Antibacterial waterproof breathable membrane and its preparation method and application

Abstract

The present invention discloses an antibacterial waterproof breathable membrane, its preparation method, and application, relating to the technical field of waterproof materials. In preparing the antibacterial waterproof breathable membrane, the present invention comprises reacting hexadecyldimethyl tertiary amine with epichlorohydrin to produce hexadecyldimethyl glycidyl ammonium chloride; reacting nanosilica with diethylenetriaminopropyltrimethoxysilane and hexadecyldimethyl glycidyl ammonium chloride in sequence to produce modified nanosilica; then reacting allyl glycidyl ether, methyl methacrylate, ethyl acrylate, and (perfluorohexyl)ethylene to produce an acrylate copolymer; and finally, blending acid-decomposed polyamide, modified nanosilica, and the acrylate copolymer and subjecting them to electrostatic spinning to produce the antibacterial waterproof breathable membrane. The antibacterial waterproof breathable membrane prepared by the present invention exhibits excellent antibacterial, waterproof, breathable, and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of waterproof materials, in particular to an antibacterial waterproof breathable membrane and a preparation method and application thereof. Background Art

[0002] my country has a vast territory and significant climate variations. In areas with heavy rainfall and humid air, buildings are susceptible to moisture in the air, causing them to mold and crack. This not only significantly affects the building's appearance and increases maintenance costs for residents, but the "cold bridge effect" created by gaps in the walls significantly increases heating costs, shortens the building's lifespan, and in severe cases, even threatens the safety of residents and their property. The moisture that causes mold and cracking in buildings comes from rainwater or condensation in the air. The application of waterproof and breathable membrane technology is of great significance. While protecting the main structure, it also reduces energy consumption to a certain extent. Research has shown that when buildings are covered with waterproof and breathable membranes, summer roof temperatures can be reduced, saving on heating and cooling costs and reducing air leakage rates.

[0003] While traditional waterproof and breathable membranes protect buildings from rain, they struggle to prevent the migration and diffusion of vaporous water molecules within building walls. Vaporous water migrates in a pattern, generally from high-temperature to low-temperature areas. Therefore, when indoor temperatures are high, water vapor tends to migrate outward. In this situation, if the exterior wall's waterproof layer is impermeable, water vapor will accumulate in the insulation layer, reducing its thermal insulation performance and potentially causing condensation and mildew on the wall. Therefore, the present invention provides an antibacterial waterproof and breathable membrane. Summary of the Invention

[0004] The purpose of the present invention is to provide an antibacterial waterproof breathable membrane and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] The invention discloses an antibacterial waterproof breathable membrane, which is prepared by electrostatic spinning by blending acid-decomposed polyamide, modified nano-silica and acrylate copolymer.

[0007] As an optimization, the polyamide masterbatch model is 101F, which comes from Shanghai Junyilong New Material Technology Co., Ltd.

[0008] As an optimization, the modified nano-silica is prepared by reacting nano-silica with diethylenetriaminopropyltrimethoxysilane and hexadecyldimethylglycidylammonium chloride in sequence.

[0009] As an optimization, the nano-silica model is PST-G02, which comes from Nanjing Baoket New Materials Co., Ltd.

[0010] As an optimization, the hexadecyldimethyl epoxypropyl ammonium chloride is prepared by reacting hexadecyldimethyl tertiary amine and epichlorohydrin.

[0011] As an optimization, the acrylic ester copolymer is prepared by reacting allyl glycidyl ether, methyl methacrylate, ethyl acrylate and (perfluorohexyl)ethylene.

[0012] A method for preparing an antibacterial waterproof breathable membrane comprises the following steps:

[0013] (1) Hexadecyldimethylamine is heated to 50-70°C, and epichlorohydrin in an amount 2-3 times the mass of hexadecyldimethylamine is added dropwise at a uniform rate over 30-60 minutes. The reaction is continued for 1-3 hours. After standing at 120-140°C for 4-6 hours, acetone in an amount 8-10 times the mass of hexadecyldimethylamine is added for recrystallization, and the mixture is washed with ether 3-5 times and dried at 40-50°C for 4-6 hours to obtain hexadecyldimethyl glycidyl ammonium chloride.

[0014] (2) Diethylenetriaminopropyltrimethoxysilane and 70-80% ethanol aqueous solution are mixed at a mass ratio of 1: (40-60), ultrasonically shaken for 1-2 hours to obtain diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and 70-80% ethanol aqueous solution are mixed at a mass ratio of 1: (40-60), ultrasonically shaken for 30-60 minutes, and diethylenetriaminopropyltrimethoxysilane hydrolyzate with a mass of 20-30 times the mass of nano-silica is added, reacted at 50-70°C for 10-12 hours, cooled to room temperature and centrifuged, washed with anhydrous ethanol 3-5 times, and heated at 40-50°C. Drying for 6 to 8 hours to obtain pre-modified nano-silica; mixing the pre-modified nano-silica and a 70-80% ethanol aqueous solution at a mass ratio of 1:(40-50), ultrasonically shaking for 40 to 60 minutes, adding 0.02 to 0.03 times the mass of the pre-modified nano-silica, and then adding a 1.2 mol / L sodium hydroxide aqueous solution to adjust the pH to 10 to 12, heating to 70 to 80° C., reacting at 100 to 200 rpm for 6 to 8 hours, and then centrifuging, washing with deionized water 3 to 5 times, and drying at 60 to 70° C. for 10 to 12 hours to obtain modified nano-silica;

