WO2022053075A1 - Thermally comfortable pm2.5-proof nanofiber mask filter element and manufacturing method therefor - Google Patents

Thermally comfortable pm2.5-proof nanofiber mask filter element and manufacturing method therefor Download PDF

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Publication number
WO2022053075A1
WO2022053075A1 PCT/CN2021/126729 CN2021126729W WO2022053075A1 WO 2022053075 A1 WO2022053075 A1 WO 2022053075A1 CN 2021126729 W CN2021126729 W CN 2021126729W WO 2022053075 A1 WO2022053075 A1 WO 2022053075A1
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filter element
nanofiber
solution
spinning solution
mask
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PCT/CN2021/126729
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French (fr)
Chinese (zh)
Inventor
蔡容容
雷杨
张立志
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华南理工大学
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Publication of WO2022053075A1 publication Critical patent/WO2022053075A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
    • A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/02—Layered materials
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B23/00—Filters for breathing-protection purposes
    • A62B23/02—Filters for breathing-protection purposes for respirators
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B7/00—Respiratory apparatus
    • A62B7/10—Respiratory apparatus with filter elements
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/20—Halides of elements of Groups 4 or 14 of the Periodic Table, e.g. zirconyl chloride
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides

Definitions

  • the invention belongs to the technical field of air filter materials, and in particular relates to a thermal comfort and PM 2.5 -proof nanofiber mask filter element and a preparation method thereof.
  • Electrospinning technology is a simple and effective method to prepare nanoporous polymer fiber materials. It has the advantages of controllable pore size, easy functionalization, and convenient operation. It is widely used in filter materials.
  • the patent CN104740934A disclosed a three-dimensional electrospinning filter material for masks and a preparation method thereof.
  • the patent uses electrospinning technology to change the receiving device into a metal mesh that fits the three-dimensional model of the human face.
  • the fiber diameter of the electrospun micro-nanofiber membrane is between 0.2 and 1 ⁇ m, and the three-dimensional shape has a high degree of closeness to the human face.
  • the filtration efficiency of PM 2.5 and PM 1.0 reaches 100%, and the air permeability is less than or equal to 200 Pa.
  • This patent satisfies the wearer's facial comfort in terms of physical structure, but does not consider the sultry feeling of the human face.
  • the patent CN110660875A disclosed a method for cooling photovoltaic modules using transparent mid-infrared radiation cellulose films.
  • This patent embeds transparent materials with infrared radiation capability into photovoltaic modules so that they can pass through the atmosphere in working conditions.
  • the thermal radiation in the window band can be used to cool photovoltaic modules, but this zero-energy surface cooling technology has not been applied to human face filters.
  • the purpose of the present invention is to: provide a kind of thermal comfort anti-PM 2.5 nanofiber mask filter element suitable for human face and preparation method thereof, mainly using the principle of radiation cooling, processing functionalities by methods such as electrospinning and chemical technology A polymer material, a mask filter element material with good PM 2.5 filterability and facial thermal comfort is prepared.
  • the filter element material is composed of a polymer nanofiber film that can pass through the mid-infrared band of the human body and a nanofiber film that can block the visible light band of the atmospheric environment.
  • nano-particles with anti-reflection infrared function are added to the infrared-transmitting nanofiber membrane to achieve the purpose of assisting the dissipation of thermal radiation generated by the human body, and serve as the inner layer of the thermal comfort mask filter element.
  • the nanofiber membrane that blocks visible light is added with radiation heat-insulating particles to reduce the thermal radiation of the atmospheric environment to the human body, which is used as the outer layer of the thermal comfort mask filter element.
  • a thermal comfort anti-PM 2.5 nanofiber mask filter element includes an infrared-transmitting inner layer filter element close to the skin side and a visible light-blocking outer layer filter element close to the environment side, and the two-layer filter element is densely sewn.
  • the inner filter element is a nanofiber film added with nanoparticles having anti-reflection infrared function
  • the outer filter element is a nanofiber film added with visible radiation blocking particles.
  • the infrared-transmitting polymer of the inner and outer layers of the filter element is one or more of polyacrylonitrile, polyethylene, polyamide and polyethylene terephthalate.
  • the particles with anti-reflection infrared function may be one or more of calcium fluoride, magnesium fluoride, zinc oxide, and the like.
  • the heat insulating nanoparticles can be one or more of silicon dioxide, titanium dioxide and chromium dioxide, and the particle size is 10-80 nm.
  • the thermal comfort filter element has the function of penetrating the infrared radiation of the human body and blocking the visible light of the atmospheric environment; the transmittance to the infrared band of the human body is ⁇ 85%, and the transmittance to the visible light band is ⁇ 60%.
  • the inner filter element can pass through the thermal radiation emitted by the human face, and the infrared transmittance to the human body is ⁇ 85%, so as to achieve the purpose of dissipating the radiant heat of the human body.
  • the outer filter element can block the thermal radiation of the surrounding environment to the human body, and the transmittance of the outer filter element to the visible light thermal radiation in the atmosphere is less than or equal to 60%.
  • the filter element of the mask has a gram weight of 3.3 to 5 g/m 2 , a moisture permeability of 0.01 to 0.02 g/(cm 2 h), a porosity of ⁇ 85%, and an average fiber diameter of 0.2 to 1 ⁇ m.
  • the filtration efficiency of 0.3 ⁇ m particles is 90% ⁇ 99.95%, and the resistance is 3 ⁇ 200 Pa, which can achieve high-efficiency filtration of PM 2.5 .
  • Electrospinning First, change the roller metal plate of the electrospinning device to a copper mesh plate with better conductivity, adjust the process parameters, set the environmental parameters, and add the spinning solution A to the electrospinning device. , the nanofiber membrane material was prepared by electrospinning;
  • step (3) drying the nanofiber membrane material prepared in step (2) in a constant temperature environment of 25-35 °C to obtain the inner layer a of the high-efficiency filter mask filter element with infrared permeation performance;
  • spinning solution B Mix the polymer and solvent, and stir at room temperature for 8-10 h to obtain spinning solution B. Note that the polymer and solvent of spinning solution B are the same as those of spinning solution A;
  • solution C Add inorganic particles M into an aqueous solution of hydrochloric acid to obtain solution C, soak the nanofiber membrane b in solution C and activate it for 2 to 20 min, remove the membrane and wash it with deionized water for 1 to 3 times to obtain nanofiber membrane c;
  • precursor solution D add solute N into water to obtain solution D, soak the nanofiber membrane c in solution D and put it into the diluted acidic aqueous solution E, then put it into an ultrasonic instrument, and sonicate it for 4 to 6 hours. Wash 1 to 3 times with deionized water and absolute ethanol, respectively, to obtain nanofiber membrane d;
  • the polymer in step (1) is one or more of polyacrylonitrile, polyethylene, polyamide and polyethylene terephthalate;
  • the solvent in step (1) is formic acid, N , one or more of N-dimethylformamide;
  • the particles with anti-reflection infrared function described in step (1) are one or more of calcium fluoride, magnesium fluoride and zinc oxide.
  • the mass concentration of the polymer described in step (1) in the spinning solution is 12 ⁇ 20 wt.%; the concentration of particles with anti-reflection infrared function in the polymer solution is 0.02 ⁇ 0.16 mol/L;
  • the drying time described in step (3) is 18 to 24 hours;
  • the inorganic particles M are one or more of tin dichloride and palladium chloride; in step (7), the solute N is ammonium fluorotitanate, one of zirconium oxychloride or Several; the acidic aqueous solution can be one or more of boric acid, hydrochloric acid and formic acid.
  • the electrospinning device includes a bolus injection system, a spinning solution injection system, an electrostatic high voltage system and an improved copper rotating roller receiving system; the electrospinning system
  • the process parameters are set as the electrospinning voltage is 15 ⁇ 25 KV, the receiving distance is 10 ⁇ 20 cm, the injection speed is 0.05 ⁇ 0.25 mm/min, temperature is 18 ⁇ 35°C, relative humidity is 30 ⁇ 70%;
  • the mass concentration of the polymer described in step (4) in the spinning solution is 12 ⁇ 20 wt.%;
  • the mass concentration of the inorganic particles M in the solution C described in step (6) is 0.3 to 0.5 wt.%;
  • the concentration of the solute N in the precursor solution D described in step (7) is 0.01-0.05 mol/L, and the concentration of the acidic aqueous solution is 0.02-0.03 mol/L;
  • the vacuum drying time in step (8) is 8-10 hours.
