CN114032678A - Antibacterial waterproof fabric and preparation method thereof - Google Patents

Antibacterial waterproof fabric and preparation method thereof Download PDF

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CN114032678A
CN114032678A CN202111400972.6A CN202111400972A CN114032678A CN 114032678 A CN114032678 A CN 114032678A CN 202111400972 A CN202111400972 A CN 202111400972A CN 114032678 A CN114032678 A CN 114032678A
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fabric
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antibacterial waterproof
waterproof fabric
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CN114032678B (en
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沈禹辰
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Fujian Ruifeng Garment Co ltd
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
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    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
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    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
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Abstract

The invention discloses an antibacterial waterproof fabric and a preparation method thereof, and relates to the technical field of textile materials. When the antibacterial waterproof fabric is prepared, firstly, spinning is carried out to prepare porous fibers from modified polyacrylic acid, then the porous fibers are woven into fabric base cloth, then, first-stage bionic treatment is carried out to press polythiophene on the fabric base cloth and form a nano conductive column matrix structure, then, second-stage bionic treatment is carried out on the basis of the first-stage bionic treatment to prepare a second-stage bionic fabric, and finally, the second-stage bionic fabric is modified by amino glyceryl propionate mixed solution and sodium hydroxide solution to prepare the antibacterial waterproof fabric. The antibacterial waterproof fabric prepared by the invention has good antibacterial property and waterproofness.

Description

Antibacterial waterproof fabric and preparation method thereof
Technical Field
The invention relates to the technical field of textile materials, in particular to an antibacterial waterproof fabric and a preparation method thereof.
Background
Along with the development of the society, people have higher and higher requirements on the quality of fabrics and more requirements on the performance, so that the special textile market and the high-end textile market are developed vigorously, a large number of fabrics with various functions such as ultraviolet resistance, antibiosis, sound absorption, dust prevention, water prevention, dirt resistance and the like appear in the market, and the fabrics are well applied to various environmental places.
The waterproof fabric applied to the raincoat in the market at present has a good waterproof effect, but the waterproof surface is one layer of tarpaulin, adhesive tape or plastic film, and the flowing of gas has also been prevented in waterproof, can make the comfort level reduce, and people who arrive at the destination are used to fold the waterproof fabric into a group and put into the basket of non-motor vehicle or under the cushion, and adnexed water is difficult to evaporate, easily breeds the bacterium and easily makes the human skin of poor health produce the hypersensitivity simultaneously. According to the invention, according to the waterproof principle of lotus leaves and water fly legs in nature, the fabric is made to form a super-hydrophobic surface for waterproofing, and simultaneously, the water is easy to be discharged from the inside, so that the fabric has the functions of sweat absorption and exhaust, can be comfortably worn in a rainwater-free environment, and can be sterilized through static electricity and osmotic pressure.
Disclosure of Invention
The invention aims to provide an antibacterial waterproof fabric and a preparation method thereof, and aims to solve the problems in the prior art.
A preparation method of an antibacterial waterproof fabric mainly comprises the following preparation steps: spinning, weaving, primary bionic treatment, secondary bionic treatment and modification treatment.
As optimization, the preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at the temperature of 20-30 ℃ for 20-30 min, and then soaking and washing the fibers with pure water for 3-5 min under ultrasonic vibration at the temperature of 40-50 ℃ and at the frequency of 30-40 kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50-80D by a fiber braiding machine, and braiding to 180-220 g/m2Weighing the fabric to obtain fabric base cloth;
(3) first-stage bionic treatment: attaching 3, 4-dihydroxythiophene deposited surface of polythiophene membrane to butyl ether at a concentration of 1g/cm2Pressing the surface of the fabric base cloth with the same area, which is wetted, at the temperature of 70-90 ℃ for 40-60 min under the pressure of 1-2 MPa to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, absorbing the moisture on the outer surface of polythiophene of the pressed fabric by using filter paper, keeping the rest part wet, performing laser etching once, washing the fabric by using ethanol and pure water for 3-5 times in sequence, and drying the fabric base cloth at the temperature of 1-10 ℃ for 6-8 h under the pressure of 5-10 Pa to obtain a first-level bionic fabric;
(4) secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, sucking the surface moisture of primary bionic treatment of the primary bionic fabric by using filter paper, keeping the rest parts wet, performing secondary laser etching, washing for 3-5 times by using ethanol and pure water in sequence, and drying for 6-8 hours at the temperature of 1-10 ℃ and under the pressure of 5-10 Pa to obtain a secondary bionic fabric;
(5) modification treatment: fixing the untreated surface of the secondary bionic fabric on a glass plate upwards, placing the glass plate on a reaction tank, adding a glycerol aminopropionate mixed solution with the mass 5-8 times that of the secondary bionic fabric, reacting for 3-5 min under the ultrasonic vibration of 30-40 kHz at 80-90 ℃, then soaking the fabric into a sodium hydroxide solution with the mass 5% 8-10 times that of the secondary bionic fabric, reacting for 5-10 min under the ultrasonic vibration of 30-40 kHz at 40-50 ℃, washing for 3-5 times with pure water at 60-80 ℃, and drying for 6-8 h under the pressure of 5-10 Pa at 1-10 ℃ to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a sheet with the thickness of 1-2 mm, and irradiating the sheet with a radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere to prepare the polyacrylic acid.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: the voltage is 15-20 kV, the fluid supply speed is 20-25 mu L/min, the environment humidity is 10-20%, the receiving distance is 15cm, the inner aperture of the spinning nozzle is 0.5mm, and the temperature is 30-40 ℃.
