CN114032678B - Antibacterial waterproof fabric and preparation method thereof - Google Patents

Antibacterial waterproof fabric and preparation method thereof Download PDF

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CN114032678B
CN114032678B CN202111400972.6A CN202111400972A CN114032678B CN 114032678 B CN114032678 B CN 114032678B CN 202111400972 A CN202111400972 A CN 202111400972A CN 114032678 B CN114032678 B CN 114032678B
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fabric
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antibacterial waterproof
polythiophene
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CN114032678A (en
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沈禹辰
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Fujian Ruifeng Garment Co ltd
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Fujian Ruifeng Garment Co ltd
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    • D—TEXTILES; PAPER
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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
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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
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    • 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, primary bionic treatment is carried out to enable polythiophene to be pressed on the fabric base cloth and form a nano conductive column matrix structure, secondary bionic treatment is carried out on the basis of the primary bionic treatment to prepare the secondary bionic fabric, and finally, the secondary bionic fabric is modified by using aminopropionic acid glyceride 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 waterproof property.

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 society, people have higher and higher requirements on quality of fabrics and higher requirements on performance, so that special textile markets and high-end textile markets are developed vigorously, a large number of fabrics with various functions such as ultraviolet resistance, antibacterial property, sound absorption, dust resistance, water resistance, dirt resistance and the like appear on the markets, and the fabrics are well applied to various different environmental sites.
Waterproof fabric applied to raincoats in the market at present has good waterproof effect, but the waterproof surface is one layer of tarpaulin, rubberized fabric or plastic film, so that the waterproof fabric is waterproof, gas flow is prevented, comfort level is reduced, people get to a destination to habit to fold the waterproof fabric into groups and put the groups into a basket or under a cushion of a non-motor vehicle, attached water is difficult to evaporate, bacteria are easy to breed, and skin of people with poor physique is easy to cause allergy. According to the principle of water prevention of lotus leaves and water flies in the nature, the fabric is made to form a super-hydrophobic surface for water prevention, meanwhile, water is easy to discharge from the inside, the fabric has the function of sweat absorption and air exhaust, the fabric is comfortable to wear in a rainwater-free environment, and sterilization can be performed through static electricity and osmotic pressure.
Disclosure of Invention
The invention aims to provide an antibacterial waterproof fabric and a preparation method thereof, which are used for solving the problems in the prior art.
The preparation method of the 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: the 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 20-30 ℃ for 20-30 min, and then immersing and washing the fibers with pure water for 3-5 min under ultrasonic vibration at 40-50 ℃ and 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/m 2 The grammage fabric is used for preparing fabric base cloth;
(3) Primary bionic treatment: attaching the 3, 4-dihydroxythiophene deposition surface of the polythiophene film to a substrate with butyl ether at 1g/cm 2 Pressing the surface of the fabric base cloth with the same area and wetted by the amount at 70-90 ℃ for 40-60 min at 1-2 MPa to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, then sucking the water on the outer surface of the polythiophene of the pressed fabric to be dry by using filter paper, keeping the rest part of the pressed fabric to be wet, carrying out one-time laser etching, washing with ethanol and pure water for 3-5 times in sequence, and drying for 6-8 h at 1-10 ℃ and 5-10 Pa to obtain the first-stage bionic fabric;
(4) Secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, then using filter paper to absorb the water on the surface of the primary bionic fabric subjected to primary bionic treatment, keeping the rest part moist, performing secondary laser etching, washing 3-5 times by ethanol and pure water in sequence, and drying for 6-8 hours under the pressure of 5-10 Pa at the temperature of 1-10 ℃ to prepare the secondary bionic fabric;
(5) Modification treatment: the untreated surface of the secondary bionic fabric is upwards fixed on a glass plate and placed in a reaction tank, and the mixed solution of aminopropionic acid glyceride with the mass of 5-8 times of that of the secondary bionic fabric is added, and then the mixed solution reacts for 3-5 min under the ultrasonic vibration of 30-40 kHz at the temperature of 80-90 ℃, and then is immersed in the sodium hydroxide solution with the mass fraction of 5% with the mass of 8-10 times of that of the secondary bionic fabric, and then reacts for 5-10 min under the ultrasonic vibration of 40-50 kHz at the temperature of 30-40 kHz, and then is washed for 3-5 times by pure water with the temperature of 60-80 ℃, and is dried for 6-8 h under the pressure of 5-10 Pa at the temperature of 1-10 ℃ to prepare the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: the polyacrylic acid is pressed into a sheet with the thickness of 1-2 mm, and the sheet is irradiated to the radiation dose of 120KGy by an electron beam accelerator in the nitrogen atmosphere.
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 ambient humidity is 10-20%, the receiving distance is 15cm, the inner hole of the spinneret is 0.5mm, and the temperature is 30-40 ℃.