  • the present invention has the following advantages and beneficial effects:
  • the invention introduces the concept of radiative cooling, combines zero energy consumption surface cooling technology with nanofiber filter material, and realizes thermal comfort of human face and efficient filtration of PM 2.5 by enhancing the transmittance of infrared light and weakening the transmittance of visible light. sex.
  • the present invention ensures that the fiber filter element material has the anti-PM 2.5 function while satisfying the thermal comfort of the human body to the face by controlling the porosity of the nanofiber material and the diameter of the material by controlling the porosity of the nanofiber material and the radiation cooling property of the material through the chemical process method mainly based on the electrospinning process. demand.
  • the manufacturing method of the thermal comfort mask filter element material of the present invention is relatively simple. Preparation of thermal comfort mask filter element membrane material.
  • FIG. 1 is a schematic structural diagram of an electrospinning device used in the present invention.
  • FIG. 2 is a schematic structural diagram of the thermal comfort mask filter element material of the present invention.
  • Example 3 is the Fourier infrared transform spectrogram of the filter element material of Example 1 and the disposable mask of Comparative Test Example 1.
  • Fig. 4 is the Fourier infrared transform spectrogram of embodiment 2 filter element material and the disposable mask of comparative test example 1.
  • Fig. 5 is the Fourier infrared transform spectrogram of embodiment 3 filter element material and the disposable mask of comparative test example 1.
  • Fig. 6 is the UV-Vis spectrophotometer test chart of the filter element material of the embodiment.
  • Fig. 8 is the filtration pressure drop comparison diagram of the disposable mask of embodiment 1-3 and comparative test example 3 and KN95 mask.
  • thermo comfort anti-PM 2.5 nanofiber mask filter element A preparation method of a thermal comfort anti-PM 2.5 nanofiber mask filter element, the specific steps are:
  • the injection system for adding the spinning solution A to the electrospinning device (see FIG. 1 ), which includes a bolus injection system 1 , an injection system 2 , an electrostatic high voltage system 3 and a receiving system 4 .
  • the receiving system was improved to a copper mesh receiving plate, and the electrospinning process parameters were as follows: the receiving distance was 15 cm, the electrostatic high voltage was 20 KV, the injection speed was 0.1 mm/min, the temperature was 35 °C, and the relative humidity was 60%.
  • the nanofiber membrane was obtained after 30 min of spinning time;
  • the infrared transmittance of the filter element of the mask made in this example is 85 to 90% in the human body (see Figure 3), and the transmittance of the filter element material to visible light is ⁇ 50% (see Figure 6); the SEM image is analyzed using image-Proplus software.
  • the average fiber diameter of the obtained mask filter element is 200 nm, using the filter material test platform built in the laboratory to obtain the filter material when the wind speed is 5.3 cm/s, the filtration efficiency of 0.3 ⁇ m particles is 96.49% (see Figure 7), and the pressure drop is 102 Pa (see Figure 8) .
  • thermo comfort anti-PM 2.5 nanofiber mask filter element A preparation method of a thermal comfort anti-PM 2.5 nanofiber mask filter element, the specific steps are:
  • the injection system for adding the spinning solution A to the electrospinning device (see FIG. 1 ), which includes a bolus injection system 1 , an injection system 2 , an electrostatic high voltage system 3 and a receiving system 4 .
  • the receiving system was improved to a copper mesh receiving plate, and the electrospinning process parameters were: receiving distance of 10 cm, electrostatic high voltage of 25 KV, injection speed of 0.05 mm/min, temperature of 28 °C, relative humidity of 35%, The spinning time was 30 min to obtain a nanofiber membrane;
  • Electrospinning (4) spinning solution B wherein the equipment and parameters are the same as in step (2), to obtain nanofiber membrane b;
  • the infrared transmittance in the human body of the mask filter element prepared in this example is 87.13 to 97.63% (see Figure 4), and the transmittance of the filter element material to visible light is ⁇ 60% (see Figure 6); the SEM image is analyzed by image-Proplus software.
  • the average fiber diameter of the obtained mask filter element obtained by analysis was 365 nm, and the moisture permeability was 0.0131 g/cm 2 /h.
  • the filter material test platform built by the laboratory was used to obtain the filter material at a wind speed of 5.3. At cm/s, the filtration efficiency for 0.3 ⁇ m particles is 97.12% (see Figure 7), and the pressure drop is 80 Pa (see Figure 8).
  • thermo comfort anti-PM 2.5 nanofiber mask filter element A preparation method of a thermal comfort anti-PM 2.5 nanofiber mask filter element, the specific steps are:
  • the injection system for adding the spinning solution A to the electrospinning device (see FIG. 1 ), which includes a bolus injection system 1 , an injection system 2 , an electrostatic high voltage system 3 and a receiving system 4 .
  • the receiving system was improved to a copper mesh receiving plate, and the electrospinning process parameters were as follows: the receiving distance was 20 cm, the electrostatic high voltage was 20 KV, the injection speed was 0.1 mm/min, the temperature was 26 °C, and the relative humidity was 50%. Spinning time is 40min, obtains nanofiber membrane;
  • Electrospinning (4) spinning solution B wherein the equipment and parameters are the same as in step (2), to obtain nanofiber membrane b;
  • the infrared transmittance of the mask filter element made in this example is 81.94-98.1% in the human body (see Figure 5), and the transmittance of the filter element material to visible light is less than or equal to 60% (see Figure 6); use image-Proplus software to analyze the SEM image
  • the average fiber diameter of the obtained mask filter element was 662 nm, and the filter material test platform built in the laboratory was used to obtain the filter element material at a wind speed of 5.3 nm. At cm/s, the filtration efficiency for 0.3 ⁇ m particles is 92.97% (see Figure 7) and the pressure drop is 27 Pa (see Figure 8).
  • the Fourier infrared transform spectrum test of the disposable mask is the same as that of Example 1-3; its mid-infrared transmittance ⁇ 5%, and the test result is shown in Figure 3-5.

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Abstract

The invention discloses a thermally comfortable PM2.5-proof nanofiber mask filter element and a manufacturing method therefor, comprising an infrared light transmitting inner layer filter element (5) on the side near to the skin, and a visible light blocking outer layer filter element (6) on the side near to the environment. The two layers of filter elements are densely stitched. The manufacturing method comprises the following steps: (1) preparing a spinning solution A; (2) electrostatic spinning; (3) drying the nanofiber filter element film material prepared in step (2) in a constant temperature environment of 25-35°C to obtain a high-efficiency filtration mask filter element inner layer a; (4) preparing a spinning solution B; (5) adding spinning solution B to the electrostatic spinning apparatus of step (2), and by means of electrostatic spinning, obtaining a polymer nanofiber film b; (6) preparing a nanofiber film c; (7) preparing a nanofiber film d; (8) drying the nanofiber film d prepared in step (7) in a vacuum environment at 60-90°C to obtain a mask filter element outer layer e coated in thermally insulating particles and having a visible light blocking function; and (9) densely stitch the filter element inner layer a and the filter element outer layer e to obtain a thermally comfortable PM2.5-proof mask filter element.

Description

热舒适性防PM2.5的纳米纤维口罩滤芯及其制备方法Thermal comfort anti-PM2.5 nanofiber mask filter element and preparation method thereof 技术领域technical field
本发明属于空气过滤材料技术领域，具体涉及一种热舒适性防PM 2.5的纳米纤维口罩滤芯及其制备方法。 The invention belongs to the technical field of air filter materials, and in particular relates to a thermal comfort and PM 2.5 -proof nanofiber mask filter element and a preparation method thereof.
背景技术Background technique
空气中悬浮的颗粒物以及附着在颗粒物上的病菌严重影响到人们的日常生活和身体健康，受新冠肺炎的影响，口罩已成为人们日常生活中不可或缺的防护品。人们在追求有效过滤颗粒污染物的同时，对口罩的舒适性也提出了新的要求。The particulate matter suspended in the air and the bacteria attached to the particulate matter seriously affect people's daily life and health. Affected by the new coronary pneumonia, masks have become an indispensable protective item in people's daily life. While people are pursuing effective filtering of particulate pollutants, new requirements are also put forward for the comfort of masks.
佩戴口罩产生的面部闷热感普遍存在，目前商用普通一次性口罩轻薄却不能有效防护PM 2.5，一次性医用口罩和N95口罩防护性能好但并未考虑人体面部的热舒适性。 Face sultry feeling caused by wearing a mask is common. At present, commercial ordinary disposable masks are light and thin but cannot effectively protect PM 2.5 . Disposable medical masks and N95 masks have good protective performance but do not consider the thermal comfort of the human face.
