CN114540979B - Antifouling and antibacterial fabric for protective clothing and preparation method thereof - Google Patents

Antifouling and antibacterial fabric for protective clothing and preparation method thereof Download PDF

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CN114540979B
CN114540979B CN202210211713.7A CN202210211713A CN114540979B CN 114540979 B CN114540979 B CN 114540979B CN 202210211713 A CN202210211713 A CN 202210211713A CN 114540979 B CN114540979 B CN 114540979B
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antibacterial
microgel
fabric
antifouling
protective clothing
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CN114540979A (en
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袁强
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Jiangxi Feilikang Clothing Co ltd
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Jiangxi Feilikang Clothing Co ltd
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00Materials specially adapted for outerwear
    • A41D31/04Materials specially adapted for outerwear characterised by special function or use
    • A41D31/30Antimicrobial, e.g. antibacterial
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/04Dry spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/103Agents inhibiting growth of microorganisms
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses an antifouling and antibacterial fabric for protective clothing and a preparation method thereof. The preparation process is simplified, and the operation of further antibacterial treatment on the fabric is omitted; the anti-fouling antibacterial fabric for the protective clothing has good antibacterial effect, and can reduce adhesion and infiltration of dirt, so that the protective performance is further improved.

Description

Antifouling and antibacterial fabric for protective clothing and preparation method thereof
Technical Field
The invention relates to the technical field of fabrics, in particular to an antifouling and antibacterial fabric for protective clothing and a preparation method thereof.
Background
The protective clothing is mainly applied to the use under the environments of industry, electronics, medical treatment, chemical defense, bacterial infection prevention and the like, and has differences due to different protective purposes and protective principles. The existing protective clothing sold on the market has the problem of poor ventilation and moisture permeability, and the comfort level of the environment in the protective clothing is reduced due to the rising of temperature and humidity along with the increase of the working time of wearers. Users can feel extremely painful when working in high temperature and humidity environments for a long time, which will also affect their working efficiency. Therefore, the design principle of the protective clothing fabric needs to meet both national standard protective performance and wearing comfort.
The electrostatic spinning nanofiber has a unique three-dimensional structure, so that the porosity of the electrostatic spinning nanofiber is higher than that of melt-blown fabric, and the fabric has better air permeability. Because a large amount of static charges are carried in the electrostatic spinning nanofiber, electrostatic adsorption can be generated, and the electrostatic spinning nanofiber can be used as a filtering material and is expected to become an ideal antifouling and antibacterial fabric material for protective clothing in the future. The traditional single-component electrostatic spinning nanofiber fabric lacks of multifunction, and modification of the fabric improves the performance of the fabric, so that the problem to be solved is urgent.
CN 113430661A discloses an antifouling and antibacterial fabric for protective clothing, a preparation process thereof and an antifouling and antibacterial fabric for protective clothing, which comprises the following raw materials in parts by weight: 60-75 parts of meta-aramid fiber, 17-25 parts of titanium dioxide modified spandex, 17-25 parts of white carbon black modified polyester, 10-18 parts of rich fiber, 3-10 parts of bamboo charcoal fiber and 10-20 parts of polyimide fiber; the titanium dioxide modified spandex is prepared by adding titanium dioxide into the spandex after vacuum melting at 220-230 ℃, preserving heat for 20-25 min, stirring for 15-20 min at 57-59 rpm, and then spinning by a wet method; the white carbon black modified polyester is prepared by uniformly mixing white carbon black and polyester, vacuum melting at 260-270 ℃, preserving heat for 13-15min, and dry spinning. The invention has the advantages of light gram weight, good flame retardance, good high temperature resistance and high fiber strength.
CN 112189918A discloses a reusable anti-fouling and antibacterial fabric for protective clothing and a preparation process thereof, wherein the anti-fouling and antibacterial fabric for protective clothing is composed of two layers of materials, the surface layer is active chlorine modified high-density nylon, and the inner layer is polyurethane nanofiber membrane. The preparation method comprises the steps of firstly, soaking chinlon in a mixed solution containing active chlorine with the concentration of 1000-10000ppm and a nonionic surfactant TX-100 to obtain the surface active chlorine modified high-density chinlon; adding thermoplastic polyurethane granules into an N, N-dimethylformamide solvent to prepare a polyurethane solution; carrying out electrostatic spinning to obtain a thermoplastic polyurethane nanofiber membrane; the prepared active chlorine modified high-density nylon is used as a surface layer, the polyurethane nanofiber membrane is used as an inner layer, and the active chlorine modified high-density nylon is coated on the polyurethane nanofiber membrane to form the antifouling and antibacterial fabric for protective clothing. The nylon fabric modified by active chlorine for the antifouling and antibacterial fabric of the protective clothing has the same rapid and efficient sterilization and virus killing performance.
