CN117818156A - Radiation-proof breathable fabric and preparation method thereof - Google Patents

Radiation-proof breathable fabric and preparation method thereof Download PDF

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Publication number
CN117818156A
CN117818156A CN202211097732.8A CN202211097732A CN117818156A CN 117818156 A CN117818156 A CN 117818156A CN 202211097732 A CN202211097732 A CN 202211097732A CN 117818156 A CN117818156 A CN 117818156A
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radiation
mass
proof
breathable fabric
polyimide prepolymer
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夏龙
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Individual
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • 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
    • A41D31/14—Air permeable, i.e. capable of being penetrated by gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • 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
    • D01F6/88—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
    • D01F6/94—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 other polycondensation products
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00—Materials for garments
    • A41D2500/20—Woven
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/08—Animal fibres, e.g. hair, wool, silk
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention discloses a radiation-proof breathable fabric and a preparation method thereof, and relates to the technical field of fabrics. The radiation-proof breathable fabric prepared by the invention comprises a skin-friendly layer and a radiation-proof layer from bottom to top; firstly, mixing 3-bromo-5-nitroaniline, pyromellitic dianhydride and p-phenylenediamine to prepare polyimide prepolymer; then mixing 5-cyano isophthalic acid and m-phenylenediamine to prepare cyano m-phthalamide; then blending and spinning polyimide prepolymer, acidified carbon nano tube and cyano-isophthalamide, co-twisting and braiding to prepare an anti-radiation layer; then blending and spinning the vitamin A palmitate, the vitamin E polyethylene glycol succinate and the silk fibroin, co-twisting and braiding to prepare a skin-friendly layer; finally, the skin-friendly layer and the radiation-proof layer are sequentially paved from bottom to top, and sodium hydroxide solution and ferric chloride are used for secondary impregnation, so that the radiation-proof breathable fabric with good air permeability, washability, tear resistance and radiation resistance is prepared.

