-resistant layer material.

[0021] In the above process, the synthetic reaction formula of the wear-resistant layer material is as follows:

[0022]

[0023] The results of mass spectrometry analysis of intermediate product 1 were: m / z: 298.06 (100.0%), 299.06 (14.3%), 300.06 (1.7%); the results of mass spectrometry analysis of intermediate product 2 were: m / z: 447.07 (100.0%), 448.07 (22.0%), 449.07 (3.7%), 448.06 (1.1%); the results of mass spectrometry analysis of intermediate product 3 were: m / z: 387.12 (100.0%), 388.12 (22.8%), 389.13 (2.3%).

[0024] Preferably, in S1, the molar ratio of 4-aminophenol, 2-chloro-5-nitrotrifluorotoluene and potassium carbonate is (0.09-0.12): (0.09-0.11): (0.068-0.073), the temperature of the reaction is 80-90 ° C, the reaction time is 10-12 hours, and recrystallization is performed using ethanol; the molar ratio of 4-nitrobenzoyl chloride, pyridine and intermediate 1 is (0.01-0.015): (0.018-0.026): (0.017-0.025), the reaction time is 30-45 minutes, the stirring time in an ice bath is 3-5 hours, the temperature of the reaction is 60-80 ° C, the time is 10-12 hours, and the product is recrystallized using N, N-dimethylformamide.

[0025] Preferably, in S2, the amount ratio of the intermediate product 2, ethanol, palladium activated carbon and hydrazine hydrate is (4.47-5.82) g: (150-175) mL: (0.18-0.21) g: (25-35) mL, the stirring time is 2-4 h, the heating reaction temperature is 70-75 ° C, the reaction time is 1-2 h, the insulation reflux reaction temperature is 70-75 ° C, the reaction time is 12-14 h, and recrystallization is carried out with ethanol.

[0026] Preferably, in S3, the amount ratio of intermediate 3, N,N-dimethylacetamide and 3,4,9,10-perylenetetracarboxylic dianhydride is (8-12) g: (15-25) mL: (6-8) g, the mixing reaction time at room temperature is 10-14 h, the heating temperature is 80-85 ° C, the time is 5-7 h, and the temperature rise curing process is: reaction at 100 ° C for 2 h, reaction at 150 ° C for 1 h, reaction at 200 ° C for 1 h, reaction at 250 ° C for 1 h, and reaction at 300 ° C for 1 h.

[0027] Preferably, the method for preparing the antibacterial composite non-woven fabric comprises the following steps:

[0028] Step 1: Mixing the composite antibacterial agent and polyacrylic acid, and then electrospinning to obtain an antibacterial layer material;

[0029] Step 2: placing the spunbond nonwoven fabric between the antibacterial layer material and the wear-resistant layer material, preheating, hot pressing, cooling and shaping, and cutting to obtain the antibacterial composite nonwoven fabric.

[0030] Preferably, in step 1, the usage ratio of the composite antibacterial agent and polyacrylic acid is (3-6) g: (60-90) g.

[0031] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0032] 1. The present invention first uses 3-phenyl-2-acryloyl chloride, ethanolamine hydrochloride, butyl methacrylate and 1H-pyrazole-1-carboxamidine hydrochloride as raw materials to prepare a composite antibacterial agent, and then compounds the composite antibacterial agent with polyacrylic acid to obtain an antibacterial layer material. Subsequently, 4-aminophenol, 2-chloro-5-nitrotrifluorotoluene, 4-nitrobenzoyl chloride, hydrazine hydrate and 3,4,9,10-perylenetetracarboxylic dianhydride are used as raw materials to prepare a wear-resistant layer material. The antibacterial layer material, the wear-resistant layer material and the lining layer are compounded to obtain a composite non-woven fabric with excellent antibacterial properties, wear resistance and heat resistance.

[0033] 2. The present invention adds the prepared composite antibacterial agent to the non-woven fabric, which can effectively improve its antibacterial properties. The guanidine group contained in the composite antibacterial agent has a positive charge, which can interact with the negative charge on the cell membrane, destroying the integrity of the cell membrane, thereby causing the bacterial contents to flow out and quickly killing the bacteria. The composite antibacterial agent can enter the bacterial cells, interfere with their metabolic process, inhibit the DNA or RNA synthesis of the bacteria, and interfere with the synthesis of protein, thereby inhibiting the growth and reproduction of bacteria. At the same time, the composite antibacterial agent is tightly combined with polyacrylic acid to form a stable antibacterial layer material, which maintains its antibacterial effect for a long time and is not easily destroyed by the external environment.