As optimization, the preparation method of the polythiophene film in the step (3) comprises the following steps: ferric chloride at a concentration of 1g/m 2 Spreading and dispersing the materials on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen to exhaust air, enabling the temperature of the glass plate loaded with ferric chloride to reach 100-120 ℃, heating 3, 4-dihydroxythiophene with the mass of 20-30 times of the ferric chloride to 90-100 ℃ to be converted into gas state, enabling the gas to enter the deposition chamber through a pipeline at the flow rate of 0.5m/s, continuing to deposit for 10-15 min after the 3, 4-dihydroxythiophene is ventilated, heating thiophene with the mass of 80-120 times of the ferric chloride to 90-100 ℃ to be converted into gas state, enabling the gas to enter the deposition chamber through the pipeline at the flow rate of 0.5m/s, continuing to deposit for 20-30 min, introducing nitrogen to exhaust deposited gas, cooling to 20-30 ℃, taking out deposited films on the glass plate, washing the deposited films 3-5 times respectively by absolute ethyl alcohol and pure water, and drying the deposited films at the temperature of 60-80 ℃ for 6-8 h to obtain the polythiophene film.
As optimization, the technological 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/cm 2 The number of pulses is 240-280, and the off-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/cm 2 The number of pulses is 240-280, and the off-focal length is-3 mm.
As optimization, the mixed solution of the aminopropionic acid glyceride in the step (5) is prepared by mixing the aminopropionic acid glyceride, a hydrochloric acid solution with the mass fraction of 0.1% and butyl ether according to the mass ratio of 1:10:10 are evenly mixed to prepare the product.
As optimization, the preparation method of the aminopropionic acid glyceride comprises the following steps: mixing L-aminopropionic acid, glycerol and the mass fraction: the mass ratio of the sodium hydroxide solution with 20 percent to the butyl ether is 1:1:3:10 are evenly mixed, react for 2 to 4 hours at the temperature of 80 to 90 ℃ and the rotating speed of 1000 to 2000r/min, then are concentrated and crystallized, recrystallized for 3 to 5 times in pure water, and dried for 6 to 8 hours at the temperature of minus 10 to minus 1 ℃ and the pressure of 5 to 10Pa, thus obtaining the aminopropionic glyceride.
As 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 aminopropionic acid glyceride mixed solution; the fabric base cloth is woven by porous fibers prepared by spinning modified polyacrylic acid, polyethylene glycol and ethanol; the polythiophene film is prepared by sequentially depositing 3, 4-dihydroxythiophene and thiophene; the mixed solution of the aminopropionic acid glyceride is prepared from the aminopropionic acid glyceride, 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 weaving the porous fibers into fabric base cloth, then carrying out primary bionic treatment and secondary bionic treatment, and finally carrying out modification treatment by using aminopropionic acid glyceride 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 a polythiophene film, pressing the surface of the polythiophene film with 3, 4-dihydroxythiophene with a matrix fabric, enabling hydroxyl at the bottom of the polythiophene film to react with carboxyl on the matrix fabric to be bonded on the matrix fabric to form a polythiophene outer surface, then performing laser processing to form a nano conductive column matrix structure, forming a layer of air film between the nano conductive column matrixes when water is on the surface, blocking permeation of water, and performing hydrophobic synergism of the polythiophene, so that the polythiophene outer surface of the pressed fabric has waterproof performance, the nano conductive columns can absorb static electricity generated by friction of the fabric in the using process, bacterial liquid charge in bacteria is abnormal to achieve a sterilization effect, discomfort caused by static adhesion of the fabric on a body is prevented, and meanwhile, the nano conductive columns can generate electrons-holes, and heat can be transferred to the bottom through unordered heat movement of electrons; the secondary processing is carried out on the basis of the nano conductive column matrix structure formed by the primary bionic processing, a water-like fly leg bristle structure is formed, a tiny included angle is formed between each bristle and the main body nano column, air is more prone to be retained, when external water permeates, the included angle is increased under the pressure of water, the included angle and the bristles of adjacent main bodies jointly prevent water from permeating, surface pore channels of porous fibers can be blocked, waterproof performance is improved, meanwhile, when internal water is transmitted to the outer surface, the bristles are gathered towards the main body nano column by the aid of the pressure of the water, water can smoothly pass through the pore guide, and finally the manufactured fabric has the function of transmitting internal water outwards.
Secondly, the glycerol aminopropionate is generated through the reaction of L-aminopropionic acid and glycerol and grafted on the surface without a bionic structure, so that the surface has good skin affinity, the hydroxyl on the glycerol can have good adsorption effect on sweat generated by skin, the skin is dry and comfortable, the reaction is carried out by using a strong sodium oxide solution and carboxyl on the inner porous structure of the fabric subjected to secondary bionic treatment to form organic sodium salt, when the water absorbed by the glycerol is transmitted, the organic sodium salt is dissolved, the inner concentration is increased, thereby accelerating the absorption of sweat on a human body, and the water is discharged out of the outer surface under the action of pressure and thermal evaporation, so that the sweat-discharging comfortable effect is achieved, meanwhile, the concentration of the sweat is increased through the dissolution of the organic sodium salt, bacteria can be dehydrated and dead, meanwhile, the pH of the sweat is increased through the combination of carboxylate radical with hydrogen ions, the pH influences the activity of various reactive enzymes of bacteria, and further the bacterial metabolism is disturbed, and the antibacterial effect is achieved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the method for testing each index of the antibacterial waterproof fabric manufactured in the following examples is as follows:
waterproof property: the antibacterial waterproof fabric obtained in each example and the comparative example material are taken to have the same area and size, the waterproof surface is upwards and is flatly fixed on a glass plate by double-sided adhesive tape to be horizontally prevented, pure water with the same volume is dripped on the surface in the same environmental atmosphere, the glass plate is inclined until water drops of each component material roll, and the rolling angle is recorded.