静电纺丝技术是制备纳米多孔聚合物纤维材料的一种简单有效的方法，具有孔径可控、易于实现功能化、操作方便等的优势，被广泛用于过滤材料中。Electrospinning technology is a simple and effective method to prepare nanoporous polymer fiber materials. It has the advantages of controllable pore size, easy functionalization, and convenient operation. It is widely used in filter materials.
2017年5月，专利CN107048538A公开了一种三层复合抗菌防雾霾口罩及其制备方法，该专利通过静电纺丝法制得纳米纤维材料，之后经预氧化、碳化、再次直接电纺等处理方式获得抗菌纤维膜，且能滤杀有害菌。其过滤效率≥99%，透气率≥18 cm/s，过滤阻力＜120 Pa。该滤料可以实现高效过滤，杀害病菌，但未考虑人体面部闷湿感，影响人体佩戴时的舒适度。In May 2017, patent CN107048538A disclosed a three-layer composite antibacterial and anti-haze mask and its preparation method. The patent obtained nanofiber material by electrospinning method, and then processed by pre-oxidation, carbonization, and direct electrospinning again. Obtain antibacterial fiber membrane, and can filter and kill harmful bacteria. The filtration efficiency is ≥99%, the air permeability is ≥18 cm/s, and the filtration resistance is less than 120 Pa. The filter material can achieve high-efficiency filtration and kill germs, but does not consider the stuffy and wet feeling on the human face, which affects the comfort of the human body when wearing it.
2013年12月，专利CN104740934A公开了一种口罩用立体型静电纺丝过滤材料及其制备方法，该专利采用静电纺丝技术，将接收装置改变成贴合人体面部立体模型的金属网，所述静电纺微纳米纤维膜的纤维直径在0.2 ~ 1 μm之间，立体形状与人脸部密合程度高，对PM 2.5、PM 1.0过滤效率达到100%，透气率≤200 Pa。该专利在物理结构方面满足佩戴者的面部舒适感，但是人体面部闷热感未被考虑。 In December 2013, the patent CN104740934A disclosed a three-dimensional electrospinning filter material for masks and a preparation method thereof. The patent uses electrospinning technology to change the receiving device into a metal mesh that fits the three-dimensional model of the human face. The fiber diameter of the electrospun micro-nanofiber membrane is between 0.2 and 1 μm, and the three-dimensional shape has a high degree of closeness to the human face. The filtration efficiency of PM 2.5 and PM 1.0 reaches 100%, and the air permeability is less than or equal to 200 Pa. This patent satisfies the wearer's facial comfort in terms of physical structure, but does not consider the sultry feeling of the human face.
2019年10月，专利CN110660875A公开了一种利用透明中红外辐射纤维素薄膜冷却光伏组件的方法，该专利将具有红外辐射能力的透明材料嵌入到光伏组件中，使其在工作状态下可以通过大气窗口波段的热辐射，从而达到冷却光伏组件的目的，但这种零能耗的表面冷却技术未被应用于人体面部过滤器中。In October 2019, the patent CN110660875A disclosed a method for cooling photovoltaic modules using transparent mid-infrared radiation cellulose films. This patent embeds transparent materials with infrared radiation capability into photovoltaic modules so that they can pass through the atmosphere in working conditions. The thermal radiation in the window band can be used to cool photovoltaic modules, but this zero-energy surface cooling technology has not been applied to human face filters.
技术解决方案technical solutions
本发明的目的是：提供一种适用于人体面部的热舒适性防PM 2.5的纳米纤维口罩滤芯及其制备方法，主要是利用辐射冷却原理，通过静电纺丝及化学工艺等方法加工处理功能性聚合物材料，制备得到具有良好PM 2.5过滤性和面部热舒适性的口罩滤芯材料。 The purpose of the present invention is to: provide a kind of thermal comfort anti-PM 2.5 nanofiber mask filter element suitable for human face and preparation method thereof, mainly using the principle of radiation cooling, processing functionalities by methods such as electrospinning and chemical technology A polymer material, a mask filter element material with good PM 2.5 filterability and facial thermal comfort is prepared.
该滤芯材料由可以透过人体中红外波段的聚合物纳米纤维薄膜和可以阻挡大气环境可见光波段的纳米纤维薄膜组成。其中透红外纳米纤维膜中添加了具有增透红外功能的纳米颗粒，达到辅助散失人体产生热辐射的目的，作为热舒适性口罩滤芯内层。其中阻可见光的纳米纤维膜中添加了辐射隔热颗粒，减少大气环境对人体的热辐射，作为热舒适性口罩滤芯外层。The filter element material is composed of a polymer nanofiber film that can pass through the mid-infrared band of the human body and a nanofiber film that can block the visible light band of the atmospheric environment. Among them, nano-particles with anti-reflection infrared function are added to the infrared-transmitting nanofiber membrane to achieve the purpose of assisting the dissipation of thermal radiation generated by the human body, and serve as the inner layer of the thermal comfort mask filter element. Among them, the nanofiber membrane that blocks visible light is added with radiation heat-insulating particles to reduce the thermal radiation of the atmospheric environment to the human body, which is used as the outer layer of the thermal comfort mask filter element.
本发明的目的通过以下技术方案实现。The object of the present invention is achieved through the following technical solutions.
一种热舒适性防PM 2.5的纳米纤维口罩滤芯，包括靠近皮肤侧的透红外内层滤芯以及靠近环境侧的阻可见光外层滤芯，所述两层滤芯进行密集型缝合。 A thermal comfort anti-PM 2.5 nanofiber mask filter element includes an infrared-transmitting inner layer filter element close to the skin side and a visible light-blocking outer layer filter element close to the environment side, and the two-layer filter element is densely sewn.
优选的，所述内层滤芯为添加了具有增透红外功能的纳米颗粒的纳米纤维薄膜，所述外层滤芯为添加了阻可见辐射颗粒的纳米纤维薄膜。Preferably, the inner filter element is a nanofiber film added with nanoparticles having anti-reflection infrared function, and the outer filter element is a nanofiber film added with visible radiation blocking particles.
优选的，所述滤芯内外层的透红外聚合物为聚丙烯腈、聚乙烯、聚酰胺和聚对苯二甲酸乙二酯中的一种或几种。Preferably, the infrared-transmitting polymer of the inner and outer layers of the filter element is one or more of polyacrylonitrile, polyethylene, polyamide and polyethylene terephthalate.
优选的，所述具有增透红外功能的颗粒可为氟化钙、氟化镁、氧化锌等中的一种或几种。Preferably, the particles with anti-reflection infrared function may be one or more of calcium fluoride, magnesium fluoride, zinc oxide, and the like.
优选的，所述隔热纳米颗粒可为二氧化硅、二氧化钛和二氧化铬中的一种或几种，粒径为10 ~ 80 nm。Preferably, the heat insulating nanoparticles can be one or more of silicon dioxide, titanium dioxide and chromium dioxide, and the particle size is 10-80 nm.
优选的，所述的热舒适性滤芯具有透过人体红外辐射、阻挡大气环境可见光的功能；对人体红外波段的透过率≥ 85%，对可见光波段的透过率≤60%。Preferably, the thermal comfort filter element has the function of penetrating the infrared radiation of the human body and blocking the visible light of the atmospheric environment; the transmittance to the infrared band of the human body is ≥ 85%, and the transmittance to the visible light band is ≤ 60%.
优选的，所述内层滤芯可以透过人体面部散发的热辐射，对人体红外透过率≥ 85%，从而达到散发人体辐射热的目的。Preferably, the inner filter element can pass through the thermal radiation emitted by the human face, and the infrared transmittance to the human body is ≥ 85%, so as to achieve the purpose of dissipating the radiant heat of the human body.
优选的，所述外层滤芯可以阻挡周围环境对人体的热辐射，所述外层滤芯对大气可见光热辐射的透过率≤ 60%。Preferably, the outer filter element can block the thermal radiation of the surrounding environment to the human body, and the transmittance of the outer filter element to the visible light thermal radiation in the atmosphere is less than or equal to 60%.
优选的，所述口罩滤芯的克重为3.3 ~ 5 g/m 2，透湿性能0.01 ~ 0.02 g/(cm 2 h)，孔隙率≥85%，平均纤维直径为0.2 ~ 1 μm，对≥ 0.3 μm颗粒的过滤效率90% ~ 99.95%，阻力为3 ~ 200 Pa，可以实现对PM 2.5的高效过滤。 Preferably, the filter element of the mask has a gram weight of 3.3 to 5 g/m 2 , a moisture permeability of 0.01 to 0.02 g/(cm 2 h), a porosity of ≥85%, and an average fiber diameter of 0.2 to 1 μm. The filtration efficiency of 0.3 μm particles is 90% ~ 99.95%, and the resistance is 3 ~ 200 Pa, which can achieve high-efficiency filtration of PM 2.5 .