[0034] 3. The present invention applies the prepared wear-resistant layer material to non-woven fabrics, which can effectively improve the wear resistance and heat resistance of the non-woven fabrics. The wear-resistant layer material contains high-energy amide bonds and imide bonds, which ensures that it is not easy to break when heated. The introduction of aromatic diamines not only increases the rigidity of the wear-resistant layer material, but also further significantly improves the heat resistance. At the same time, the high melting point and stable conjugated system of the 3,4,9,10-perylenetetracarboxylic dianhydride used also enhance the thermal stability of the wear-resistant layer material. In addition, the alternating arrangement of amide bonds and imide bonds will form a cross-linked structure, which limits the molecular chain movement of the wear-resistant layer material, reduces the movement of chain segments during thermal decomposition, and further improves the heat resistance. The cross-linked structure formed by the wear-resistant layer material effectively improves its tear strength, enables it to resist damage from external forces, and improves its wear resistance. DETAILED DESCRIPTION

[0035] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] Example 1: This example discloses a method for preparing a composite antibacterial agent, comprising the following steps:

[0037] Q1: 2.71 g of 3-phenyl-2-acryloyl chloride and 1.05 g of ethanolamine hydrochloride were added to a container purged with nitrogen and equipped with a condenser, followed by the addition of 0.012 g of hydroquinone. The mixture was heated to 95°C for 2 h, stirred vigorously, then cooled to 75°C for 4 h, cooled to 25°C, diluted with tetrahydrofuran, precipitated with n-pentane, washed with distilled water, dried, and recrystallized with a mixed solution of ethyl acetate and isopropanol in a volume ratio of 7:3, and dried to obtain monomer 1.

[0038] Q2: 1.4 g of monomer 1 and 2.2 g of butyl methacrylate were added to a container equipped with a magnetic stirrer, nitrogen was introduced, and then 17.5 mL of dimethyl sulfoxide was added. The temperature was raised to 75°C, and 0.055 g of azobisisobutyronitrile was dissolved in 4 mL of dimethyl sulfoxide and slowly added dropwise to the container. The mixture was reacted for 14 h, precipitated with acetone, washed, redissolved with dimethyl sulfoxide, precipitated again with acetone, washed, and dried at 45°C to obtain monomer 2.

[0039] Q3: 1.15 g of monomer 2, 3.4 g of trimethylamine and 1.67 g of 1H-pyrazole-1-carboximidamide hydrochloride were added to a container containing 60 mL of deionized water. After nitrogen was introduced, the mixture was reacted at room temperature for 24 h. After the reaction was completed, the mixture was dialyzed using a dialysis bag with a molecular weight cutoff of 1000 for 48 h, concentrated by rotary evaporation, and freeze-dried to obtain a composite antibacterial agent.

[0040] This embodiment discloses a method for preparing a wear-resistant layer material, comprising the following steps:

[0041] S1: 11.45 g of 4-aminophenol, 22.56 g of 2-chloro-5-nitrotrifluorotoluene, and 9.72 g of potassium carbonate were added to a container containing 60 mL of N,N-dimethylformamide, and the temperature was raised to 80°C for reaction for 12 h. After the reaction was completed, the temperature was lowered, distilled water was added, and the mixture was stirred. The crude product was collected and recrystallized from ethanol to obtain intermediate product 1; 2.32 g of 4-nitrobenzoyl chloride was added to a container containing 30 mL of tetrahydrofuran, and the mixture was stirred until completely dissolved. 1.738 g of pyridine was added dropwise and the reaction was carried out for 45 min. Then, 6.258 g of intermediate product 1 was dissolved in 30 mL of tetrahydrofuran and the mixture was slowly added dropwise to the container, stirred in an ice bath for 5 h, and the temperature was raised to 80°C for reaction for 12 h. The mixture was cooled, poured into distilled water, filtered, and recrystallized from N,N-dimethylformamide to obtain intermediate product 2 by suction filtration;

[0042] S2: Under nitrogen atmosphere, 5.31 g of intermediate 2 was added to a container containing 157.5 mL of ethanol and stirred for 3 h. Then, 0.2 g of palladium activated carbon was added and the reaction was heated at 75°C for 2 h. Subsequently, 30 mL of hydrazine hydrate was added dropwise and the reaction was refluxed at 75°C for 12 h. After the reaction was completed, the filtrate was collected by hot filtration and rotary evaporation to obtain a crude product, which was recrystallized from ethanol to obtain intermediate 3.

[0043] S3: Add 10 g of intermediate 3 to a container containing 20 mL of N,N-dimethylacetamide, stir and dissolve, then add 7 g of 3,4,9,10-perylenetetracarboxylic dianhydride, stir, mix and react at room temperature under nitrogen for 12 h, spread flat, heat at 85 ° C for 5 h, and heat to cure. The process is: react at 100 ° C for 2 h, react at 150 ° C for 1 h, react at 200 ° C for 1 h, react at 250 ° C for 1 h, react at 300 ° C for 1 h, cool, and obtain the wear-resistant layer material.