Antibacterial properties: the dirt-resistant clothing 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 aminopropionic acid glyceride mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) Spinning: the 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 immersing and washing the fibers with pure water for 5min under ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber braiding machine, braiding 180g/m 2 The grammage fabric is used for preparing fabric base cloth;
(3) Primary bionic treatment: attaching the 3, 4-dihydroxythiophene deposition surface of the polythiophene film to a substrate with butyl ether at 1g/cm 2 Pressing the surface of the fabric base cloth with the same area and wetted by the amount at 70 ℃ for 60min under the pressure of 1MPa to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, and using filter paper to obtain the polythiophene appearance of the pressed fabricThe surface moisture is absorbed, the rest part is kept moist, one-time laser etching is carried out, ethanol and pure water are sequentially used for washing 3 times, and the drying is carried out for 8 hours under the pressure of 5Pa at the temperature of 1 ℃ to prepare the first-class bionic fabric;
(4) Secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, then using filter paper to absorb water on the surface of the primary bionic fabric subjected to primary bionic treatment, keeping the rest part moist, performing secondary laser etching, washing with ethanol and pure water for 3 times in sequence, and drying for 8 hours under the pressure of 5Pa at the temperature of 1 ℃ to obtain a secondary bionic fabric;
(5) Modification treatment: the untreated surface of the secondary bionic fabric is upwards fixed on a glass plate and placed in a reaction tank, and the mixed solution of aminopropionic acid glyceride with the mass of 5 times of that of the secondary bionic fabric is added, and then the mixture is reacted for 5min under the ultrasonic vibration of 30kHz at 80 ℃, and then is immersed in the sodium hydroxide solution with the mass fraction of 5% with the mass of 8 times of that of the secondary bionic fabric, and then reacted for 10min under the ultrasonic vibration of 40 ℃ and 30kHz, and then the mixture is washed for 3 times by pure water with the temperature of 60 ℃, and is dried for 8h under the pressure of 5Pa at 1 ℃ to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: the polyacrylic acid was pressed into a 1mm sheet, and (3) irradiating the mixture to the radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: the voltage was 15kV, the fluid supply rate was 20. Mu.L/min, the ambient humidity was 10%, the receiving distance was 15cm, the bore diameter in the spinneret was 0.5mm, and the temperature was 30 ℃.
As optimization, the preparation method of the polythiophene film in the step (3) comprises the following steps: ferric chloride at a concentration of 1g/m 2 Spreading and dispersing on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen to exhaust air, enabling the temperature of the glass plate loaded with ferric chloride to reach 100 ℃, heating 3, 4-dihydroxythiophene with 20 times of the ferric chloride to 90 ℃ to be converted into gas state, enabling the gas to enter the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit for 10min after the ventilation of the 3, 4-dihydroxythiophene is finished, heating thiophene with 80 times of the ferric chloride to 90 ℃ to be converted into gas state, and enabling the gas to pass through the deposition chamber at a flow rate of 0.5m/sAnd (3) putting the pipeline into a deposition chamber, continuing to deposit for 20min after thiophene ventilation is finished, then introducing nitrogen to remove deposition gas, cooling to 20 ℃, taking out a deposited film on a glass plate, washing 3 times by using absolute ethyl alcohol and pure water respectively, and drying at 60 ℃ for 8h to obtain the polythiophene film.
As optimization, the technological 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/cm 2 The number of pulses was 240 and the off-focal length was-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/cm 2 The number of pulses was 240 and the off-focal length was-3 mm.
As optimization, the mixed solution of the aminopropionic acid glyceride in the step (5) is prepared by mixing the aminopropionic acid glyceride, a hydrochloric acid solution with the mass fraction of 0.1% and butyl ether according to the mass ratio of 1:10:10 are evenly mixed to prepare the product.
As optimization, the preparation method of the aminopropionic acid glyceride comprises the following steps: mixing L-aminopropionic acid, glycerol and the mass fraction: the mass ratio of the sodium hydroxide solution with 20 percent to the butyl ether is 1:1:3:10, reacting for 4 hours at 80 ℃ and a rotating speed of 1000r/min, concentrating and crystallizing, recrystallizing in pure water for 3 times, and drying for 8 hours at-10 ℃ and a pressure of 5Pa to obtain the aminopropionic glyceride.
