Antibacterial composite nonwoven fabric

Abstract

The invention discloses an antibacterial composite non-woven fabric, comprising an antibacterial layer, an adsorption layer and a breathable waterproof layer, wherein one surface of the adsorption layer is ablated by needle punching the composite antibacterial layer, and the other surface of the adsorption layer is bonded with a meshed polyurethane hot melt adhesive to form a breathable waterproof layer. The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 15-25 parts of flame retardant, 30-40 parts of mixed alcohol, 25-35 parts of polybutylene terephthalate and 1-3 parts of nano titanium dioxide. The synthesized flame retardant comprises a melamine structure, a phospholipid structure, a long alkyl chain and a benzophenone structure, and has good dispersibility in the modified polypropylene, and the obtained composite non-woven fabric has excellent flame retardancy and anti-ultraviolet performance. The synthesized modified polypropylene comprises a fluorocarbon segment, a sulfonamide structure, a quaternary ammonium salt structure, a maleic anhydride structure and an N-vinyl pyrrolidone structure, etc., so that the surface wettability of the adsorption layer is good, and the antibacterial and heat resistance of the composite non-woven fabric are excellent.

Description

Technical Field

[0001] The invention relates to the field of non-woven fabrics, and in particular to an antibacterial composite non-woven fabric. Background Art

[0002] Polypropylene fiber is a fiber product made of polypropylene as raw material through melt spinning. It is the fastest growing variety of synthetic fibers in recent years. According to the processing method, it can be divided into ordinary filaments, composite fiber bulked yarns, staple fibers, non-woven fabrics, etc. Among them, non-woven fabrics have developed rapidly due to their advantages of light weight, softness, breathability, and easy molding. They are widely used in disposable diapers, physiological products, sanitary products, clothing raw materials, bandages, packaging materials and other fields. Polypropylene fiber itself has good physical and chemical properties, but due to its own non-polar structure, the lack of hydrophilic groups in the molecular chain, the poor hydrophilicity of the product, limiting its application field, so it is necessary to hydrophilically modify it to meet more usage requirements. The traditional method to enhance the antibacterial property of non-woven fabrics is to add antibacterial agents through pre-treatment or post-treatment, but small molecule antibacterial agents have the risk of falling off after long-term use. Therefore, it is necessary to improve the antibacterial property of polymers through modification methods such as grafting, so that the comprehensive performance of non-woven fabrics can meet the usage requirements. Previously, some studies have prepared maleic anhydride grafted polypropylene copolymers using comonomers such as butyl methacrylate to improve the hydrophilicity of polypropylene. In order to make the non-woven fabric also have antibacterial properties, new grafting monomers need to be developed.

[0003] In addition, polypropylene non-woven fabrics are made of polypropylene fiber monofilaments, which leads to a low ignition point and relatively poor flame retardancy, resulting in safety hazards during use and affecting the storage and transportation of non-woven fabrics. At present, the method of using flame retardant emulsions to modify fabrics is one of the important research methods. Commonly used flame retardant monomers for preparing fabric flame retardant emulsions include phosphates, aluminum hydroxide and halogen flame retardants, but the flame retardant monomers used have the disadvantages of insufficient photochemical stability, so the development of flame retardant monomers with excellent comprehensive performance is still an important research topic. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an antibacterial composite non-woven fabric.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An antibacterial composite nonwoven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer. One surface of the adsorption layer is composited with the antibacterial layer by needle punching, and the other surface of the adsorption layer is bonded with the breathable waterproof layer by a mesh polyurethane hot melt adhesive.

[0007] The antibacterial layer is prepared by immersing cotton fiber in a silver ammonia solution of glucose, drying and baking the cotton fiber at 170°C; the silver ammonia solution of glucose is prepared by adding silver nitrate to deionized water, and then adding concentrated ammonia water and glucose solution, and mixing and stirring, wherein the dosage ratio of silver nitrate, deionized water, concentrated ammonia water and glucose solution is 1g:250g:2.5L:250g; the glucose solution is prepared by adding glucose to deionized water and stirring and mixing, and the dosage ratio of glucose to deionized water is 1g:250g.

[0008] The breathable and waterproof layer is made of polyethylene fiber.

[0009] The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 15-25 parts of flame retardant, 30-40 parts of mixed alcohol, 25-35 parts of polybutylene terephthalate and 1-3 parts of nano titanium dioxide.

[0010] The mixed alcohol is a mixture of ethanol with a volume fraction of 95% and n-butanol with a volume ratio of 1:1.

[0011] The flame retardant is prepared by the following steps:

[0012] Step A1: add phosphorus oxychloride to toluene, add 2-hydroxy-4-n-octyloxybenzophenone in a 0°C ice-water bath with stirring, and react for 3-4 hours to obtain intermediate a. The amount ratio of phosphorus oxychloride, toluene and 2-hydroxy-4-n-octyloxybenzophenone is 0.3 mol: 200 mL: 0.3 mol;

[0013] During the reaction, 2-hydroxy-4-n-octyloxybenzophenone reacts with phosphorus oxychloride to generate a phosphorus oxychloride intermediate. The structure of intermediate a is shown below:

[0014]

[0015] Step A2: First, add 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stir and mix to obtain a mixed solution 1, and prepare three portions of the mixed solution 1 for standby use; then add trichloronitrile and 1,4-dioxane into a flask, stir for 5-10 minutes, place the flask in a 0°C ice water bath, slowly dropwise add the first portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is complete, stir and react for 3 hours, heat to 50°C, then slowly dropwise add the second portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is complete, stir and react for 3 hours. h, raise the temperature to 85°C, and finally slowly drop the third portion of the mixed solution 1 into the flask under stirring. After the dropwise addition is completed, stir and react for 11 hours, cool to room temperature, add deionized water, wash with deionized water, and dry in a drying oven at 60°C for 12 hours to obtain intermediate b. The amount ratio of 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, trichloronitrile and 1,4-dioxane is 0.30 mol: 0.30 mol: 180-210 mL: 0.10 mol: 300 mL;

