阅读说明：本技术 一种防水透气抑菌复合无纺布及其制备方法和应用 (Waterproof breathable bacteriostatic composite non-woven fabric and preparation method and application thereof ) 是由 黎扬程 于 2020-11-17 设计创作，主要内容包括：本发明属于无纺布制品技术领域,具体涉及一种防水透气抑菌复合无纺布及其制备方法和应用,先将聚丙烯腈、聚偏氟乙烯、填料、水溶性致孔剂混合熔融,然后经喷丝板喷出、气流牵伸、成网、热压粘合、水浸除去致孔剂即得；其中,填料是以氧化锌-电气石复合体、端氨基含氟聚合物以及1-烯丙基-3-甲基咪唑四氟硼酸盐为原料制成。该无纺布具有良好的防水透气性,且抗菌性能佳。(The invention belongs to the technical field of non-woven fabric products, and particularly relates to a waterproof breathable bacteriostatic composite non-woven fabric, and a preparation method and application thereof, wherein polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent are mixed and melted, and then the mixture is sprayed out by a spinneret plate, air flow drafted, formed into a net, hot-pressed and bonded, and subjected to water immersion to remove the pore-forming agent; wherein, the filler is prepared by taking a zinc oxide-tourmaline complex, an amino-terminated fluorine-containing polymer and 1-allyl-3-methylimidazolium tetrafluoroborate as raw materials. The non-woven fabric has good waterproof and air permeability and good antibacterial performance.)

1. A preparation method of a waterproof breathable bacteriostatic composite non-woven fabric is characterized by mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent, then spraying by a spinneret plate, air flow drafting, net forming, hot-pressing adhesion and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain a modified complex;

(3) and finally, soaking the modified complex in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the filler.

2. The preparation method according to claim 1, wherein the mass ratio of polyacrylonitrile, polyvinylidene fluoride, filler and pore-forming agent is 100: 15-20: 1-2: 1-2, wherein the pore-foaming agent is polyethylene glycol 600.

3. The method of claim 1, wherein the composite nonwoven fabric is prepared by the following steps: mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding on the fiber web and water immersion to remove the pore-forming agent to obtain the non-woven fabric.

4. The preparation method according to claim 1, wherein the specific method of step (1) comprises the following steps in parts by weight: putting 1 part of zinc acetate into an agate mortar, grinding for 5-8 minutes, adding 0.3-0.4 part of sodium tripolyphosphate, grinding for 40-50 minutes, adding 0.04-0.05 part of sodium hydroxide, grinding for 30-40 minutes, finally adding 5-8 parts of porous tourmaline, grinding for 40-50 minutes, and performing aftertreatment to obtain the zinc oxide-tourmaline complex.

5. The method for preparing porous tourmaline according to claim 4, wherein the method for preparing porous tourmaline comprises the following steps: adding 1 part of sodium silicate into 10-12 parts of water, uniformly stirring, adding 8-10 parts of tourmaline powder while stirring, press-forming, drying, sintering at 750-800 ℃ for 5-8 hours, and crushing to obtain the porous tourmaline.

6. The method of claim 4, wherein the post-processing comprises: and alternately washing the mixture with deionized water and absolute ethyl alcohol for 2-3 times, and drying the mixture for 3-4 hours at the temperature of 60-70 ℃.

7. The preparation method according to claim 1, wherein the specific method of the step (2) comprises the following steps in parts by weight:

(2-1) adding 1 part of zinc oxide-tourmaline complex into 5-7 parts of 3- (2, 3-glycidoxy) propyl trimethoxy silane, stirring and reacting at 80-90 ℃ for 6-9 hours, and filtering to obtain an epoxidized complex;

(2-2) adding the epoxy compound and 2-3 parts of the amino-terminated fluorine-containing polymer into a sodium hydroxide solution with the mass concentration of 25-35%, uniformly oscillating with ultrasonic waves, reacting at 85-95 ℃ for 15-18 hours under the atmosphere of nitrogen, washing to be neutral, and drying at 40-50 ℃ for 15-20 hours to obtain the modified compound.

8. The method according to claim 1, wherein in the step (2), the amino-terminated fluoropolymer is prepared by the following method in parts by weight: mixing 1 part of hexafluorobutyl methacrylate and 2-3 parts of N, N' -dimethylformamide, heating to 60 ℃, adding 0.04-0.06 part of cysteamine hydrochloride and 0.03-0.04 part of azobisisobutyronitrile, stirring and reacting for 8 hours, dropwise adding triethylamine until the pH value is 8, adding 0.05-0.07 part of formaldehyde water solution with the mass concentration of 37%, fully stirring for 1 hour, distilling under reduced pressure to remove the solvent, and stirring and polymerizing for 30-40 minutes at 80-90 ℃ to obtain the composite material.

9. A waterproof breathable bacteriostatic composite non-woven fabric obtained by the preparation method of any one of claims 1-8.

10. The use of the waterproof, breathable and bacteriostatic composite nonwoven fabric according to claim 9 in infant diapers, adult diapers or feminine sanitary napkins.

Technical Field

The invention belongs to the technical field of non-woven fabric products. More particularly, relates to a waterproof breathable bacteriostatic composite non-woven fabric, and a preparation method and application thereof.

Background

With the improvement of living standard, people have higher and higher requirements on disposable sanitary products such as baby diapers, adult diapers, women sanitary napkins and the like, and have higher and higher requirements on comfort level and product quality.