[0044] This embodiment discloses a method for preparing an antibacterial composite non-woven fabric, comprising the following steps:

[0045] Step 1: 4.5 g of the composite antibacterial agent and 75 g of polyacrylic acid are mixed, and then electrospun to obtain an antibacterial layer material;

[0046] Step 2: placing the spunbond nonwoven fabric between the antibacterial layer material and the wear-resistant layer material, preheating, hot pressing, cooling and shaping, and cutting to obtain the antibacterial composite nonwoven fabric.

[0047] Example 2: This example discloses a method for preparing a composite antibacterial agent, comprising the following steps:

[0048] Q1: 2.499 g of 3-phenyl-2-acryloyl chloride and 0.975 g of ethanolamine hydrochloride were added to a container purged with nitrogen and equipped with a condenser, followed by the addition of 0.012 g of hydroquinone. The mixture was heated to 95°C for 2 h, stirred vigorously, then cooled to 75°C for 4 h, cooled to 25°C, diluted with tetrahydrofuran, precipitated with n-pentane, washed with distilled water, dried, and recrystallized with a mixed solution of ethyl acetate and isopropanol in a volume ratio of 7:3, and dried to obtain monomer 1.

[0049] Q2: 1.8 g of monomer 1 and 2.4 g of butyl methacrylate were added to a container equipped with a magnetic stirrer, nitrogen was introduced, and then 15 mL of dimethyl sulfoxide was added. The temperature was raised to 75°C, and 0.04 g of azobisisobutyronitrile was dissolved in 5 mL of dimethyl sulfoxide and slowly added dropwise to the container. The mixture was reacted for 14 h, precipitated with acetone, washed, redissolved with dimethyl sulfoxide, precipitated again with acetone, washed, and dried at 45°C to obtain monomer 2.

[0050] Q3: 1.3 g of monomer 2, 3.8 g of trimethylamine and 1.95 g of 1H-pyrazole-1-carboximidamide hydrochloride were added to a container containing 60 mL of deionized water. After nitrogen was introduced, the mixture was reacted at room temperature for 24 h. After the reaction was completed, the mixture was dialyzed using a dialysis bag with a molecular weight cutoff of 1000 for 48 h, concentrated by rotary evaporation, and freeze-dried to obtain a composite antibacterial agent.

[0051] This embodiment discloses a method for preparing a wear-resistant layer material, comprising the following steps:

[0052] S1: 9.81 g of 4-aminophenol, 20.304 g of 2-chloro-5-nitrotrifluorotoluene, and 9.38 g of potassium carbonate were added to a container containing 60 mL of N,N-dimethylformamide, and the temperature was raised to 80°C for reaction for 12 h. After the reaction was completed, the temperature was lowered, distilled water was added, and the mixture was stirred. The crude product was collected and recrystallized from ethanol to obtain intermediate product 1; 2.784 g of 4-nitrobenzoyl chloride was added to a container containing 30 mL of tetrahydrofuran, and the mixture was stirred until completely dissolved. 1.422 g of pyridine was added dropwise and the reaction was carried out for 45 min. Then, 5.066 g of intermediate product 1 was dissolved in 30 mL of tetrahydrofuran and the mixture was slowly added dropwise to the container, stirred in an ice bath for 5 h, and the temperature was raised to 80°C for reaction for 12 h. The mixture was cooled, poured into distilled water, filtered, and recrystallized from N,N-dimethylformamide to obtain intermediate product 2 by suction filtration;

[0053] S2: Under nitrogen atmosphere, 4.47 g of intermediate 2 was added to a container containing 150 mL of ethanol and stirred for 3 h. Then, 0.18 g of palladium activated carbon was added and the reaction was heated at 75°C for 2 h. Subsequently, 25 mL of hydrazine hydrate was added dropwise and the reaction was refluxed at 75°C for 12 h. After the reaction was completed, the filtrate was collected by hot filtration and rotary evaporation to obtain a crude product, which was recrystallized from ethanol to obtain intermediate 3;

[0054] S3: Add 8 g of intermediate 3 to a container containing 15 mL of N,N-dimethylacetamide, stir and dissolve, then add 8 g of 3,4,9,10-perylenetetracarboxylic dianhydride, stir, mix and react at room temperature under nitrogen for 12 hours, spread flat, heat at 85°C for 5 hours, and heat to cure. The process is: react at 100°C for 2 hours, react at 150°C for 1 hour, react at 200°C for 1 hour, react at 250°C for 1 hour, react at 300°C for 1 hour, cool, and obtain the wear-resistant layer material.