CN 113584893A discloses a nanofiber medical thermal insulation protective clothing fabric and a preparation method thereof, wherein nonwoven fabric textile fibers are used as base fabric, single-sided magnetron sputtering nanoparticle coating is carried out, and treated nonwoven fabric is obtained; dissolving and dispersing a polymer and zinc oxide nano particles in a spinning solvent to obtain a polymer spinning solution; and (3) carrying out coaxial electrostatic spinning to obtain a polymer particle composite nano film serving as an intermediate layer, respectively taking the treated non-woven fabric as a surface layer and a bottom layer, and bonding by ultrasonic waves to obtain the medical heat-insulating protective clothing fabric integrating the functions of electrostatic spinning ventilation, hollow fiber heat preservation, anion antibacterial, antistatic and the like, wherein the medical heat-insulating protective clothing fabric has comfort and protection safety. The fabric prepared by the method has the dual advantages of nano materials and fiber materials, and is particularly suitable for serving as a heat insulation material.
In the prior art, the method for preparing the protective clothing fabric through electrostatic spinning is complex, and the effects of sterilization, ventilation and the like can be achieved only through additional infiltration operation. It is necessary to mix the functional material with the fiber precursor and spin the fabric to make the protective garment.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the technical problems to be solved by the present invention are: (1) The antifouling and antibacterial fabric for the protective clothing is provided, so that the antifouling and antibacterial fabric has good antibacterial performance and air permeability; (2) The mechanical property of the antifouling and antibacterial fabric for the protective clothing is improved, and the antifouling and antibacterial fabric has antifouling capacity; (3) The dyeing performance of the dye on the antifouling and antibacterial fabric for the protective clothing is improved.
Because of the special use environment, compared with common clothes, the antifouling and antibacterial fabric for protective clothing has higher requirements on antibacterial performance. In order to make the antifouling and antibacterial fabric for protective clothing have a certain antibacterial property, antibacterial substances are often introduced into the antifouling and antibacterial fabric for protective clothing by adopting a soaking treatment or an antibacterial coating deposition mode in the prior art. The mode of soaking the fabric by adopting the antibacterial agent solution has the characteristic of simple operation, but a large amount of antibacterial treatment liquid is needed in the treatment process, so that waste is easy to cause, and the pollution of waste liquid to the environment is large; in addition, the antibacterial components are fixed in the fabric in a physical adsorption mode, the attaching capability is limited, and the antibacterial effect is unstable. The antibacterial coating is prepared on the surface of the fabric, and the fabric and the coating are combined in a grafting or crosslinking mode, so that the fabric is poor in air permeability due to the fact that the coating is compact in texture after grafting or crosslinking, heat and sweat are difficult to dissipate in the long-term wearing process, and the wearing comfort level is greatly reduced.
In order to meet both the requirements of antibacterial property and air permeability, in long-term production practice, the inventors tried to introduce antibacterial substances directly into the spinning dope of dry spinning to make the fiber bodies constituting the fabric antibacterial. However, the inventors have observed that in order to smoothly spray the spinning dope, the spinning dope should be maintained in a relatively viscous state, and thus the dispersibility is poor due to the direct addition of the antibacterial substance. Because the antibacterial substance particles are tiny and easy to aggregate, the antibacterial substance particles are difficult to disperse and spread in the spinning solution, and the prepared fabric has poor uniformity. The inventor makes improvement on the method, firstly, microgel particles with shell-core structures are prepared, antibacterial substances are dispersed in the microgel particles under the environment of lower viscosity, and microgels with antibacterial performance are obtained. Because the microgel is polymer particles with an intramolecular cross-linking structure, and the compatibility of the polymer particles with organic materials and solvents in the spinning solution is better, the microgel has good dispersibility in the spinning solution, thereby promoting the dispersion of antibacterial substances and improving the uniformity of the antibacterial substances in the fabric. Specifically, the inventors used silver nitrate as an antimicrobial silver ion source and polyetherimide as the shell of the core-shell structured microgel; compared with a dispersion system formed by physical diffusion, silver ions can participate in the process of forming hydrogen bonds by polyetherimide, and amino groups or carbonyl groups on the surface of the polyetherimide shell are tightly combined into a polymer network of the shell, so that the retention of antibacterial substances is facilitated.
The preparation method of the antifouling and antibacterial fabric for the protective clothing comprises the following steps:
(1) Uniformly mixing a polymerization monomer solution and polyetherimide, adding ammonium persulfate to react, and removing a water phase to obtain polyetherimide microgel;
(2) Uniformly mixing polyetherimide microgel and silver nitrate aqueous solution, and removing aqueous phase to obtain silver-containing microgel;
(3) And (3) co-dissolving silver-containing microgel and polyacrylonitrile in a solvent, uniformly mixing to obtain a microgel spinning stock solution, and spinning into cloth by a dry method to obtain the antifouling and antibacterial fabric for protective clothing.