Users of these disposable sanitary products include infants, bed-ridden adults, menstrual women, and other fragile people. If the air permeability of the sanitary product is poor, the skin of the fragile people wrapped in the sanitary product or in contact with the sanitary product for a long time is in a humid environment for a long time, the fragile people slightly become red and erupted, and the fragile people seriously become light or serious skin inflammation, which affects the life quality of users and even causes chronic skin diseases. In addition, the sanitary articles are used for conveniently treating the dirt discharged by a user, reducing the pollution to bed sheets, bedding, clothes and the like and reducing the manual nursing difficulty and the manual cleaning workload, so the leakage-proof performance of the sanitary articles is also important, and the technical key for restricting the leakage-proof effect is the water penetration resistance. That is, the basic requirement of these disposable hygienic articles is to be waterproof and breathable, i.e. able to block water molecules but allow the passage of gases.

At present, the bottom film of the sanitary towel is mostly made of a waterproof plastic film, which is waterproof but not breathable, and the sanitary towel cannot permeate moisture for a long time, so that people feel uncomfortable. In contrast to sanitary napkins, the users of diapers are mainly babies. The skin of the baby is delicate and is directly contacted with the paper diaper, so that the relatively high end of the basement membrane of the paper diaper is claimed to have the waterproof and breathable functions. The basement membrane of the common high-end paper diaper on the market at present is mostly made of PE plastic membrane. PE plastic films are further classified into PE solvent type films and PE curtain films. The PE solvent type film has high cost and is difficult to be marketed, so the PE film is commonly used as the bottom film of the paper diaper. The PE laminated film used as the base film of the paper diaper also has air permeability and moisture permeability by needling, and on one hand, the process has limited number of needling air holes (too many air holes can greatly influence the strength and toughness of the base film of the paper diaper), and the air permeability is small. On the other hand, the ventilation mode of the basement membrane is closed ventilation, water molecules can hardly permeate when no pressure difference exists between the two sides of the basement membrane, the needling air holes of the membrane are enlarged by the pressure difference to enable air and the water molecules to permeate, the waterproof effect is achieved, and moisture between the paper diaper and the skin can not diffuse out.

The common point of the disposable sanitary product is that the surface layer is basically non-woven fabric, taking a paper diaper as an example, the paper diaper is a disposable product, is more convenient and sanitary compared with the traditional diaper, and is more and more popular among young parents. The paper diaper is generally made of materials such as non-woven fabrics, toilet paper, fluff pulp, high-molecular water-absorbent resin, PE films, rubber bands and the like, wherein the surface material is the non-woven fabrics. The key to the technical improvement lies in improving the waterproof and breathable performance of the non-woven fabric.

In the case of a diaper or a sanitary napkin, urine and the like generated by the applicable people are easily combined with oxygen in the air in a warm and humid environment to breed bacteria, and the bacteria may damage the applicable people. Therefore, in addition to waterproof and breathable properties, antimicrobial action is also very important for disposable hygiene articles,

disclosure of Invention

The invention aims to overcome the defects and shortcomings of poor waterproof and air permeability, unsatisfactory antibacterial property and the like of the existing disposable sanitary products, and provides a waterproof and air permeable composite non-woven fabric and a preparation method and application thereof.

The invention aims to provide a preparation method of a waterproof breathable composite non-woven fabric.

The invention also aims to provide the waterproof breathable composite non-woven fabric obtained by the preparation method.

The invention also aims to provide application of the waterproof breathable composite non-woven fabric.

The above purpose of the invention is realized by the following technical scheme:

a preparation method of waterproof and breathable composite non-woven fabric comprises the steps of mixing and melting polyacrylonitrile, polyvinylidene fluoride, filler and water-soluble pore-forming agent, then spraying through a spinneret plate, air flow drafting, web forming, hot-press bonding and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain a modified complex;

(3) and finally, soaking the modified complex in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the filler.

Preferably, the mass ratio of polyacrylonitrile, polyvinylidene fluoride, filler and pore-foaming agent is 100: 15-20: 1-2: 1-2, wherein the pore-foaming agent is polyethylene glycol 600.

Preferably, the preparation method of the composite non-woven fabric is as follows: mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding on the fiber web and water immersion to remove the pore-forming agent to obtain the non-woven fabric.

Further preferably, the extrusion melting temperature is 320-350 ℃.

More preferably, the aperture of the spinneret plate is 0.2-0.25 mm.

Further preferably, the temperature of the side cold air is 10-12 ℃, and the air speed is 1.5-1.8 m/s.

Further preferably, the speed of air flow drafting is 4000-5000 m/min.

Further preferably, the process conditions of the hot-press bonding are as follows: the temperature is 150-160 ℃, and the linear pressure is 40-50 MPa.

Further preferably, the concrete method for treating the pore-foaming agent by water immersion comprises the following steps: soaking in primary water at 40-50 ℃ for 10-12 hours, taking out and naturally drying.

Preferably, the specific method of the step (1) comprises the following steps in parts by weight: putting 1 part of zinc acetate into an agate mortar, grinding for 5-8 minutes, adding 0.3-0.4 part of sodium tripolyphosphate, grinding for 40-50 minutes, adding 0.04-0.05 part of sodium hydroxide, grinding for 30-40 minutes, finally adding 5-8 parts of porous tourmaline, grinding for 40-50 minutes, and performing aftertreatment to obtain the zinc oxide-tourmaline complex.