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 aminopropionic acid glyceride mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) Spinning: the 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 ultrasonic vibration at 45 ℃ and 35kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 65D by a fiber braiding machine, braiding to 200g/m 2 The grammage fabric is used for preparing fabric base cloth;
(3) Primary bionic treatment: attaching the 3, 4-dihydroxythiophene deposition surface of the polythiophene film to a substrate with butyl ether at 1g/cm 2 Pressing the surface of the fabric base cloth with the same area and wetted by the amount at 80 ℃ for 50min at the pressure of 1.5MPa to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, then sucking the water on the outer surface of the polythiophene of the pressed fabric to dryness by using filter paper, keeping the rest part of the polythiophene wet, carrying out one-time laser etching, washing with ethanol and pure water for 4 times in sequence, and drying for 7h at the pressure of 8Pa at the temperature of 5 ℃ to obtain the first-stage bionic fabric;
(4) Secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, then using filter paper to absorb water on the surface of the primary bionic fabric subjected to primary bionic treatment, keeping the rest part moist, performing secondary laser etching, washing with ethanol and pure water for 4 times in sequence, and drying for 7 hours under the pressure of 8Pa at the temperature of 5 ℃ to obtain a secondary bionic fabric;
(5) Modification treatment: the untreated surface of the secondary bionic fabric is upwards fixed on a glass plate and placed in a reaction tank, and the mixed solution of aminopropionic acid glyceride with the mass of 6 times of that of the secondary bionic fabric is added, and then the mixed solution reacts for 4min under the ultrasonic vibration of 35kHz at the temperature of 85 ℃, and then the mixed solution is immersed in the sodium hydroxide solution with the mass of 9 times of that of the secondary bionic fabric and the mass fraction of 5%, reacts for 8min under the ultrasonic vibration of 35kHz at the temperature of 45 ℃, and then the mixed solution is washed for 4 times by pure water at the temperature of 70 ℃ and dried for 7h under the pressure of 8Pa at the temperature of 5 ℃ to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: the polyacrylic acid is pressed into a sheet with the thickness of 1.5mm, and the sheet is irradiated to the radiation dose of 120KGy by an electron beam accelerator under the nitrogen atmosphere to prepare the high-temperature high-pressure high-temperature high-energy-density polyethylene.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: the voltage was 18kV, the fluid supply rate was 23. Mu.L/min, the ambient humidity was 15%, the receiving distance was 15cm, the bore diameter in the spinneret was 0.5mm, and the temperature was 35 ℃.
As optimization, the preparation method of the polythiophene film in the step (3) comprises the following steps: ferric chloride at a concentration of 1g/m 2 Spreading and dispersing the materials on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen to exhaust air, enabling the temperature of the glass plate loaded with ferric chloride to reach 110 ℃, heating 3, 4-dihydroxythiophene with the mass of 25 times of the ferric chloride to 95 ℃ to be converted into a gaseous state, enabling the gaseous state to enter the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit for 13min after the aeration of 3, 4-dihydroxythiophene is finished, heating thiophene with the mass of 100 times of the ferric chloride to 95 ℃ to be converted into the gaseous state, enabling the gaseous state to enter the deposition chamber through the pipeline at a flow rate of 0.5m/s, continuing to deposit for 25min after the aeration of the thiophene is finished, introducing nitrogen to remove the deposited gas, cooling to 25 ℃, taking out a deposited film on the glass plate, washing the glass plate for 4 times respectively by using absolute ethyl alcohol and pure water, and drying the glass plate at 70 ℃ for 7h to obtain the polythiophene film.
As optimization, the technological 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/cm 2 The number of pulses was 260 and the off-focal length was-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/cm 2 The number of pulses was 260 and the off-focal length was-3 mm.
As optimization, the mixed solution of the aminopropionic acid glyceride in the step (5) is prepared by mixing the aminopropionic acid glyceride, a hydrochloric acid solution with the mass fraction of 0.1% and butyl ether according to the mass ratio of 1:10:10 are evenly mixed to prepare the product.
As optimization, the preparation method of the aminopropionic acid glyceride comprises the following steps: mixing L-aminopropionic acid, glycerol and the mass fraction: the mass ratio of the sodium hydroxide solution with 20 percent to the butyl ether is 1:1:3:10, reacting for 3h at a speed of 1500r/min at 85 ℃, concentrating and crystallizing, recrystallizing in pure water for 4 times, and drying for 7h at-5 ℃ and a pressure of 8Pa to obtain the aminopropionic glyceride.