Further preferably, the preparation method of the antifouling and antibacterial fabric for protective clothing comprises the following steps in parts by weight:
s1, 14-18 parts of monomer is dissolved in 90-150 parts of water to obtain a polymerized monomer solution;
s2, adding 70-90 parts of polyetherimide into the polymerization monomer solution obtained in the step S1 in an oxygen-free environment, and mixing; adding 0.16-0.8 part of ammonium persulfate after the completion of the mixing, and separating and removing a water phase after the reaction to obtain polyetherimide microgel;
s3, mixing 32.5-58 parts of aqueous solution of silver nitrate with the polyetherimide microgel obtained in the step S2, combining silver ions with the polyetherimide microgel through dispersion operation, and then separating and removing water phase to obtain silver-containing microgel;
s4, uniformly mixing the silver-containing microgel obtained in the step S3, 9-15 parts of polyacrylonitrile and 15-30 parts of solvent to obtain a microgel spinning solution, and spinning into cloth by a dry method to obtain the antifouling and antibacterial fabric for protective clothing.
Preferably, the monomer is N-ethylacrylamide.
Preferably, the temperature of the reaction in the step S2 is 105-120 ℃ and the reaction time is 1-3 h; the separation uses centrifugal separation, the centrifugal speed is 12000-16000 rpm, and the centrifugal time is 15-30 min.
Preferably, the dispersing operation in step S3 is as follows: carrying out ultrasonic treatment for 5-15 min at 80-100 ℃, wherein the ultrasonic power is 550-800W, and the ultrasonic frequency is 28-40 kHz; the separation uses centrifugal separation, the centrifugal speed is 12000-16000 rpm, and the centrifugal time is 15-30 min.
Preferably, the solvent is any one of tetrahydrofuran, trifluoroethanol, dichloromethane and chloroform.
Preferably, the spinneret aperture of the dry spinning in the step S4 is 0.12-0.2 mm, the solidification temperature is 70-85 ℃, and the coiling speed is 200-400 m/min.
In the production of antifouling and antibacterial fabrics for protective apparel, the inventors have observed that the formation of the inner core is critical to the preparation of core-shell structured microgel spheres by emulsion polymerization. The process of crosslinking nucleation after polymerization of N-ethyl acrylamide monomer is slower, and the phenomenon that an outer shell structure is difficult to form due to too small inner core is often accompanied in actual production, so that the prepared microgel has structural defects. Microgels with structural defects are difficult to effectively fix antibacterial components, and simultaneously, the exposed N-ethyl acrylamide inner core can continuously react with monomers to form long chains, so that the polymerization of normal microgels is seriously affected.
For the consideration of operability, the viscosity of the spinning solution is controlled in a proper range according to the requirement, so that the spinning solution is prevented from being too low in viscosity to be formed and the spinning failure caused by too high viscosity is avoided. Each component in the spinning solution has certain fluidity, and organic components in the solution are heated and solidified into filaments along with the spinning. The microgel and the matrix are converted from a liquid phase to a solid phase, and in the process, the compatibility between the microgel and the matrix is reduced due to the removal of the original solvent, and the internal phase structure may be changed after solidification, so that the uniformity of the structure is weakened and the comprehensive performance is reduced.
Aiming at the defects of the antifouling and antibacterial fabric for protective clothing, the inventor makes further optimization to prepare the antifouling and antibacterial fabric. The inventor adds N, N-methylene bisacrylamide in the preparation process of the microgel, the N, N-methylene bisacrylamide can carry out self-crosslinking, the N, N-methylene bisacrylamide after self-crosslinking reacts with N-ethylacrylamide, the nucleation speed is higher, and the formation of a shell-core structure and the improvement of the stability of the microgel are facilitated. The inventor continuously reacts the prepared microgel with vinyl methyl diethoxy silane, and introduces a long-chain structure on the surface of the microgel, thereby being beneficial to the dispersion of the microgel; in the heating and curing process, the silicon-oxygen bonds are heated to react to form a cross-arranged net structure, so that the strength of the silk fiber and the comprehensive performance of the fabric are improved. Due to the existence of the siloxane bond network structure, the hydrophobicity of the fabric is enhanced, the adhesion and infiltration of dirt can be prevented, and the protection effect of the antifouling and antibacterial fabric is enhanced.
In addition, the inventor reacts the microgel prepared with vinyl methyl diethoxy silane and 3-amino propyl triethoxy silane together to enhance the crosslinking effect, and a more stable silicon-oxygen bond network structure can be formed on the surface of the fabric after electrostatic spinning, so that the hydrophobicity of the fabric is further improved. In addition, compared with the fabric which is not treated by the 3-aminopropyl triethoxy silane, the fabric prepared by the common reaction has better absorption performance for dye, and the dyeing performance is obviously improved.