[0055] This embodiment discloses a method for preparing an antibacterial composite non-woven fabric, comprising the following steps:

[0056] Step 1: 3 g of the composite antibacterial agent and 60 g of polyacrylic acid are mixed, and then electrospun to obtain an antibacterial layer material;

[0057] Step 2: placing the spunbond nonwoven fabric between the antibacterial layer material and the wear-resistant layer material, preheating, hot pressing, cooling and shaping, and cutting to obtain the antibacterial composite nonwoven fabric.

[0058] Example 3: This example discloses a method for preparing a composite antibacterial agent, comprising the following steps:

[0059] Q1: 2.92 g of 3-phenyl-2-acryloyl chloride and 1.12 g of ethanolamine hydrochloride were added to a container purged with nitrogen and equipped with a condenser, followed by the addition of 0.012 g of hydroquinone. The reaction was heated to 95°C for 2 h, stirred vigorously, then cooled to 75°C for 4 h, cooled to 25°C, diluted with tetrahydrofuran, precipitated with n-pentane, washed with distilled water, dried, and recrystallized with a mixed solution of ethyl acetate and isopropanol in a volume ratio of 7:3, and dried to obtain monomer 1.

[0060] Q2: 1 g of monomer 1 and 2 g of butyl methacrylate were added to a container equipped with a magnetic stirrer, nitrogen was introduced, and then 20 mL of dimethyl sulfoxide was added. The temperature was raised to 75°C, 0.07 g of azobisisobutyronitrile was dissolved in 3 mL of dimethyl sulfoxide and slowly added dropwise to the container. The mixture was reacted for 14 h, precipitated with acetone, washed, redissolved with dimethyl sulfoxide, precipitated again with acetone, washed, and dried at 45°C to obtain monomer 2.

[0061] Q3: Add 1g of monomer 2, 3g of trimethylamine and 1.5g of 1H-pyrazole-1-carboximidamide hydrochloride to a container containing 60mL of deionized water, introduce nitrogen, and react at room temperature for 24h. After the reaction is completed, dialyze using a dialysis bag with a molecular weight cutoff of 1000 for 48h, concentrate by rotary evaporation, and freeze-dry to obtain a composite antibacterial agent.

[0062] This embodiment discloses a method for preparing a wear-resistant layer material, comprising the following steps:

[0063] S1: 13.08 g of 4-aminophenol, 24.82 g of 2-chloro-5-nitrotrifluorotoluene, and 10.07 g of potassium carbonate were added to a container containing 60 mL of N,N-dimethylformamide, and the temperature was raised to 80°C for reaction for 12 h. After the reaction was completed, the temperature was lowered, distilled water was added, and the mixture was stirred. The crude product was collected and recrystallized from ethanol to obtain intermediate product 1; 1.856 g of 4-nitrobenzoyl chloride was added to a container containing 30 mL of tetrahydrofuran, and the mixture was stirred until completely dissolved. 2.054 g of pyridine was added dropwise and the reaction was carried out for 45 min. Then, 7.45 g of intermediate product 1 was dissolved in 30 mL of tetrahydrofuran and the mixture was slowly added dropwise to the container, stirred in an ice bath for 5 h, and the temperature was raised to 80°C for reaction for 12 h. The mixture was cooled, poured into distilled water, filtered, and recrystallized from N,N-dimethylformamide to obtain intermediate product 2 by suction filtration;

[0064] S2: Under nitrogen atmosphere, 5.82 g of intermediate 2 was added to a container containing 175 mL of ethanol and stirred for 3 h. Then, 0.21 g of palladium activated carbon was added and the reaction was heated at 75°C for 2 h. Subsequently, 35 mL of hydrazine hydrate was added dropwise and the reaction was refluxed at 75°C for 12 h. After the reaction was completed, the filtrate was collected by hot filtration and rotary evaporation to obtain a crude product, which was recrystallized from ethanol to obtain intermediate 3;

[0065] S3: Add 12 g of intermediate 3 to a container containing 25 mL of N,N-dimethylacetamide, stir and dissolve, then add 6 g of 3,4,9,10-perylenetetracarboxylic dianhydride, stir, mix and react at room temperature under nitrogen for 12 h, spread flat, heat at 85 ° C for 5 h, and heat to cure. The process is: react at 100 ° C for 2 h, react at 150 ° C for 1 h, react at 200 ° C for 1 h, react at 250 ° C for 1 h, react at 300 ° C for 1 h, cool, and obtain the wear-resistant layer material.