[0015] (3) Allyl glycidyl ether, methyl methacrylate, ethyl acrylate, methyl isobutyl ketone and azobisisobutyronitrile are mixed in a mass ratio of 1:(0.3-0.5):(0.3-0.5):(3-5):(0.01-0.02), stirred at 20-30°C and 200-300 rpm for 30-60 min, heated to 70-80°C, and (perfluorohexyl)ethylene (4 times the mass of allyl glycidyl ether) is added dropwise at a uniform rate over 30-40 min. After continuing the reaction for 5-7 h, methyl isobutyl ketone is evaporated to dryness by rotary evaporation at 50-60°C and 0.08-0.1 MPa to obtain an acrylate copolymer;

[0016] (4) The polyamide masterbatch is crushed and sieved with 100-200 mesh to obtain polyamide powder, and the polyamide powder and hydrochloric acid with a pH value of 2-3 are mixed in a mass ratio of 1: (10-20), stirred at 60-70 ° C for 20-30 minutes, centrifuged, cooled to room temperature, washed with deionized water for 3-5 times, and dried at 40-50 ° C for 6-8 hours to obtain acid-decomposed polyamide; the acid-decomposed polyamide, N, N-dimethylformamide and butyl acetate are mixed in a mass ratio of 1:4:6, stirred at 70-80 ° C and 300-400 r / min for 22-26 hours, allowed to stand for 8-10 hours, and the acid-decomposed polyamide is added. The modified nano-silica with a mass of 0.4 to 0.6 times that of the amine and the acrylate copolymer with a mass of 0.4 to 0.6 times that of the acid-decomposed polyamide are continuously stirred for 10 to 20 minutes and allowed to stand for 10 to 20 minutes to obtain a spinning solution. The spinning solution is electrostatically spun under the conditions of a relative humidity of 35 to 45%, a temperature of 20 to 30°C, a spinning voltage of 10 to 20 kV, a receiving distance of 16 to 20 cm, and a drum speed of 200 to 400 r / min to form a membrane with a thickness of 0.5 to 0.7 mm. After completion, the membrane is allowed to stand at 80 to 100°C for 8 to 10 hours to obtain an antibacterial waterproof and breathable membrane.

[0017] As an optimization, the reaction equation of hexadecyldimethyl glycidyl ammonium chloride in step (1) is:

[0018]

[0019] As an optimization, the reaction equation of the pre-modified nano-silica in step (2) is:

[0020]

[0021] As an optimization, the reaction equation for the modified nano-silica in step (2) is:

[0022]

[0023] As an optimization, the reaction equation of the acrylic ester copolymer in step (3) is:

[0024]

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] When preparing the antibacterial waterproof and breathable membrane, the present invention comprises the following steps: reacting hexadecyldimethyl tertiary amine with epichlorohydrin to obtain hexadecyldimethyl glycidyl ammonium chloride; reacting nano-silica with diethylenetriaminopropyltrimethoxysilane and hexadecyldimethyl glycidyl ammonium chloride in sequence to obtain modified nano-silica; reacting allyl glycidyl ether, methyl methacrylate, ethyl acrylate and (perfluorohexyl)ethylene to obtain an acrylate copolymer; and finally, blending acid-decomposed polyamide, the modified nano-silica and the acrylate copolymer and subjecting them to electrostatic spinning to prepare the antibacterial waterproof and breathable membrane.

[0027] First, hexadecyldimethyl tertiary amine and epichlorohydrin are reacted to obtain hexadecyldimethyl glycidyl ammonium chloride, and then nano-silica is reacted with diethylenetriaminopropyltrimethoxysilane and hexadecyldimethyl glycidyl ammonium chloride in sequence to obtain modified nano-silica; grafting diethylenetriaminopropyltrimethoxysilane can effectively reduce the self-agglomeration effect of nano-silica and improve its dispersibility in the antibacterial waterproof and breathable membrane; the grafted hexadecyldimethyl glycidyl ammonium chloride not only gives the nano-silica antibacterial properties but also enhances its hydrophobicity.

[0028] Secondly, allyl glycidyl ether, methyl methacrylate, ethyl acrylate and (perfluorohexyl)ethylene are reacted to prepare an acrylate copolymer; then, the acid-decomposed polyamide, modified nano-silica and the acrylate copolymer are blended and electrospun to prepare an antibacterial waterproof and breathable membrane; the amino groups on the acid-decomposed polyamide react with the epoxy groups on the acrylate copolymer, thereby improving the waterproof and mechanical properties of the antibacterial waterproof and breathable membrane; at the same time, the hexadecyl dimethyl glycidyl ammonium chloride grafted on the modified nano-silica is positively charged, which can produce electrostatic bonding with the negatively charged carboxylic acid on the acid-decomposed polyamide, further improving the mechanical properties of the antibacterial waterproof and breathable membrane. DETAILED DESCRIPTION

[0029] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0030] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the test methods for the various indicators of the antibacterial waterproof breathable membrane prepared in the following examples.

[0031] Antibacterial performance: The antibacterial waterproof breathable membranes obtained in the examples and the comparative examples were tested for their antibacterial rates according to GB / T 20944.3.