Further preferably, the preparation method of the porous tourmaline comprises the following steps: adding 1 part of sodium silicate into 10-12 parts of water, uniformly stirring, adding 8-10 parts of tourmaline powder while stirring, press-forming, drying, sintering at 750-800 ℃ for 5-8 hours, and crushing to obtain the porous tourmaline.

Further preferably, the post-treatment comprises: and alternately washing the mixture with deionized water and absolute ethyl alcohol for 2-3 times, and drying the mixture for 3-4 hours at the temperature of 60-70 ℃.

Preferably, the specific method of the step (2) comprises the following steps in parts by weight:

(2-1) adding 1 part of zinc oxide-tourmaline complex into 5-7 parts of 3- (2, 3-glycidoxy) propyl trimethoxy silane, stirring and reacting at 80-90 ℃ for 6-9 hours, and filtering to obtain an epoxidized complex;

(2-2) adding the epoxy compound and 2-3 parts of the amino-terminated fluorine-containing polymer into a sodium hydroxide solution with the mass concentration of 25-35%, uniformly oscillating with ultrasonic waves, reacting at 85-95 ℃ for 15-18 hours under the atmosphere of nitrogen, washing to be neutral, and drying at 40-50 ℃ for 15-20 hours to obtain the modified compound.

Preferably, in the step (2), the amino-terminated fluoropolymer is prepared by the following method in parts by weight: mixing 1 part of hexafluorobutyl methacrylate and 2-3 parts of N, N' -dimethylformamide, heating to 60 ℃, adding 0.04-0.06 part of cysteamine hydrochloride and 0.03-0.04 part of azobisisobutyronitrile, stirring for reacting for 8 hours, dropwise adding triethylamine until the pH value is 8, adding 0.05-0.07 part of formaldehyde water solution with the mass concentration of 37%, fully stirring for 1 hour, distilling under reduced pressure to remove the solvent, and stirring and polymerizing for 30-40 minutes at 80-90 ℃ to obtain the compound;

preferably, the specific method of step (3) is: and immersing the modified complex in 5-8 times of 1-allyl-3-methylimidazole tetrafluoroborate by weight, ultrasonically oscillating for 3-5 hours at 50-70 ℃, and taking out to obtain the filler.

The invention has the following beneficial effects:

mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-foaming agent, then spraying the mixture through a spinneret plate, air-flow drafting, net forming, hot-pressing adhesion and water immersion to remove the pore-foaming agent, thus obtaining a composite non-woven fabric; wherein, the filler is prepared by taking a zinc oxide-tourmaline complex, an amino-terminated fluorine-containing polymer and 1-allyl-3-methylimidazolium tetrafluoroborate as raw materials. The non-woven fabric has good waterproof and air permeability and good antibacterial performance.

The main raw materials of the invention are polyacrylonitrile and polyvinylidene fluoride, so that the non-woven fabric has certain mechanical strength and waterproof performance, and the minimum fog drop diameter of water drops is 10 μm and the diameter of water vapor molecules is 0.4nm through the introduction and removal of water-soluble pore-forming agents, and the pore-forming agents form pores to ensure that the water drops can not penetrate and the water vapor molecules can penetrate, so that the non-woven fabric has better waterproof and breathable properties. When the spinneret plate sprays, because fluorine is introduced into the filler, polyvinylidene fluoride with better compatibility with the filler migrates to the surface of polyacrylonitrile, so that the product has good waterproofness.

The technical key point of the invention is that the filler is prepared by taking zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline as raw materials and carrying out solid-phase reaction on the raw materials to prepare a zinc oxide-tourmaline complex; then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain a modified complex; and finally, soaking the modified complex in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the modified complex.

Wherein, when preparing the zinc oxide-tourmaline complex, the tourmaline raw material is porous tourmaline with pores, thereby avoiding influencing the air permeability of the non-woven fabric after introducing filler. The zinc oxide in the complex is nano-sized and has good bactericidal performance, a hole-electron pair is formed, oxygen atoms, hydroxyl free radicals and the like are generated, and then the zinc oxide reacts with organic matters in bacteria to achieve the purpose of killing the bacteria, and the bactericidal performance of the zinc oxide is enhanced by the strong electric field on the surface of the porous tourmaline.

The zinc oxide-tourmaline compound can react with amino-terminated fluorine-containing polymer after epoxy modification, so that the compatibility of the filler with polyacrylonitrile and polyvinylidene fluoride is improved, the sterilization performance is enhanced, and the waterproof effect is further improved by introducing fluorine atoms.

And finally, the modified complex is immersed in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification, the 1-allyl-3-methylimidazole tetrafluoroborate is an ionic liquid, and positive charges and negative charges contained in the ionic liquid are adsorbed on the surface of the modified complex, so that the bactericidal performance and the waterproof performance are further enhanced.

Detailed Description

The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Unless otherwise indicated, reagents and materials used in the following examples are commercially available.

Example 1

A preparation method of waterproof and breathable composite non-woven fabric comprises the steps of mixing and melting polyacrylonitrile, polyvinylidene fluoride, filler and water-soluble pore-forming agent, then spraying through a spinneret plate, air flow drafting, web forming, hot-press bonding and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain a modified complex;

(3) and finally, soaking the modified complex in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the filler.