[0066] This embodiment discloses a method for preparing an antibacterial composite non-woven fabric, comprising the following steps:

[0067] Step 1: 6 g of the composite antibacterial agent and 90 g of polyacrylic acid are mixed, and then electrospun to obtain an antibacterial layer material;

[0068] Step 2: placing the spunbond nonwoven fabric between the antibacterial layer material and the wear-resistant layer material, preheating, hot pressing, cooling and shaping, and cutting to obtain the antibacterial composite nonwoven fabric.

[0069] Example 4: This example discloses a method for preparing a composite antibacterial agent, comprising the following steps:

[0070] Q1: 2.63 g of 3-phenyl-2-acryloyl chloride and 0.99 g of ethanolamine hydrochloride were added to a container filled with nitrogen and equipped with a condenser, followed by the addition of 0.012 g of hydroquinone. The mixture was heated to 95° C. for 2 h, stirred vigorously, then cooled to 75° C. for 4 h, cooled to 25° C., diluted with tetrahydrofuran, precipitated with n-pentane, washed with distilled water, dried, and recrystallized with a mixed solution of ethyl acetate and isopropanol in a volume ratio of 7:3, and dried to obtain monomer 1.

[0071] Q2: 1.2 g of monomer 1 and 2.1 g of butyl methacrylate were added to a container equipped with a magnetic stirrer, nitrogen was introduced, and then 16 mL of dimethyl sulfoxide was added. The temperature was raised to 75°C, and 0.05 g of azobisisobutyronitrile was dissolved in 3.5 mL of dimethyl sulfoxide and slowly added dropwise to the container. The mixture was reacted for 14 h, precipitated with acetone, washed, redissolved with dimethyl sulfoxide, precipitated again with acetone, washed, and dried at 45°C to obtain monomer 2.

[0072] Q3: 1.1 g of monomer 2, 3.2 g of trimethylamine and 1.63 g of 1H-pyrazole-1-carboximidamide hydrochloride were added to a container containing 60 mL of deionized water. After nitrogen was introduced, the mixture was reacted at room temperature for 24 h. After the reaction was completed, the mixture was dialyzed using a dialysis bag with a molecular weight cutoff of 1000 for 48 h, concentrated by rotary evaporation, and freeze-dried to obtain a composite antibacterial agent.

[0073] This embodiment discloses a method for preparing a wear-resistant layer material, comprising the following steps:

[0074] S1: 10.12 g of 4-aminophenol, 21.17 g of 2-chloro-5-nitrobenzotrifluoride, and 9.53 g of potassium carbonate were added to a container containing 60 mL of N,N-dimethylformamide, and the temperature was raised to 80°C for reaction for 12 h. After the reaction was completed, the temperature was lowered, distilled water was added, and the mixture was stirred. The crude product was collected and recrystallized from ethanol to obtain intermediate product 1; 2.513 g of 4-nitrobenzoyl chloride was added to a container containing 30 mL of tetrahydrofuran, and the mixture was stirred until completely dissolved. 1.601 g of pyridine was added dropwise and the reaction was carried out for 45 min. Then, 5.579 g of intermediate product 1 was dissolved in 30 mL of tetrahydrofuran and the mixture was slowly added dropwise to the container, stirred in an ice bath for 5 h, and the temperature was raised to 80°C for reaction for 12 h. The mixture was cooled, poured into distilled water, filtered, and recrystallized from N,N-dimethylformamide to obtain intermediate product 2 by suction filtration;

[0075] S2: Under nitrogen atmosphere, 4.93 g of intermediate 2 was added to a container containing 160 mL of ethanol and stirred for 3 h. Then, 0.19 g of palladium activated carbon was added and the reaction was heated at 75°C for 2 h. Subsequently, 27 mL of hydrazine hydrate was added dropwise and the reaction was refluxed at 75°C for 12 h. After the reaction was completed, the filtrate was collected by hot filtration and rotary evaporation to obtain a crude product, which was recrystallized from ethanol to obtain intermediate 3;

[0076] S3: Add 9 g of intermediate 3 to a container containing 17 mL of N,N-dimethylacetamide, stir and dissolve, then add 6.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride, stir, mix and react at room temperature under nitrogen for 12 h, spread flat, heat at 85 ° C for 5 h, and heat to cure. The process is: react at 100 ° C for 2 h, react at 150 ° C for 1 h, react at 200 ° C for 1 h, react at 250 ° C for 1 h, react at 300 ° C for 1 h, cool, and obtain the wear-resistant layer material.