[0016] During the reaction, 4-amino-4-methyl-pentan-1-ol and trichloronitrile react to remove hydrogen chloride to obtain intermediate b. The structure of intermediate b is shown below:

[0017]

[0018] Step A3: firstly add intermediate a to acetonitrile and stir to obtain mixed solution 2 for standby use; then add intermediate b and triethylamine to a flask, place the flask in a 0°C ice water bath, slowly dropwise add mixed solution 2 to the flask under stirring, after the dropwise addition is completed, stir to react for 1.5h, then heat to 40°C and react for another 11-12h, cool to room temperature, filter, wash the precipitate with deionized water and 1,4-dioxane, and then dry in a drying oven at 50-60°C for 6-8h to obtain a flame retardant with hyperbranched macromolecules, wherein the amount ratio of intermediate a, acetonitrile, intermediate b and triethylamine is 0.03mol:150mL:0.02mol:0.06mol;

[0019] During the reaction, intermediate a reacts with intermediate b to generate a phospholipid product, which is a flame retardant with hyperbranched macromolecules. The flame retardant includes a melamine structure, a phospholipid structure, an alkyl long chain and a benzophenone structure. The melamine structure and the phospholipid structure give the flame retardant the advantages of a phosphorus-nitrogen flame retardant system, and the combination of the two can exert the effect of condensed phase and gas phase synergistic flame retardancy; the non-polar alkyl long chain has good compatibility with the polypropylene molecular chain, enhancing the dispersibility of the flame retardant in polypropylene; the benzophenone structure makes the flame retardant have anti-ultraviolet properties.

[0020] The structure of the flame retardant is shown below:

[0021]

[0022] The modified polypropylene is prepared by the following steps:

[0023] Step B1: Add 1-(3-aminopropyl)pyrrolidine to a round-bottom flask with a magnet and start stirring in an ice-water bath at 0°C; add perfluorooctane sulfonyl fluoride to anhydrous toluene and stir at room temperature for 10-15 minutes to obtain a mixed solution a, slowly drop the mixed solution a into the above round-bottom flask, after the dropwise addition is completed, stir and react in an ice-water bath at 0°C for 2 hours, then heat to 45°C, stir and react at constant temperature for 4-4.5 hours, rotary evaporate at 80°C for 30-35 minutes, filter with suction, recrystallize in acetone, filter with suction, and finally dry in an oven at 40°C for 4-6 hours to obtain the intermediate 1, wherein the amount ratio of 1-(3-aminopropyl)pyrrolidine, perfluorooctane sulfonyl fluoride and anhydrous toluene is 0.01 mol: 0.01 mol: 55-65 mL;

[0024] During the reaction, 1-(3-aminopropyl)pyrrolidine reacts with perfluorooctanesulfonyl fluoride to generate a sulfonamide compound, namely intermediate 1. The structure of intermediate 1 is shown below:

[0025]

[0026] Step B2: 2-(2-chloroethoxy)acetic acid is added to DMF, and dithionyl chloride is added under stirring, and the mixture is refluxed and stirred at 50°C for 4-5 hours, filtered, extracted, and dried to obtain an intermediate 2, wherein the ratio of 2-(2-chloroethoxy)acetic acid, DMF, and dithionyl chloride is 0.1 mol: 100 mL: 0.2-0.3 mol;

[0027] During the reaction, 2-(2-chloroethoxy)acetic acid reacts with thionyl chloride to generate intermediate 2, the structure of which is shown below:

[0028]

[0029] Step B3: 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution b, and then the intermediate 2 is added to dimethyl sulfoxide to obtain a mixed solution c. The mixed solution c is slowly added dropwise to the mixed solution b in an ice-water bath at 0°C. After the addition is completed, the temperature is raised to 40°C, and the reaction is carried out at a constant temperature for 8-10 hours. The intermediate 3 is prepared by distillation under reduced pressure. The amount ratio of the intermediate 2, 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.1 mol: 0.01-0.015 mol: 100 mL;

[0030] During the reaction, 3-(hydroxymethyl)-4-methylfuran-2,5-dione reacts with intermediate 2 to generate an esterification product, namely intermediate 3. The structure of intermediate 3 is shown below:

[0031]

[0032] Step B4: Add intermediate 3 and intermediate 1 to a flask, then add DMF, and perform ultrasonication for 30-40 min. Then place the flask in an oil bath at 90°C and stir to react for 24 h. Rotary evaporate, add acetone to the residue in the flask, then add petroleum ether, filter and dry to obtain intermediate 4. The usage ratio of intermediate 3, intermediate 1 and DMF is 0.1 mol: 0.125-0.130 mol: 170-180 mL.