As an optimization, the preparation method of the polythiophene membrane in the step (3) comprises the following steps: adding ferric chloride at a rate of 1g/m2Spreading and dispersing the amount of the iron chloride on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen gas into the vapor deposition chamber to exhaust air, heating 3, 4-dihydroxythiophene with the weight of 20-30 times of that of the iron chloride to 90-100 ℃ to convert the iron chloride into gas state, introducing the gas state into the deposition chamber through a pipeline at the flow rate of 0.5m/s, continuously depositing for 10-15 min after the gas introduction of the 3, 4-dihydroxythiophene is finished, heating thiophene with the weight of 80-120 times of that of the iron chloride to 90-100 ℃ to convert the iron chloride into gas state, introducing the gas state into the deposition chamber through a pipeline at the flow rate of 0.5m/s, continuously depositing for 20-30 min after the gas introduction of the thiophene is finished, introducing nitrogen gas to remove the deposition gas, cooling to 20-30 ℃, taking out a deposition film on the glass plate, washing 3-5 times by using absolute ethyl alcohol and each time, drying for 6-8 h at the temperature of 60-80 ℃, and preparing the polythiophene membrane.
As optimization, the process parameters of the primary laser etching in the step (3) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 30-50 mu m, and the energy density is 1.4～1.6J/cm2The number of pulses is 240-280, and the distance from the focal length is-3 mm.
As optimization, the process parameters of the secondary laser etching in the step (4) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 3-5 μm, and the energy density is 0.1-0.3J/cm2The number of pulses is 240-280, and the distance from the focal length is-3 mm.
Preferably, the glycerol aminopropionate mixed solution in the step (5) is prepared by mixing glycerol aminopropionate, 0.1 mass percent hydrochloric acid solution and butyl ether in a mass ratio of 1: 10: 10 are mixed evenly to prepare the product.
As optimization, the preparation method of the amino glyceryl propionate comprises the following steps: mixing L-aminopropionic acid, glycerol and a mixture of the following components in percentage by mass: 20% of sodium hydroxide solution and butyl ether according to the mass ratio of 1: 1: 3: 10, uniformly mixing, reacting at the temperature of 80-90 ℃ for 2-4 h at the rotating speed of 1000-2000 r/min, concentrating and crystallizing, recrystallizing in pure water for 3-5 times, and drying at the temperature of-10-1 ℃ and under the pressure of 5-10 Pa for 6-8 h to prepare the amino glyceryl propionate.
As an optimization, the antibacterial waterproof fabric prepared by the preparation method of the antibacterial waterproof fabric mainly comprises the following components in parts by weight: 9-11 parts of fabric base cloth, 5-7 parts of polythiophene membrane and 50-80 parts of amino glyceryl propionate mixed solution; the fabric base cloth is woven by porous fibers prepared by spinning modified polyacrylic acid, polyethylene glycol and ethanol; the polythiophene membrane is prepared by sequentially depositing 3, 4-dihydroxythiophene and thiophene; the amino glyceryl propionate mixed solution is prepared from amino glyceryl propionate, a hydrochloric acid solution and butyl ether.
Compared with the prior art, the invention has the following beneficial effects:
when the antibacterial waterproof fabric is prepared, firstly, spinning is carried out to prepare porous fibers from modified polyacrylic acid, then the porous fibers are woven into fabric base cloth, then, first-stage bionic treatment and second-stage bionic treatment are carried out, and finally, the antibacterial waterproof fabric is prepared by carrying out modification treatment on amino glyceryl propionate mixed solution and sodium hydroxide solution.
Firstly, spinning and weaving to obtain fabric base cloth, then depositing 3, 4-dihydroxythiophene, then depositing thiophene to obtain polythiophene membrane, pressing the surface of the polythiophene membrane with 3, 4-dihydroxythiophene with the base fabric, making the hydroxyl group of the bottom of the polythiophene membrane react with the carboxyl group on the base fabric and adhere to the base fabric to form the outer surface of polythiophene, then processing by laser to form a nano conductive column matrix structure, when water is on the surface, forming an air membrane between the nano conductive columns to prevent the permeation of water and the hydrophobic synergistic action of polythiophene to make the outer surface of polythiophene of the pressed fabric have waterproof property, so that the nano conductive columns can absorb the static electricity generated by the friction of the fabric in the using process, make the bacterial liquid charge in bacteria abnormal to achieve the sterilization effect and prevent the fabric from generating discomfort due to the static adhesion on the body, meanwhile, the nano conductive columns can generate electron-hole by illumination, and disordered thermal movement of electrons can transfer heat to the bottom of the nano conductive columns; carry out secondary operation on the basis of the nanometer of one-level bionic processing formation leads electrical pillar matrix structure, form class water fly leg seta structure, it changes the air of being detained to form small contained angle between each seta and the main part nanometer post, when outside water permeates, contained angle grow under the pressure of seta at water, prevent the infiltration of water with the seta of adjacent main part jointly, and can block porous fiber's surface pore, waterproof performance has been improved, simultaneously when inside water toward the surface transmission, the pressure that can water makes the seta close together to the main part nanometer post, make hydroenergy lead through the hole smoothly, make the surface fabric that makes at last have the function of inside moisture content outside transmission.