The mass ratio of polyacrylonitrile, polyvinylidene fluoride, filler and pore-foaming agent is 100: 15: 2: 1, wherein the pore-foaming agent is polyethylene glycol 600.

The preparation method of the composite non-woven fabric comprises the following steps: mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding on the fiber web and water immersion to remove the pore-forming agent to obtain the non-woven fabric.

The extrusion melt temperature was 350 ℃.

The aperture of the spinneret plate is 0.2 mm.

The temperature of the side cold air is 12 ℃, and the air speed is 1.5 m/s.

The speed of the air stream draw was 5000 m/min.

The technological conditions of the hot-pressing adhesion are as follows: the temperature is 150 ℃, and the linear pressure is 50 MPa.

The concrete method for treating the pore-foaming agent by water immersion comprises the following steps: soaking in 40 deg.C primary water for 12 hr, taking out, and air drying.

The specific method of the step (1) is as follows: putting 1g of zinc acetate into an agate mortar, grinding for 5 minutes, adding 0.4g of sodium tripolyphosphate, grinding for 40 minutes, adding 0.05g of sodium hydroxide, grinding for 30 minutes, adding 8g of porous tourmaline, grinding for 40 minutes, and performing post-treatment to obtain the zinc oxide-tourmaline complex.

The preparation method of the porous tourmaline comprises the following steps: adding 1g of sodium silicate into 12g of water, uniformly stirring, adding 8g of tourmaline powder while stirring, pressing, molding, drying, sintering at 800 ℃ for 5 hours, and crushing to obtain the porous tourmaline.

The post-treatment comprises the following steps: washing with deionized water and anhydrous ethanol alternately for 3 times, and drying at 60 deg.C for 4 hr.

The specific method of the step (2) is as follows:

(2-1) firstly adding 1g of zinc oxide-tourmaline complex into 5g of 3- (2, 3-glycidoxy) propyl trimethoxy silane, stirring and reacting for 6 hours at 90 ℃, and filtering to obtain an epoxidized complex;

(2-2) adding the epoxy complex and 3g of the amino-terminated fluorine-containing polymer into a sodium hydroxide solution with the mass concentration of 25%, uniformly oscillating by ultrasonic waves, reacting at 95 ℃ for 15 hours in a nitrogen atmosphere, washing to be neutral, and drying at 50 ℃ for 15 hours to obtain the modified complex.

In the step (2), the amino-terminated fluorine-containing polymer is prepared by the following method: 1g of hexafluorobutyl methacrylate and 3g of N, N' -dimethylformamide are mixed and heated to 60 ℃, 0.04g of cysteamine hydrochloride and 0.04g of azobisisobutyronitrile are added, the mixture is stirred and reacted for 8 hours, triethylamine is added until the pH value is 8, 0.05g of formaldehyde aqueous solution with the mass concentration of 37 percent is added, and the mixture is fully stirred for 1 hourDistilling under reduced pressure to remove the solvent, and stirring and polymerizing at 90 ℃ for 30 minutes to obtain the polymer; the infrared test shows that the thickness of the coating is 3379-3558 cm^-1And 1200cm^-1The absorption peak of single peak of N-H and the absorption peak of C-N are respectively present,¹H-NMR (deuterated chloroform as solvent) showed a proton absorption peak of N-H at 2.8ppm, indicating that the end of the product is an amino group.

The specific method of the step (3) is as follows: immersing the modified complex in 8 times of 1-allyl-3-methylimidazolium tetrafluoroborate by weight, and carrying out ultrasonic oscillation at 50 ℃ for 5 hours, and taking out to obtain the filler.

Example 2

A preparation method of waterproof and breathable composite non-woven fabric comprises the steps of mixing and melting polyacrylonitrile, polyvinylidene fluoride, filler and water-soluble pore-forming agent, then spraying through a spinneret plate, air flow drafting, web forming, hot-press bonding and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain a modified complex;

(3) and finally, soaking the modified complex in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the filler.

The mass ratio of polyacrylonitrile, polyvinylidene fluoride, filler and pore-foaming agent is 100: 20: 1: 2, wherein the pore-foaming agent is polyethylene glycol 600.

The preparation method of the composite non-woven fabric comprises the following steps: mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding on the fiber web and water immersion to remove the pore-forming agent to obtain the non-woven fabric.

The extrusion melt temperature was 320 ℃.

The aperture of the spinneret plate is 0.25 mm.

The temperature of the side cold air is 10 ℃, and the air speed is 1.8 m/s.

The speed of the draft of the air stream was 4000 m/min.

The technological conditions of the hot-pressing adhesion are as follows: the temperature is 160 ℃, and the linear pressure is 40 MPa.

The concrete method for treating the pore-foaming agent by water immersion comprises the following steps: soaking in 50 deg.C water for 10 hr, taking out, and air drying.

The specific method of the step (1) is as follows: putting 1g of zinc acetate into an agate mortar, grinding for 8 minutes, adding 0.3g of sodium tripolyphosphate, grinding for 50 minutes, adding 0.04g of sodium hydroxide, grinding for 40 minutes, adding 5g of porous tourmaline, grinding for 50 minutes, and performing post-treatment to obtain the zinc oxide-tourmaline complex.

The preparation method of the porous tourmaline comprises the following steps: firstly adding 1g of sodium silicate into 10g of water, uniformly stirring, then adding 10g of tourmaline powder while stirring, pressing and forming, drying, sintering for 8 hours at 750 ℃, and crushing to obtain the porous tourmaline.