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 aminopropionic acid glyceride mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) Spinning: the 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 immersing and washing the fibers with pure water for 3min under ultrasonic vibration at 50 ℃ and 40kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 80D by a fiber braiding machine, braiding to 220g/m 2 The grammage fabric is used for preparing fabric base cloth;
(3) Primary bionic treatment: attaching the 3, 4-dihydroxythiophene deposition surface of the polythiophene film to a substrate with butyl ether at 1g/cm 2 Pressing the surface of the substrate fabric with the same area and wetted by the amount at 90 ℃ for 40min at the pressure of 2MPa to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, then sucking the water on the outer surface of the polythiophene of the pressed fabric to be dry by using filter paper, keeping the rest part of the surface of the polythiophene wet, carrying out one-time laser etching, washing with ethanol and pure water for 5 times in sequence, and drying for 6h at the pressure of 10 ℃ and 10Pa to obtain the first-stage bionic fabric;
(4) Secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, then using filter paper to absorb water on the surface of the primary bionic fabric subjected to primary bionic treatment, keeping the rest part moist, performing secondary laser etching, washing with ethanol and pure water for 5 times in sequence, and drying for 6 hours under the pressure of 10Pa at the temperature of 10 ℃ to obtain a secondary bionic fabric;
(5) Modification treatment: the untreated surface of the secondary bionic fabric is upwards fixed on a glass plate and placed in a reaction tank, and the mixed solution of the aminopropionic acid glyceride with the mass of 8 times of that of the secondary bionic fabric is added, and then the mixed solution reacts for 3min under the ultrasonic vibration of 40kHz at 90 ℃, and then is immersed in the sodium hydroxide solution with the mass fraction of 5% with the mass of 10 times of that of the secondary bionic fabric, reacts for 5min under the ultrasonic vibration of 50 ℃ and 40kHz, and is washed for 3 times by pure water with the temperature of 80 ℃, and is dried for 6h under the pressure of 10Pa at 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: the polyacrylic acid is pressed into a sheet with the thickness of 2mm, and the sheet is irradiated to the radiation dose of 120KGy by an electron beam accelerator under the nitrogen atmosphere to prepare the high-temperature-resistant high-pressure polyethylene.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: the voltage was 20kV, the fluid supply rate was 25. Mu.L/min, the ambient humidity was 20%, the receiving distance was 15cm, the bore diameter in the spinneret was 0.5mm, and the temperature was 40 ℃.
As optimization, the preparation method of the polythiophene film in the step (3) comprises the following steps: ferric chloride at a concentration of 1g/m 2 Spreading and dispersing the materials on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen to exhaust air, enabling the temperature of the glass plate loaded with ferric chloride to reach 120 ℃, heating 3, 4-dihydroxythiophene with the mass of 30 times of the ferric chloride to 100 ℃ to be converted into a gaseous state, enabling the gaseous state to enter the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit for 15min after the aeration of 3, 4-dihydroxythiophene is finished, heating thiophene with the mass of 120 times of the ferric chloride to be converted into the gaseous state, enabling the gaseous state to enter the deposition chamber through the pipeline at a flow rate of 0.5m/s, continuing to deposit for 30min after the aeration of the thiophene is finished, introducing nitrogen to remove deposition gas, cooling to 30 ℃, taking out a deposited film on the glass plate, washing 5 times respectively by absolute ethyl alcohol and pure water, and drying for 6h at 80 ℃ to obtain the polythiophene film.
As optimization, the technological 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 is 1.6J/cm 2 The number of pulses was 280 and the off-focal length was-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/cm 2 The number of pulses was 280 and the off-focal length was-3 mm.
As optimization, the mixed solution of the aminopropionic acid glyceride in the step (5) is prepared by mixing the aminopropionic acid glyceride, a hydrochloric acid solution with the mass fraction of 0.1% and butyl ether according to the mass ratio of 1:10:10 are evenly mixed to prepare the product.
As optimization, the preparation method of the aminopropionic acid glyceride comprises the following steps: mixing L-aminopropionic acid, glycerol and the mass fraction: the mass ratio of the sodium hydroxide solution with 20 percent to the butyl ether is 1:1:3:10, reacting for 2 hours at 90 ℃ at a rotating speed of 2000r/min, concentrating and crystallizing, recrystallizing in pure water for 5 times, and drying for 6 hours at-1 ℃ and a pressure of 10Pa to obtain the aminopropionic glyceride.
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 aminopropionic acid glyceride mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) Spinning: the 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 immersing and washing the fibers with pure water for 5min under ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber braiding machine, braiding 180g/m 2 The grammage fabric is used for preparing fabric base cloth;
(3) Modification treatment: fixing the fabric base cloth on a glass plate, placing the glass plate in a reaction tank, adding a mixed solution of aminopropionic acid glyceride with the mass of 5 times of the fabric base cloth, reacting for 5min under the ultrasonic vibration of 30kHz at 80 ℃, immersing the fabric base cloth in a sodium hydroxide solution with the mass fraction of 5% with the mass of 8 times of the fabric base cloth, reacting for 10min under the ultrasonic vibration of 30kHz at 40 ℃, washing for 3 times with pure water at 60 ℃, and drying for 8h under the pressure of 5Pa at 1 ℃ to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: the polyacrylic acid was pressed into a 1mm sheet, and (3) irradiating the mixture to the radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: the voltage was 15kV, the fluid supply rate was 20. Mu.L/min, the ambient humidity was 10%, the receiving distance was 15cm, the bore diameter in the spinneret was 0.5mm, and the temperature was 30 ℃.
As optimization, the mixed solution of the aminopropionic acid glyceride in the step (3) is prepared by mixing the aminopropionic acid glyceride, a hydrochloric acid solution with the mass fraction of 0.1% and butyl ether according to the mass ratio of 1:10:10 are evenly mixed to prepare the product.