Secondly, aminopropionin is generated by the reaction of L-aminopropionic acid and glycerol and is grafted on the surface without a bionic structure, so that the surface has good skin-friendly property, the hydroxyl on the glycerol has good adsorption effect on sweat generated by the skin, the skin is dry and comfortable, then strong sodium oxide solution and carboxyl on an internal porous structure of the fabric subjected to secondary bionic treatment are used for reaction to form organic sodium salt, when water adsorbed by the glycerol is transferred, the organic sodium salt is dissolved, so that the internal concentration is increased, the absorption of sweat stains on a human body is accelerated, water is discharged out of the external surface under the action of pressure and heat evaporation, the effect of perspiration and comfort is achieved, meanwhile, the concentration of the sweat is increased by dissolving the organic sodium salt, bacteria can be dehydrated and killed, meanwhile, the pH value of sweat is increased by combining carboxylate radicals with hydrogen ions, and the pH influences the activity of various bacterial reaction enzymes, thereby causing the metabolism disorder of bacteria and achieving the antibacterial effect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail, and the method for testing each index of the antibacterial waterproof fabric manufactured in the following examples is as follows:
water resistance: the antibacterial waterproof fabric obtained in each example and the comparative example material are in the same area size, the waterproof surface is upward and is flatly fixed on a glass plate by using double faced adhesive tape to be prevented horizontally, pure water with the same volume is dripped on the surface in the same environment atmosphere, the glass plate is inclined until water drops of the component materials roll, and the rolling angle is recorded.
And (3) antibacterial property: the anti-fouling clothes obtained in each example and the comparative example material are in the same size and shape, and the antibacterial rate is tested according to the quinine test method.
Example 1
An antibacterial waterproof fabric mainly comprises the following components in parts by weight: 9 parts of fabric base cloth, 5 parts of polythiophene membrane and 50 parts of amino glyceryl propionate mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at 20 ℃ for 30min, and then soaking and washing the fibers with pure water for 5min under the ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber weaving machine, and weaving to 180g/m2Weighing the fabric to obtain fabric base cloth;
(3) first-stage bionic treatment: attaching 3, 4-dihydroxythiophene deposited surface of polythiophene membrane to butyl ether at a concentration of 1g/cm2Pressing the surface of the fabric base cloth with the same area and the same amount of wetting for 60min at 70 ℃ under the pressure of 1MPa to prepare a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, absorbing the moisture on the outer surface of polythiophene of the pressed fabric by using filter paper, keeping the rest part wet, performing laser etching once, washing for 3 times by using ethanol and pure water in sequence, and drying for 8h under the pressure of 1 ℃ and 5Pa to prepare a first-stage bionic fabric;
(4) secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, sucking the surface moisture of primary bionic treatment of the primary bionic fabric by using filter paper, keeping the rest parts wet, performing secondary laser etching, washing for 3 times by using ethanol and pure water in sequence, and drying for 8 hours at the temperature of 1 ℃ and the pressure of 5Pa to obtain a secondary bionic fabric;
(5) modification treatment: fixing the untreated surface of the secondary bionic fabric on a glass plate upwards, placing the glass plate on a reaction tank, adding a glycerol aminopropionate mixed solution with the mass 5 times that of the secondary bionic fabric, reacting for 5min under the ultrasonic vibration of 80 ℃ and 30kHz, immersing the fabric in a sodium hydroxide solution with the mass fraction 5% that of the secondary bionic fabric with the mass 8 times that of the secondary bionic fabric, reacting for 10min under the ultrasonic vibration of 40 ℃ and 30kHz, washing for 3 times with pure water at 60 ℃, and drying for 8h under the pressure of 1 ℃ and 5Pa to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a 1mm slice, and irradiating the slice with an electron beam accelerator under the nitrogen atmosphere to obtain the polyacrylic acid slice with the radiation dose of 120 KGy.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: voltage 15kV, fluid supply speed 20 μ L/min, environment humidity 10%, receiving distance 15cm, inner hole diameter of spinneret 0.5mm, temperature 30 ℃.
As an optimizationThe preparation method of the polythiophene membrane in the step (3) comprises the following steps: adding ferric chloride at a rate of 1g/m2Spreading and dispersing the mixture on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen gas for exhausting air, heating the glass plate carrying ferric chloride to 100 ℃, heating 3, 4-dihydroxythiophene which is 20 times of the weight of the ferric chloride to 90 ℃ to convert the ferric chloride into a gas state, introducing the gas into the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit the 3, 4-dihydroxythiophene for 10min after the gas introduction of the 3, 4-dihydroxythiophene is finished, heating thiophene which is 80 times of the weight of the ferric chloride to 90 ℃ to convert the thiophene into the gas state, introducing the gas into the deposition chamber through the pipeline at a flow rate of 0.5m/s, continuing to deposit the gas for 20min after the thiophene introduction, introducing nitrogen gas to remove the deposition gas, cooling to 20 ℃, taking out the deposition film on the glass plate, washing the deposition film for 3 times by using absolute ethyl alcohol and pure water, and drying the film at 60 ℃ for 8h to obtain the polythiophene film.
As optimization, the process parameters of the primary laser etching in the step (3) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 30 μm, and the energy density is 1.4J/cm2The number of pulses is 240, and the distance from the focal length is-3 mm.
As optimization, the process parameters of the secondary laser etching in the step (4) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 3 μm, and the energy density is 0.1J/cm2The number of pulses is 240, and the distance from the focal length is-3 mm.
Preferably, the glycerol aminopropionate mixed solution in the step (5) is prepared by mixing glycerol aminopropionate, 0.1 mass percent hydrochloric acid solution and butyl ether in a mass ratio of 1: 10: 10 are mixed evenly to prepare the product.
As optimization, the preparation method of the amino glyceryl propionate comprises the following steps: mixing L-aminopropionic acid, glycerol and a mixture of the following components in percentage by mass: 20% of sodium hydroxide solution and butyl ether according to the mass ratio of 1: 1: 3: 10, uniformly mixing, reacting at 80 ℃ for 4h at the rotating speed of 1000r/min, concentrating and crystallizing, recrystallizing in pure water for 3 times, and drying at-10 ℃ for 8h under the pressure of 5Pa to obtain the amino glyceryl propionate.