[0033] During the reaction, intermediate 3 reacts with intermediate 1 to generate an amphiphilic compound, namely intermediate 4. The structure of intermediate 4 is shown below:

[0034]

[0035] Step B5: adding polypropylene powder, dicumyl peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer and mixing for 20-30 minutes to obtain a mixture, adding the mixture into a twin-screw extruder at 200° C. for grafting reaction, and granulating to obtain modified polypropylene, wherein the amount ratio of polypropylene powder, dicumyl peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone is 100 g: 0.08 g: 0.3 g: 0.8 g: 0.6-1.2 g;

[0036] During the reaction, polypropylene, intermediate 4 and N-vinyl pyrrolidone are melt-blended and grafted to obtain modified polypropylene, which includes fluorocarbon segments, sulfonamide structures, quaternary ammonium salt structures, maleic anhydride structures and N-vinyl pyrrolidone structures. The fluorocarbon chain segment is highly hydrophobic and highly compatible with polypropylene, and can be entangled with the main chain segments of polypropylene to enhance the toughness of the modified polypropylene; the sulfonamide structure has a broad-spectrum antibacterial effect, which makes the modified polypropylene have a strong resistance to most bacteria; the quaternary ammonium salt structure is both water-soluble and antibacterial, which gives the modified polypropylene hydrophilicity and antibacterial properties; the grafting reaction of the maleic anhydride structure on polypropylene is promoted by N-vinyl pyrrolidone, which increases the grafting rate. The polar groups introduced after successful grafting enhance the intermolecular force and become an effective nucleating agent for polypropylene, promoting the crystallization of the modified polypropylene molecular chain and improving the solvent resistance and permeation resistance of the modified polypropylene. In addition, the distribution of maleic anhydride derivatives and N-vinyl pyrrolidone structural units on the polypropylene chain has a certain inhibitory effect on the random breakage of the molecular chain during thermal degradation, thereby improving the thermal stability of the modified polypropylene.

[0037] Beneficial effects of the present invention: The antibacterial composite non-woven fabric of the present invention comprises an antibacterial layer, an adsorption layer and a breathable and waterproof layer. The adsorption layer comprises raw materials such as modified polypropylene, flame retardant, mixed alcohol, polybutylene terephthalate and nano titanium dioxide. The synthesized flame retardant comprises a melamine structure, a phospholipid structure, an alkyl long chain and a benzophenone structure. The melamine structure and the phospholipid structure give the flame retardant the advantages of the phosphorus-nitrogen flame retardant system. The combination of the two can exert the synergistic flame retardant effect of the condensed phase and the gas phase, so that the composite non-woven fabric has excellent flame retardant properties; the benzophenone structure makes the flame retardant have anti-ultraviolet properties, improves the yellowing resistance of the composite non-woven fabric, and is convenient for transportation and storage; the non-polar alkyl long chain has good compatibility with the polypropylene molecular chain, enhances the dispersibility of the flame retardant in polypropylene, so that the composite non-woven fabric has stable flame retardancy and yellowing resistance.

[0038] In addition, the synthesized modified polypropylene is obtained by grafting maleic anhydride derivatives and N-vinyl pyrrolidone into polypropylene through melt blending. The modified polypropylene includes fluorocarbon segments, sulfonamide structures, quaternary ammonium salt structures, maleic anhydride structures and N-vinyl pyrrolidone structures. The fluorocarbon segments are highly hydrophobic and highly compatible with polypropylene. They can be entangled with the main chain segments of polypropylene to enhance the toughness of the modified polypropylene and improve the mechanical properties of the composite non-woven fabric. The sulfonamide structure has a broad-spectrum antibacterial effect, which makes the modified polypropylene have a strong resistance to most bacteria, making the composite non-woven fabric have broad-spectrum antibacterial properties. The quaternary ammonium salt structure is both water-soluble and antibacterial, which gives the modified polypropylene hydrophilicity and antibacterial properties, making the composite non-woven fabric have better antibacterial effects on Escherichia coli and Staphylococcus aureus, and improving the surface wettability of the adsorption layer of the composite non-woven fabric. The maleic anhydride structure on the polypropylene The grafting reaction is promoted by N-vinyl pyrrolidone, which improves the grafting rate. The polar groups introduced after successful grafting enhance the intermolecular force and become an effective nucleating agent for polypropylene, promoting the crystallization of the modified polypropylene molecular chain, improving the solvent resistance and permeation resistance of the modified polypropylene, and also improving the solvent resistance and permeation resistance of the composite non-woven fabric. In addition, the distribution of maleic anhydride derivatives and N-vinyl pyrrolidone structural units on the polypropylene chain has a certain inhibitory effect on the random breakage of the molecular chain during the thermal degradation process, thereby improving the thermal stability of the modified polypropylene, thereby enhancing the heat resistance of the composite non-woven fabric. DETAILED DESCRIPTION

[0039] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention.

[0040] Example 1

[0041] A flame retardant is prepared by the following steps:

[0042] Step A1: add phosphorus oxychloride to toluene, add 2-hydroxy-4-n-octyloxybenzophenone in a 0°C ice-water bath with stirring, and react for 3 hours to obtain intermediate a. The amount ratio of phosphorus oxychloride, toluene and 2-hydroxy-4-n-octyloxybenzophenone is 0.3 mol: 200 mL: 0.3 mol;

[0043] Step A2: First, add 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stir and mix to obtain a mixed solution 1, and prepare three portions of the mixed solution 1 for standby use; then add trichloronitrile and 1,4-dioxane into a flask, stir for 5 minutes, place the flask in a 0°C ice water bath, slowly dropwise add the first portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is complete, stir and react for 3 hours, heat to 50°C, then slowly dropwise add the second portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is complete, stir and react 3h, raise the temperature to 85℃, and finally slowly drop the third portion of the mixed solution 1 into the flask under stirring. After the dropwise addition is completed, stir and react for 11h, cool to room temperature, add deionized water, wash with deionized water, and dry in a drying oven at 60℃ for 12h to obtain intermediate b. The dosage ratio of 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, trichloronitrile and 1,4-dioxane is 0.30mol: 0.30mol: 180mL: 0.10mol: 300mL;

[0044] Step A3: First, add intermediate a to acetonitrile and stir to obtain mixed solution 2 for use; then add intermediate b and triethylamine to a flask, place the flask in a 0°C ice-water bath, slowly dropwise add mixed solution 2 to the flask under stirring, and after the dropwise addition is completed, stir to react for 1.5 hours, then heat to 40°C and react for another 11 hours, cool to room temperature, filter, wash the precipitate with deionized water and 1,4-dioxane, and then dry in a drying oven at 50°C for 6 hours to obtain a flame retardant with hyperbranched macromolecules, and the amount ratio of intermediate a, acetonitrile, intermediate b and triethylamine is 0.03 mol:150 mL:0.02 mol:0.06 mol.