以上所述的任一种对人体面部热舒适性能的空气过滤口罩滤芯材料的制备方法，包括以下步骤：Any of the above-mentioned preparation methods for the air filter mask filter element material of the thermal comfort performance of the human face, comprising the following steps:
（1）配制纺丝液A：将聚合物与溶剂混合均匀，然后加入增透红外功能的颗粒，超声震荡直至颗粒分散均匀，室温搅拌后得到稳定的聚合物纺丝液A；(1) Preparation of spinning solution A: Mix the polymer and the solvent evenly, then add the particles with anti-reflection infrared function, ultrasonically vibrate until the particles are evenly dispersed, and stir at room temperature to obtain a stable polymer spinning solution A;
（2）静电纺丝：首先将静电纺装置的辊轴金属极板改变为导电性能更佳的紫铜网极板，调节工艺参数，设置环境参数，将纺丝液A加到静电纺丝装置中，通过静电纺丝制备得到纳米纤维膜材料；(2) Electrospinning: First, change the roller metal plate of the electrospinning device to a copper mesh plate with better conductivity, adjust the process parameters, set the environmental parameters, and add the spinning solution A to the electrospinning device. , the nanofiber membrane material was prepared by electrospinning;
（3）将步骤（2）制备的纳米纤维膜材料在25 ~35℃恒温环境中干燥，得到所述的具有透过红外性能的高效过滤口罩滤芯内层a；(3) drying the nanofiber membrane material prepared in step (2) in a constant temperature environment of 25-35 °C to obtain the inner layer a of the high-efficiency filter mask filter element with infrared permeation performance;
（4）配制纺丝液B：将聚合物与溶剂混合，室温搅拌8 ~ 10 h，得到纺丝液B，注意选择纺丝液B的聚合物和溶剂与纺丝液A相同；(4) Preparation of spinning solution B: Mix the polymer and solvent, and stir at room temperature for 8-10 h to obtain spinning solution B. Note that the polymer and solvent of spinning solution B are the same as those of spinning solution A;
（5）将纺丝液B加到静电纺丝装置中，经过静电纺丝得到聚合物纳米纤维膜b；(5) adding the spinning solution B to the electrospinning device, and obtaining the polymer nanofiber membrane b through electrospinning;
（6）配制溶液C：将无机粒子M加入盐酸的水溶液中得到溶液C，将纳米纤维膜b浸泡在溶液C后使其活化2 ~ 20 min，取出膜后用去离子水清洗1 ~ 3次得到纳米纤维膜c；(6) Preparation of solution C: Add inorganic particles M into an aqueous solution of hydrochloric acid to obtain solution C, soak the nanofiber membrane b in solution C and activate it for 2 to 20 min, remove the membrane and wash it with deionized water for 1 to 3 times to obtain nanofiber membrane c;
（7）配制前驱体溶液D：将溶质N加入水中得到溶液D，将纳米纤维膜c浸泡在溶液D后放入被稀释的酸性水溶液E，然后放入超声仪中，超声4 ~ 6 h后用去离子水和无水乙醇分别清洗1 ~ 3次，得到纳米纤维膜d；(7) Preparation of precursor solution D: add solute N into water to obtain solution D, soak the nanofiber membrane c in solution D and put it into the diluted acidic aqueous solution E, then put it into an ultrasonic instrument, and sonicate it for 4 to 6 hours. Wash 1 to 3 times with deionized water and absolute ethanol, respectively, to obtain nanofiber membrane d;
（8）将（7）制备的纤维膜d在60 ~ 90 °C的真空环境中干燥，得到由隔热颗粒包覆的具有阻挡可见光功能的口罩滤芯外层e；(8) drying the fiber membrane d prepared in (7) in a vacuum environment of 60-90 °C to obtain the outer layer e of the mask filter element with the function of blocking visible light covered by heat insulating particles;
（9）将滤芯内层a与滤芯外层e经过密集型缝合得到热舒适性防PM 2.5口罩滤芯。 (9) The inner layer a of the filter element and the outer layer e of the filter element are intensively stitched to obtain a thermally comfortable anti-PM 2.5 mask filter element.
优选的，步骤（1）所述聚合物为聚丙烯腈、聚乙烯、聚酰胺和聚对苯二甲酸乙二酯中的一种或几种；步骤（1）所述的溶剂为甲酸、N，N-二甲基甲酰胺中的一种或几种；步骤（1）所述的增透红外功能的颗粒为氟化钙、氟化镁、氧化锌中的一种或几种。Preferably, the polymer in step (1) is one or more of polyacrylonitrile, polyethylene, polyamide and polyethylene terephthalate; the solvent in step (1) is formic acid, N , one or more of N-dimethylformamide; the particles with anti-reflection infrared function described in step (1) are one or more of calcium fluoride, magnesium fluoride and zinc oxide.
优选的，步骤（1）所述的聚合物在纺丝液中的质量浓度为12 ~ 20 wt.%；具有增透红外功能的颗粒在聚合物溶液中的浓度为0.02 ~ 0.16 mol/L；Preferably, the mass concentration of the polymer described in step (1) in the spinning solution is 12 ~ 20 wt.%; the concentration of particles with anti-reflection infrared function in the polymer solution is 0.02 ~ 0.16 mol/L;
优选的，步骤（3）所述的干燥时间为18 ~ 24个小时；Preferably, the drying time described in step (3) is 18 to 24 hours;
优选的，步骤（6）中无机粒子M为二氯化锡、氯化钯中的一种或几种；步骤（7）中溶质N为氟钛酸铵，氧氯化锆中的一种或几种；酸性水溶液可以是硼酸、盐酸、甲酸中的一种或几种。Preferably, in step (6), the inorganic particles M are one or more of tin dichloride and palladium chloride; in step (7), the solute N is ammonium fluorotitanate, one of zirconium oxychloride or Several; the acidic aqueous solution can be one or more of boric acid, hydrochloric acid and formic acid.
优选的，步骤（2）和步骤（5）中，所述静电纺丝装置包括推注***、纺丝溶液注射***、静电高压***和改进后的紫铜旋转辊轴接收***；所述静电纺丝工艺参数设定为静电纺丝电压为15 ~ 25 KV，接收距离为10 ~ 20 cm，注射速度为0.05 ~ 0.25 mm/min，温度为18 ~ 35℃，相对湿度为30 ~ 70%；Preferably, in step (2) and step (5), the electrospinning device includes a bolus injection system, a spinning solution injection system, an electrostatic high voltage system and an improved copper rotating roller receiving system; the electrospinning system The process parameters are set as the electrospinning voltage is 15 ~ 25 KV, the receiving distance is 10 ~ 20 cm, the injection speed is 0.05 ~ 0.25 mm/min, temperature is 18 ~ 35℃, relative humidity is 30 ~ 70%;
优选的，步骤（4）所述的聚合物在纺丝液中的质量浓度为12 ~ 20 wt.%；Preferably, the mass concentration of the polymer described in step (4) in the spinning solution is 12 ~ 20 wt.%;
优选的，步骤（6）所述的溶液C中无机粒子M的质量浓度为0.3 ~ 0.5 wt.%；Preferably, the mass concentration of the inorganic particles M in the solution C described in step (6) is 0.3 to 0.5 wt.%;
优选的，步骤（7）所述的前驱体溶液D中溶质N的浓度为0.01 ~ 0.05 mol/L，酸性水溶液的浓度为0.02 ~ 0.03 mol/L；Preferably, the concentration of the solute N in the precursor solution D described in step (7) is 0.01-0.05 mol/L, and the concentration of the acidic aqueous solution is 0.02-0.03 mol/L;
优选的，步骤（8）所述的真空干燥时间为8 ~10个小时。Preferably, the vacuum drying time in step (8) is 8-10 hours.