Example 2
An antibacterial waterproof fabric mainly comprises the following components in parts by weight: 10 parts of fabric base cloth, 6 parts of polythiophene membrane and 70 parts of amino glyceryl propionate mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at 25 ℃ for 25min, and then soaking and washing the fibers with pure water for 4min under the ultrasonic vibration of 45 ℃ and 35kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 65D by a fiber weaving machine, and weaving to 200g/m2Weighing the fabric to obtain fabric base cloth;
(3) first-stage bionic treatment: attaching 3, 4-dihydroxythiophene deposited surface of polythiophene membrane to butyl ether at a concentration of 1g/cm2Pressing the surface of the fabric base cloth with the same area and the wet amount for 50min at the temperature of 80 ℃ under the pressure of 1.5MPa to prepare a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, absorbing the moisture on the outer surface of polythiophene of the pressed fabric by using filter paper, keeping the rest part wet, carrying out laser etching once, washing for 4 times by using ethanol and pure water in sequence, and drying for 7h under the pressure of 5 ℃ and 8Pa to prepare a first-stage bionic fabric;
(4) secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, sucking the surface moisture of the primary bionic treatment of the primary bionic fabric by using filter paper, keeping the rest parts wet, performing secondary laser etching, washing for 4 times by using ethanol and pure water in sequence, and drying for 7 hours at the temperature of 5 ℃ and the pressure of 8Pa to obtain a secondary bionic fabric;
(5) modification treatment: fixing the untreated surface of the secondary bionic fabric on a glass plate upwards, placing the glass plate on a reaction tank, adding a glycerol aminopropionate mixed solution with the mass 6 times that of the secondary bionic fabric, reacting for 4min under the ultrasonic vibration of 85 ℃ and 35kHz, immersing the fabric in a sodium hydroxide solution with the mass fraction 5% that of the secondary bionic fabric with the mass 9 times that of the secondary bionic fabric, reacting for 8min under the ultrasonic vibration of 45 ℃ and 35kHz, washing for 4 times with pure water at 70 ℃, and drying for 7h under the pressure of 5 ℃ and 8Pa to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a 1.5mm thin sheet, and irradiating the sheet with a radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere to prepare the polyacrylic acid.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: voltage 18kV, fluid supply speed 23 μ L/min, ambient humidity 15%, receiving distance 15cm, inner hole diameter 0.5mm of spinneret, and temperature 35 ℃.
As an optimization, the preparation method of the polythiophene membrane in the step (3) comprises the following steps: adding ferric chloride at a rate of 1g/m2Spreading and dispersing the mixture on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen gas for exhausting air, heating the glass plate carrying ferric chloride to 110 ℃, heating 3, 4-dihydroxythiophene with the weight 25 times that of the ferric chloride to 95 ℃ to convert the ferric chloride into a gas state, introducing the gas into the deposition chamber through a pipeline at the flow rate of 0.5m/s, continuing to deposit the 3, 4-dihydroxythiophene for 13min after the gas introduction of the 3, 4-dihydroxythiophene is finished, heating thiophene with the weight 100 times that of the ferric chloride to 95 ℃ to convert the thiophene into the gas state, introducing the gas into the deposition chamber through the pipeline at the flow rate of 0.5m/s, continuing to deposit the gas for 25min after the gas introduction of the thiophene, introducing nitrogen gas to remove the deposition gas, cooling to 25 ℃, taking out the deposition film on the glass plate, washing the deposition film for 4 times by using absolute ethyl alcohol and pure water, and drying the film at 70 ℃ for 7 hours to obtain the polythiophene film.
As optimization, the process parameters of the primary laser etching in the step (3) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 40 μm, and the energy density is 1.5J/cm2The number of pulses is 260, and the distance from the focal length is-3 mm.
As optimization, the process parameters of the secondary laser etching in the step (4) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 4 μm, and the energy density is 0.2J/cm2The number of pulses is 260, and the distance from the focal length is-3 mm.
Preferably, the glycerol aminopropionate mixed solution in the step (5) is prepared by mixing glycerol aminopropionate, 0.1 mass percent hydrochloric acid solution and butyl ether in a mass ratio of 1: 10: 10 are mixed evenly to prepare the product.
As optimization, the preparation method of the amino glyceryl propionate comprises the following steps: mixing L-aminopropionic acid, glycerol and a mixture of the following components in percentage by mass: 20% of sodium hydroxide solution and butyl ether according to the mass ratio of 1: 1: 3: 10, uniformly mixing, reacting at 85 ℃ at a rotating speed of 1500r/min for 3h, concentrating and crystallizing, recrystallizing in pure water for 4 times, and drying at-5 ℃ under the pressure of 8Pa for 7h to obtain the amino glyceryl propionate.
Example 3
An antibacterial waterproof fabric mainly comprises the following components in parts by weight: 11 parts of fabric base cloth, 7 parts of polythiophene membrane and 80 parts of amino glyceryl propionate mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at 30 ℃ for 20min, and then soaking and washing the fibers with pure water for 3min under the ultrasonic vibration at 50 ℃ and 40kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 80D by a fiber braiding machine, and braiding to 220g/m2Weighing the fabric to obtain fabric base cloth;
(3) first-stage bionic treatment: attaching 3, 4-dihydroxythiophene deposited surface of polythiophene membrane to butyl ether at a concentration of 1g/cm2Pressing the surface of the fabric base cloth with the same area and the same amount of wetting for 40min at 90 ℃ under the pressure of 2MPa to prepare a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, absorbing the moisture on the outer surface of polythiophene of the pressed fabric by using filter paper, keeping the rest part wet, performing laser etching once, washing for 5 times by using ethanol and pure water in sequence, and drying for 6h under the pressure of 10 ℃ and 10Pa to prepare a first-stage bionic fabric;
(4) secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, sucking the surface moisture of the primary bionic treatment of the primary bionic fabric by using filter paper, keeping the rest parts wet, performing secondary laser etching, washing for 5 times by using ethanol and pure water in sequence, and drying for 6 hours at the temperature of 10 ℃ and under the pressure of 10Pa to obtain a secondary bionic fabric;
(5) modification treatment: fixing the untreated surface of the secondary bionic fabric on a glass plate upwards, placing the glass plate on a reaction tank, adding 8 times of amino glyceryl propionate mixed solution by mass of the secondary bionic fabric, reacting for 3min under ultrasonic vibration at 90 ℃ and 40kHz, immersing the fabric in 5% sodium hydroxide solution by mass of 10 times of the secondary bionic fabric, reacting for 5min under ultrasonic vibration at 50 ℃ and 40kHz, washing for 3 times with pure water at 80 ℃, and drying for 6h under the pressure of 10Pa to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a 2mm sheet, and irradiating the sheet with a radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere to prepare the polyacrylic acid.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: voltage 20kV, fluid supply speed 25 μ L/min, environment humidity 20%, receiving distance 15cm, inner hole diameter of spinneret 0.5mm, and temperature 40 deg.C.