[0045] Example 2

[0046] A flame retardant is prepared by the following steps:

[0047] Step A1: add phosphorus oxychloride to toluene, add 2-hydroxy-4-n-octyloxybenzophenone in a 0°C ice-water bath with stirring, and react for 3.5 hours to obtain intermediate a. The amount ratio of phosphorus oxychloride, toluene and 2-hydroxy-4-n-octyloxybenzophenone is 0.3 mol: 200 mL: 0.3 mol;

[0048] Step A2: First, add 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stir and mix to obtain a mixed solution 1, and prepare three portions of the mixed solution 1 for standby use; then add trichloronitrile and 1,4-dioxane into a flask, stir for 8 minutes, place the flask in a 0°C ice water bath, slowly drop the first portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is complete, stir and react for 3 hours, heat to 50°C, then slowly drop the second portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is complete, stir and react 3h, raise the temperature to 85℃, and finally slowly drop the third portion of the mixed solution 1 into the flask under stirring. After the dropwise addition is completed, stir and react for 11h, cool to room temperature, add deionized water, wash with deionized water, and dry in a drying oven at 60℃ for 12h to obtain intermediate b. The dosage ratio of 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, trichloronitrile and 1,4-dioxane is 0.30mol: 0.30mol: 195mL: 0.10mol: 300mL;

[0049] Step A3: First, add intermediate a to acetonitrile and stir to obtain mixed solution 2 for use; then add intermediate b and triethylamine to a flask, place the flask in a 0°C ice-water bath, slowly dropwise add mixed solution 2 to the flask under stirring, and after the dropwise addition is completed, stir to react for 1.5 hours, then heat to 40°C and react for another 11 hours, cool to room temperature, filter, wash the precipitate with deionized water and 1,4-dioxane, and then dry in a drying oven at 55°C for 7 hours to obtain a flame retardant with hyperbranched macromolecules, and the amount ratio of intermediate a, acetonitrile, intermediate b and triethylamine is 0.03 mol:150 mL:0.02 mol:0.06 mol.

[0050] Example 3

[0051] A flame retardant is prepared by the following steps:

[0052] Step A1: add phosphorus oxychloride to toluene, add 2-hydroxy-4-n-octyloxybenzophenone in a 0°C ice-water bath with stirring, and react for 4 hours to obtain intermediate a. The amount ratio of phosphorus oxychloride, toluene and 2-hydroxy-4-n-octyloxybenzophenone is 0.3 mol: 200 mL: 0.3 mol;

[0053] Step A2: First, 4-amino-4-methyl-pentan-1-ol and sodium hydroxide were added to deionized water, and the mixture was stirred to obtain a mixture 1. Three portions of the mixture 1 were prepared for standby use; then, trichloronitrile and 1,4-dioxane were added to a flask, and the mixture was stirred for 10 minutes. The flask was placed in a 0°C ice water bath, and the first portion of the mixture 1 was slowly added dropwise to the flask under stirring. After the addition was completed, the mixture was stirred for reaction for 3 hours, and the temperature was raised to 50°C. Then, the second portion of the mixture 1 was slowly added dropwise to the flask under stirring. After the addition was completed, the mixture was stirred for reaction. 3h, raise the temperature to 85℃, and finally slowly drop the third portion of the mixed solution 1 into the flask under stirring. After the dropwise addition is completed, stir and react for 11h, cool to room temperature, add deionized water, wash with deionized water, and dry in a drying oven at 60℃ for 12h to obtain intermediate b. The dosage ratio of 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, trichloronitrile and 1,4-dioxane is 0.30mol: 0.30mol: 210mL: 0.10mol: 300mL;

[0054] Step A3: First, add intermediate a to acetonitrile and stir to obtain mixed solution 2 for use; then add intermediate b and triethylamine to a flask, place the flask in a 0°C ice-water bath, slowly dropwise add mixed solution 2 to the flask under stirring, and after the dropwise addition is completed, stir to react for 1.5 hours, then heat to 40°C and react for another 12 hours, cool to room temperature, filter, wash the precipitate with deionized water and 1,4-dioxane, and then dry in a drying oven at 60°C for 8 hours to obtain a flame retardant with hyperbranched macromolecules, and the amount ratio of intermediate a, acetonitrile, intermediate b and triethylamine is 0.03 mol:150 mL:0.02 mol:0.06 mol.

[0055] Example 4

[0056] A modified polypropylene is prepared by the following steps:

[0057] Step B1: Add 1-(3-aminopropyl)pyrrolidine to a round-bottom flask with a magnet and start stirring in an ice-water bath at 0°C; add perfluorooctane sulfonyl fluoride to anhydrous toluene and stir at room temperature for 10 minutes to obtain a mixed solution a, slowly drop the mixed solution a into the above round-bottom flask, after the dropwise addition is completed, stir and react in an ice-water bath at 0°C for 2 hours, then heat to 45°C, stir and react at constant temperature for 4 hours, rotary evaporate at 80°C for 30 minutes, filter with suction, recrystallize in acetone, filter with suction, and finally dry in an oven at 40°C for 4 hours to obtain the intermediate 1, wherein the amount ratio of 1-(3-aminopropyl)pyrrolidine, perfluorooctane sulfonyl fluoride and anhydrous toluene is 0.01 mol: 0.01 mol: 55 mL;