The post-treatment comprises the following steps: washing with deionized water and anhydrous ethanol alternately for 2 times, and drying at 70 deg.C for 3 hr.

The specific method of the step (2) is as follows:

(2-1) firstly adding 1g of zinc oxide-tourmaline complex into 7g of 3- (2, 3-glycidoxy) propyl trimethoxy silane, stirring and reacting for 9 hours at 80 ℃, and filtering to obtain an epoxidized complex;

(2-2) adding the epoxy complex and 2g of the amino-terminated fluorine-containing polymer into a sodium hydroxide solution with the mass concentration of 35%, uniformly oscillating by ultrasonic waves, reacting at 85 ℃ for 18 hours in a nitrogen atmosphere, washing to be neutral, and drying at 40 ℃ for 20 hours to obtain the modified complex.

In the step (2), the amino-terminated fluorine-containing polymer is prepared by the following method: firstly, 1g of hexafluorobutyl methacrylate and 2g of N, N' -dimethylformamide are mixed and heated to 60 ℃, 0.06g of cysteamine hydrochloride and 0.03g of azobisisobutyronitrile are added, the mixture is stirred and reacted for 8 hours, triethylamine is added dropwise until the pH value is 8, then 0.07g of formaldehyde water solution with the mass concentration of 37 percent is added, the mixture is fully stirred for 1 hour, the solvent is removed by reduced pressure distillation, and the mixture is stirred and polymerized for 40 minutes at 80 ℃ to obtain the compound.

The specific method of the step (3) is as follows: immersing the modified complex in 5 times of 1-allyl-3-methylimidazolium tetrafluoroborate by weight, and carrying out ultrasonic oscillation at 70 ℃ for 3 hours, and taking out to obtain the filler.

Example 3

A preparation method of waterproof and breathable composite non-woven fabric comprises the steps of mixing and melting polyacrylonitrile, polyvinylidene fluoride, filler and water-soluble pore-forming agent, then spraying through a spinneret plate, air flow drafting, web forming, hot-press bonding and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain a modified complex;

(3) and finally, soaking the modified complex in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the filler.

The mass ratio of polyacrylonitrile, polyvinylidene fluoride, filler and pore-foaming agent is 100: 18: 1.5: 1.5, wherein the pore-foaming agent is polyethylene glycol 600.

The preparation method of the composite non-woven fabric comprises the following steps: mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding on the fiber web and water immersion to remove the pore-forming agent to obtain the non-woven fabric.

The extrusion melt temperature was 330 ℃.

The aperture of the spinneret plate is 0.21 mm.

The temperature of the side cold air is 11 ℃, and the air speed is 1.7 m/s.

The speed of the draft of the air stream was 4500 m/min.

The technological conditions of the hot-pressing adhesion are as follows: the temperature is 155 ℃, and the linear pressure is 45 MPa.

The concrete method for treating the pore-foaming agent by water immersion comprises the following steps: soaking in 45 deg.C water for 11 hr, taking out, and air drying.

The specific method of the step (1) is as follows: and (2) putting 1g of zinc acetate into an agate mortar, grinding for 6 minutes, then adding 0.35g of sodium tripolyphosphate, grinding for 45 minutes, then adding 0.045g of sodium hydroxide, grinding for 35 minutes, finally adding 6g of porous tourmaline, grinding for 45 minutes, and carrying out aftertreatment to obtain the zinc oxide-tourmaline complex.

The preparation method of the porous tourmaline comprises the following steps: adding 1g of sodium silicate into 11g of water, uniformly stirring, adding 9g of tourmaline powder while stirring, pressing, molding, drying, sintering at 780 ℃ for 7 hours, and crushing to obtain the porous tourmaline.

The post-treatment comprises the following steps: washing with deionized water and anhydrous ethanol alternately for 3 times, and drying at 65 deg.C for 3.5 hr.

The specific method of the step (2) is as follows:

(2-1) firstly adding 1g of zinc oxide-tourmaline complex into 6g of 3- (2, 3-glycidoxy) propyl trimethoxy silane, stirring and reacting for 8 hours at 85 ℃, and filtering to obtain an epoxidized complex;

(2-2) adding the epoxy complex and 2.5g of the amino-terminated fluorine-containing polymer into a sodium hydroxide solution with the mass concentration of 30%, uniformly oscillating by ultrasonic waves, reacting at 90 ℃ for 17 hours in a nitrogen atmosphere, washing to be neutral, and drying at 45 ℃ for 18 hours to obtain the modified complex.

In the step (2), the amino-terminated fluorine-containing polymer is prepared by the following method: mixing 1g of hexafluorobutyl methacrylate and 2.5g of N, N' -dimethylformamide, heating to 60 ℃, adding 0.05g of cysteamine hydrochloride and 0.035g of azobisisobutyronitrile, stirring for reacting for 8 hours, dropwise adding triethylamine until the pH value is 8, adding 0.06g of formaldehyde aqueous solution with the mass concentration of 37%, fully stirring for 1 hour, distilling under reduced pressure to remove the solvent, and stirring and polymerizing for 35 minutes at 85 ℃ to obtain the compound preparation.

The specific method of the step (3) is as follows: immersing the modified complex in 6 times of 1-allyl-3-methylimidazolium tetrafluoroborate by weight, carrying out ultrasonic oscillation at 60 ℃ for 4 hours, and taking out to obtain the filler.