As an optimization, the preparation method of the polythiophene membrane in the step (3) comprises the following steps: adding ferric chloride at a rate of 1g/m2Spreading and dispersing the mixture on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen gas for exhausting air, heating the glass plate carrying ferric chloride to 120 ℃, heating 3, 4-dihydroxythiophene 30 times the weight of the ferric chloride to 100 ℃ to convert the ferric chloride into a gas state, introducing the gas into the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit for 15min after the gas introduction of the 3, 4-dihydroxythiophene is finished, heating thiophene 120 times the weight of the ferric chloride to 100 ℃ to convert the thiophene into the gas state, introducing the gas into the deposition chamber through the pipeline at a flow rate of 0.5m/s, continuing to deposit for 30min after the gas introduction of the thiophene is finished, introducing nitrogen gas to remove the deposited gas, cooling to 30 ℃, taking out the deposited film on the glass plate, washing the film for 5 times by using absolute ethyl alcohol and pure water respectively, and drying the film for 6h at 80 ℃ to obtain the polythiophene film.
As optimization, the process parameters of the primary laser etching in the step (3) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 50 μm, and the energy density isIs 1.6J/cm2The number of pulses is 280, and the distance from the focal length is-3 mm.
As optimization, the process parameters of the secondary laser etching in the step (4) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 5 μm, and the energy density is 0.3J/cm2The number of pulses is 280, and the distance from the focal length is-3 mm.
Preferably, the glycerol aminopropionate mixed solution in the step (5) is prepared by mixing glycerol aminopropionate, 0.1 mass percent hydrochloric acid solution and butyl ether in a mass ratio of 1: 10: 10 are mixed evenly to prepare the product.
As optimization, the preparation method of the amino glyceryl propionate comprises the following steps: mixing L-aminopropionic acid, glycerol and a mixture of the following components in percentage by mass: 20% of sodium hydroxide solution and butyl ether according to the mass ratio of 1: 1: 3: 10, uniformly mixing, reacting at 90 ℃ for 2h at the rotating speed of 2000r/min, concentrating and crystallizing, recrystallizing in pure water for 5 times, and drying at-1 ℃ under the pressure of 10Pa for 6h to obtain the amino glyceryl propionate.
Comparative example 1
An antibacterial waterproof fabric mainly comprises the following components in parts by weight: 9 parts of fabric base cloth and 50 parts of amino glyceryl propionate mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at 20 ℃ for 30min, and then soaking and washing the fibers with pure water for 5min under the ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber weaving machine, and weaving to 180g/m2Weighing the fabric to obtain fabric base cloth;
(3) modification treatment: fixing the fabric base cloth on a glass plate, placing the glass plate on a reaction tank, adding a 5-time amino glyceryl propionate mixed solution by mass of the fabric base cloth, reacting for 5min under ultrasonic vibration of 80 ℃ and 30kHz, immersing the fabric base cloth in a 5 mass percent sodium hydroxide solution by mass of 8 times, reacting for 10min under ultrasonic vibration of 40 ℃ and 30kHz, washing for 3 times by using pure water at 60 ℃, and drying for 8h under the pressure of 1 ℃ and 5Pa to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a 1mm slice, and irradiating the slice with an electron beam accelerator under the nitrogen atmosphere to obtain the polyacrylic acid slice with the radiation dose of 120 KGy.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: voltage 15kV, fluid supply speed 20 μ L/min, environment humidity 10%, receiving distance 15cm, inner hole diameter of spinneret 0.5mm, temperature 30 ℃.
Preferably, the glycerol aminopropionate mixed solution in the step (3) is prepared by mixing glycerol aminopropionate, 0.1 mass percent hydrochloric acid solution and butyl ether in a mass ratio of 1: 10: 10 are mixed evenly to prepare the product.
As optimization, the preparation method of the amino glyceryl propionate comprises the following steps: mixing L-aminopropionic acid, glycerol and a mixture of the following components in percentage by mass: 20% of sodium hydroxide solution and butyl ether according to the mass ratio of 1: 1: 3: 10, uniformly mixing, reacting at 80 ℃ for 4h at the rotating speed of 1000r/min, concentrating and crystallizing, recrystallizing in pure water for 3 times, and drying at-10 ℃ for 8h under the pressure of 5Pa to obtain the amino glyceryl propionate.