[0032] Waterproofness: The antibacterial waterproof breathable membranes obtained in each example and the comparative membrane were cut into a size of 15 cm * 15 cm and tested using a YG812C water permeability tester. The water pressure was set at a rising rate of 10 kPa / min until three drops of water appeared on the surface of the fabric. The water pressure resistance was recorded and the waterproof performance was determined by the water pressure resistance.

[0033] Air permeability: The antibacterial waterproof breathable membranes obtained in each example and the comparative example membrane were tested for moisture permeability according to GB / T12704 to determine the air permeability.

[0034] Mechanical properties: The antibacterial waterproof breathable membranes obtained in each example and the comparative example membrane were cut into a size of 10 mm*3 mm, and the breaking strength was tested using an XQ-1C single fiber strength and elongation tester to determine the mechanical properties.

[0035] Example 1

[0036] A method for preparing an antibacterial waterproof breathable membrane, comprising the following steps:

[0037] (1) Hexadecyldimethylamine was heated to 50°C, and epichlorohydrin (2 times the mass of hexadecyldimethylamine) was added dropwise at a constant rate over 60 minutes. The reaction was continued for 1 hour. After standing at 120°C for 6 hours, acetone (8 times the mass of hexadecyldimethylamine) was added for recrystallization. The mixture was washed with ether 3 times and dried at 40°C for 6 hours to obtain hexadecyldimethyl glycidyl ammonium chloride.

[0038] (2) Diethylenetriaminopropyltrimethoxysilane and a 70% ethanol aqueous solution were mixed at a mass ratio of 1:60, and ultrasonically vibrated for 1 hour to obtain a diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and a 70% ethanol aqueous solution were mixed at a mass ratio of 1:60, and ultrasonically vibrated for 30 minutes, and 20 times the mass of nano-silica was added to the diethylenetriaminopropyltrimethoxysilane hydrolyzate, reacted at 50°C for 12 hours, cooled to room temperature, centrifuged, washed with anhydrous ethanol 3 times, and heated at 4 0 ° C and dried for 8 hours to obtain pre-modified nano-silica; the pre-modified nano-silica and a 70% ethanol aqueous solution were mixed at a mass ratio of 1:50, ultrasonically shaken for 40 minutes, 0.02 times the mass of the pre-modified nano-silica was added with hexadecyldimethylglycidyl ammonium chloride, and then a 1.2 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 10, the temperature was raised to 70 ° C and 100 rpm, the reaction was carried out for 8 hours, and then centrifuged, washed with deionized water 3 times, and dried at 60 ° C for 12 hours to obtain modified nano-silica;

[0039] (3) Allyl glycidyl ether, methyl methacrylate, ethyl acrylate, methyl isobutyl ketone and azobisisobutyronitrile were mixed in a mass ratio of 1:0.3:0.3:3:0.01, stirred at 20°C and 200 rpm for 60 minutes, heated to 70°C, and (perfluorohexyl)ethylene (4 times the mass of allyl glycidyl ether) was added dropwise at a constant rate over 30 minutes. After the reaction was continued for 5 hours, methyl isobutyl ketone was rotary evaporated to dryness at 50°C and 0.08 MPa to obtain an acrylate copolymer;

[0040] (4) The polyamide masterbatch was crushed and sieved through 100 mesh to obtain polyamide powder, and the polyamide powder was mixed with hydrochloric acid with a pH value of 2 at a mass ratio of 1:20, stirred at 60°C for 30 minutes, centrifuged, cooled to room temperature, washed with deionized water three times, and dried at 40°C for 8 hours to obtain acid-decomposed polyamide; the acid-decomposed polyamide, N,N-dimethylformamide and butyl acetate were mixed at a mass ratio of 1:4:6, stirred at 70°C and 300 r / min for 26 hours, allowed to stand for 10 hours, and acid-decomposed polyamide was added. The modified nano-silica with a mass of 0.4 times that of polyamide and the acrylate copolymer with a mass of 0.4 times that of acid-decomposed polyamide were stirred for 10 minutes and allowed to stand for 10 minutes to obtain a spinning solution. The spinning solution was electrospun at a relative humidity of 35%, a temperature of 20°C, a spinning voltage of 10 kV, a receiving distance of 16 cm, and a drum speed of 200 r / min and deposited into a membrane with a thickness of 0.5 mm. After completion, the membrane was allowed to stand at 80°C for 8 hours to obtain an antibacterial waterproof and breathable membrane.

[0041] Example 2

[0042] A method for preparing an antibacterial waterproof breathable membrane, comprising the following steps:

[0043] (1) Hexadecyldimethylamine was heated to 60°C, and epichlorohydrin (2.5 times the mass of hexadecyldimethylamine) was added dropwise at a constant rate over 45 minutes. The reaction was continued for 2 hours. After standing at 130°C for 5 hours, acetone (9 times the mass of hexadecyldimethylamine) was added for recrystallization. The mixture was washed with ether 4 times and dried at 45°C for 5 hours to obtain hexadecyldimethyl glycidyl ammonium chloride.