Comparative example 1

A method for preparing waterproof and breathable composite non-woven fabric comprises the steps of mixing and melting polyacrylonitrile, filler and water-soluble pore-forming agent, then spraying through a spinneret plate, air-flow drafting, net forming, hot-press bonding and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain a modified complex;

(3) and finally, soaking the modified complex in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the filler.

The mass ratio of polyacrylonitrile, filler and pore-foaming agent is 100: 2: 1, wherein the pore-foaming agent is polyethylene glycol 600.

The preparation method of the composite non-woven fabric comprises the following steps: mixing and melting polyacrylonitrile, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding and water immersion on the fiber web to remove the pore-forming agent to obtain the non-woven fabric.

The extrusion melt temperature was 350 ℃.

The aperture of the spinneret plate is 0.2 mm.

The temperature of the side cold air is 12 ℃, and the air speed is 1.5 m/s.

The speed of the air stream draw was 5000 m/min.

The technological conditions of the hot-pressing adhesion are as follows: the temperature is 150 ℃, and the linear pressure is 50 MPa.

The concrete method for treating the pore-foaming agent by water immersion comprises the following steps: soaking in 40 deg.C primary water for 12 hr, taking out, and air drying.

The specific method of the step (1) is as follows: putting 1g of zinc acetate into an agate mortar, grinding for 5 minutes, adding 0.4g of sodium tripolyphosphate, grinding for 40 minutes, adding 0.05g of sodium hydroxide, grinding for 30 minutes, adding 8g of porous tourmaline, grinding for 40 minutes, and performing post-treatment to obtain the zinc oxide-tourmaline complex.

The preparation method of the porous tourmaline comprises the following steps: adding 1g of sodium silicate into 12g of water, uniformly stirring, adding 8g of tourmaline powder while stirring, pressing, molding, drying, sintering at 800 ℃ for 5 hours, and crushing to obtain the porous tourmaline.

The post-treatment comprises the following steps: washing with deionized water and anhydrous ethanol alternately for 3 times, and drying at 60 deg.C for 4 hr.

The specific method of the step (2) is as follows:

(2-1) firstly adding 1g of zinc oxide-tourmaline complex into 5g of 3- (2, 3-glycidoxy) propyl trimethoxy silane, stirring and reacting for 6 hours at 90 ℃, and filtering to obtain an epoxidized complex;

(2-2) adding the epoxy complex and 3g of the amino-terminated fluorine-containing polymer into a sodium hydroxide solution with the mass concentration of 25%, uniformly oscillating by ultrasonic waves, reacting at 95 ℃ for 15 hours in a nitrogen atmosphere, washing to be neutral, and drying at 50 ℃ for 15 hours to obtain the modified complex.

In the step (2), the amino-terminated fluorine-containing polymer is prepared by the following method: firstly mixing 1g of hexafluorobutyl methacrylate and 3g of N, N' -dimethylformamide, heating to 60 ℃, adding 0.04g of cysteamine hydrochloride and 0.04g of azobisisobutyronitrile, stirring for reacting for 8 hours, dropwise adding triethylamine until the pH value is 8, then adding 0.05g of formaldehyde aqueous solution with the mass concentration of 37%, fully stirring for 1 hour, distilling under reduced pressure to remove the solvent, and stirring and polymerizing for 30 minutes at 90 ℃ to obtain the compound preparation.

The specific method of the step (3) is as follows: immersing the modified complex in 8 times of 1-allyl-3-methylimidazolium tetrafluoroborate by weight, and carrying out ultrasonic oscillation at 50 ℃ for 5 hours, and taking out to obtain the filler.

Comparative example 2

A preparation method of waterproof and breathable composite non-woven fabric comprises the steps of mixing and melting polyacrylonitrile, polyvinylidene fluoride, filler and water-soluble pore-forming agent, then spraying through a spinneret plate, air flow drafting, web forming, hot-press bonding and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain a modified complex;

(3) and finally, soaking the modified complex in 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the filler.

The mass ratio of polyacrylonitrile, polyvinylidene fluoride, filler and pore-foaming agent is 100: 15: 2: 1, wherein the pore-foaming agent is polyethylene glycol 600.

The preparation method of the composite non-woven fabric comprises the following steps: mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding on the fiber web and water immersion to remove the pore-forming agent to obtain the non-woven fabric.

The extrusion melt temperature was 350 ℃.

The aperture of the spinneret plate is 0.2 mm.

The temperature of the side cold air is 12 ℃, and the air speed is 1.5 m/s.

The speed of the air stream draw was 5000 m/min.

The technological conditions of the hot-pressing adhesion are as follows: the temperature is 150 ℃, and the linear pressure is 50 MPa.

The concrete method for treating the pore-foaming agent by water immersion comprises the following steps: soaking in 40 deg.C primary water for 12 hr, taking out, and air drying.

The specific method of the step (1) is as follows: and (2) putting 1g of zinc acetate into an agate mortar, grinding for 5 minutes, adding 0.4g of sodium tripolyphosphate, grinding for 40 minutes, adding 0.05g of sodium hydroxide, grinding for 30 minutes, adding 8g of tourmaline, grinding for 40 minutes, and performing post-treatment to obtain the zinc oxide-tourmaline complex.

The post-treatment comprises the following steps: washing with deionized water and anhydrous ethanol alternately for 3 times, and drying at 60 deg.C for 4 hr.