Further preferably, the monomer is a mixture of N-ethylacrylamide and N, N-methylenebisacrylamide according to the mass ratio of (14-18) to (1.6-2.1).
Further preferably, the step S3 may further be: mixing 32.5-58 parts by weight of silver nitrate aqueous solution with the polyetherimide microgel obtained in the step S2, and combining silver ions with the polyetherimide microgel through dispersion operation to obtain silver-containing microgel suspension; the obtained silver-containing microgel suspension reacts with 3.5 to 14 parts of vinyl methyl diethoxy silane, and the water phase is removed by separation to obtain the antibacterial polyetherimide microgel for standby.
Most preferably, the step S3 may further be: mixing 32.5-58 parts by weight of silver nitrate aqueous solution with the polyetherimide microgel obtained in the step S2, and combining silver ions with the polyetherimide microgel through dispersion operation to obtain silver-containing microgel suspension; and (3) reacting the silver-containing microgel suspension with 3-10 parts of vinyl methyl diethoxy silane and 0.5-4 parts of 3-aminopropyl triethoxy silane, and separating to remove the water phase to obtain the antibacterial polyetherimide microgel.
Further preferably, the step S4 may further be: and (3) taking the antibacterial polyetherimide microgel obtained in the step (S3), 9-15 parts of polyacrylonitrile and 15-30 parts of solvent to be uniformly mixed to obtain a microgel spinning solution, and spinning into cloth by a dry method to obtain the antifouling and antibacterial fabric for protective clothing.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the invention.
The invention has the following description and functions of partial raw materials in the formula:
n-ethyl acrylamide: an organic matter, colorless liquid. The invention is used as monomer raw material for preparing microgel inner core by emulsion polymerization.
N, N-methylenebisacrylamide: an organic matter, white powdery crystal, can be self-crosslinked under high temperature or strong light. As a raw material for preparing the microgel, the self-crosslinking property of the self-crosslinking type microgel is used for nucleation firstly and then reacts with N-ethylacrylamide to form a microgel core.
The invention has the beneficial effects that:
compared with the prior art, the invention prepares the fabric with antibacterial property by dispersing antibacterial components in microgel, taking the microgel as a spinning raw material, and spinning into cloth through dry spinning; simplifying the preparation process and omitting the operation of further antibacterial treatment on the fabric.
Compared with the prior art, the microgel with the shell-core structure can be effectively combined with antibacterial components, so that the dispersibility and stability of antibacterial substances in spinning solution are improved, and the antibacterial activity of the antifouling and antibacterial fabric can be still maintained after repeated washing.
Compared with the prior art, the antifouling and antibacterial fabric for the protective clothing has excellent mechanical property and good air permeability; the antibacterial agent has good antibacterial effect, and can reduce adhesion and infiltration of dirt, so that the protective performance is further improved.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The comparative example and the examples of the present invention have the following parameters of part of raw materials:
n-ethyl acrylamide, CAS no: 5883-17-0;
n, N-methylenebisacrylamide, CAS number: 110-26-9.
Example 1
The antifouling and antibacterial fabric for the protective clothing is prepared by the following method:
s1, dissolving 14kg of N-ethyl acrylamide in 120kg of water to obtain a polymerized monomer solution for later use;
under the protection of S2 nitrogen, 78kg of polyether imide is added into the polymerization monomer solution obtained in the step S1, and the mixture is mixed; after the mixing is completed, 0.35kg of ammonium persulfate is added, the temperature is raised to 115 ℃ and the mixture is reacted for 2 hours at the temperature; centrifuging at 14000rpm for 25min to remove water phase to obtain polyetherimide microgel;
s3, dissolving 4.5kg of silver nitrate in 40kg of water to obtain an aqueous solution of silver nitrate; mixing the aqueous solution of silver nitrate with the polyetherimide microgel obtained in the step S2, and carrying out ultrasonic treatment at 85 ℃ for 8min, wherein the ultrasonic power is 550W, and the ultrasonic frequency is 40kHz; combining silver ions with polyetherimide microgel, and then centrifugally separating at a speed of 12000rpm for 20min to remove water phase, so as to obtain silver-containing microgel for later use;
s4, taking the silver-containing microgel obtained in the step S3 and 12kg of polyacrylonitrile to be co-dissolved in 22kg of tetrahydrofuran, so as to obtain a microgel spinning solution; the microgel spinning solution is subjected to dry spinning and spinning to obtain cloth, so that the antifouling and antibacterial fabric for protective clothing is obtained, the density of the antifouling and antibacterial fabric for protective clothing is 210T, and the yarn is 70D-70D.