[0044] (2) Diethylenetriaminopropyltrimethoxysilane and 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 1.5 hours to obtain diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 45 minutes, and diethylenetriaminopropyltrimethoxysilane hydrolyzate with a mass of 25 times that of nano-silica was added, reacted at 60°C for 11 hours, cooled to room temperature, centrifuged, washed with anhydrous ethanol 4 times, and then heated at 4 5 ° C drying for 7 hours to obtain pre-modified nano-silica; the pre-modified nano-silica and a 75% mass fraction of ethanol aqueous solution were mixed in a mass ratio of 1:45, ultrasonically shaken for 50 minutes, 0.025 times the mass of the pre-modified nano-silica was added with hexadecyldimethylglycidyl ammonium chloride, and then a 1.2 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 11, the temperature was raised to 75 ° C, 150 rpm, and the reaction was carried out for 7 hours, followed by centrifugation, washing with deionized water 4 times, and drying at 65 ° C for 11 hours to obtain modified nano-silica;

[0045] (3) Allyl glycidyl ether, methyl methacrylate, ethyl acrylate, methyl isobutyl ketone and azobisisobutyronitrile were mixed in a mass ratio of 1:0.4:0.4:4:0.015, stirred at 25°C and 250 rpm for 45 minutes, heated to 75°C, and (perfluorohexyl)ethylene (4 times the mass of allyl glycidyl ether) was added dropwise at a constant rate over 35 minutes. After the reaction was continued for 6 hours, methyl isobutyl ketone was rotary evaporated to dryness at 55°C and 0.09 MPa to obtain an acrylate copolymer;

[0046] (4) The polyamide masterbatch was crushed and sieved through 150 mesh to obtain polyamide powder, and the polyamide powder was mixed with hydrochloric acid with a pH value of 2.5 in a mass ratio of 1:15, stirred at 65°C for 25 minutes, centrifuged, cooled to room temperature, washed with deionized water 4 times, and dried at 45°C for 7 hours to obtain acid-decomposed polyamide; the acid-decomposed polyamide, N,N-dimethylformamide and butyl acetate were mixed in a mass ratio of 1:4:6, stirred at 75°C and 350r / min for 24 hours, allowed to stand for 9 hours, and acid was added. The modified nano-silica with a mass of 0.5 times that of the decomposed polyamide and the acrylate copolymer with a mass of 0.5 times that of the acid-decomposed polyamide were stirred for 15 minutes and allowed to stand for 15 minutes to obtain a spinning solution. The spinning solution was electrospun at a relative humidity of 40%, a temperature of 25°C, a spinning voltage of 15kV, a receiving distance of 18cm, and a drum speed of 300r / min and deposited into a membrane with a thickness of 0.6mm. After completion, the membrane was allowed to stand at 90°C for 9 hours to obtain an antibacterial waterproof and breathable membrane.

[0047] Example 3

[0048] A method for preparing an antibacterial waterproof breathable membrane, comprising the following steps:

[0049] (1) Hexadecyldimethylamine was heated to 70°C, and epichlorohydrin (3 times the mass of hexadecyldimethylamine) was added dropwise at a constant rate over 30 minutes. The reaction was continued for 3 hours. After standing at 140°C for 4 hours, acetone (10 times the mass of hexadecyldimethylamine) was added for recrystallization. The mixture was washed with ether 5 times and dried at 50°C for 4 hours to obtain hexadecyldimethyl glycidyl ammonium chloride.

[0050] (2) Diethylenetriaminopropyltrimethoxysilane and 80% ethanol aqueous solution were mixed at a mass ratio of 1:40, ultrasonically shaken for 2 hours to obtain diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and 80% ethanol aqueous solution were mixed at a mass ratio of 1:40, ultrasonically shaken for 60 minutes, and diethylenetriaminopropyltrimethoxysilane hydrolyzate with a mass of 30 times that of nano-silica was added, reacted at 70°C for 10 hours, cooled to room temperature, centrifuged, washed with anhydrous ethanol 5 times, and then heated at 5 0 ° C and dried for 6 hours to obtain pre-modified nano-silica; the pre-modified nano-silica and a mass fraction of 80% ethanol aqueous solution were mixed in a mass ratio of 1:40, ultrasonically shaken for 60 minutes, 0.03 times the mass of the pre-modified nano-silica was added with hexadecyldimethylglycidyl ammonium chloride, and then a 1.2 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 12, the temperature was raised to 80 ° C and 200 rpm, the reaction was carried out for 6 hours, and then centrifuged, washed with deionized water 5 times, and dried at 70 ° C for 10 hours to obtain modified nano-silica;

[0051] (3) Allyl glycidyl ether, methyl methacrylate, ethyl acrylate, methyl isobutyl ketone and azobisisobutyronitrile were mixed in a mass ratio of 1:0.5:0.5:5:0.02, stirred at 30°C and 300 rpm for 30 minutes, heated to 80°C, and (perfluorohexyl)ethylene (4 times the mass of allyl glycidyl ether) was added dropwise at a constant rate over 40 minutes. After the reaction was continued for 7 hours, methyl isobutyl ketone was rotary evaporated to dryness at 60°C and 0.1 MPa to obtain an acrylate copolymer;

[0052] (4) The polyamide masterbatch was crushed and sieved through 200 mesh to obtain polyamide powder, and the polyamide powder was mixed with hydrochloric acid with a pH value of 3 in a mass ratio of 1:10, stirred at 70°C for 20 minutes, centrifuged, cooled to room temperature, washed with deionized water 5 times, and dried at 50°C for 6 hours to obtain acid-decomposed polyamide; the acid-decomposed polyamide, N,N-dimethylformamide and butyl acetate were mixed in a mass ratio of 1:4:6, stirred at 80°C and 400 r / min for 22 hours, allowed to stand for 8 hours, and acid-decomposed polyamide was added. The modified nano-silica with 0.6 times the mass of amide and the acrylate copolymer with 0.6 times the mass of acid-decomposed polyamide were stirred for 20 minutes and allowed to stand for 20 minutes to obtain a spinning solution. The spinning solution was electrospun at a relative humidity of 45%, a temperature of 30°C, a spinning voltage of 20kV, a receiving distance of 20cm, and a drum speed of 400r / min and deposited into a membrane with a thickness of 0.7mm. After completion, it was allowed to stand at 100°C for 8 hours to obtain an antibacterial waterproof and breathable membrane.