有益效果beneficial effect
与现有的技术相比，本发明具有如下优点及有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
本发明的热舒适性防PM 2.5的纳米纤维口罩滤芯的平均纤维直径为0.2 ~ 1 μm，膜的孔隙率≥ 85%，透湿性能0.01 ~ 0.02 g/(cm 2 h)，对≥0.3 µm颗粒的过滤效率为90% ~ 99.95%，阻力为3 ~ 200 Pa，所制备的热舒适性口罩滤芯对人体红外透过率≥85%，对环境中携带大量辐射热的可见光透过率≤60%。 The thermal comfort and anti-PM 2.5 nanofiber mask filter element of the present invention has an average fiber diameter of 0.2 to 1 μm, a porosity of the membrane ≥ 85%, a moisture permeability of 0.01 to 0.02 g/(cm 2 h), and an average fiber diameter of ≥ 0.3 μm. The filtration efficiency of particles is 90% to 99.95%, and the resistance is 3 to 200 Pa. The infrared transmittance of the prepared thermal comfort mask filter element to the human body is ≥85%, and the visible light transmittance that carries a large amount of radiant heat in the environment is ≤60%. %.
本发明引入辐射冷却概念，将零能耗表面冷却技术与纳米纤维过滤材料结合，通过增强红外光的透过率，减弱可见光的透过率，实现人体面部的热舒适性与PM 2.5的高效过滤性。 The invention introduces the concept of radiative cooling, combines zero energy consumption surface cooling technology with nanofiber filter material, and realizes thermal comfort of human face and efficient filtration of PM 2.5 by enhancing the transmittance of infrared light and weakening the transmittance of visible light. sex.
本发明通过以静电纺丝工艺为主的化学工艺手段，通过控制纳米纤维材料的孔隙率与直径控制材料的辐射制冷性，保证纤维滤芯材料具有防PM 2.5功能的同时满足人体对面部热舒适性的需求。 The present invention ensures that the fiber filter element material has the anti-PM 2.5 function while satisfying the thermal comfort of the human body to the face by controlling the porosity of the nanofiber material and the diameter of the material by controlling the porosity of the nanofiber material and the radiation cooling property of the material through the chemical process method mainly based on the electrospinning process. demand.
本发明的热舒适性口罩滤芯材料的制作方法较为简单，以静电纺丝工艺为主，以超声处理等化学工艺手段为辅即可完成，不需要特殊的装置和设备，可适用于一系列广泛的热舒适性口罩滤芯膜材料制备。The manufacturing method of the thermal comfort mask filter element material of the present invention is relatively simple. Preparation of thermal comfort mask filter element membrane material.
附图说明Description of drawings
图1是本发明所用静电纺丝装置的结构示意图。FIG. 1 is a schematic structural diagram of an electrospinning device used in the present invention.
图中编号说明如下：1-静电纺丝装置的推注***；2-纺丝溶液注射器；3-静电高压***；4-旋转辊轴接收***。The numbers in the figure are explained as follows: 1- Bolus injection system of the electrospinning device; 2- Spinning solution injector; 3- Electrostatic high voltage system; 4- Rotating roller shaft receiving system.
图2是本发明的热舒适性口罩滤芯材料结构示意图。2 is a schematic structural diagram of the thermal comfort mask filter element material of the present invention.
图中编号说明如下：5-透红外口罩滤芯内层；6-阻可见口罩滤芯外层。The numbers in the figure are explained as follows: 5-transmitting the inner layer of the filter element of the infrared mask; 6-blocking the outer layer of the filter element of the visible mask.
图3是实施例1滤芯材料与对比测试例1的一次性口罩的傅里叶红外变换光谱图。3 is the Fourier infrared transform spectrogram of the filter element material of Example 1 and the disposable mask of Comparative Test Example 1.
图4是实施例2滤芯材料与对比测试例1的一次性口罩的傅里叶红外变换光谱图。Fig. 4 is the Fourier infrared transform spectrogram of embodiment 2 filter element material and the disposable mask of comparative test example 1.
图5是实施例3滤芯材料与对比测试例1的一次性口罩的傅里叶红外变换光谱图。Fig. 5 is the Fourier infrared transform spectrogram of embodiment 3 filter element material and the disposable mask of comparative test example 1.
图6是实施例滤芯材料的紫外可见分光光度计测试图。Fig. 6 is the UV-Vis spectrophotometer test chart of the filter element material of the embodiment.
图7是实施例1-3与对比测试例2的一次性口罩和KN95口罩对不同直径颗粒的捕获效率对比图。7 is a comparison diagram of the capture efficiency of the disposable masks and KN95 masks of Examples 1-3 and Comparative Test Example 2 to particles of different diameters.
图8是实施例1-3与对比测试例3的一次性口罩和KN95口罩的过滤压降对比图。Fig. 8 is the filtration pressure drop comparison diagram of the disposable mask of embodiment 1-3 and comparative test example 3 and KN95 mask.
本发明的实施方式Embodiments of the present invention
以下结合具体实施例和附图对本发明的具体实施作进一步说明，但本发明的实施和保护范围不限于此。The specific implementation of the present invention will be further described below with reference to specific embodiments and accompanying drawings, but the implementation and protection scope of the present invention are not limited thereto.
实施例Example 11
一种热舒适性防PM 2.5的纳米纤维口罩滤芯的制备方法，具体步骤为： A preparation method of a thermal comfort anti-PM 2.5 nanofiber mask filter element, the specific steps are:
（1）将2 g聚酰胺66添加到8 g甲酸中混合，用玻璃棒搅拌均匀，注意在取用甲酸时打开通风橱操作；将0.75 g氧化锌（纯度99.5%，平均粒径20 nm）置于上述混合溶剂中，用超声震荡仪震荡1.5 h，搅拌均匀配制成溶液A；(1) Add 2 g of polyamide 66 to 8 g of formic acid and mix, stir evenly with a glass rod, pay attention to open the fume hood when taking formic acid; add 0.75 g of zinc oxide (purity 99.5%, average particle size 20 nm) Placed in the above mixed solvent, shaken with an ultrasonic oscillator for 1.5 h, and stirred evenly to prepare solution A;
（2）将纺丝溶液A加到静电纺丝装置中的注射***（参见图1），图1中包括推注***1、注射***2、静电高压***3和接收***4。将接收***改进为紫铜网接收极板，静电纺丝工艺参数为：接收距离为15 cm，静电高压为20 KV，推注速度为0.1 mm/min，温度为35℃，相对湿度为60%。经过30 min的纺丝时间后得到纳米纤维膜；(2) The injection system for adding the spinning solution A to the electrospinning device (see FIG. 1 ), which includes a bolus injection system 1 , an injection system 2 , an electrostatic high voltage system 3 and a receiving system 4 . The receiving system was improved to a copper mesh receiving plate, and the electrospinning process parameters were as follows: the receiving distance was 15 cm, the electrostatic high voltage was 20 KV, the injection speed was 0.1 mm/min, the temperature was 35 °C, and the relative humidity was 60%. The nanofiber membrane was obtained after 30 min of spinning time;
（3）将膜置于30℃恒温环境中干燥24 h后得到透红外口罩滤芯内层a；(3) After drying the membrane in a constant temperature environment of 30 °C for 24 h, the inner layer a of the filter element of the infrared transparent mask was obtained;
（4）将2 g聚酰胺66与8 g甲酸混合，玻璃棒搅拌混合均匀，磁力搅拌9h得到纺丝液B； (4) Mix 2 g of polyamide 66 with 8 g of formic acid, stir and mix with a glass rod, and magnetically stir for 9 hours to obtain spinning solution B;
（5）将（4）纺丝液B通过静电纺丝，其中的设备与参数同步骤（2）一致，得到纳米纤维膜b；(5) Electrospinning (4) spinning solution B, wherein the equipment and parameters are the same as in step (2), to obtain nanofiber membrane b;
（6）将4 g二氯化锡加入到1 L盐酸（质量分数为37%）中配制成溶液C；将（5）得到的纤维膜b浸泡在C中5 min，取出后用去离子水洗3遍，得到被润湿的纳米纤维膜c；(6) Add 4 g of tin dichloride to 1 L of hydrochloric acid (37% by mass) to prepare solution C; soak the fiber membrane b obtained in (5) in C for 5 min, take it out and wash with deionized water 3 times to obtain the wetted nanofiber membrane c;
（7）将2 g氟钛酸铵加入1 L水中配制成溶液D；在硼酸溶液中添加水配制成浓度为0.03 mol/L的溶液E，将（6）得到的纤维膜c先后浸泡在溶液D和溶液E中，超声5 h后用去离子水和无水乙醇分别清洗2次，得到由二氧化钛包覆的纳米纤维膜d；(7) Add 2 g of ammonium fluorotitanate to 1 L of water to prepare solution D; add water to the boric acid solution to prepare solution E with a concentration of 0.03 mol/L, and soak the fiber membrane c obtained in (6) successively in the solution In D and solution E, sonicated for 5 h and washed twice with deionized water and absolute ethanol, respectively, to obtain nanofiber membrane d coated by titanium dioxide;
（8）将（7）得到的纤维膜d放置到60 ~ 90℃的真空环境中干燥8 h，得到阻可见口罩滤芯外层e；(8) Place the fiber membrane d obtained in (7) in a vacuum environment of 60 to 90 °C for 8 h to dry to obtain the outer layer e of the filter element of the visible mask;
（9）将滤芯内层a与滤芯外层e进行密集型缝合得到所述的具有热舒适性防PM 2.5功能的口罩滤芯膜材料。 (9) Intensive suturing of the inner layer a of the filter element and the outer layer e of the filter element to obtain the described mask filter element membrane material with thermal comfort and anti-PM 2.5 function.