The specific method of the step (2) is as follows:

(2-1) firstly adding 1g of zinc oxide-tourmaline complex into 5g of 3- (2, 3-glycidoxy) propyl trimethoxy silane, stirring and reacting for 6 hours at 90 ℃, and filtering to obtain an epoxidized complex;

(2-2) adding the epoxy complex and 3g of the amino-terminated fluorine-containing polymer into a sodium hydroxide solution with the mass concentration of 25%, uniformly oscillating by ultrasonic waves, reacting at 95 ℃ for 15 hours in a nitrogen atmosphere, washing to be neutral, and drying at 50 ℃ for 15 hours to obtain the modified complex.

In the step (2), the amino-terminated fluorine-containing polymer is prepared by the following method: firstly mixing 1g of hexafluorobutyl methacrylate and 3g of N, N' -dimethylformamide, heating to 60 ℃, adding 0.04g of cysteamine hydrochloride and 0.04g of azobisisobutyronitrile, stirring for reacting for 8 hours, dropwise adding triethylamine until the pH value is 8, then adding 0.05g of formaldehyde aqueous solution with the mass concentration of 37%, fully stirring for 1 hour, distilling under reduced pressure to remove the solvent, and stirring and polymerizing for 30 minutes at 90 ℃ to obtain the compound preparation.

The specific method of the step (3) is as follows: immersing the modified complex in 8 times of 1-allyl-3-methylimidazolium tetrafluoroborate by weight, and carrying out ultrasonic oscillation at 50 ℃ for 5 hours, and taking out to obtain the filler.

Comparative example 3

A preparation method of waterproof and breathable composite non-woven fabric comprises the steps of mixing and melting polyacrylonitrile, polyvinylidene fluoride, filler and water-soluble pore-forming agent, then spraying through a spinneret plate, air flow drafting, web forming, hot-press bonding and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) omitting;

(3) then dipping the zinc oxide-tourmaline complex into 1-allyl-3-methylimidazole tetrafluoroborate for surface modification to obtain the filler.

The mass ratio of polyacrylonitrile, polyvinylidene fluoride, filler and pore-foaming agent is 100: 15: 2: 1, wherein the pore-foaming agent is polyethylene glycol 600.

The preparation method of the composite non-woven fabric comprises the following steps: mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding on the fiber web and water immersion to remove the pore-forming agent to obtain the non-woven fabric.

The extrusion melt temperature was 350 ℃.

The aperture of the spinneret plate is 0.2 mm.

The temperature of the side cold air is 12 ℃, and the air speed is 1.5 m/s.

The speed of the air stream draw was 5000 m/min.

The technological conditions of the hot-pressing adhesion are as follows: the temperature is 150 ℃, and the linear pressure is 50 MPa.

The concrete method for treating the pore-foaming agent by water immersion comprises the following steps: soaking in 40 deg.C primary water for 12 hr, taking out, and air drying.

The specific method of the step (1) is as follows: putting 1g of zinc acetate into an agate mortar, grinding for 5 minutes, adding 0.4g of sodium tripolyphosphate, grinding for 40 minutes, adding 0.05g of sodium hydroxide, grinding for 30 minutes, adding 8g of porous tourmaline, grinding for 40 minutes, and performing post-treatment to obtain the zinc oxide-tourmaline complex.

The preparation method of the porous tourmaline comprises the following steps: adding 1g of sodium silicate into 12g of water, uniformly stirring, adding 8g of tourmaline powder while stirring, pressing, molding, drying, sintering at 800 ℃ for 5 hours, and crushing to obtain the porous tourmaline.

The post-treatment comprises the following steps: washing with deionized water and anhydrous ethanol alternately for 3 times, and drying at 60 deg.C for 4 hr.

The specific method of the step (3) is as follows: immersing the zinc oxide-tourmaline complex in 8 times of 1-allyl-3-methylimidazolium tetrafluoroborate, and carrying out ultrasonic oscillation at 50 ℃ for 5 hours, and taking out to obtain the filler.

Comparative example 4

A preparation method of waterproof and breathable composite non-woven fabric comprises the steps of mixing and melting polyacrylonitrile, polyvinylidene fluoride, filler and water-soluble pore-forming agent, then spraying through a spinneret plate, air flow drafting, web forming, hot-press bonding and water immersion to remove the pore-forming agent, thus obtaining the composite non-woven fabric; wherein the filler is prepared by the following method:

(1) firstly, zinc acetate, sodium tripolyphosphate, sodium hydroxide and porous tourmaline are used as raw materials to prepare a zinc oxide-tourmaline complex through solid phase reaction;

(2) and then carrying out epoxy modification on the zinc oxide-tourmaline complex, and then reacting with an amino-terminated fluorine-containing polymer to obtain the filler.

The mass ratio of polyacrylonitrile, polyvinylidene fluoride, filler and pore-foaming agent is 100: 15: 2: 1, wherein the pore-foaming agent is polyethylene glycol 600.

The preparation method of the composite non-woven fabric comprises the following steps: mixing and melting polyacrylonitrile, polyvinylidene fluoride, a filler and a water-soluble pore-forming agent to obtain a hot melt, spraying the hot melt from a spinneret plate, cooling by side cold air to obtain a nascent filament, drafting the nascent filament by air flow to obtain fibers, forming a fiber web, and finally performing hot-press bonding on the fiber web and water immersion to remove the pore-forming agent to obtain the non-woven fabric.