[0053] Comparative Example 1

[0054] A method for preparing an antibacterial waterproof breathable membrane, comprising the following steps:

[0055] (1) Diethylenetriaminopropyltrimethoxysilane and a 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 1.5 hours to obtain a diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and a 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 45 minutes, and 25 times the mass of the nano-silica was added to the diethylenetriaminopropyltrimethoxysilane hydrolyzate. The mixture was reacted at 60°C for 11 hours, cooled to room temperature, centrifuged, washed with anhydrous ethanol 4 times, and dried at 45°C for 7 hours to obtain modified nano-silica;

[0056] (2) Allyl glycidyl ether, methyl methacrylate, ethyl acrylate, methyl isobutyl ketone and azobisisobutyronitrile were mixed in a mass ratio of 1:0.4:0.4:4:0.015, stirred at 25°C and 250 rpm for 45 minutes, heated to 75°C, and (perfluorohexyl)ethylene (4 times the mass of allyl glycidyl ether) was added dropwise at a constant rate over 35 minutes. After the reaction was continued for 6 hours, methyl isobutyl ketone was rotary evaporated to dryness at 55°C and 0.09 MPa to obtain an acrylate copolymer;

[0057] (3) The polyamide masterbatch was crushed and sieved through 150 mesh to obtain polyamide powder, and the polyamide powder was mixed with hydrochloric acid with a pH value of 2.5 in a mass ratio of 1:15, stirred at 65 ° C for 25 minutes, centrifuged, cooled to room temperature, washed with deionized water 4 times, and dried at 45 ° C for 7 hours to obtain acid-decomposed polyamide; the acid-decomposed polyamide, N, N-dimethylformamide and butyl acetate were mixed in a mass ratio of 1:4:6, stirred at 75 ° C and 350 r / min for 24 hours, and allowed to stand for 9 hours. The modified nano-silica with a mass of 0.5 times that of the decomposed polyamide and the acrylate copolymer with a mass of 0.5 times that of the acid-decomposed polyamide were stirred for 15 minutes and allowed to stand for 15 minutes to obtain a spinning solution. The spinning solution was electrospun at a relative humidity of 40%, a temperature of 25°C, a spinning voltage of 15kV, a receiving distance of 18cm, and a drum speed of 300r / min and deposited into a membrane with a thickness of 0.6mm. After completion, the membrane was allowed to stand at 90°C for 9 hours to obtain an antibacterial waterproof and breathable membrane.

[0058] Comparative Example 2

[0059] A method for preparing an antibacterial waterproof breathable membrane, comprising the following steps:

[0060] (1) Hexadecyldimethylamine was heated to 60°C, and epichlorohydrin (2.5 times the mass of hexadecyldimethylamine) was added dropwise at a constant rate over 45 minutes. The reaction was continued for 2 hours. After standing at 130°C for 5 hours, acetone (9 times the mass of hexadecyldimethylamine) was added for recrystallization. The mixture was washed with ether 4 times and dried at 45°C for 5 hours to obtain hexadecyldimethyl glycidyl ammonium chloride.

[0061] (2) Diethylenetriaminopropyltrimethoxysilane and 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 1.5 hours to obtain diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 45 minutes, and diethylenetriaminopropyltrimethoxysilane hydrolyzate with a mass of 25 times that of nano-silica was added, reacted at 60°C for 11 hours, cooled to room temperature, centrifuged, washed with anhydrous ethanol 4 times, and then heated at 4 5 ° C drying for 7 hours to obtain pre-modified nano-silica; the pre-modified nano-silica and a 75% mass fraction of ethanol aqueous solution were mixed in a mass ratio of 1:45, ultrasonically shaken for 50 minutes, 0.025 times the mass of the pre-modified nano-silica was added with hexadecyldimethylglycidyl ammonium chloride, and then a 1.2 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 11, the temperature was raised to 75 ° C, 150 rpm, and the reaction was carried out for 7 hours, followed by centrifugation, washing with deionized water 4 times, and drying at 65 ° C for 11 hours to obtain modified nano-silica;

[0062] (3) Allyl glycidyl ether, methyl methacrylate, ethyl acrylate, methyl isobutyl ketone, and azobisisobutyronitrile were mixed in a mass ratio of 1:0.4:0.4:4:0.015, stirred at 25°C and 250 rpm for 45 minutes, heated to 75°C, reacted for 6 hours, and methyl isobutyl ketone was evaporated to dryness by rotary evaporation at 55°C and 0.09 MPa to obtain an acrylate copolymer;