本实施例所制得口罩滤芯人体中红外透过率为85 ~ 90%（参见图3），滤芯材料对可见光的透过率≤50%（参见图6）；利用image-Proplus软件对SEM图像分析得到所制得口罩滤芯的平均纤维直径为200 nm，利用实验室搭建的滤料测试平台得到该滤芯材料在风速为5.3 cm/s时，对0.3 μm颗粒的过滤效率为96.49%（参见图7），压降为102 Pa（参见图8）。The infrared transmittance of the filter element of the mask made in this example is 85 to 90% in the human body (see Figure 3), and the transmittance of the filter element material to visible light is ≤ 50% (see Figure 6); the SEM image is analyzed using image-Proplus software. The average fiber diameter of the obtained mask filter element is 200 nm, using the filter material test platform built in the laboratory to obtain the filter material when the wind speed is 5.3 cm/s, the filtration efficiency of 0.3 μm particles is 96.49% (see Figure 7), and the pressure drop is 102 Pa (see Figure 8) .
实施例Example 22
一种热舒适性防PM 2.5的纳米纤维口罩滤芯的制备方法，具体步骤为： A preparation method of a thermal comfort anti-PM 2.5 nanofiber mask filter element, the specific steps are:
（1）将1.2 g 聚酰胺6与8.6 g甲酸混合均匀，注意在取用甲酸时佩戴防毒面具并打开通风橱操作；将0.12 g氟化钙置于上述混合溶剂中，用超声震荡仪震荡1.5 h，搅拌均匀配制成溶液A；(1) Mix 1.2 g of polyamide 6 and 8.6 g of formic acid evenly, pay attention to wear a gas mask and open the fume hood when handling formic acid; put 0.12 g of calcium fluoride in the above mixed solvent, shake it with an ultrasonic oscillator for 1.5 h, stir to prepare solution A;
（2）将纺丝溶液A加到静电纺丝装置中的注射***（参见图1），图1中包括推注***1、注射***2、静电高压***3和接收***4。将接收***改进为紫铜网接收极板，静电纺丝工艺参数为：接收距离为10 cm，静电高压为25 KV，推注速度为0.05 mm/min，温度为28℃，相对湿度为35%，纺丝时间为30 min，得到纳米纤维膜；(2) The injection system for adding the spinning solution A to the electrospinning device (see FIG. 1 ), which includes a bolus injection system 1 , an injection system 2 , an electrostatic high voltage system 3 and a receiving system 4 . The receiving system was improved to a copper mesh receiving plate, and the electrospinning process parameters were: receiving distance of 10 cm, electrostatic high voltage of 25 KV, injection speed of 0.05 mm/min, temperature of 28 °C, relative humidity of 35%, The spinning time was 30 min to obtain a nanofiber membrane;
（3）将膜置于25℃恒温环境中干燥22 h得到透红外滤芯内层a；(3) Dry the membrane in a constant temperature environment of 25 °C for 22 h to obtain the inner layer a of the infrared transparent filter element;
（4）将1.2 g聚酰胺6与8.6 g甲酸混合均匀，室温搅拌10h得到纺丝溶液B；(4) Mix 1.2 g of polyamide 6 and 8.6 g of formic acid uniformly, and stir at room temperature for 10 h to obtain spinning solution B;
（5）将（4）纺丝液B通过静电纺丝，其中的设备与参数同步骤（2）一致，得到纳米纤维膜b；(5) Electrospinning (4) spinning solution B, wherein the equipment and parameters are the same as in step (2), to obtain nanofiber membrane b;
（6）将5 g二氯化锡加入到1 L盐酸（质量分数为37%）中配制成溶液C；将（5）得到的纤维膜b浸泡在C中3 min，取出后用去离子水洗3遍，得到纳米纤维膜c；(6) Add 5 g of tin dichloride to 1 L of hydrochloric acid (37% by mass) to prepare solution C; soak the fiber membrane b obtained in (5) in C for 3 min, take it out and wash with deionized water 3 times to obtain nanofiber membrane c;
（7）将2 g氟钛酸铵加入1 L水中配制成溶液D；在硼酸溶液中添加水配制成浓度为0.03 mol/L的溶液E，将（6）得到的纤维膜c先后浸泡在溶液D和溶液E中，超声6 h后用去离子水和无水乙醇分别清洗2次，得到由二氧化钛包覆的纳米纤维膜d；(7) Add 2 g of ammonium fluorotitanate to 1 L of water to prepare solution D; add water to the boric acid solution to prepare solution E with a concentration of 0.03 mol/L, and soak the fiber membrane c obtained in (6) successively in the solution D and solution E were washed twice with deionized water and absolute ethanol after sonication for 6 h, respectively, to obtain nanofiber membrane d coated by titanium dioxide;
（8）将（7）得到的纤维膜d放置到60 ~ 90℃的真空环境中干燥9 h，得到阻可见口罩滤芯外层e；(8) Place the fiber membrane d obtained in (7) in a vacuum environment of 60 to 90 °C for 9 hours to dry to obtain the outer layer e of the filter element of the mask with visible resistance;
（9）将滤芯内层a与滤芯外层e进行密集型缝合得到所述的具有热舒适性防PM 2.5功能的口罩滤芯膜材料。 (9) Intensive suturing of the inner layer a of the filter element and the outer layer e of the filter element to obtain the described mask filter element membrane material with thermal comfort and anti-PM 2.5 function.
本实施例所制得口罩滤芯人体中红外透过率为87.13 ~ 97.63%（参见图4），滤芯材料对可见光的透过率≤ 60%（参见图6）；利用image-Proplus软件对SEM图像分析得到所制得口罩滤芯的所制得口罩滤芯的平均纤维直径为365 nm，透湿性能为0.0131 g/cm 2/h，利用实验室搭建的滤料测试平台得到该滤芯材料在风速为5.3 cm/s时，对0.3 μm颗粒过滤效率为97.12%（参见图7），压降为80 Pa（参见图8）。 The infrared transmittance in the human body of the mask filter element prepared in this example is 87.13 to 97.63% (see Figure 4), and the transmittance of the filter element material to visible light is ≤ 60% (see Figure 6); the SEM image is analyzed by image-Proplus software. The average fiber diameter of the obtained mask filter element obtained by analysis was 365 nm, and the moisture permeability was 0.0131 g/cm 2 /h. The filter material test platform built by the laboratory was used to obtain the filter material at a wind speed of 5.3. At cm/s, the filtration efficiency for 0.3 μm particles is 97.12% (see Figure 7), and the pressure drop is 80 Pa (see Figure 8).
实施例Example 33
一种热舒适性防PM 2.5的纳米纤维口罩滤芯的制备方法，具体步骤为： A preparation method of a thermal comfort anti-PM 2.5 nanofiber mask filter element, the specific steps are:
（1）将1.87 g 聚丙烯腈与13.68 g N，N-二甲基甲酰胺混合均匀；将0.15 g氟化镁置于上述混合溶剂中，用超声震荡仪震荡1.5 h，搅拌均匀配制成溶液A；(1) Mix 1.87 g of polyacrylonitrile and 13.68 g of N,N-dimethylformamide uniformly; put 0.15 g of magnesium fluoride in the above mixed solvent, shake it with an ultrasonic oscillator for 1.5 h, and stir to prepare a solution. A;
（2）将纺丝溶液A加到静电纺丝装置中的注射***（参见图1），图1中包括推注***1、注射***2、静电高压***3和接收***4。将接收***改进为紫铜网接收极板，静电纺丝工艺参数为：接收距离为20 cm，静电高压为20 KV，推注速度为0.1 mm/min，温度为26℃，相对湿度为50%，纺丝时间为40min，得到纳米纤维膜；(2) The injection system for adding the spinning solution A to the electrospinning device (see FIG. 1 ), which includes a bolus injection system 1 , an injection system 2 , an electrostatic high voltage system 3 and a receiving system 4 . The receiving system was improved to a copper mesh receiving plate, and the electrospinning process parameters were as follows: the receiving distance was 20 cm, the electrostatic high voltage was 20 KV, the injection speed was 0.1 mm/min, the temperature was 26 °C, and the relative humidity was 50%. Spinning time is 40min, obtains nanofiber membrane;
（3）将膜置于35℃恒温环境中干燥18 h得到透红外滤芯内层a；(3) Dry the membrane in a constant temperature environment of 35 °C for 18 h to obtain the inner layer a of the infrared transparent filter element;
（4）将1.87 g 聚丙烯腈与13.68 g N，N-二甲基甲酰胺混合均匀，室温搅拌8h得到纺丝溶液B， (4) Mix 1.87 g of polyacrylonitrile and 13.68 g of N,N-dimethylformamide uniformly, and stir at room temperature for 8 h to obtain spinning solution B.