The aperture of the spinneret plate for dry spinning in the step S4 is 0.16mm, the solidification temperature is 85 ℃, and the coiling speed is 240m/min.
Example 2
An antifouling and antibacterial fabric is prepared by the following method:
s1, dissolving 14kg of N-ethyl acrylamide and 1.8kg of N, N-methylene bisacrylamide in 120kg of water to obtain a polymerized monomer solution for later use;
under the protection of S2 nitrogen, 78kg of polyether imide is added into the polymerization monomer solution obtained in the step S1, and the mixture is mixed; after the mixing is completed, 0.35kg of ammonium persulfate is added, the temperature is raised to 115 ℃ and the mixture is reacted for 2 hours at the temperature; centrifuging at 14000rpm for 25min to remove water phase to obtain polyetherimide microgel;
s3, dissolving 4.5kg of silver nitrate in 40kg of water to obtain an aqueous solution of silver nitrate; mixing the aqueous solution of silver nitrate with the polyetherimide microgel obtained in the step S2, and carrying out ultrasonic treatment at 85 ℃ for 8min, wherein the ultrasonic power is 550W, and the ultrasonic frequency is 40kHz; combining silver ions with polyetherimide microgel, and then centrifugally separating at a speed of 12000rpm for 20min to remove water phase, so as to obtain silver-containing microgel for later use;
s4, taking the silver-containing microgel obtained in the step S3 and 12kg of polyacrylonitrile to be co-dissolved in 22kg of tetrahydrofuran, so as to obtain a microgel spinning solution; the microgel spinning solution is subjected to dry spinning and weaving to obtain the antifouling and antibacterial fabric, wherein the density of the antifouling and antibacterial fabric is 210T, and the yarn is 70D-70D.
The aperture of the spinneret plate for dry spinning in the step S4 is 0.16mm, the solidification temperature is 85 ℃, and the coiling speed is 240m/min.
Example 3
An antifouling and antibacterial fabric is prepared by the following method:
s1, dissolving 14kg of N-ethyl acrylamide in 120kg of water to obtain a polymerized monomer solution for later use;
under the protection of S2 nitrogen, 78kg of polyether imide is added into the polymerization monomer solution obtained in the step S1, and the mixture is mixed; after the mixing is completed, 0.35kg of ammonium persulfate is added, the temperature is raised to 115 ℃ and the mixture is reacted for 2 hours at the temperature; centrifuging at 14000rpm for 25min to remove water phase to obtain polyetherimide microgel;
s3, dissolving 4.5kg of silver nitrate in 40kg of water to obtain an aqueous solution of silver nitrate; mixing the aqueous solution of silver nitrate with the polyetherimide microgel obtained in the step S2, and carrying out ultrasonic treatment at 85 ℃ for 8min, wherein the ultrasonic power is 550W, and the ultrasonic frequency is 40kHz; combining silver ions with polyetherimide microgel to obtain silver-containing microgel suspension for later use;
s4, adding 7kg of vinyl methyl diethoxy silane into the silver-containing microgel suspension obtained in the step S3, and reacting for 1.5 hours at 72 ℃; centrifuging at 12000rpm for 20min after the reaction is finished to remove the water phase, thus obtaining the antibacterial polyetherimide microgel for later use;
s5, taking the antibacterial polyetherimide microgel obtained in the step S4 and 12kg of polyacrylonitrile to be co-dissolved in 22kg of tetrahydrofuran to obtain a microgel spinning solution; the microgel spinning solution is subjected to dry spinning and weaving to obtain the antifouling and antibacterial fabric, wherein the density of the antifouling and antibacterial fabric is 210T, and the yarn is 70D-70D.
The aperture of the spinneret plate for dry spinning in the step S5 is 0.16mm, the solidification temperature is 85 ℃, and the coiling speed is 240m/min.