As optimization, the preparation method of the aminopropionic acid glyceride comprises the following steps: mixing L-aminopropionic acid, glycerol and the mass fraction: the mass ratio of the sodium hydroxide solution with 20 percent to the butyl ether is 1:1:3:10, reacting for 4 hours at 80 ℃ and a rotating speed of 1000r/min, concentrating and crystallizing, recrystallizing in pure water for 3 times, and drying for 8 hours at-10 ℃ and a pressure of 5Pa to obtain the aminopropionic glyceride.
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 aminopropionic acid glyceride mixed solution.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) Spinning: the 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 immersing and washing the fibers with pure water for 5min under ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber braiding machine, braiding 180g/m 2 The grammage fabric is used for preparing fabric base cloth;
(3) Bionic treatment: attaching the 3, 4-dihydroxythiophene deposition surface of the polythiophene film to a substrate with butyl ether at 1g/cm 2 Pressing the surface of the fabric base cloth with the same area and wetted by the amount at 70 ℃ for 60min at 1MPa to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, then sucking the water on the outer surface of the polythiophene of the pressed fabric to dryness by using filter paper, keeping the rest part wet, carrying out laser etching, washing with ethanol and pure water for 3 times in sequence at 1 ℃ and 5PaDrying for 8 hours under pressure to obtain the bionic fabric;
(4) Modification treatment: the untreated surface of the bionic fabric is upwards fixed on a glass plate and placed in a reaction tank, the mixed solution of aminopropionic acid glyceride with the mass of 5 times of that of the first-stage bionic fabric is added, the mixture is reacted for 5min under the ultrasonic vibration of 30kHz at 80 ℃, then the mixture is immersed in the sodium hydroxide solution with the mass fraction of 5% with the mass of 8 times of that of the bionic fabric, the mixture is reacted for 10min under the ultrasonic vibration of 30kHz at 40 ℃, then the mixture is washed for 3 times by pure water at 60 ℃, and the mixture is dried for 8h under the pressure of 5Pa at 1 ℃ to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: the polyacrylic acid was pressed into a 1mm sheet, and (3) irradiating the mixture to the radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: the voltage was 15kV, the fluid supply rate was 20. Mu.L/min, the ambient humidity was 10%, the receiving distance was 15cm, the bore diameter in the spinneret was 0.5mm, and the temperature was 30 ℃.
As optimization, the preparation method of the polythiophene film in the step (3) comprises the following steps: ferric chloride at a concentration of 1g/m 2 Spreading and dispersing the materials on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen to exhaust air, enabling the temperature of the glass plate loaded with ferric chloride to reach 100 ℃, heating 3, 4-dihydroxythiophene with the mass of 20 times of the ferric chloride to 90 ℃ to be converted into a gaseous state, enabling the gaseous state to enter the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit for 10min after the aeration of 3, 4-dihydroxythiophene is finished, heating thiophene with the mass of 80 times of the ferric chloride to be converted into the gaseous state, enabling the gaseous state to enter the deposition chamber through the pipeline at a flow rate of 0.5m/s, continuing to deposit for 20min after the aeration of the thiophene is finished, introducing nitrogen to remove the deposited gas, cooling to 20 ℃, taking out a deposited film on the glass plate, respectively washing 3 times by absolute ethyl alcohol and pure water, and drying for 8h at 60 ℃ to obtain the polythiophene film.
As optimization, the technological parameters of the 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/cm 2 The number of pulses was 240 and the off-focal length was-3 mm.
As optimization, the mixed solution of the aminopropionic acid glyceride in the step (4) is prepared by mixing the aminopropionic acid glyceride, a hydrochloric acid solution with the mass fraction of 0.1% and butyl ether according to the mass ratio of 1:10:10 are evenly mixed to prepare the product.
As optimization, the preparation method of the aminopropionic acid glyceride comprises the following steps: mixing L-aminopropionic acid, glycerol and the mass fraction: the mass ratio of the sodium hydroxide solution with 20 percent to the butyl ether is 1:1:3:10, reacting for 4 hours at 80 ℃ and a rotating speed of 1000r/min, concentrating and crystallizing, recrystallizing in pure water for 3 times, and drying for 8 hours at-10 ℃ and a pressure of 5Pa to obtain the aminopropionic glyceride.
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 film.
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) Spinning: the 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 immersing and washing the fibers with pure water for 5min under ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber braiding machine, braiding 180g/m 2 The grammage fabric is used for preparing fabric base cloth;
(3) Primary bionic treatment: attaching the 3, 4-dihydroxythiophene deposition surface of the polythiophene film to a substrate with butyl ether at 1g/cm 2 Pressing the surface of the substrate fabric with the same area and wetted by the amount at 70 ℃ for 60min at 1MPa to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, then sucking the water on the outer surface of the polythiophene of the pressed fabric to be dry by using filter paper, keeping the rest part of the surface of the polythiophene wet, carrying out one-time laser etching, washing with ethanol and pure water for 3 times in sequence, and drying for 8h at 1 ℃ and 5Pa to obtain the first-stage bionic fabric;
(4) Secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, then using filter paper to absorb the surface water of the primary bionic treatment of the primary bionic fabric, keeping the rest part moist, carrying out secondary laser etching, washing with ethanol and pure water for 3 times in sequence, and drying for 8 hours under the pressure of 5Pa at the temperature of 1 ℃ to obtain the antibacterial waterproof fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: the polyacrylic acid was pressed into a 1mm sheet, and (3) irradiating the mixture to the radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: the voltage was 15kV, the fluid supply rate was 20. Mu.L/min, the ambient humidity was 10%, the receiving distance was 15cm, the bore diameter in the spinneret was 0.5mm, and the temperature was 30 ℃.