Comparative example 2
An antibacterial waterproof fabric mainly comprises the following components in parts by weight: 9 parts of fabric base cloth, 5 parts of polythiophene membrane and 50 parts of amino glyceryl propionate mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at 20 ℃ for 30min, and then soaking and washing the fibers with pure water for 5min under the ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber weaving machine, and weaving to 180g/m2Weighing the fabric to obtain fabric base cloth;
(3) performing bionic treatment: attaching 3, 4-dihydroxythiophene deposited surface of polythiophene membrane to butyl ether at a concentration of 1g/cm2Pressing the surface of the fabric base cloth with the same area and the same amount of wetting for 60min at 70 ℃ under the pressure of 1MPa to prepare a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, absorbing the moisture on the outer surface of polythiophene of the pressed fabric by using filter paper, keeping the rest part wet, performing laser etching, washing for 3 times by using ethanol and pure water in sequence, and drying for 8h under the pressure of 1 ℃ and 5Pa to prepare the bionic fabric;
(4) modification treatment: fixing the untreated surface of the bionic fabric on a glass plate upwards, placing the glass plate on a reaction tank, adding a glycerol aminopropionate mixed solution with the mass 5 times that of the first-stage bionic fabric, reacting for 5min under the ultrasonic vibration of 80 ℃ and 30kHz, immersing the bionic fabric in a sodium hydroxide solution with the mass fraction 5% that of 8 times that of the bionic fabric, reacting for 10min under the ultrasonic vibration of 40 ℃ and 30kHz, washing for 3 times with pure water at 60 ℃, and drying for 8h under the pressure of 1 ℃ and 5Pa to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a 1mm slice, and irradiating the slice with an electron beam accelerator under the nitrogen atmosphere to obtain the polyacrylic acid slice with the radiation dose of 120 KGy.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: voltage 15kV, fluid supply speed 20 μ L/min, environment humidity 10%, receiving distance 15cm, inner hole diameter of spinneret 0.5mm, temperature 30 ℃.
As an optimization, the preparation method of the polythiophene membrane in the step (3) comprises the following steps: adding ferric chloride at a rate of 1g/m2Spreading and dispersing the amount of the iron chloride on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen for exhausting air, heating the glass plate loaded with the iron chloride to 100 ℃, heating 3, 4-dihydroxythiophene 20 times the mass of the iron chloride to 90 ℃ to convert the iron chloride into a gas state, introducing the gas into the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit for 10min after the gas introduction of the 3, 4-dihydroxythiophene is finished, heating thiophene 80 times the mass of the iron chloride to 90 ℃ to convert the thiophene into the gas state, and introducing the thiophene into the deposition chamber at a flow rate of 0.5m/sEntering a deposition chamber through a pipeline, continuing deposition for 20min after the thiophene is ventilated, introducing nitrogen to remove deposition gas, cooling to 20 ℃, taking out the deposition film on the glass plate, washing 3 times by using absolute ethyl alcohol and pure water respectively, and drying for 8h at 60 ℃ to obtain the polythiophene film.
As optimization, the laser etching process parameters in the step (3) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 30 μm, and the energy density is 1.4J/cm2The number of pulses is 240, and the distance from the focal length is-3 mm.
Preferably, the glycerol aminopropionate mixed solution in the step (4) is prepared by mixing glycerol aminopropionate, 0.1 mass percent hydrochloric acid solution and butyl ether in a mass ratio of 1: 10: 10 are mixed evenly to prepare the product.
As optimization, the preparation method of the amino glyceryl propionate comprises the following steps: mixing L-aminopropionic acid, glycerol and a mixture of the following components in percentage by mass: 20% of sodium hydroxide solution and butyl ether according to the mass ratio of 1: 1: 3: 10, uniformly mixing, reacting at 80 ℃ for 4h at the rotating speed of 1000r/min, concentrating and crystallizing, recrystallizing in pure water for 3 times, and drying at-10 ℃ for 8h under the pressure of 5Pa to obtain the amino glyceryl propionate.
Comparative example 3
An antibacterial waterproof fabric mainly comprises the following components in parts by weight: 9 parts of fabric base cloth and 5 parts of polythiophene membrane.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at 20 ℃ for 30min, and then soaking and washing the fibers with pure water for 5min under the ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber weaving machine, and weaving to 180g/m2Weighing the fabric to obtain fabric base cloth;
(3) first-stage bionic treatment: attaching the 3, 4-dihydroxythiophene deposited surface of the polythiophene membrane to butyl ether1g/cm2Pressing the surface of the fabric base cloth with the same area and the same amount of wetting for 60min at 70 ℃ under the pressure of 1MPa to prepare a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, absorbing the moisture on the outer surface of polythiophene of the pressed fabric by using filter paper, keeping the rest part wet, performing laser etching once, washing for 3 times by using ethanol and pure water in sequence, and drying for 8h under the pressure of 1 ℃ and 5Pa to prepare a first-stage bionic fabric;
(4) secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, sucking the surface moisture of the primary bionic treatment of the primary bionic fabric by using filter paper, keeping the rest parts wet, performing secondary laser etching, washing for 3 times by using ethanol and pure water in sequence, and drying for 8 hours at the temperature of 1 ℃ and under the pressure of 5Pa to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a 1mm slice, and irradiating the slice with an electron beam accelerator under the nitrogen atmosphere to obtain the polyacrylic acid slice with the radiation dose of 120 KGy.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: voltage 15kV, fluid supply speed 20 μ L/min, environment humidity 10%, receiving distance 15cm, inner hole diameter of spinneret 0.5mm, temperature 30 ℃.