[0077] This embodiment discloses a method for preparing an antibacterial composite non-woven fabric, comprising the following steps:

[0078] Step 1: 4 g of the composite antibacterial agent and 70 g of polyacrylic acid are mixed, and then electrospun to obtain an antibacterial layer material;

[0079] Step 2: placing the spunbond non-woven fabric between the antibacterial layer material and the wear-resistant layer material, preheating, hot pressing, cooling and shaping, and cutting to obtain the antibacterial composite non-woven fabric.

[0080] Example 5: This example discloses a method for preparing a composite antibacterial agent, comprising the following steps:

[0081] Q1: 2.81 g of 3-phenyl-2-acryloyl chloride and 1.08 g of ethanolamine hydrochloride were added to a container purged with nitrogen and equipped with a condenser, followed by the addition of 0.012 g of hydroquinone. The mixture was heated to 95°C for 2 h, stirred vigorously, then cooled to 75°C for 4 h, cooled to 25°C, diluted with tetrahydrofuran, precipitated with n-pentane, washed with distilled water, dried, and recrystallized with a mixed solution of ethyl acetate and isopropanol in a volume ratio of 7:3, and dried to obtain monomer 1.

[0082] Q2: 1.6 g of monomer 1 and 2.3 g of butyl methacrylate were added to a container equipped with a magnetic stirrer, nitrogen was introduced, and then 19 mL of dimethyl sulfoxide was added. The temperature was raised to 75°C, and 0.06 g of azobisisobutyronitrile was dissolved in 4.5 mL of dimethyl sulfoxide and slowly added dropwise to the container. The mixture was reacted for 14 h, precipitated with acetone, washed, redissolved with dimethyl sulfoxide, precipitated again with acetone, washed, and dried at 45°C to obtain monomer 2.

[0083] Q3: 1.2 g of monomer 2, 3.6 g of trimethylamine and 1.87 g of 1H-pyrazole-1-carboximidamide hydrochloride were added to a container containing 60 mL of deionized water. After nitrogen was introduced, the mixture was reacted at room temperature for 24 h. After the reaction was completed, the mixture was dialyzed using a dialysis bag with a molecular weight cutoff of 1000 for 48 h, concentrated by rotary evaporation, and freeze-dried to obtain a composite antibacterial agent.

[0084] This embodiment discloses a method for preparing a wear-resistant layer material, comprising the following steps:

[0085] S1: 12.37 g of 4-aminophenol, 23.49 g of 2-chloro-5-nitrotrifluorotoluene, and 9.97 g of potassium carbonate were added to a container containing 60 mL of N,N-dimethylformamide, and the temperature was raised to 80°C for reaction for 12 h. After the reaction was completed, the temperature was lowered, distilled water was added, and the mixture was stirred. The crude product was collected and recrystallized from ethanol to obtain intermediate product 1; 1.997 g of 4-nitrobenzoyl chloride was added to a container containing 30 mL of tetrahydrofuran, and the mixture was stirred until completely dissolved. 1.973 g of pyridine was added dropwise and the reaction was carried out for 45 min. Then, 6.873 g of intermediate product 1 was dissolved in 30 mL of tetrahydrofuran and the mixture was slowly added dropwise to the container, stirred in an ice bath for 5 h, and the temperature was raised to 80°C for reaction for 12 h. The mixture was cooled, poured into distilled water, filtered, and recrystallized from N,N-dimethylformamide to obtain intermediate product 2 by suction filtration;

[0086] S2: Under nitrogen atmosphere, 5.67 g of intermediate 2 was added to a container containing 170 mL of ethanol and stirred for 3 h. Then, 0.2 g of palladium activated carbon was added and the reaction was heated at 75°C for 2 h. Subsequently, 32 mL of hydrazine hydrate was added dropwise and the reaction was refluxed at 75°C for 12 h. After the reaction was completed, the filtrate was collected by hot filtration and rotary evaporation to obtain a crude product, which was recrystallized from ethanol to obtain intermediate 3.

[0087] S3: Add 11 g of intermediate 3 to a container containing 22 mL of N,N-dimethylacetamide, stir and dissolve, then add 7.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride, stir, mix and react at room temperature under nitrogen for 12 h, spread flat, heat at 85 ° C for 5 h, and heat to cure. The process is: react at 100 ° C for 2 h, react at 150 ° C for 1 h, react at 200 ° C for 1 h, react at 250 ° C for 1 h, react at 300 ° C for 1 h, cool, and obtain the wear-resistant layer material.

[0088] This embodiment discloses a method for preparing an antibacterial composite non-woven fabric, comprising the following steps:

[0089] Step 1: 5 g of the composite antibacterial agent and 80 g of polyacrylic acid are mixed, and then electrospun to obtain an antibacterial layer material;

[0090] Step 2: placing the spunbond non-woven fabric between the antibacterial layer material and the wear-resistant layer material, preheating, hot pressing, cooling and shaping, and cutting to obtain the antibacterial composite non-woven fabric.