（5）将（4）纺丝液B通过静电纺丝，其中的设备与参数同步骤（2）一致，得到纳米纤维膜b；(5) Electrospinning (4) spinning solution B, wherein the equipment and parameters are the same as in step (2), to obtain nanofiber membrane b;
（6）将4 g二氯化锡加入到1 L盐酸（质量分数为37%）中配制成溶液C；将（5）得到的纤维膜b浸泡在C中8 min，取出后用去离子水洗3遍，得到纳米纤维膜c；(6) Add 4 g of tin dichloride to 1 L of hydrochloric acid (37% by mass) to prepare solution C; soak the fiber membrane b obtained in (5) in C for 8 min, take it out and wash with deionized water 3 times to obtain nanofiber membrane c;
（7）将3 g氟钛酸铵加入1L水中配制成溶液D；在硼酸溶液中添加水配制成浓度为0.03 mol/L的溶液E，将（6）得到的纤维膜c先后浸泡在溶液D和溶液E中，超声5 h后用去离子水和无水乙醇分别清洗3次，得到由二氧化钛包覆的纳米纤维膜d；(7) Add 3 g of ammonium fluorotitanate to 1 L of water to prepare solution D; add water to the boric acid solution to prepare solution E with a concentration of 0.03 mol/L, and soak the fiber membrane c obtained in (6) in solution D successively and solution E, washed with deionized water and absolute ethanol for 3 times respectively after sonicating for 5 h to obtain the nanofiber membrane d coated by titanium dioxide;
（8）将（7）得到的纤维膜d放置到60 ~ 90℃的真空环境中干燥10 h，得到阻可见口罩滤芯外层e；(8) Place the fiber membrane d obtained in (7) in a vacuum environment of 60 to 90 °C for 10 hours to dry to obtain the outer layer e of the filter element of the mask with visible resistance;
（9）将滤芯内层a与滤芯外层e进行密集型缝合得到所述的具有热舒适性防PM 2.5功能的口罩滤芯膜材料。 (9) Intensive suturing of the inner layer a of the filter element and the outer layer e of the filter element to obtain the described mask filter element membrane material with thermal comfort and anti-PM 2.5 function.
本实施例所制得口罩滤芯人体中红外透过率为81.94 ~ 98.1%（参见图5），滤芯材料对可见光的透过率≤ 60%（参见图6）；利用image-Proplus软件对SEM图像分析得到所制得口罩滤芯的所制得口罩滤芯平均纤维直径为662 nm，利用实验室搭建的滤料测试平台得到该滤芯材料在风速为5.3 cm/s时，对0.3 μm颗粒的过滤效率为92.97%（参见图7），压降为27 Pa（参见图8）。The infrared transmittance of the mask filter element made in this example is 81.94-98.1% in the human body (see Figure 5), and the transmittance of the filter element material to visible light is less than or equal to 60% (see Figure 6); use image-Proplus software to analyze the SEM image The average fiber diameter of the obtained mask filter element was 662 nm, and the filter material test platform built in the laboratory was used to obtain the filter element material at a wind speed of 5.3 nm. At cm/s, the filtration efficiency for 0.3 μm particles is 92.97% (see Figure 7) and the pressure drop is 27 Pa (see Figure 8).
对比测试例Comparative test case 11
一次性口罩的傅里叶红外变换光谱测试，测试与实施例1-3相同；其对中红外透过率≤ 5%，测试结果参见图3-5。The Fourier infrared transform spectrum test of the disposable mask, the test is the same as that of Example 1-3; its mid-infrared transmittance≤5%, and the test result is shown in Figure 3-5.
对比测试例Comparative test case 22
一次性口罩和KN95口罩对不同直径颗粒的捕获效率测试，测试条件与实施例1-3相同；一次性口罩对≤ 1.0μm粒径的粒子捕获能力≤ 65%，KN95口罩对颗粒的捕获性能仅次于实施例。测试结果参见图7。The capture efficiency test of disposable masks and KN95 masks for particles of different diameters, the test conditions are the same as in Example 1-3; next to the examples. The test results are shown in Figure 7.
对比测试例Comparative test case 33
一次性口罩和KN95口罩的过滤压降测试，测试条件与实施例1-3相同；The filter pressure drop test of disposable masks and KN95 masks, the test conditions are the same as those of Example 1-3;
测试结果参见图8。The test results are shown in Figure 8.
以上所述，仅为本发明的较佳实施例而已，并非对本发明做任何形式上的限定。凡本领域的技术人员利用本发明的技术方案对上述实施例做出的任何等同的变动、修饰或演变等，均仍属于本发明技术方案的范围内。The above descriptions are merely preferred embodiments of the present invention, and do not limit the present invention in any form. Any equivalent changes, modifications or evolutions made by those skilled in the art to the above embodiments by utilizing the technical solutions of the present invention still fall within the scope of the technical solutions of the present invention.

Claims (10)

  1. 一种热舒适性防PM 2.5的纳米纤维口罩滤芯，其特征在于，包括靠近皮肤侧的透红外内层滤芯以及靠近环境侧的阻可见光外层滤芯，所述两层滤芯进行密集型缝合。 A thermal comfort anti-PM 2.5 nanofiber mask filter, characterized in that it includes an infrared-transmitting inner filter close to the skin side and an outer visible light blocking filter close to the environment, and the two-layer filter is intensively stitched.
  2. 根据权利要求1所述的一种热舒适性防PM 2.5的纳米纤维口罩滤芯，其特征在于，所述内层滤芯为添加了具有增透红外功能的纳米颗粒的纳米纤维薄膜，所述外层滤芯为添加了阻可见辐射颗粒的纳米纤维薄膜。 A kind of thermal comfort anti-PM 2.5 nanofiber mask filter core according to claim 1, is characterized in that, described inner layer filter core is the nanofiber film that adds the nanoparticle with anti-reflection infrared function, described outer layer The filter element is a nanofiber membrane with added visible radiation blocking particles.
  3. 根据权利要求1所述的一种热舒适性防PM 2.5的纳米纤维口罩滤芯，其特征在于，所述内层滤芯可以透过人体面部散发的热辐射，对人体红外透过率≥ 85%；所述外层滤芯可以阻挡周围环境对人体的热辐射，所述外层滤芯对大气可见光热辐射的透过率≤ 60%。 A kind of thermal comfort anti-PM 2.5 nanofiber mask filter core according to claim 1, is characterized in that, described inner layer filter core can pass through the thermal radiation that human face emits, to human body infrared transmittance ≥ 85%; The outer layer filter element can block the thermal radiation of the surrounding environment to the human body, and the transmittance of the outer layer filter element to the visible light thermal radiation in the atmosphere is less than or equal to 60%.
  4. 根据权利要求1所述的一种热舒适性防PM 2.5的纳米纤维口罩滤芯，其特征在于，所述纳米纤维口罩滤芯的平均纤维直径为0.2 ~ 1 μm，所述纳米纤维口罩滤芯的孔隙率≥ 85%，对≥ 0.3 µm颗粒的过滤效率为90% ~ 99.95%，阻力为3 ~ 200 Pa，能实现对PM 2.5的高效过滤。 A kind of thermal comfort anti-PM 2.5 nanofiber mask filter core according to claim 1, is characterized in that, the average fiber diameter of described nanofiber mask filter core is 0.2～1 μm, the porosity of described nanofiber mask filter core ≥ 85%, the filtration efficiency for ≥ 0.3 µm particles is 90% ~ 99.95%, and the resistance is 3 ~ 200 Pa, which can achieve high-efficiency filtration of PM 2.5 .