As an optimization, the preparation method of the polythiophene membrane in the step (3) comprises the following steps: adding ferric chloride at a rate of 1g/m2Spreading and dispersing the mixture on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen gas for exhausting air, heating the glass plate carrying ferric chloride to 100 ℃, heating 3, 4-dihydroxythiophene which is 20 times of the weight of the ferric chloride to 90 ℃ to convert the ferric chloride into a gas state, introducing the gas into the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit the 3, 4-dihydroxythiophene for 10min after the gas introduction of the 3, 4-dihydroxythiophene is finished, heating thiophene which is 80 times of the weight of the ferric chloride to 90 ℃ to convert the thiophene into the gas state, introducing the gas into the deposition chamber through the pipeline at a flow rate of 0.5m/s, continuing to deposit the gas for 20min after the thiophene introduction, introducing nitrogen gas to remove the deposition gas, cooling to 20 ℃, taking out the deposition film on the glass plate, washing the deposition film for 3 times by using absolute ethyl alcohol and pure water, and drying the film at 60 ℃ for 8h to obtain the polythiophene film.
As optimization, the process parameters of the primary laser etching in the step (3) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 30 μm, and the energy density is 1.4J/cm2The number of pulses is 240, and the distance from the focal length is-3 mm.
As optimization, the process parameters of the secondary laser etching in the step (4) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 3 μm, and the energy density is 0.1J/cm2The number of pulses is 240, and the distance from the focal length is-3 mm.
Comparative example 4
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at 20 ℃ for 30min, and then soaking and washing the fibers with pure water for 5min under the ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber weaving machine, and weaving to 180g/m2And (5) weighing the fabric to obtain the fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a 1mm slice, and irradiating the slice with an electron beam accelerator under the nitrogen atmosphere to obtain the polyacrylic acid slice with the radiation dose of 120 KGy.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: voltage 15kV, fluid supply speed 20 μ L/min, environment humidity 10%, receiving distance 15cm, inner hole diameter of spinneret 0.5mm, temperature 30 ℃.
Examples of effects
Table 1 below gives the analysis results of the water repellency and the antibacterial property of the antibacterial waterproof fabrics using examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
Roll angle Rate of inhibition of bacteria Roll angle Rate of inhibition of bacteria
Example 1 3.3° 99.2％ Comparative example 1 Is free of 86.3％
Example 2 2.8° 98.9％ Comparative example 2 9.6° 96.4％
Example 3 3.1° 98.8％ Comparative example 3 3.2° 83.5％
Comparative example 4 Is free of 68.5％
The comparison of experimental data in table 1 shows that the water resistance and the antibacterial property of the material can be obviously improved after the first-stage bionic treatment, the second-stage bionic treatment and the modification treatment; compared with experimental data of examples 1, 2 and 3 and comparative example 1, the experimental data show that the examples 1, 2 and 3 have very small rolling angles and increased antibacterial rate compared with the comparative example 1, which indicates that the first-stage bionic treatment and the second-stage bionic treatment are carried out, the formed hydrophobic surface with the microstructure can form an air film and reduce the contact area between water drops and the surface, the waterproof effect is achieved, the rolling angles are smaller, and the hydrophobic surface enables bacteria to be not easily attached and increases survival difficulty, so that the antibacterial effect is improved; the experimental data comparison of examples 1, 2 and 3 with comparative example 2 shows that the rolling angles of examples 1, 2 and 3 with comparative example 2 are smaller, which indicates that the bristle structure formed by the secondary biomimetic treatment can improve the hydrophobicity of the surface, make the water more difficult to permeate and retain, and improve the waterproofness of the material; from the comparison of experimental data of examples 1, 2 and 3 with comparative example 3, it can be seen that the antibacterial rate of examples 1, 2 and 3 with comparative example 3 is increased, which illustrates that after the modification treatment, organic sodium salt is formed in the material, the organic sodium salt is dissolved to increase the ion concentration in water, so that bacteria can be dehydrated and killed, and meanwhile, the pH value of sweat is increased by combining carboxylate radicals with hydrogen ions, so that the pH affects the activity of various enzymes of bacteria, further, the metabolism of the bacteria is disturbed, and the antibacterial property of the material is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The preparation method of the antibacterial waterproof fabric is characterized by mainly comprising the following preparation steps: spinning, weaving, primary bionic treatment, secondary bionic treatment and modification treatment.
2. The preparation method of the antibacterial waterproof fabric according to claim 1, which is characterized by mainly comprising the following preparation steps of:
(1) spinning: modified polyacrylic acid, polyethylene glycol and absolute ethyl alcohol are mixed according to the mass ratio of 2: 3: 5, uniformly mixing, carrying out electrostatic spinning to obtain fibers, standing the fibers in an air environment at the temperature of 20-30 ℃ for 20-30 min, and then soaking and washing the fibers with pure water for 3-5 min under ultrasonic vibration at the temperature of 40-50 ℃ and at the frequency of 30-40 kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50-80D by a fiber braiding machine, and braiding to 180-220 g/m2Weighing the fabric to obtain fabric base cloth;
(3) first-stage bionic treatment: attaching 3, 4-dihydroxythiophene deposited surface of polythiophene membrane to butyl ether at a concentration of 1g/cm2Pressing the surface of the fabric base cloth with the same area, which is wetted, at the temperature of 70-90 ℃ for 40-60 min under the pressure of 1-2 MPa to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, absorbing the moisture on the outer surface of polythiophene of the pressed fabric by using filter paper, keeping the rest part wet, performing laser etching once, washing the fabric by using ethanol and pure water for 3-5 times in sequence, and drying the fabric base cloth at the temperature of 1-10 ℃ for 6-8 h under the pressure of 5-10 Pa to obtain a first-level bionic fabric;
(4) secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, sucking the surface moisture of primary bionic treatment of the primary bionic fabric by using filter paper, keeping the rest parts wet, performing secondary laser etching, washing for 3-5 times by using ethanol and pure water in sequence, and drying for 6-8 hours at the temperature of 1-10 ℃ and under the pressure of 5-10 Pa to obtain a secondary bionic fabric;
(5) modification treatment: fixing the untreated surface of the secondary bionic fabric on a glass plate upwards, placing the glass plate on a reaction tank, adding a glycerol aminopropionate mixed solution with the mass 5-8 times that of the secondary bionic fabric, reacting for 3-5 min under the ultrasonic vibration of 30-40 kHz at 80-90 ℃, then soaking the fabric into a sodium hydroxide solution with the mass 5% 8-10 times that of the secondary bionic fabric, reacting for 5-10 min under the ultrasonic vibration of 30-40 kHz at 40-50 ℃, washing for 3-5 times with pure water at 60-80 ℃, and drying for 6-8 h under the pressure of 5-10 Pa at 1-10 ℃ to obtain the antibacterial waterproof fabric.