[0063] (4) The polyamide masterbatch was crushed and sieved through 150 mesh to obtain polyamide powder, and the polyamide powder was mixed with hydrochloric acid with a pH value of 2.5 in a mass ratio of 1:15, stirred at 65°C for 25 minutes, centrifuged, cooled to room temperature, washed with deionized water 4 times, and dried at 45°C for 7 hours to obtain acid-decomposed polyamide; the acid-decomposed polyamide, N,N-dimethylformamide and butyl acetate were mixed in a mass ratio of 1:4:6, stirred at 75°C and 350r / min for 24 hours, allowed to stand for 9 hours, and acid was added. The modified nano-silica with a mass of 0.5 times that of the decomposed polyamide and the acrylate copolymer with a mass of 0.5 times that of the acid-decomposed polyamide were stirred for 15 minutes and allowed to stand for 15 minutes to obtain a spinning solution. The spinning solution was electrospun at a relative humidity of 40%, a temperature of 25°C, a spinning voltage of 15kV, a receiving distance of 18cm, and a drum speed of 300r / min and deposited into a membrane with a thickness of 0.6mm. After completion, the membrane was allowed to stand at 90°C for 9 hours to obtain an antibacterial waterproof and breathable membrane.

[0064] Comparative Example 3

[0065] A method for preparing an antibacterial waterproof breathable membrane, comprising the following steps:

[0066] (1) Hexadecyldimethylamine was heated to 60°C, and epichlorohydrin (2.5 times the mass of hexadecyldimethylamine) was added dropwise at a constant rate over 45 minutes. The reaction was continued for 2 hours. After standing at 130°C for 5 hours, acetone (9 times the mass of hexadecyldimethylamine) was added for recrystallization. The mixture was washed with ether 4 times and dried at 45°C for 5 hours to obtain hexadecyldimethyl glycidyl ammonium chloride.

[0067] (2) Diethylenetriaminopropyltrimethoxysilane and 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 1.5 hours to obtain diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 45 minutes, and diethylenetriaminopropyltrimethoxysilane hydrolyzate with a mass of 25 times that of nano-silica was added, reacted at 60°C for 11 hours, cooled to room temperature, centrifuged, washed with anhydrous ethanol 4 times, and then heated at 4 5 ° C drying for 7 hours to obtain pre-modified nano-silica; the pre-modified nano-silica and a 75% mass fraction of ethanol aqueous solution were mixed in a mass ratio of 1:45, ultrasonically shaken for 50 minutes, 0.025 times the mass of the pre-modified nano-silica was added with hexadecyldimethylglycidyl ammonium chloride, and then a 1.2 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 11, the temperature was raised to 75 ° C, 150 rpm, and the reaction was carried out for 7 hours, followed by centrifugation, washing with deionized water 4 times, and drying at 65 ° C for 11 hours to obtain modified nano-silica;

[0068] (3) Methyl methacrylate, ethyl acrylate, methyl isobutyl ketone, and azobisisobutyronitrile were mixed in a mass ratio of 0.4:0.4:4:0.015, stirred at 25°C and 250 rpm for 45 minutes, heated to 75°C, and (perfluorohexyl)ethylene (1.6 times the mass of methyl methacrylate) was added dropwise at a constant rate over 35 minutes. After the reaction was continued for 6 hours, methyl isobutyl ketone was rotary evaporated to dryness at 55°C and 0.09 MPa to obtain an acrylate copolymer;

[0069] (4) The polyamide masterbatch was crushed and sieved through 150 mesh to obtain polyamide powder, and the polyamide powder was mixed with hydrochloric acid with a pH value of 2.5 in a mass ratio of 1:15, stirred at 65°C for 25 minutes, centrifuged, cooled to room temperature, washed with deionized water 4 times, and dried at 45°C for 7 hours to obtain acid-decomposed polyamide; the acid-decomposed polyamide, N,N-dimethylformamide and butyl acetate were mixed in a mass ratio of 1:4:6, stirred at 75°C and 350r / min for 24 hours, allowed to stand for 9 hours, and acid was added. The modified nano-silica with a mass of 0.5 times that of the decomposed polyamide and the acrylate copolymer with a mass of 0.5 times that of the acid-decomposed polyamide were stirred for 15 minutes and allowed to stand for 15 minutes to obtain a spinning solution. The spinning solution was electrospun at a relative humidity of 40%, a temperature of 25°C, a spinning voltage of 15kV, a receiving distance of 18cm, and a drum speed of 300r / min and deposited into a membrane with a thickness of 0.6mm. After completion, the membrane was allowed to stand at 90°C for 9 hours to obtain an antibacterial waterproof and breathable membrane.

[0070] Comparative Example 4

[0071] A method for preparing an antibacterial waterproof breathable membrane, comprising the following steps:

[0072] (1) Hexadecyldimethylamine was heated to 60°C, and epichlorohydrin (2.5 times the mass of hexadecyldimethylamine) was added dropwise at a constant rate over 45 minutes. The reaction was continued for 2 hours. After standing at 130°C for 5 hours, acetone (9 times the mass of hexadecyldimethylamine) was added for recrystallization. The mixture was washed with ether 4 times and dried at 45°C for 5 hours to obtain hexadecyldimethyl glycidyl ammonium chloride.