Example 4
An antifouling and antibacterial fabric is prepared by the following method:
s1, dissolving 14kg of N-ethyl acrylamide and 1.8kg of N, N-methylene bisacrylamide in 120kg of water to obtain a polymerized monomer solution for later use;
under the protection of S2 nitrogen, 78kg of polyether imide is added into the polymerization monomer solution obtained in the step S1, and the mixture is mixed; after the mixing is completed, 0.35kg of ammonium persulfate is added, the temperature is raised to 115 ℃ and the mixture is reacted for 2 hours at the temperature; centrifuging at 14000rpm for 25min to remove water phase to obtain polyetherimide microgel;
s3, dissolving 4.5kg of silver nitrate in 40kg of water to obtain an aqueous solution of silver nitrate; mixing the aqueous solution of silver nitrate with the polyetherimide microgel obtained in the step S2, and carrying out ultrasonic treatment at 85 ℃ for 8min, wherein the ultrasonic power is 550W, and the ultrasonic frequency is 40kHz; combining silver ions with polyetherimide microgel to obtain silver-containing microgel suspension for later use;
s4, adding 7kg of vinyl methyl diethoxy silane into the silver-containing microgel suspension obtained in the step S3, and reacting for 1.5 hours at 72 ℃; centrifuging at 12000rpm for 20min after the reaction is finished to remove the water phase, thus obtaining the antibacterial polyetherimide microgel for later use;
s5, taking the antibacterial polyetherimide microgel obtained in the step S4 and 12kg of polyacrylonitrile to be co-dissolved in 22kg of tetrahydrofuran to obtain a microgel spinning solution; the microgel spinning solution is subjected to dry spinning and weaving to obtain the antifouling and antibacterial fabric, wherein the density of the antifouling and antibacterial fabric is 210T, and the yarn is 70D-70D.
The aperture of the spinneret plate for dry spinning in the step S5 is 0.16mm, the solidification temperature is 85 ℃, and the coiling speed is 240m/min.
Example 5
An antifouling and antibacterial fabric is prepared by the following method:
s1, dissolving 14kg of N-ethyl acrylamide and 1.8kg of N, N-methylene bisacrylamide in 120kg of water to obtain a polymerized monomer solution for later use;
under the protection of S2 nitrogen, 78kg of polyether imide is added into the polymerization monomer solution obtained in the step S1, and the mixture is mixed; after the mixing is completed, 0.35kg of ammonium persulfate is added, the temperature is raised to 115 ℃ and the mixture is reacted for 2 hours at the temperature; centrifuging at 14000rpm for 25min to remove water phase to obtain polyetherimide microgel;
s3, dissolving 4.5kg of silver nitrate in 40kg of water to obtain an aqueous solution of silver nitrate; mixing the aqueous solution of silver nitrate with the polyetherimide microgel obtained in the step S2, and carrying out ultrasonic treatment at 85 ℃ for 8min, wherein the ultrasonic power is 550W, and the ultrasonic frequency is 40kHz; combining silver ions with polyetherimide microgel to obtain silver-containing microgel suspension for later use;
s4, adding 5kg of vinyl methyl diethoxy silane and 2kg of 3-aminopropyl triethoxy silane into the silver-containing microgel suspension obtained in the step S3, and reacting for 1.5 hours at 72 ℃; centrifuging at 12000rpm for 20min after the reaction is finished to remove the water phase, thus obtaining the antibacterial polyetherimide microgel for later use;
s5, taking the antibacterial polyetherimide microgel obtained in the step S4 and 12kg of polyacrylonitrile to be co-dissolved in 22kg of tetrahydrofuran to obtain a microgel spinning solution; the microgel spinning solution is subjected to dry spinning and weaving to obtain the antifouling and antibacterial fabric, wherein the density of the antifouling and antibacterial fabric is 210T, and the yarn is 70D-70D.
The aperture of the spinneret plate for dry spinning in the step S5 is 0.16mm, the solidification temperature is 85 ℃, and the coiling speed is 240m/min.
Comparative example 1
The breathable fabric is prepared by the following steps: taking 12kg of polyacrylonitrile and dissolving the polyacrylonitrile in 22kg of tetrahydrofuran to obtain spinning solution; the spinning solution is subjected to dry spinning and weaving to obtain the breathable fabric, wherein the density of the breathable fabric is 210T, and the yarns are 70D.
Test example 1
The antifouling and antibacterial fabric for protective clothing is sampled, the samples are divided into three groups, 3 small samples are taken from each group, the sizes of the small samples are 10cm multiplied by 10cm, and the small samples are cut into 2 pieces on average. Of the three groups of samples, the first group was not subjected to the washing operation, the second group was washed 50 times, and the third group was washed 100 times; the washing operation was carried out with reference to specific steps in GB/T8629-2017 household washing and drying program for textile test, washing using a standard washing machine of type C, washing program number 4N. Three groups of antibacterial properties were tested, test reference GB/T20944.2-2007, evaluation of antibacterial properties of textiles section 2: the specific steps in the absorption method are carried out. The result of bacteriostasis rate is obtained according to the required average value of the arithmetic and is repaired to the whole digit. The results of the antibacterial properties of the antifouling and antibacterial fabrics for protective clothing after washing are shown in table 1.