As optimization, the preparation method of the polythiophene film in the step (3) comprises the following steps: ferric chloride at a concentration of 1g/m 2 Spreading and dispersing the materials on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen to exhaust air, enabling the temperature of the glass plate loaded with ferric chloride to reach 100 ℃, heating 3, 4-dihydroxythiophene with the mass of 20 times of the ferric chloride to 90 ℃ to be converted into a gaseous state, enabling the gaseous state to enter the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit for 10min after the aeration of 3, 4-dihydroxythiophene is finished, heating thiophene with the mass of 80 times of the ferric chloride to be converted into the gaseous state, enabling the gaseous state to enter the deposition chamber through the pipeline at a flow rate of 0.5m/s, continuing to deposit for 20min after the aeration of the thiophene is finished, introducing nitrogen to remove the deposited gas, cooling to 20 ℃, taking out a deposited film on the glass plate, respectively washing 3 times by absolute ethyl alcohol and pure water, and drying for 8h at 60 ℃ to obtain the polythiophene film.
As optimization, the technological 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/cm 2 The number of pulses was 240 and the off-focal length was-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/cm 2 The number of pulses was 240 and the off-focal length was-3 mm.
Comparative example 4
The preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) Spinning: the 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 immersing and washing the fibers with pure water for 5min under ultrasonic vibration at 40 ℃ and 30kHz to obtain the porous fibers.
(2) Weaving: twisting the porous fiber to 50D by a fiber braiding machine, braiding 180g/m 2 And (5) preparing the fabric by using the gram weight fabric.
As optimization, the preparation method of the modified polyacrylic acid in the step (1) comprises the following steps: the polyacrylic acid was pressed into a 1mm sheet, and (3) irradiating the mixture to the radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere.
As optimization, the electrostatic spinning process parameters in the step (1) are as follows: the voltage was 15kV, the fluid supply rate was 20. Mu.L/min, the ambient humidity was 10%, the receiving distance was 15cm, the bore diameter in the spinneret was 0.5mm, and the temperature was 30 ℃.
Effect example
The following table 1 gives the analysis results of the water repellency and the antibacterial property of the antibacterial waterproof fabrics employing examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
Roll angle Antibacterial rate Roll angle Antibacterial rate
Example 1 3.3° 99.2％ Comparative example 1 Without any means for 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 Without any means for 68.5％
As can be found from the comparison of the experimental data in the table 1, the water resistance and the antibacterial property of the material can be obviously improved after the primary bionic treatment, the secondary bionic treatment and the modification treatment; from comparison of experimental data of examples 1, 2 and 3 and comparative example 1, examples 1, 2 and 3 and comparative example 1 have small rolling angles and the antibacterial rate is increased, which indicates that the primary bionic treatment and the secondary bionic treatment are performed, the formed hydrophobic surface with 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 small, bacteria are not easy to adhere by the hydrophobic surface, the survival difficulty is increased, and the antibacterial effect is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative example 2, it can be found that the rolling angle of examples 1, 2 and 3 and comparative example 2 is smaller, which demonstrates that the bristle structure formed by the secondary bionic treatment can improve the hydrophobicity of the surface, so that water is more difficult to permeate and stay, and the water resistance of the material is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative example 3, it can be found that the antibacterial rate of the examples 1, 2 and 3 and comparative example 3 is increased, which shows that after 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 are dehydrated and killed, and simultaneously carboxylate radical is combined with hydrogen ions to increase the pH of sweat, the pH influences the activity of various enzymes of bacteria, and thus bacterial metabolism is disturbed, so that 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 characteristics 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 (8)

1. The preparation method of the antibacterial waterproof fabric is characterized by mainly comprising the following steps of: 9-11 parts of fabric base cloth, 5-7 parts of polythiophene membrane and 50-80 parts of aminopropionic acid glyceride mixed solution; the fabric base cloth is woven by porous fibers prepared by modified polyacrylic acid, polyethylene glycol and ethanol spinning; the polythiophene film is prepared by sequentially depositing 3, 4-dihydroxythiophene and thiophene; the mixed solution of the aminopropionic acid glyceride is prepared from the aminopropionic acid glyceride, a hydrochloric acid solution and butyl ether;
the preparation method of the antibacterial waterproof fabric mainly comprises the following preparation steps:
(1) Spinning: the 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 20-30 ℃ for 20-30 min, and then immersing and washing the fibers with pure water for 3-5 min under ultrasonic vibration at 40-50 ℃ and 30-40 kHz to obtain porous fibers;
(2) Weaving: twisting the porous fiber to 50-80D by a fiber braiding machine, and braiding to 180-220 g/m 2 The grammage fabric is used for preparing fabric base cloth;