[0073] (2) Diethylenetriaminopropyltrimethoxysilane and 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 1.5 hours to obtain diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and 75% ethanol aqueous solution were mixed at a mass ratio of 1:50, and ultrasonically vibrated for 45 minutes, and diethylenetriaminopropyltrimethoxysilane hydrolyzate with a mass of 25 times that of nano-silica was added, reacted at 60°C for 11 hours, cooled to room temperature, centrifuged, washed with anhydrous ethanol 4 times, and then heated at 4 5 ° C drying for 7 hours to obtain pre-modified nano-silica; the pre-modified nano-silica and a 75% mass fraction of ethanol aqueous solution were mixed in a mass ratio of 1:45, ultrasonically shaken for 50 minutes, 0.025 times the mass of the pre-modified nano-silica was added with hexadecyldimethylglycidyl ammonium chloride, and then a 1.2 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 11, the temperature was raised to 75 ° C, 150 rpm, and the reaction was carried out for 7 hours, followed by centrifugation, washing with deionized water 4 times, and drying at 65 ° C for 11 hours to obtain modified nano-silica;

[0074] (3) Allyl glycidyl ether, methyl methacrylate, ethyl acrylate, methyl isobutyl ketone and azobisisobutyronitrile were mixed in a mass ratio of 1:0.4:0.4:4:0.015, stirred at 25°C and 250 rpm for 45 minutes, heated to 75°C, and (perfluorohexyl)ethylene (4 times the mass of allyl glycidyl ether) was added dropwise at a constant rate over 35 minutes. After the reaction was continued for 6 hours, methyl isobutyl ketone was rotary evaporated to dryness at 55°C and 0.09 MPa to obtain an acrylate copolymer;

[0075] (4) The polyamide masterbatch was crushed and sieved through 150 mesh to obtain polyamide powder; the polyamide powder, N,N-dimethylformamide and butyl acetate were mixed in a mass ratio of 1:4:6, stirred at 75°C and 350 r / min for 24 h, allowed to stand for 9 h, modified nano-silica with a mass of 0.5 times that of the acid-decomposed polyamide and acrylate copolymer with a mass of 0.5 times that of the acid-decomposed polyamide were added, and the mixture was stirred for 15 min, allowed to stand for 15 min to obtain a spinning solution, and the spinning solution was electrospun under the conditions of a relative humidity of 40%, a temperature of 25°C, a spinning voltage of 15 kV, a receiving distance of 18 cm, and a drum speed of 300 r / min and deposited into a film with a thickness of 0.6 mm. After completion, the mixture was allowed to stand at 90°C for 9 h to obtain an antibacterial waterproof and breathable film.

[0076] Effect Examples

[0077] Table 1 below shows the analysis results of the antibacterial properties, waterproof properties, air permeability and mechanical properties of the antibacterial waterproof breathable membranes of Examples 1 to 3 of the present invention and Comparative Examples 1 to 4.

[0078] Table 1

[0079] Antibacterial rate Water pressure resistance Moisture permeability Breaking strength Example 1 99.6％ 32.63kPa <![CDATA[312.3g / (m 2 ·24h)]]> 3.79MPa Example 2 99.8％ 33.53kPa <![CDATA[325.1g / (m 2 ·24h)]]> 3.88MPa Example 3 99.1％ 31.65kPa <![CDATA[317.4g / (m 2 ·24h)]]> 3.61MPa Comparative Example 1 45.6％ 18.76kPa <![CDATA[322.3g / (m 2 ·24h)]]> 2.65MPa Comparative Example 2 98.9％ 29.32kPa <![CDATA[316.2g / (m 2 ·24h)]]> 1.48MPa Comparative Example 3 98.6％ 14.36kPa <![CDATA[321.5g / (m 2 ·24h)]]> 2.87MPa Comparative Example 4 98.4％ 30.37kPa <![CDATA[322.1g / (m 2 ·24h)]]> 1.46MPa

[0080] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 1, it can be found that the antibacterial waterproof breathable membrane prepared in the present invention has good antibacterial properties, waterproof properties, breathable properties and mechanical properties.

[0081] By comparison, there is no significant difference in the moisture permeability between Examples 1 to 3 and Comparative Examples 1 to 4, which shows that the antibacterial waterproof breathable membranes prepared by the electrospinning method of the present invention all have good breathability.

[0082] By comparison, Examples 1, 2, and 3 have higher antibacterial rates and water pressure resistance than Comparative Example 1, indicating that the nano-silica is modified and hexadecyl dimethyl glycidyl ammonium chloride side chains are grafted onto the modified nano-silica, thereby improving the antibacterial properties of the modified nano-silica. At the same time, the hexadecyl dimethyl glycidyl ammonium chloride side chains contain long carbon chains, and more carbon-carbon bonds increase the non-polar part of the molecule, thereby improving the waterproof performance of the antibacterial waterproof and breathable membrane.

[0083] By comparison, Examples 1, 2, and 3 have higher breaking strength than Comparative Example 2, indicating that the allyl glycidyl ether side chains on the acrylate copolymer undergo polymerization reaction to increase the molecular weight and improve the mechanical properties of the antibacterial waterproof breathable membrane.

[0084] By comparison, Examples 1, 2, and 3 have higher water pressure resistance than Comparative Example 3, which shows that the (perfluorohexyl)ethylene side chains on the acrylate copolymer contain more fluorine atoms. The fluorine atoms have stronger electronegativity, which increases the non-polar part of the molecule and improves the waterproof performance of the antibacterial waterproof and breathable membrane.