[0058] Step B2: 2-(2-chloroethoxy)acetic acid was added to DMF, and dithionyl chloride was added under stirring, and the mixture was refluxed and stirred at 50°C for 4 hours, filtered, extracted, and dried to obtain an intermediate 2, wherein the ratio of 2-(2-chloroethoxy)acetic acid, DMF, and dithionyl chloride was 0.1 mol: 100 mL: 0.2 mol;

[0059] Step B3: 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution b, and then the intermediate 2 is added to dimethyl sulfoxide to obtain a mixed solution c. The mixed solution c is slowly added dropwise to the mixed solution b in an ice-water bath at 0°C. After the addition is completed, the temperature is raised to 40°C, and the reaction is carried out at a constant temperature for 8 hours. The intermediate 3 is prepared by distillation under reduced pressure. The amount ratio of the intermediate 2, 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.1 mol: 0.01 mol: 100 mL;

[0060] Step B4: Add intermediate 3 and intermediate 1 to a flask, then add DMF, and ultrasonicate for 30 minutes. Then place the flask in an oil bath at 90°C and stir to react for 24 hours. Rotary evaporate, add acetone to the residue in the flask, then add petroleum ether, filter and dry to obtain intermediate 4. The usage ratio of intermediate 3, intermediate 1 and DMF is: 0.1 mol: 0.125 mol: 170 mL;

[0061] Step B5: Add polypropylene powder, diisopropylbenzene peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer and mix for 20 minutes to obtain a mixture. Add the mixture into a twin-screw extruder at 200°C for grafting reaction and granulate to obtain modified polypropylene. The amount ratio of polypropylene powder, diisopropylbenzene peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone is 100g:0.08g:0.3g:0.8g:0.6g.

[0062] Example 5

[0063] A modified polypropylene is prepared by the following steps:

[0064] Step B1: Add 1-(3-aminopropyl)pyrrolidine to a round-bottom flask with a magnet and start stirring in an ice-water bath at 0°C; add perfluorooctane sulfonyl fluoride to anhydrous toluene and stir at room temperature for 12 minutes to obtain a mixed solution a, slowly drop the mixed solution a into the above round-bottom flask, after the dropwise addition is completed, stir and react in an ice-water bath at 0°C for 2 hours, then heat to 45°C, stir and react at constant temperature for 4.2 hours, rotary evaporate at 80°C for 32 minutes, filter with suction, recrystallize in acetone, filter with suction, and finally dry in an oven at 40°C for 5 minutes to obtain an intermediate 1, wherein the amount ratio of 1-(3-aminopropyl)pyrrolidine, perfluorooctane sulfonyl fluoride and anhydrous toluene is 0.01 mol: 0.01 mol: 60 mL;

[0065] Step B2: 2-(2-chloroethoxy)acetic acid was added to DMF, and dithionyl chloride was added under stirring, and the mixture was refluxed and stirred at 50°C for 4.5 hours, filtered, extracted, and dried to obtain an intermediate 2, wherein the ratio of 2-(2-chloroethoxy)acetic acid, DMF, and dithionyl chloride was 0.1 mol: 100 mL: 0.25 mol;

[0066] Step B3: 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution b, and then the intermediate 2 is added to dimethyl sulfoxide to obtain a mixed solution c. The mixed solution c is slowly added dropwise to the mixed solution b in an ice-water bath at 0°C. After the addition is completed, the temperature is raised to 40°C, and the reaction is carried out at a constant temperature for 9 hours. The intermediate 3 is obtained by distillation under reduced pressure. The amount ratio of the intermediate 2, 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.1 mol: 0.012 mol: 100 mL;

[0067] Step B4: Add intermediate 3 and intermediate 1 to a flask, then add DMF, ultrasonicate for 35 min, then place the flask in a 90°C oil bath for constant temperature stirring and reaction for 24 h, rotary evaporate, add acetone to the residue in the flask, then add petroleum ether, filter and dry to obtain intermediate 4, the usage ratio of intermediate 3, intermediate 1 and DMF is 0.1 mol: 0.127 mol: 175 mL;

[0068] Step B5: Add polypropylene powder, diisopropylbenzene peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer and mix for 25 minutes to obtain a mixture. Add the mixture into a twin-screw extruder at 200°C for grafting reaction and granulate to obtain modified polypropylene. The amount ratio of polypropylene powder, diisopropylbenzene peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone is 100g:0.08g:0.3g:0.8g:0.9g.

[0069] Example 6

[0070] A modified polypropylene is prepared by the following steps:

[0071] Step B1: Add 1-(3-aminopropyl)pyrrolidine to a round-bottom flask with a magnet and start stirring in an ice-water bath at 0°C; add perfluorooctane sulfonyl fluoride to anhydrous toluene and stir at room temperature for 15 minutes to obtain a mixed solution a, slowly drop the mixed solution a into the above round-bottom flask, after the dropwise addition is completed, stir and react in an ice-water bath at 0°C for 2 hours, then heat to 45°C, stir and react at constant temperature for 4.5 hours, rotary evaporate at 80°C for 35 minutes, filter with suction, recrystallize in acetone, filter with suction, and finally dry in an oven at 40°C for 6 hours to obtain the intermediate 1, wherein the amount ratio of 1-(3-aminopropyl)pyrrolidine, perfluorooctane sulfonyl fluoride and anhydrous toluene is 0.01 mol: 0.01 mol: 65 mL;

[0072] Step B2: 2-(2-chloroethoxy)acetic acid was added to DMF, and dithionyl chloride was added under stirring, and the mixture was refluxed and stirred at 50°C for 5 h, filtered, extracted, and dried to obtain an intermediate 2, wherein the ratio of 2-(2-chloroethoxy)acetic acid, DMF, and dithionyl chloride was 0.1 mol: 100 mL: 0.3 mol;