(3) Primary bionic treatment: attaching the 3, 4-dihydroxythiophene deposition surface of the polythiophene film to a substrate with butyl ether at 1g/cm 2 Pressing the surface of the fabric base cloth with the same area and wetted by the amount at 70-90 ℃ under the pressure of 1-2 MPa for 40-60 min to obtain a pressed fabric, immersing the pressed fabric in an ammonium acetate solution with the mass fraction of 10%, then sucking the water on the outer surface of the polythiophene of the pressed fabric to be dry by using filter paper, keeping the rest of the polythiophene to be wet, carrying out one-time laser etching, washing with ethanol and pure water for 3-5 times in sequence, and drying for 6-8 h under the pressure of 5-10 Pa at the temperature of 1-10 ℃ to obtain the first-stage bionic fabric;
(4) Secondary bionic treatment: immersing the primary bionic fabric in an ammonium acetate solution with the mass fraction of 10%, then using filter paper to absorb water on the surface of the primary bionic fabric subjected to primary bionic treatment, keeping the rest part moist, performing secondary laser etching, washing with ethanol and pure water for 3-5 times in sequence, and drying for 6-8 hours at the temperature of 1-10 ℃ and the pressure of 5-10 Pa to obtain the secondary bionic fabric;
(5) Modification treatment: and (3) fixing the untreated surface of the secondary bionic fabric on a glass plate upwards, placing the glass plate in a reaction tank, adding a mixed solution of aminopropionic acid glyceride with the mass of 5-8 times of that of the secondary bionic fabric, reacting for 3-5 min under the ultrasonic vibration of 30-40 kHz at 80-90 ℃, immersing the glass plate in a sodium hydroxide solution with the mass fraction of 5% with the mass of 8-10 times of that of the secondary bionic fabric, reacting for 5-10 min under the ultrasonic vibration of 40-50 kHz, 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.
2. The method for preparing the antibacterial waterproof fabric according to claim 1, wherein the method for preparing the modified polyacrylic acid in the step (1) is as follows: and (3) pressing the polyacrylic acid into a sheet with the thickness of 1-2 mm, and radiating the sheet to the radiation dose of 120KGy by using an electron beam accelerator in a nitrogen atmosphere.
3. The method for preparing the antibacterial waterproof fabric according to claim 1, wherein 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 ambient humidity is 10% -20%, the receiving distance is 15cm, the inner hole of the spinneret is 0.5mm, and the temperature is 30-40 ℃.
4. The method for preparing the antibacterial waterproof fabric according to claim 1, wherein the method for preparing the polythiophene film in the step (3) comprises the following steps: ferric chloride at a concentration of 1g/m 2 Spreading and dispersing the amount of the 3, 4-dihydroxythiophene on the surface of a glass plate, placing the glass plate in a vapor deposition chamber, introducing nitrogen to exhaust air, enabling the temperature of the glass plate loaded with ferric chloride to reach 100-120 ℃, heating 3, 4-dihydroxythiophene with the iron chloride amount of 20-30 times to 90-100 ℃ to be converted into gas state, enabling the gas to enter the deposition chamber through a pipeline at a flow rate of 0.5m/s, continuing to deposit for 10-15 min after the 3, 4-dihydroxythiophene is ventilated, heating thiophene with the iron chloride amount of 80-120 times to 90-100 ℃ to be converted into gas state, enabling the gas to enter the deposition chamber through the pipeline at a flow rate of 0.5m/s, continuing to deposit for 20-30 min after the thiophene is ventilated, introducing nitrogen to exhaust deposited gas, cooling to 20-30 ℃, and finally depositing the thiophene on the glass plateAnd taking out the deposited film, washing with absolute ethyl alcohol and pure water for 3-5 times respectively, and drying at 60-80 ℃ for 6-8 hours to obtain the polythiophene film.
5. The method for preparing the antibacterial waterproof fabric according to claim 1, wherein the technological 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/cm 2 The number of pulses is 240-280, and the off-focal length is-3 mm.
6. The method for preparing the antibacterial waterproof fabric according to claim 1, wherein the technological 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/cm 2 The number of pulses is 240-280, and the off-focal length is-3 mm.
7. The preparation method of the antibacterial waterproof fabric as claimed in claim 1, wherein the aminopropionic acid glyceride mixed solution in the step (5) is prepared by mixing aminopropionic acid glyceride, a hydrochloric acid solution with the mass fraction of 0.1% and butyl ether according to the mass ratio of 1:10:10 are evenly mixed to prepare the product.
8. The method for preparing the antibacterial waterproof fabric according to claim 1, wherein the preparation method of the aminopropionic acid glyceride is as follows: mixing L-aminopropionic acid, glycerol and the mass fraction: the mass ratio of the sodium hydroxide solution with 20 percent to the butyl ether is 1:1:3:10, uniformly mixing, reacting for 2-4 hours at the temperature of 80-90 ℃ at the rotating speed of 1000-2000 r/min, concentrating and crystallizing, recrystallizing in pure water for 3-5 times, and drying for 6-8 hours at the temperature of-10 to-1 ℃ under the pressure of 5-10 Pa to obtain the aminopropionic glyceride.
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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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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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