[0085] By comparison, the breaking strength of Examples 1, 2, and 3 is higher than that of Comparative Example 4, which shows that the amino groups on the acid-decomposed polyamide react with the epoxy groups on the acrylate copolymer to improve the mechanical properties of the antibacterial waterproof and breathable membrane; at the same time, the carboxylic acid on the acid-decomposed polyamide is negatively charged, which can produce electrostatic bonding with the positively charged hexadecyldimethylglycidylammonium chloride grafted on the modified nano-silica, further improving the mechanical properties.

[0086] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A method for preparing an antibacterial waterproof breathable membrane, characterized in that: The method comprises the following preparation steps: (1) Hexadecyldimethylamine is heated to 50-70°C, and epichlorohydrin in an amount 2-3 times the mass of hexadecyldimethylamine is added dropwise at a uniform rate over 30-60 minutes. The reaction is continued for 1-3 hours. After standing at 120-140°C for 4-6 hours, acetone in an amount 8-10 times the mass of hexadecyldimethylamine is added for recrystallization, and the mixture is washed with ether 3-5 times and dried at 40-50°C for 4-6 hours to obtain hexadecyldimethyl glycidyl ammonium chloride. (2) Diethylenetriaminopropyltrimethoxysilane and 70-80% ethanol aqueous solution are mixed at a mass ratio of 1: (40-60), ultrasonically shaken for 1-2 hours to obtain diethylenetriaminopropyltrimethoxysilane hydrolyzate; nano-silica and 70-80% ethanol aqueous solution are mixed at a mass ratio of 1: (40-60), ultrasonically shaken for 30-60 minutes, and diethylenetriaminopropyltrimethoxysilane hydrolyzate with a mass of 20-30 times the mass of nano-silica is added, reacted at 50-70°C for 10-12 hours, cooled to room temperature and centrifuged, washed with anhydrous ethanol 3-5 times, and heated at 40-50°C. Drying for 6 to 8 hours to obtain pre-modified nano-silica; mixing the pre-modified nano-silica and a 70-80% ethanol aqueous solution at a mass ratio of 1:(40-50), ultrasonically shaking for 40 to 60 minutes, adding 0.02 to 0.03 times the mass of the pre-modified nano-silica, and then adding a 1.2 mol / L sodium hydroxide aqueous solution to adjust the pH to 10 to 12, heating to 70 to 80° C., reacting at 100 to 200 rpm for 6 to 8 hours, and then centrifuging, washing with deionized water 3 to 5 times, and drying at 60 to 70° C. for 10 to 12 hours to obtain modified nano-silica; (3) Allyl glycidyl ether, methyl methacrylate, ethyl acrylate, methyl isobutyl ketone and azobisisobutyronitrile are mixed in a mass ratio of 1:(0.3-0.5):(0.3-0.5):(3-5):(0.01-0.02), stirred at 20-30°C and 200-300 rpm for 30-60 min, heated to 70-80°C, and (perfluorohexyl)ethylene (4 times the mass of allyl glycidyl ether) is added dropwise at a uniform rate over 30-40 min. After continuing the reaction for 5-7 h, methyl isobutyl ketone is evaporated to dryness by rotary evaporation at 50-60°C and 0.08-0.1 MPa to obtain an acrylate copolymer; (4) The polyamide masterbatch is crushed and sieved with 100-200 mesh to obtain polyamide powder, and the polyamide powder and hydrochloric acid with a pH value of 2-3 are mixed in a mass ratio of 1: (10-20), stirred at 60-70 ° C for 20-30 minutes, centrifuged, cooled to room temperature, washed with deionized water for 3-5 times, and dried at 40-50 ° C for 6-8 hours to obtain acid-decomposed polyamide; the acid-decomposed polyamide, N, N-dimethylformamide and butyl acetate are mixed in a mass ratio of 1:4:6, stirred at 70-80 ° C and 300-400 r / min for 22-26 hours, allowed to stand for 8-10 hours, and the acid-decomposed polyamide is added. The modified nano-silica with a mass of 0.4 to 0.6 times that of the amine and the acrylate copolymer with a mass of 0.4 to 0.6 times that of the acid-decomposed polyamide are continuously stirred for 10 to 20 minutes and allowed to stand for 10 to 20 minutes to obtain a spinning solution. The spinning solution is electrostatically spun under the conditions of a relative humidity of 35 to 45%, a temperature of 20 to 30°C, a spinning voltage of 10 to 20 kV, a receiving distance of 16 to 20 cm, and a drum speed of 200 to 400 r / min to form a membrane with a thickness of 0.5 to 0.7 mm. After completion, the membrane is allowed to stand at 80 to 100°C for 8 to 10 hours to obtain an antibacterial waterproof and breathable membrane.

2. The method for preparing an antibacterial waterproof breathable membrane according to claim 1, characterized in that: The reaction equation of the hexadecyldimethyl glycidyl ammonium chloride in step (1) is:

3. The method for preparing an antibacterial waterproof breathable membrane according to claim 1, characterized in that: The reaction equation of the pre-modified nano-silica in step (2) is:

4. The method for preparing an antibacterial waterproof breathable membrane according to claim 1, characterized in that: The reaction equation for the modified nano-silica in step (2) is:

5. The method for preparing an antibacterial waterproof breathable membrane according to claim 1, characterized in that: The reaction equation of the acrylic ester copolymer in step (3) is:

6. An antibacterial waterproof breathable membrane prepared according to the method for preparing an antibacterial waterproof breathable membrane according to any one of claims 1 to 5.

7. Use of the antibacterial waterproof breathable membrane according to claim 6.

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