[0073] Step B3: 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution b, and then the intermediate 2 is added to dimethyl sulfoxide to obtain a mixed solution c. The mixed solution c is slowly added dropwise to the mixed solution b in an ice-water bath at 0°C. After the addition is completed, the temperature is raised to 40°C, and the reaction is carried out at a constant temperature for 10 hours. The intermediate 3 is obtained by distillation under reduced pressure. The amount ratio of the intermediate 2, 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.1 mol: 0.015 mol: 100 mL;

[0074] Step B4: Add intermediate 3 and intermediate 1 to a flask, then add DMF, ultrasonicate for 40 min, then place the flask in an oil bath at 90°C for constant temperature stirring and reaction for 24 h, rotary evaporate, add acetone to the residue in the flask, then add petroleum ether, filter and dry to obtain intermediate 4, the amount ratio of intermediate 3, intermediate 1 and DMF is 0.1 mol: 0.130 mol: 180 mL;

[0075] Step B5: Add polypropylene powder, diisopropylbenzene peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer and mix for 30 minutes to obtain a mixture. Add the mixture into a twin-screw extruder at 200°C for grafting reaction and granulate to obtain modified polypropylene. The amount ratio of polypropylene powder, diisopropylbenzene peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone is 100g:0.08g:0.3g:0.8g:1.2g.

[0076] Example 7

[0077] An antibacterial composite nonwoven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer. One surface of the adsorption layer is composited with the antibacterial layer by needle punching, and the other surface of the adsorption layer is bonded with the breathable waterproof layer by a mesh polyurethane hot melt adhesive.

[0078] The antibacterial layer is made of cotton fiber added to a silver ammonia solution of glucose, then dried and baked at 170°C; the silver ammonia solution of glucose is obtained by adding silver nitrate to deionized water, then adding concentrated ammonia water and glucose solution, and mixing and stirring, and the usage ratio of silver nitrate, deionized water, concentrated ammonia water and glucose solution is 1g:250g:2.5L:250g; the glucose solution is obtained by adding glucose to deionized water and stirring and mixing, and the usage ratio of glucose to deionized water is 1g:250g. The breathable and waterproof layer is polyethylene fiber.

[0079] The adsorption layer comprises the following raw materials by weight: 100 parts of modified polypropylene, 15 parts of flame retardant, 30 parts of mixed alcohol, 25 parts of polybutylene terephthalate and 1 part of nano titanium dioxide; the mixed alcohol is a mixture of ethanol with a volume fraction of 95% and n-butanol with a volume ratio of 1:1;

[0080] The adsorption layer is prepared by the following steps:

[0081] Step S1: Dry the modified polypropylene and polybutylene terephthalate obtained in Example 4 at 40°C for 4h, add nano titanium dioxide, mix the materials using a twin-screw extruder, and then spin; use an opener to open and mix the materials to obtain opened filaments; comb the opened filaments, and then use a web laying machine to lay the web, arrange and shape, and then use a double-roll hot calender to spunbond, cool and roll, and obtain a non-woven fabric. The roller temperature of the double-roll hot calender is 140°C;

[0082] Step S2: Add the flame retardant obtained in Example 1 to the mixed alcohol and stir for 10 minutes to obtain a flame retardant emulsion. Soak the non-woven fabric in the flame retardant emulsion for 20 minutes, and then pass through a benchtop roller once; then soak for another 20 minutes, pass through a benchtop roller once, and finally place in an oven at 100°C and dry for 4 hours to obtain an adsorption layer.

[0083] The antibacterial composite nonwoven fabric is prepared by the following steps:

[0084] One side of the adsorption layer is attached to the antibacterial layer and then compounded by needle punching, and the other side of the adsorption layer is bonded to the breathable and waterproof layer by a mesh medical polyurethane hot melt adhesive to obtain the antibacterial composite non-woven fabric.

[0085] Example 8

[0086] An antibacterial composite nonwoven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer. One surface of the adsorption layer is composited with the antibacterial layer by needle punching, and the other surface of the adsorption layer is bonded with the breathable waterproof layer by a mesh polyurethane hot melt adhesive.

[0087] The antibacterial layer is made of cotton fiber added to a silver ammonia solution of glucose, then dried and baked at 170°C; the silver ammonia solution of glucose is obtained by adding silver nitrate to deionized water, then adding concentrated ammonia water and glucose solution, and mixing and stirring, and the usage ratio of silver nitrate, deionized water, concentrated ammonia water and glucose solution is 1g:250g:2.5L:250g; the glucose solution is obtained by adding glucose to deionized water and stirring and mixing, and the usage ratio of glucose to deionized water is 1g:250g. The breathable and waterproof layer is polyethylene fiber.

[0088] The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 20 parts of flame retardant, 35 parts of mixed alcohol, 30 parts of polybutylene terephthalate and 2 parts of nano titanium dioxide; the mixed alcohol is a mixture of ethanol with a volume fraction of 95% and n-butanol with a volume ratio of 1:1;

[0089] The adsorption layer is prepared by the following steps:

[0090] Step S1: Dry the modified polypropylene and polybutylene terephthalate obtained in Example 5 at 40°C for 4h, add nano titanium dioxide, mix the materials using a twin-screw extruder, and then spin; use an opener to open and mix the materials to obtain opened filaments; comb the opened filaments, and then use a web laying machine to lay the web, arrange and shape, and then use a double-roll hot calender to spunbond, cool and roll, and obtain a non-woven fabric. The roller temperature of the double-roll hot calender is 145°C;

[0091] Step S2: Add the flame retardant obtained in Example 2 to the mixed alcohol and stir for 12 minutes to obtain a flame retardant emulsion. Soak the non-woven fabric in the flame retardant emulsion for 20 minutes, and then pass through a benchtop roller once; then soak for another 20 minutes, pass through a benchtop roller once, and finally place in an oven at 100°C and dry for 4.5 hours to obtain an adsorption layer.