3. The preparation method of the antibacterial waterproof fabric according to claim 2, wherein the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: pressing polyacrylic acid into a sheet with the thickness of 1-2 mm, and irradiating the sheet with a radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere to prepare the polyacrylic acid.
4. The preparation method of the antibacterial waterproof fabric according to claim 3, wherein the electrostatic spinning in the step (1) has the following technological parameters: the voltage is 15-20 kV, the fluid supply speed is 20-25 mu L/min, the environment humidity is 10-20%, the receiving distance is 15cm, the inner aperture of the spinning nozzle is 0.5mm, and the temperature is 30-40 ℃.
5. The preparation method of the antibacterial waterproof fabric according to claim 4, wherein the preparation method of the polythiophene membrane in the step (3) comprises the following steps: adding ferric chloride at a rate of 1g/m2The amount of the iron chloride is spread and dispersed on the surface of a glass plate, the glass plate is placed in a vapor deposition chamber, nitrogen is introduced into the chamber for exhausting air, the temperature of the glass plate loaded with the iron chloride reaches 100-120 ℃, and 3, 4-dihydroxythiophene with the mass of 20-30 times that of the iron chloride is heatedConverting the solution into a gaseous state at 90-100 ℃ and allowing the gaseous state to enter a deposition chamber through a pipeline at a flow rate of 0.5m/s, continuously depositing for 10-15 min after the 3, 4-dihydroxythiophene is ventilated, heating thiophene with 80-120 times of the mass of ferric chloride to 90-100 ℃ and converting the thiophene into a gaseous state and allowing the gaseous state to enter the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuously depositing for 20-30 min after the thiophene is ventilated, introducing nitrogen to remove deposition gas, cooling to 20-30 ℃, taking out the deposition film on the glass plate, washing 3-5 times with absolute ethyl alcohol and pure water respectively, and drying for 6-8 h at 60-80 ℃ to obtain the polythiophene film.
6. The preparation method of the antibacterial waterproof fabric according to claim 5, wherein the process parameters of the primary laser etching in the step (3) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 30-50 μm, and the energy density is 1.4-1.6J/cm2The number of pulses is 240-280, and the distance from the focal length is-3 mm.
7. The preparation method of the antibacterial waterproof fabric according to claim 6, wherein the process parameters of the secondary laser etching in the step (4) are as follows: the laser type is femtosecond laser, the scanning mode is orthogonal scanning, the scanning interval is 3-5 μm, and the energy density is 0.1-0.3J/cm2The number of pulses is 240-280, and the distance from the focal length is-3 mm.
8. The preparation method of the antibacterial waterproof fabric according to claim 7, wherein the glycerol aminopropionate mixed solution obtained in the step (5) is prepared by mixing glycerol aminopropionate, 0.1 mass percent hydrochloric acid solution and butyl ether in a mass ratio of 1: 10: 10 are mixed evenly to prepare the product.
9. The preparation method of the antibacterial waterproof fabric according to claim 8, wherein the preparation method of the amino glyceryl propionate comprises the following steps: mixing L-aminopropionic acid, glycerol and a mixture of the following components in percentage by mass: 20% of sodium hydroxide solution and butyl ether according to the mass ratio of 1: 1: 3: 10, uniformly mixing, reacting at the temperature of 80-90 ℃ for 2-4 h at the rotating speed of 1000-2000 r/min, concentrating and crystallizing, recrystallizing in pure water for 3-5 times, and drying at the temperature of-10-1 ℃ and under the pressure of 5-10 Pa for 6-8 h to prepare the amino glyceryl propionate.
10. The preparation method of the antibacterial waterproof fabric according to claim 9, wherein the antibacterial waterproof fabric prepared by the preparation method of the antibacterial waterproof fabric mainly comprises the following components in parts by weight: 9-11 parts of fabric base cloth, 5-7 parts of polythiophene membrane and 50-80 parts of amino glyceryl propionate mixed solution; the fabric base cloth is woven by porous fibers prepared by spinning modified polyacrylic acid, polyethylene glycol and ethanol; the polythiophene membrane is prepared by sequentially depositing 3, 4-dihydroxythiophene and thiophene; the amino glyceryl propionate mixed solution is prepared from amino glyceryl propionate, a hydrochloric acid solution and butyl ether.
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WO2017148099A1 (en) * 2016-02-29 2017-09-08 广州市电纺生物科技有限公司 Wound dressing and preparation method therefor
CN110777541A (en) * 2019-11-05 2020-02-11 宁波故乡行雨具有限公司 Anti-aging and antibacterial raincoat fabric
CN111676539A (en) * 2020-05-19 2020-09-18 邓生平 Breathable and antibacterial functional fabric and preparation method thereof

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CN110777541A (en) * 2019-11-05 2020-02-11 宁波故乡行雨具有限公司 Anti-aging and antibacterial raincoat fabric
CN111676539A (en) * 2020-05-19 2020-09-18 邓生平 Breathable and antibacterial functional fabric and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN116905216A (en) * 2023-07-18 2023-10-20 汕头市英华织造实业有限公司 Preparation process of antibacterial breathable fabric

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