TABLE 1
According to the definition in GB/T20944.2-2007, when the bacteriostasis rate is more than or equal to 90%, the sample has an antibacterial effect; when the antibacterial rate is more than or equal to 99%, the sample has good antibacterial effect. As can be seen from the comparison between the examples and the comparative examples, the antifouling and antibacterial fabric can still maintain good antibacterial effect after being washed for a plurality of times. The reason for this phenomenon may be that the antibacterial substance is dispersed in the microgel particles under the environment of low viscosity, and the microgel is a polymer particle with an intramolecular cross-linking structure, so that the compatibility between the microgel and the organic raw material and the solvent in the spinning solution is better, and the microgel has good dispersibility in the spinning solution, thereby promoting the dispersion of the antibacterial substance and improving the antibacterial property of the fabric; compared with a dispersion system formed by physical diffusion, silver ions can participate in the process of forming hydrogen bonds by polyetherimide, and amino or carbonyl on the surface of the polyetherimide shell is tightly combined into a polymer network of the shell, so that the retention of antibacterial substances is facilitated, and antibacterial components in the fabric can still exert an effect after multiple times of washing. In addition, in the heating and curing process, the fibers of the antifouling and antibacterial fabric react to form a cross-arranged reticular structure due to the heating of the silicon-oxygen bonds, the hydrophobicity is enhanced, the adhesion of dirt is reduced, and the antibacterial performance of the fabric is possibly improved. Based on the above effects, example 5, in which vinylmethyldiethoxysilane and 3-aminopropyl triethoxysilane were added to react with microgel together, had the best antibacterial performance, and the antibacterial performance was not significantly reduced after 100 times of washing. This is probably because vinyl methyl diethoxy silane and 3-amino propyl triethoxy silane produce crosslinking, and form a network structure formed by interconnecting siloxane bonds with a more stable three-dimensional structure after electrostatic spinning, so that antibacterial components are stabilized, and the overall hydrophobicity is enhanced.
Test example 2
The air permeability of the antifouling and antibacterial fabric for protective clothing is carried out by referring to the specific requirements in GB/T5453-1997 determination of air permeability of textile fabrics. Test area of 20cm 2 The test pressure drop was 100Pa and the remaining test steps were in accordance with the criteria described above. Each group tested 5 samples and the results were arithmetically averaged. The results of the air permeability test of the antifouling and antibacterial fabric for protective clothing are shown in table 2.
TABLE 2
Test set Air permeability (mm/s)
Example 1 183
Example 2 186
Example 3 191
Example 4 197
Example 5 201
Comparative example 1 174
The air permeability reflects the good and bad air permeability of the clothes. As can be seen from the comparison between the examples and the comparative examples, the air permeability of the fabric used in the invention is more than or equal to 180mm/s, which means that the antibacterial fabric prepared by the processing method of the invention has good air permeability, is not stuffy after being worn, and is beneficial to improving the comfort of the antifouling antibacterial fabric. The reason for this phenomenon may be that the antibacterial component is dispersed in the microgel, and the microgel is used as a raw material of spinning stock solution, and the fabric with antibacterial performance is directly manufactured by dry spinning and spinning into cloth; compared with the traditional method for carrying out subsequent soaking treatment or depositing a coating to increase the antibacterial property, the fabric disclosed by the invention has the advantages that the fibers are more loose and breathable, and the surface layer is not provided with a compact antibacterial coating, so that sweat can be discharged smoothly.
Test example 3
Rectangular long strip-shaped test pieces with the dimensions of 200mm×50mm were taken on antifouling and antibacterial fabrics for protective clothing, and the tear strength of the test pieces was tested. The test of the tearing strength is carried out with reference to the specific requirements of GB/T3917.2-2009 "determination of the tearing Strength of trouser samples (Single slit) part 2 of the tearing Property of textile fabrics". Cutting a slit which is 100mm long and parallel to the length direction from the center of the width direction according to the requirement of the sample, and testing; the tensile speed was measured at 100mm/min and the gauge length at 100mm. Each group tested 5 samples and the results were arithmetically averaged. The results of the tear strength test for the anti-fouling antibacterial fabric for protective apparel are shown in table 3.
TABLE 3 Table 3
Test set Tear strength (N)
Example 1 36.5
Example 2 37.2
Example 3 40.3
Example 4 43.0
Example 5 43.8
Comparative example 1 38.1
The tearing strength represents the firmness degree of the combination between the fibers of the clothes. As a fabric for protecting clothing, the antifouling and antibacterial fabric for protecting clothing should have high tearing strength to prevent breakage during use. As can be seen from the comparison of the above examples and comparative examples, example 5 has the highest tear strength. The reason for the generation of the result is probably that the microgel prepared by the method continuously reacts with vinyl methyl diethoxy silane and 3-aminopropyl triethoxy silane, and a long-chain structure is introduced on the surface of the microgel, so that the microgel is beneficial to dispersion; the introduction of more amino groups has a certain repulsive interaction with the gel matrix, so that the reaction rate at the initial stage of the crosslinking is reduced, and the structural defect caused by local aggregation is prevented; in the heating and curing process, the silicon-oxygen bonds are heated to form a network structure formed by interconnecting the silicon-oxygen bonds with a more stable three-dimensional structure, so that the strength of the silk fiber and the tearing strength of the fabric are improved.