[0092] The antibacterial composite nonwoven fabric is prepared by the following steps:

[0093] One side of the adsorption layer is attached to the antibacterial layer and then compounded by needle punching, and the other side of the adsorption layer is bonded to the breathable and waterproof layer by a mesh medical polyurethane hot melt adhesive to obtain the antibacterial composite non-woven fabric.

[0094] Example 9

[0095] An antibacterial composite nonwoven fabric comprises an antibacterial layer, an adsorption layer and a breathable waterproof layer. One surface of the adsorption layer is composited with the antibacterial layer by needle punching, and the other surface of the adsorption layer is bonded with the breathable waterproof layer by a mesh polyurethane hot melt adhesive.

[0096] The antibacterial layer is made of cotton fiber added to a silver ammonia solution of glucose, then dried and baked at 170°C; the silver ammonia solution of glucose is obtained by adding silver nitrate to deionized water, then adding concentrated ammonia water and glucose solution, and mixing and stirring, and the usage ratio of silver nitrate, deionized water, concentrated ammonia water and glucose solution is 1g:250g:2.5L:250g; the glucose solution is obtained by adding glucose to deionized water and stirring and mixing, and the usage ratio of glucose to deionized water is 1g:250g. The breathable and waterproof layer is polyethylene fiber.

[0097] The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 25 parts of flame retardant, 40 parts of mixed alcohol, 35 parts of polybutylene terephthalate and 3 parts of nano titanium dioxide; the mixed alcohol is a mixture of ethanol with a volume fraction of 95% and n-butanol with a volume ratio of 1:1;

[0098] The adsorption layer is prepared by the following steps:

[0099] Step S1: Dry the modified polypropylene and polybutylene terephthalate obtained in Example 6 at 40°C for 4h, add nano titanium dioxide, mix the materials using a twin-screw extruder, and then spin; use an opener to open and mix the materials to obtain opened filaments; comb the opened filaments, and then use a web laying machine to lay the web, arrange and shape, and then use a double-roll hot calender to spunbond, cool and roll, and obtain a non-woven fabric. The roller temperature of the double-roll hot calender is 150°C;

[0100] Step S2: Add the flame retardant obtained in Example 3 to the mixed alcohol and stir for 15 minutes to obtain a flame retardant emulsion. Soak the non-woven fabric in the flame retardant emulsion for 20 minutes, and then pass through a benchtop roller once; then soak for another 20 minutes, pass through a benchtop roller once, and finally place in an oven at 100°C and dry for 5 hours to obtain an adsorption layer.

[0101] The antibacterial composite nonwoven fabric is prepared by the following steps:

[0102] One side of the adsorption layer is attached to the antibacterial layer and then compounded by needle punching, and the other side of the adsorption layer is bonded to the breathable waterproof layer by a mesh polyurethane hot melt adhesive to obtain the antibacterial composite non-woven fabric.

[0103] Comparative Example 1

[0104] This comparative example is a commercially available composite nonwoven fabric.

[0105] Comparative Example 2

[0106] Compared with Example 9, the modified polypropylene is replaced by polypropylene, and the other steps are exactly the same as Example 9 to obtain a composite non-woven fabric.

[0107] Comparative Example 3

[0108] Compared with Example 9, the flame retardant was replaced with melamine, and the other steps were exactly the same as Example 9 to obtain a composite non-woven fabric.

[0109] The properties of the obtained composite nonwoven fabric were tested according to relevant standards such as GB / T21510-2008, FZ / T 6000, GB / T5456-1997 and GB / T18830. The results are shown in Table 1:

[0110] Table 1:

[0111]

[0112] According to the data in Table 1, it can be seen from the comparison of Example 7, Example 8 and Example 9 with Comparative Example 1 that compared with the commercially available composite non-woven fabric, the antibacterial composite non-woven fabric prepared by the present invention has a good inhibitory effect on Escherichia coli, golden staphylococcus and enteric Salmonella, and has excellent mechanical properties, flame retardant properties and anti-ultraviolet properties. Compared with the use of modified polypropylene, the composite non-woven fabric made of unmodified polypropylene has no antibacterial groups such as quaternary ammonium salts and sulfonamides, and the antibacterial property of the composite non-woven fabric decreases. Fluorocarbon segments, maleic anhydride and N-vinyl pyrrolidone structures are not introduced by grafting, and the mechanical properties of the composite non-woven fabric decrease. Compared with the flame retardant synthesized by the present invention, melamine is used as a flame retardant and the benzophenone structure is not introduced, and the anti-ultraviolet performance of the resulting composite non-woven fabric decreases more.