  5. 一种热舒适性防PM 2.5的纳米纤维口罩滤芯的制备方法，其特征在于，包括如下步骤： A preparation method of a thermal comfort anti-PM 2.5 nanofiber mask filter element, characterized in that, comprising the steps:
    （1）配制纺丝液A：将聚合物与溶剂混合均匀，然后加入增透红外功能的颗粒，超声震荡直至颗粒分散均匀，室温搅拌后得到稳定的聚合物纺丝液A；(1) Preparation of spinning solution A: Mix the polymer and the solvent evenly, then add the particles with anti-reflection infrared function, ultrasonically vibrate until the particles are evenly dispersed, and stir at room temperature to obtain a stable polymer spinning solution A;
    （2）静电纺丝：首先将静电纺装置的辊轴金属极板改变为导电性能更佳的紫铜网极板，调节工艺参数，设置环境参数，将所述纺丝液A加到静电纺丝装置中，通过静电纺丝制备得到纳米纤维滤芯膜材料；(2) Electrospinning: First, change the roller metal plate of the electrospinning device to a copper mesh plate with better electrical conductivity, adjust the process parameters, set the environmental parameters, and add the spinning solution A to the electrospinning. In the device, the nanofiber filter element membrane material is prepared by electrospinning;
    （3）将步骤（2）制备的所述纳米纤维滤芯膜材料在25 ~ 35℃恒定温度环境干燥，得到所述的具有透过红外性能的高效过滤口罩滤芯内层a；(3) drying the nanofiber filter element membrane material prepared in step (2) at a constant temperature of 25-35 °C to obtain the inner layer a of the high-efficiency filter mask filter element with infrared permeation performance;
    （4）配制纺丝液B：将聚合物与溶剂混合，室温搅拌8 ~10 h，得到纺丝液B，所述纺丝液B的聚合物和溶剂与步骤（1）所述纺丝液A的聚合物和溶剂相同；(4) Preparation of spinning solution B: Mix the polymer and solvent, and stir at room temperature for 8-10 h to obtain spinning solution B. The polymer and solvent of spinning solution B are the same as the spinning solution in step (1). The polymer and solvent of A are the same;
    （5）将所述纺丝液B加到步骤（2）所述静电纺丝装置中，经过静电纺丝得到聚合物纳米纤维膜b；(5) adding the spinning solution B to the electrospinning device of step (2), and obtaining a polymer nanofiber membrane b through electrospinning;
    （6）配制溶液C：将无机粒子M加入盐酸的水溶液中得到溶液C，将所述纳米纤维膜b浸泡在所述溶液C后使其活化2 ~ 20 min，取出所述纳米纤维膜b后用去离子水清洗1 ~ 3次，得到纳米纤维膜c；(6) Preparation of solution C: adding inorganic particles M into an aqueous solution of hydrochloric acid to obtain solution C, soaking the nanofiber membrane b in the solution C and then activating it for 2-20 min, take out the nanofiber membrane b and wash it with deionized water for 1 to 3 times to obtain the nanofiber membrane c;
    （7）配制前驱体溶液D：将溶质N加入水中得到溶液D，将所述纳米纤维膜c浸泡在所述溶液D后，再放入被稀释的酸性水溶液E中，取出纤维膜后放入超声仪中，超声4 ~ 6 h后用去离子水和无水乙醇分别清洗1 ~ 3次，得到纳米纤维膜d；(7) Preparation of precursor solution D: add solute N into water to obtain solution D, soak the nanofiber membrane c in the solution D, and then put it into the diluted acidic aqueous solution E, take out the fiber membrane and put it into the solution D. In the ultrasonic instrument, after ultrasonication for 4 to 6 hours, the nanofiber membrane d is obtained by washing with deionized water and absolute ethanol for 1 to 3 times respectively;
    （8）将（7）制备的所述纳米纤维膜d在60 ~ 90°C的真空环境中干燥，得到由隔热颗粒包覆的具有阻挡可见光功能的口罩滤芯外层e；(8) drying the nanofiber membrane d prepared in (7) in a vacuum environment of 60～90° C. to obtain the outer layer e of the mask filter element with the function of blocking visible light covered by heat insulating particles;
    （9）将所述滤芯内层a与所述滤芯外层e经过密集型缝合得到的热舒适性防PM 2.5口罩滤芯。 (9) The thermal comfort anti-PM 2.5 mask filter element obtained by intensive stitching of the inner layer a of the filter element and the outer layer e of the filter element.
  6. 根据权利要求5所述的制备方法，其特征在于，步骤（1）所述聚合物为聚丙烯腈、聚乙烯、聚酰胺和聚对苯二甲酸乙二酯中的一种或几种；步骤（1）所述的溶剂为甲酸、N，N-二甲基甲酰胺中的一种或几种；步骤（1）所述的增透红外功能的颗粒为氟化钙、氟化镁、氧化锌中的一种或几种。The preparation method according to claim 5, wherein the polymer in step (1) is one or more of polyacrylonitrile, polyethylene, polyamide and polyethylene terephthalate; step (1) The solvent is one or more of formic acid and N,N-dimethylformamide; the particles with antireflection infrared function described in step (1) are calcium fluoride, magnesium fluoride, oxide One or more of zinc.
  7. 根据权利要求5所述的制备方法，其特征在于，步骤（1）得到的所述纺丝液A中增透红外功能的颗粒浓度为0.02 ~ 0.16 mol/L；步骤（1）所述聚合物在纺丝液A中的质量浓度为12 ~ 20 wt.% ；步骤（3）所述的干燥时间为18 ~ 24个小时。The preparation method according to claim 5, wherein the concentration of particles with anti-reflection infrared function in the spinning solution A obtained in step (1) is 0.02 to 0.16 mol/L; the polymer in step (1) The mass concentration in spinning solution A is 12 ~ 20 wt.%; the drying time described in step (3) is 18 to 24 hours.
  8. 根据权利要求5所述的制备方法，其特征在于，步骤（6）中所述无机粒子M为二氯化锡、氯化钯中的一种或几种；步骤（7）中所述溶质N为氟钛酸铵、氧氯化锆中的一种或几种，所述酸性水溶液是硼酸、盐酸、甲酸中的一种或几种。The preparation method according to claim 5, wherein the inorganic particles M in step (6) are one or more of tin dichloride and palladium chloride; the solute N in step (7) It is one or more of ammonium fluorotitanate and zirconium oxychloride, and the acidic aqueous solution is one or more of boric acid, hydrochloric acid and formic acid.
  9. 根据权利要求5所述的制备方法，其特征在于，步骤（4）所述的聚合物在纺丝液中的质量浓度为12 ~ 20 wt.%；步骤（6）中无机粒子M的质量浓度为0.3 ~ 0.5 wt.% ；步骤（7）中前驱体溶液D中溶质N的浓度为0.01 ~ 0.05 mol/L，酸性水溶液E的浓度为0.02 ~0.03 mol/L；步骤（8）所述的干燥时间为8 ~10个小时。The preparation method according to claim 5, wherein the mass concentration of the polymer described in step (4) in the spinning solution is 12-20 wt.%; the mass concentration of the inorganic particles M in step (6) is 0.3-0.5 wt.%; in the step (7), the concentration of the solute N in the precursor solution D is 0.01-0.05 mol/L, and the concentration of the acidic aqueous solution E is 0.02-0.03 mol/L; the step (8) described Drying time is 8 to 10 hours.
  10. 根据权利要求5~9任一项所述的一种热舒适性防PM 2.5的纳米纤维口罩滤芯制备方法，其特征在于，步骤（2）和步骤（5）所述静电纺丝装置包括推注***、纺丝溶液注射***、静电高压***和改进后的紫铜旋转辊轴接收***；步骤（2）和步骤（5）所述静电纺丝工艺参数为：纺丝电压为15 ~ 25 KV，接收距离为10 ~ 20 cm，注射速度为0.05 ~ 0.25 mm/min，温度为18 ~ 35℃，相对湿度为30 ~ 70%。 The method for preparing a thermal comfort anti-PM 2.5 nanofiber mask filter element according to any one of claims 5 to 9, wherein the electrospinning device in step (2) and step (5) comprises a bolus injection system, a spinning solution injection system, an electrostatic high-voltage system and an improved copper rotating roller receiving system; the electrospinning process parameters described in steps (2) and (5) are: the spinning voltage is 15-25 KV, the receiving system is The distance is 10 ~ 20 cm, the injection speed is 0.05 ~ 0.25 mm/min, the temperature is 18 ~ 35 ℃, and the relative humidity is 30 ~ 70%.
      
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