[0091] Comparative Example 1: Compared with Example 1, in the process of preparing the composite antibacterial agent in Comparative Example 1, 3-phenyl-2-acryloyl chloride was not added, and other conditions remained unchanged.

[0092] Comparative Example 2: Compared with Example 1, in Comparative Example 2, during the preparation of the wear-resistant layer material, 3,4,9,10-perylenetetracarboxylic dianhydride was not added, and other conditions remained unchanged.

[0093] Comparative Example 3: Compared with Example 1, in Comparative Example 3, during the preparation of the antibacterial composite non-woven fabric, no composite antibacterial agent was added, and other conditions remained unchanged.

[0094] Comparative Example 4: Compared with Example 1, in Comparative Example 4, during the preparation of the antibacterial composite non-woven fabric, no wear-resistant layer material was added, and other conditions remained unchanged.

[0095] Experimental Example: The antibacterial composite non-woven fabrics prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to performance tests. The wear resistance of the samples was tested according to GB / T 20991-2007, the antibacterial performance of the samples was tested according to FZ / T 62015-2009, and the heat resistance of the samples was tested according to GB / T 13767-1992. The test results are shown in Table 1:

[0096] Table 1

[0097]

[0098] As can be seen from the test results in Table 1, the antibacterial composite non-woven fabrics prepared in Examples 1-5 of the present invention have excellent wear resistance, antibacterial properties, and heat resistance. By comparing Comparative Example 1 with Examples 1-5, it can be seen that the addition of 3-phenyl-2-acryloyl chloride can effectively improve the antibacterial properties of the antibacterial composite non-woven fabric; by comparing Comparative Example 2 with Examples 1-5, it can be seen that the addition of 3,4,9,10-perylenetetracarboxylic dianhydride can effectively improve the wear resistance and heat resistance of the antibacterial composite non-woven fabric; by comparing Comparative Example 3 with Examples 1-5, it can be seen that the addition of a composite antibacterial agent can effectively improve the antibacterial properties of the antibacterial composite non-woven fabric; by comparing Comparative Example 4 with Examples 1-5, it can be seen that the use of a wear-resistant layer material can effectively improve the wear resistance and heat resistance of the antibacterial composite non-woven fabric.

[0099] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

[0100] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An antibacterial composite nonwoven fabric, characterized in that: The invention comprises a wear-resistant layer, an inner lining layer and an antibacterial layer, wherein the inner lining layer is located between the wear-resistant layer and the antibacterial layer, and the layers are bonded by hot pressing. The antibacterial layer material is prepared from a composite antibacterial agent and polyacrylic acid, the inner lining layer material is composed of a spunbonded non-woven fabric, and the wear-resistant layer material is prepared from 4-aminophenol, 2-chloro-5-nitrotrifluorotoluene, 4-nitrobenzoyl chloride, hydrazine hydrate and 3,4,9,10-perylenetetracarboxylic dianhydride; The preparation method of the composite antibacterial agent comprises the following steps: Q1: 3-phenyl-2-acryloyl chloride and ethanolamine hydrochloride are added to a container filled with nitrogen and equipped with a condenser, and then hydroquinone is added. The temperature is raised to react, vigorously stirred, then the temperature is lowered to react, cooled, diluted, precipitated, washed, dried, recrystallized, and dried to obtain monomer 1; Q2: Monomer 1 and butyl methacrylate are added to a container equipped with a magnetic stirrer, nitrogen is introduced, and then dimethyl sulfoxide is added. The temperature is raised, and azobisisobutyronitrile is dissolved in dimethyl sulfoxide and slowly added dropwise to the container. The reaction is allowed to proceed, precipitated, washed, redissolved, precipitated, washed, and dried to obtain monomer 2. Q3: Monomer 2, trimethylamine and 1H-pyrazole-1-carboxamidine hydrochloride were added to a container containing deionized water, nitrogen was introduced, and the reaction was carried out at room temperature. After the reaction was completed, the mixture was dialyzed, concentrated by rotary evaporation, and freeze-dried to obtain a composite antibacterial agent; The preparation method of the wear-resistant layer material comprises the following steps: S1: Add 4-aminophenol, 2-chloro-5-nitrotrifluorotoluene, and potassium carbonate to a container containing N,N-dimethylformamide, heat the reaction, cool the temperature, add distilled water, stir, collect the crude product, and recrystallize to obtain intermediate product 1; add 4-nitrobenzoyl chloride to a container containing tetrahydrofuran, stir until completely dissolved, add pyridine dropwise, react, then dissolve intermediate product 1 in tetrahydrofuran and slowly add dropwise to the container, stir in an ice bath, heat the reaction, cool, pour into distilled water, filter, recrystallize, and filter to obtain intermediate product 2; S2: Under nitrogen atmosphere, intermediate product 2 was added to a container containing ethanol and stirred. Then, palladium activated carbon was added and the temperature was raised to react. Subsequently, hydrazine hydrate was added dropwise and the temperature was kept under reflux. After the reaction was completed, the filtrate was collected by hot filtration and rotary evaporation to obtain a crude product, which was recrystallized to obtain intermediate 3. S3: Add intermediate 3 to a container containing N,N-dimethylacetamide, stir and dissolve, then add 3,4,9,10-perylenetetracarboxylic dianhydride, stir, mix and react at room temperature under nitrogen environment, spread flat, heat, heat and solidify, and cool to obtain a wear-resistant layer material.

2. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In Q1, the molar ratio of 3-phenyl-2-acryloyl chloride and ethanolamine hydrochloride is (3-3.5): (2-2.3), the reaction temperature is 90-95°C, the reaction time is 1-2 hours, the cooling reaction temperature is 70-75°C, the reaction time is 2-4 hours, and the mixture is cooled to 25-30°C, diluted with tetrahydrofuran, precipitated with n-pentane, washed with distilled water, and recrystallized with a mixed solution of ethyl acetate and isopropanol in a volume ratio of 7:

3.

3. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In Q2, the amount ratio of monomer 1, butyl methacrylate, dimethyl sulfoxide, azobisisobutyronitrile, and dimethyl sulfoxide in which azobisisobutyronitrile is dissolved is (1-1.8) g: (2-2.4) g: (15-20) mL: (0.04-0.07) g: (3-5) mL. The heating temperature is 70-75° C., the reaction time is 12-16 h, the reaction is precipitated with acetone, washed, redissolved with dimethyl sulfoxide, precipitated again with acetone, washed, and dried at 40-45° C. In Q3, the amount ratio of monomer 2, trimethylamine, and 1H-pyrazole-1-carboxamidine hydrochloride is (1-1.3) g: (3-3.8) g: (1.5-1.95) g. The reaction time at room temperature is 20-24 h. The molecular weight cutoff of the dialysis bag is 1000, and the dialysis time is 48-56 h.

4. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In S1, the molar ratio of 4-aminophenol, 2-chloro-5-nitrotrifluorotoluene and potassium carbonate is (0.09-0.12): (0.09-0.11): (0.068-0.073), the temperature of the reaction is 80-90°C, the reaction time is 10-12 hours, and recrystallization is performed using ethanol; the molar ratio of 4-nitrobenzoyl chloride, pyridine and intermediate 1 is (0.01-0.015): (0.018-0.026): (0.017-0.025), the reaction time is 30-45 minutes, the stirring time in an ice bath is 3-5 hours, the temperature of the reaction is 60-80°C, the reaction time is 10-12 hours, and recrystallization is performed using N,N-dimethylformamide.

5. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In the S2, the usage ratio of the intermediate product 2, ethanol, palladium activated carbon and hydrazine hydrate is (4.47-5.82) g: (150-175) mL: (0.18-0.21) g: (25-35) mL, the stirring time is 2-4 h, the heating reaction temperature is 70-75 ° C, the reaction time is 1-2 h, the insulation reflux reaction temperature is 70-75 ° C, the reaction time is 12-14 h, and recrystallization is performed with ethanol.

6. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In S3, the usage ratio of intermediate 3, N,N-dimethylacetamide and 3,4,9,10-perylenetetracarboxylic dianhydride is (8-12) g: (15-25) mL: (6-8) g, the mixing reaction time at room temperature is 10-14 h, the heating temperature is 80-85°C, the time is 5-7 h, and the temperature rise curing process is: reaction at 100°C for 2 h, reaction at 150°C for 1 h, reaction at 200°C for 1 h, reaction at 250°C for 1 h, and reaction at 300°C for 1 h.

7. The method for preparing the antibacterial composite nonwoven fabric according to any one of claims 1 to 6, wherein: The following steps are involved: Step 1: Mixing the composite antibacterial agent and polyacrylic acid, and then electrospinning to obtain an antibacterial layer material; Step 2: placing the spunbond non-woven fabric between the antibacterial layer material and the wear-resistant layer material, preheating, hot pressing, cooling and shaping, and cutting to obtain the antibacterial composite non-woven fabric.

8. The method for preparing the antibacterial composite nonwoven fabric according to claim 7, characterized in that: In the step 1, the usage ratio of the composite antibacterial agent and polyacrylic acid is (3-6) g: (60-90) g.

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