[0113] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. An antibacterial composite nonwoven fabric, characterized in that: It comprises an antibacterial layer, an adsorption layer and a breathable and waterproof layer. One surface of the adsorption layer is affixed with a composite antibacterial layer by needle puncture, and the other surface of the adsorption layer is bonded with a breathable and waterproof layer by a mesh polyurethane hot melt adhesive. The antibacterial layer is made of cotton fiber added to a silver ammonia solution of glucose, and then dried and baked at 170°C. The silver ammonia solution of glucose is obtained by adding silver nitrate to deionized water, and then adding concentrated ammonia water and glucose solution, and mixing and stirring. The amount ratio of silver nitrate, deionized water, concentrated ammonia water and glucose solution is 1g:250g:2.5L:250g. The glucose solution is obtained by adding glucose to deionized water and stirring and mixing. The amount ratio of glucose to deionized water is 1g:250g. The breathable and waterproof layer is polyethylene fiber. The adsorption layer comprises the following raw materials in parts by weight: 100 parts of modified polypropylene, 15-25 parts of flame retardant, 30-40 parts of mixed alcohol, 25-35 parts of polybutylene terephthalate and 1-3 parts of nano titanium dioxide; the mixed alcohol is a mixture of ethanol with a volume fraction of 95% and n-butanol with a volume ratio of 1:1; The flame retardant is prepared by the following steps: Step A1: add phosphorus oxychloride to toluene, add 2-hydroxy-4-n-octyloxybenzophenone in an ice-water bath at 0°C with stirring, and react with stirring for 3-4h to obtain intermediate a; Step A2: first, add 4-amino-4-methyl-pentan-1-ol and sodium hydroxide into deionized water, stir and mix to obtain a mixed solution 1, and prepare three portions of the mixed solution 1 for standby use; then, add trichloronitrile and 1,4-dioxane into a flask, stir for 5-10 minutes, place the flask in a 0°C ice water bath, slowly drop the first portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is completed, stir and react for 3 hours, heat to 50°C, then slowly drop the second portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is completed, stir and react for 3 hours, heat to 85°C, finally slowly drop the third portion of the mixed solution 1 into the flask under stirring, after the dropwise addition is completed, stir and react for 11 hours, cool to room temperature, add deionized water, wash with deionized water, and dry in a drying oven at 60°C for 12 hours to obtain intermediate b; Step A3: First, add intermediate a to acetonitrile and stir to obtain mixed solution 2 for standby use; then add intermediate b and triethylamine to a flask, place the flask in a 0°C ice-water bath, slowly dropwise add mixed solution 2 to the flask under stirring, and after the dropwise addition is complete, stir to react for 1.5 hours, then heat to 40°C and react for another 11-12 hours, cool to room temperature, filter, wash the precipitate with deionized water and 1,4-dioxane, and then dry in a drying oven at 50-60°C for 6-8 hours to obtain a flame retardant with hyperbranched macromolecules; The modified polypropylene is prepared by the following steps: Step B1: Add 1-(3-aminopropyl)pyrrolidine to a round-bottom flask with a magnet and start stirring in an ice-water bath at 0°C; add perfluorooctanesulfonyl fluoride to anhydrous toluene and stir at room temperature for 10-15 minutes to obtain a mixed solution a, slowly dropwise add the mixed solution a to the above round-bottom flask, after the dropwise addition is complete, stir in an ice-water bath at 0°C for 2 hours, then heat to 45°C, stir and react at constant temperature for 4-4.5 hours, rotary evaporate at 80°C for 30-35 minutes, then filter with suction, then recrystallize in acetone, filter with suction, and finally dry in an oven at 40°C for 4-6 hours to obtain intermediate 1; Step B2: 2-(2-chloroethoxy)acetic acid is added to DMF, and dichlorothionyl is added under stirring, and the mixture is refluxed and stirred at 50° C. for 4-5 hours, filtered, extracted, and dried to obtain intermediate 2; Step B3: Add 3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution b, then add the intermediate 2 into dimethyl sulfoxide to obtain a mixed solution c, slowly dropwise add the mixed solution c into the mixed solution b in an ice-water bath at 0°C, after the dropwise addition is completed, heat to 40°C, react at this temperature for 8-10 hours, and distill under reduced pressure to obtain the intermediate 3; Step B4: Add intermediate 3 and intermediate 1 to a flask, then add DMF, and perform ultrasonication for 30-40 min. Then place the flask in an oil bath at 90°C and stir to react for 24 h. Rotary evaporate, add acetone to the residue in the flask, then add petroleum ether, filter and dry to obtain intermediate 4. Step B5: Add polypropylene powder, diisopropylbenzene peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone into a high-speed mixer and mix for 20-30 minutes to obtain a mixture, add the mixture into a twin-screw extruder at 200° C. for grafting reaction, and granulate to obtain modified polypropylene.

2. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In step A1, the usage ratio of phosphorus oxychloride, toluene and 2-hydroxy-4-n-octyloxybenzophenone is 0.3 mol:200 mL:0.3 mol.

3. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In step A2, the usage ratio of 4-amino-4-methyl-pentan-1-ol, sodium hydroxide, deionized water, trichloronitrile and 1,4-dioxane is 0.30 mol: 0.30 mol: 180-210 mL: 0.10 mol: 300 mL.

4. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In step A3, the usage ratio of intermediate a, acetonitrile, intermediate b and triethylamine is 0.03 mol:150 mL:0.02 mol:0.06 mol.

5. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In step B1, the usage ratio of 1-(3-aminopropyl)pyrrolidine, perfluorooctanesulfonyl fluoride and anhydrous toluene is 0.01 mol:0.01 mol:55-65 mL.

6. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In step B2, the usage ratio of 2-(2-chloroethoxy)acetic acid, DMF and dichlorothionyl is 0.1 mol:100 mL:0.2-0.3 mol; in step B3, the usage ratio of intermediate 2,3-(hydroxymethyl)-4-methylfuran-2,5-dione, potassium carbonate and dimethyl sulfoxide is 0.1 mol:0.1 mol:0.01-0.015 mol:100 mL.

7. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In step B4, the usage ratio of intermediate 3, intermediate 1 and DMF is 0.1 mol: 0.125-0.130 mol: 170-180 mL.

8. The antibacterial composite nonwoven fabric according to claim 1, characterized in that: In step B5, the usage ratio of polypropylene powder, diisopropylbenzene peroxide, antioxidant 1010, intermediate 4 and N-vinyl pyrrolidone is 100 g: 0.08 g: 0.3 g: 0.8 g: 0.6-1.2 g.

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