Test example 4
The antifouling and antibacterial fabric for protective clothing prepared by the invention is dyed. Immersing the fabric in a dyeing liquid, wherein the bath ratio of the fabric to the dyeing liquid is 1:20kg/L, pH of the dyeing liquid is 6, and the concentration of the dyeing agent is C.I. acid yellow 114; heating to 90 ℃ at a heating rate of 1.5 ℃/min at 25 ℃ and maintaining for 60min; and after dyeing, fishing out and hanging the fabric until no free liquid falls, then soaking the fabric in 2g/L nonionic detergent water solution, heating to 90 ℃, washing for 10min, fishing out the fabric after finishing, and drying at 80 ℃ for 3h to obtain the dyed fabric.
The soaping-resistant color fastness of the fabric is tested by referring to GB/T3921-2008 "textile color fastness test soaping-resistant color fastness". As shown in Table 4, the higher the grade, the less likely to fade during washing and the better the color fastness.
TABLE 4 Table 4
From the results in Table 4, it can be seen that example 5 has the highest color fastness. The reason for this result may be that the crosslinking of vinylmethyldiethoxysilane, 3-aminopropyl triethoxysilane introduces stable amino groups, and the increased number of protonatable sites enhances the interaction between dye molecules and the fabric, thereby increasing dye penetration in the fabric; based on the electrostatic spinning process, the silica bonds on the surface of the fabric are not only on the outer surface of the fabric, but also are connected with the microcavity structure of the fabric fibers, once dye molecules are absorbed into the fibers, the molecular weight and plane configuration of the dye molecules are extended, the formation of intermolecular hydrogen bonds and Van der Waals forces is promoted, and the formation of the dye molecules with good washing fastness is enhanced.

Claims (7)

1. The preparation method of the antifouling and antibacterial fabric for the protective clothing is characterized by comprising the following steps of:
s1, dissolving 14-18 parts of monomer in 90-150 parts of water to obtain a polymerized monomer solution;
s2, adding 70-90 parts of polyetherimide into the polymerization monomer solution obtained in the step S1 in an oxygen-free environment, and mixing; adding 0.16-0.8 part of ammonium persulfate after the completion of the mixing, and separating and removing a water phase after the reaction to obtain polyetherimide microgel;
s3, mixing 32.5-58 parts of aqueous solution of silver nitrate with the polyetherimide microgel obtained in the step S2, and combining silver ions with the polyetherimide microgel through dispersion operation to obtain silver-containing microgel suspension; reacting the silver-containing microgel suspension, 3-10 parts of vinyl methyl diethoxy silane and 0.5-4 parts of 3-aminopropyl triethoxy silane, and separating to remove a water phase to obtain an antibacterial polyetherimide microgel;
s4, uniformly mixing the antibacterial polyetherimide microgel obtained in the step S3, 9-15 parts of polyacrylonitrile and 15-30 parts of solvent to obtain a microgel spinning solution, and spinning into cloth by a dry method to obtain an antifouling and antibacterial fabric for protective clothing;
the monomer is N-ethyl acrylamide and N, N-methylene bisacrylamide which are mixed according to the mass ratio of (14-18) (1.6-2.1).
2. The method for preparing the antifouling and antibacterial fabric for protective clothing according to claim 1, wherein: and in the step S2, the reaction temperature is 105-120 ℃ and the reaction time is 1-3 h.
3. The method for preparing the antifouling and antibacterial fabric for protective clothing according to claim 1, wherein: and (3) in the step (S2), centrifugal separation is adopted, the centrifugal speed is 12000-16000 rpm, and the centrifugal time is 15-30 min.
4. The method for producing an antifouling and antibacterial fabric for protective clothing according to claim 1, wherein the dispersing operation in step S3 is: and carrying out ultrasonic treatment for 5-15 min at the temperature of 80-100 ℃, wherein the ultrasonic power is 550-800W, and the ultrasonic frequency is 28-40 kHz.
5. The method for preparing the antifouling and antibacterial fabric for protective clothing according to claim 1, wherein: and in the step S3, centrifugal separation is used, the centrifugal speed is 12000-16000 rpm, and the centrifugal time is 15-30 min.
6. The method for preparing the antifouling and antibacterial fabric for protective clothing according to claim 1, wherein: and in the step S4, the aperture of a spinneret plate for dry spinning is 0.12-0.2 mm, the solidification temperature is 70-85 ℃, and the coiling speed is 200-400 m/min.
7. A antifouling antibacterial surface fabric for protective clothing, its characterized in that: the method according to any one of claims 1 to 6.
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