The extrusion melt temperature was 350 ℃.

The aperture of the spinneret plate is 0.2 mm.

The temperature of the side cold air is 12 ℃, and the air speed is 1.5 m/s.

The speed of the air stream draw was 5000 m/min.

The technological conditions of the hot-pressing adhesion are as follows: the temperature is 150 ℃, and the linear pressure is 50 MPa.

The concrete method for treating the pore-foaming agent by water immersion comprises the following steps: soaking in 40 deg.C primary water for 12 hr, taking out, and air drying.

The specific method of the step (1) is as follows: putting 1g of zinc acetate into an agate mortar, grinding for 5 minutes, adding 0.4g of sodium tripolyphosphate, grinding for 40 minutes, adding 0.05g of sodium hydroxide, grinding for 30 minutes, adding 8g of porous tourmaline, grinding for 40 minutes, and performing post-treatment to obtain the zinc oxide-tourmaline complex.

The preparation method of the porous tourmaline comprises the following steps: adding 1g of sodium silicate into 12g of water, uniformly stirring, adding 8g of tourmaline powder while stirring, pressing, molding, drying, sintering at 800 ℃ for 5 hours, and crushing to obtain the porous tourmaline.

The post-treatment comprises the following steps: washing with deionized water and anhydrous ethanol alternately for 3 times, and drying at 60 deg.C for 4 hr.

The specific method of the step (2) is as follows:

(2-1) firstly adding 1g of zinc oxide-tourmaline complex into 5g of 3- (2, 3-glycidoxy) propyl trimethoxy silane, stirring and reacting for 6 hours at 90 ℃, and filtering to obtain an epoxidized complex;

(2-2) adding the epoxy complex and 3g of the amino-terminated fluorine-containing polymer into a sodium hydroxide solution with the mass concentration of 25%, uniformly oscillating by ultrasonic waves, reacting at 95 ℃ for 15 hours in a nitrogen atmosphere, washing to be neutral, and drying at 50 ℃ for 15 hours to obtain the modified complex.

In the step (2), the amino-terminated fluorine-containing polymer is prepared by the following method: firstly mixing 1g of hexafluorobutyl methacrylate and 3g of N, N' -dimethylformamide, heating to 60 ℃, adding 0.04g of cysteamine hydrochloride and 0.04g of azobisisobutyronitrile, stirring for reacting for 8 hours, dropwise adding triethylamine until the pH value is 8, then adding 0.05g of formaldehyde aqueous solution with the mass concentration of 37%, fully stirring for 1 hour, distilling under reduced pressure to remove the solvent, and stirring and polymerizing for 30 minutes at 90 ℃ to obtain the compound preparation.

Test examples

The nonwoven fabrics obtained in examples 1-3 and comparative examples 1-4 were subjected to performance tests, and the relevant detection standards were as follows:

FZ/T60005-91 determination of breaking Strength and elongation at Break of nonwoven Fabric;

GB/T5453-1997 determination of the air Permeability of textile fabrics;

GB/T4745-1997 test method for moisture resistance of fabric surfaces; YG (B)812-120 type fabric water permeability tester measures the water pressure resistance;

GB/T20944.3-2008 evaluation of antibacterial performance of textiles section 3: the jar shaking method. The strains are Candida albicans and Escherichia coli, and the concentration of the bacteria liquid is 10⁵～10⁷cfu/mL. Firstly, adding buffered normal saline and a dressing product into a triangular flask, sterilizing for 20min in 0.1MPa steam at 121 ℃ and cooling to room temperature, transferring 1mL of bacterial liquid by using a 1mL sterile graduated pipette, and adding the bacterial liquid into the triangular flask. To force the sample into contact with the bacteria, the shaker was shaken for several hours at 37 ℃. Spreading 0.1mL of the solution before and after shaking on nutrient agar culture medium, and performing constant temperature culture at 37 deg.C for 24 hr.

The detection results are shown in tables 1-3.

TABLE 1 results of mechanical Properties measurements

TABLE 2 Water repellency and air permeability test results

TABLE 4 results of the antibacterial Properties

	Candida albicans inhibitory rate (%)	Escherichia coli inhibitory rate (%)
			Example 1	≥99.9	≥99.9
Example 2	≥99.9	≥99.9
			Example 3	≥99.9	≥99.9
Comparative example 2	96.1	95.9
			Comparative example 3	90.2	89.6
Comparative example 4	87.7	85.9

As can be seen from tables 1 to 3, the nonwoven fabrics obtained in examples 1 to 3 have excellent mechanical properties, good waterproof and air-permeable properties, and excellent antibacterial properties.

Comparative example 1 omitting polyvinylidene fluoride, the mechanical properties and water resistance of the obtained nonwoven fabric were significantly deteriorated; comparative example 2 when preparing the filler, tourmaline replaces porous tourmaline, thus affecting the air permeability of the product and obviously deteriorating the sterilization performance; comparative example 3 in the preparation of filler, step (2) was omitted, resulting in poor compatibility of the filler, and further affecting the mechanical properties, waterproof properties and antibacterial properties of the nonwoven fabric; comparative example 4 in the preparation of the filler, step (3) was omitted, and ionic liquid surface modification was absent, resulting in significant deterioration of water resistance and antibacterial properties of the nonwoven fabric.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.