Description

Radiation-proof breathable fabric and preparation method thereof
Technical Field
The invention relates to the technical field of fabrics, in particular to a radiation-proof breathable fabric and a preparation method thereof.
Background
Along with the continuous improvement of the living standard of people, the requirements of people on textiles are not limited to original basic characteristics such as warmth retention and comfort, but the eyesight is concentrated on the functional fabric with special functions such as health care and safety, and the radiation-proof fabric is one of the functional fabrics.
The radiation source can release certain electromagnetic wave radiation in surrounding televisions, refrigerators, air conditioners, microwave ovens, computers, mobile phones and the like, and people working, learning and living in an environment with concentrated radiation sources are easy to suffer from symptoms such as insomnia, dreaminess, hypomnesis, asthenia, hypodynamia and the like. For pregnant women, abortion can be caused, and the old provided with the heart pacemaker can disable the device, thereby threatening lives. Therefore, necessary preventive measures should be taken for the aged, children, pregnant women or people who are sensitive to electromagnetic wave radiation and work in an electromagnetic radiation environment with ultra-dosage for a long time.
The most direct mode of preventing electromagnetic wave radiation is to wear radiation-proof clothes, and the aim of reducing or completely isolating the electromagnetic wave radiation is fulfilled by special radiation-proof fibers or radiation-proof coating metal in the clothes. However, although the purpose of preventing electromagnetic wave radiation can be achieved by directly implanting the metal wires into the fabric, due to the diversity of the combination modes of the metal wires and the fabric fibers, the handle of the fabric of the clothing is deteriorated by some treatment modes, and if the metal wires are directly contacted with the skin, skin infection or discomfort is caused, so that the usability of the clothing is reduced; therefore, the technician chooses to compound the radiation protection layer on the surface of the skin-friendly fabric to solve the problem. However, in the using process, people find that the anti-radiation fabric prepared by the method has poor air permeability, and the anti-radiation layer is very easy to peel and tear in the using process, so that the clothing wearability and the service life of the clothing are greatly reduced. Therefore, the fabric with good air permeability, washability, tear resistance and radiation resistance is prepared, and the fabric becomes a difficult problem to be solved in the current field.
The invention focuses on the phenomenon, and solves the problem by preparing the radiation-proof breathable fabric.
Disclosure of Invention
The invention aims to provide a radiation-proof breathable fabric and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a radiation-proof breathable fabric is obtained by paving a skin-friendly layer and a radiation-proof layer from bottom to top in sequence and performing secondary dip rolling by using sodium hydroxide solution and ferric chloride.
Further, the skin-friendly layer is obtained by blending spinning, co-twisting and braiding of vitamin A palmitate, vitamin E polyethylene glycol succinate and silk fibroin.
Further, the radiation-proof layer is formed by blending spinning, co-twisting and braiding polyimide prepolymer, acidified carbon nano tube and cyano-isophthalamide.
Further, the polyimide prepolymer is prepared by mixing 3-bromo-5-nitroaniline, pyromellitic dianhydride and p-phenylenediamine.
Further, the cyano-isophthalamide is prepared by mixing 5-cyano-isophthalic acid and m-phenylenediamine.
Further, a preparation method of the radiation-proof breathable fabric comprises the following preparation steps:
(1) At room temperature, calcium chloride, ethanol and deionized water are mixed according to the mass ratio of 1:0.82:1.28 to 1:0.84:1.3, uniformly mixing to prepare a mixed solvent; placing the silkworm cocoons subjected to pupation removal into sodium bicarbonate solution with the mass fraction of 0.5% which is 100-200 times of that of the silkworm cocoons subjected to pupation removal, and boiling for 3 times at 100 ℃ with each time of 28-32 min, then taking out, washing with deionized water for 3-5 times, drying for 1-3 hours at 60 ℃, stirring for 55-65 minutes at 1200-1400 r/min in a mixed solvent at 70 ℃, naturally cooling to room temperature, putting into a 250-7u dialysis bag, dialyzing for 70-74 hours in distilled water with the mass 100-200 times of that of the bag, filtering, freezing for 12-14 hours at-10-0 ℃, and then freezing and drying for 46-50 hours at 10-20 Pa and-55-45 ℃ to obtain the silk fibroin sponge; at 85 ℃, vitamin A palmitate and vitamin E polyethylene glycol succinate are mixed according to the mass ratio of 1:1.8 to 1:2.2, mixing, heating to 85 ℃, preserving heat for 40-60 min, and then adding deionized water with the vitamin A palmitate of 100 ℃ according to the mass ratio of 1:4.5 to 1:5.5, mixing, stirring for 18-22 min at 1200-1400 r/min, then continuously stirring for 110-130 min at room temperature, and then mixing according to the mass ratio of 1:5 to 1:7 adding silk fibroin sponge and deionized water, wherein the mass of the silk fibroin is 9-11 times of that of vitamin A palmitate, continuously stirring for 2-4 h, carrying out electrostatic spinning at a voltage of 20kV and a liquid feeding rate of 0.3ml/h, then carrying out cross-blowing cooling solidification for 25-35 min under the conditions of 10-20 ℃ and humidity of 60-80% and wind speed of 0.9-1.3 m/s, and then co-twisting and braiding to obtain 200-240 g/m 2 Is a skin-friendly layer of (a);
(2) Under the protection of nitrogen, polyimide prepolymer, cyano-isophthalamide, potassium carbonate and copper bromide are mixed according to the mass ratio of 1:0.3:0.2: 0.09-1: 0.5:0.4: mixing 0.11, heating to 160-180 ℃, stirring for 11.5-12.5 h at 1200-1400 r/min, adding chloroform with the mass of 1-3 times of polyimide prepolymer, filtering, steaming for 30-50 min at 2000-3000 r/min at 10-20 Pa and 70-80 ℃, adding nano nickel with the mass of 0.02-0.04 times of polyimide prepolymer and deionized water with the mass of 2-3 times of polyimide prepolymer, uniformly mixing, and steaming for 3-5 m at 110-150 ℃ and 1.5-2 MPa 3 Introducing hydrogen with the mass 1-2 times of that of the polyimide prepolymer, continuously stirring for 1.5-2.5 hours, then cooling to 90-110 ℃, adding sulfuric acid solution with the mass 0.1-0.3 time of that of the polyimide prepolymer and the mass fraction of 70%, continuously stirring for 2-4 hours, cooling to 70-90 ℃, adding acidified carbon nano tubes with the mass 0.4-0.6 time of that of the polyimide prepolymer, and dripping the polyimide with the mass of 40-60 drops/minThe concentrated sulfuric acid with the mass fraction of 98% of the amine prepolymer of 0.08-0.1 times is continuously stirred for 2-4 hours, the mixture is put into a spinning box at 300-400 ℃, a screw extruder is used for spinning at the spinning speed of 800-1000 m/min, the cross-blowing cooling solidification is carried out for 25-35 min at the temperature of 10-20 ℃ under the conditions that the humidity is 60-80% and the wind speed is 0.9-1.3 m/s, and then the mixture is co-twisted and woven to obtain 200-240 g/m 2 Is arranged on the radiation-proof layer;
(3) Under the condition of room temperature and nitrogen protection, paving a skin-friendly layer and a radiation-proof layer from bottom to top, immersing the skin-friendly layer and the radiation-proof layer in 10% sodium hydroxide solution by mass fraction, flushing the sodium hydroxide solution with the radiation-proof layer, heating the solution to 85 ℃, performing ultrasonic treatment for 0.3-0.5 h at 40-60 kHz, dripping 6-10% hydrochloric acid solution by mass fraction at 40-60 drops/min to adjust the pH value to 7, adding a mixed oxidant which is 0.2-0.4 times of the skin-friendly layer, continuing ultrasonic treatment for 40-60 min, performing microwave treatment for 80-100 min at 2400-2500 MHz and 700-900W, fishing out, washing for 2-4 times by acetone, placing the fabric into an oven for drying for 40-60 min at 58-62 ℃, then immersing the fabric into 6-8% ferric chloride ethanol solution, continuing ultrasonic treatment for 60-80 min at 80 ℃, standing for 30-50 min, fishing out, washing the fabric by deionized water and ethanol for 2-4 times, and placing the fabric into the oven for 2-4 h to obtain the radiation-proof breathable fabric.
Further, the preparation method of the polyimide prepolymer in the step (2) comprises the following steps: under the conditions of 0-4 ℃ and nitrogen protection, p-phenylenediamine and N, N-dimethylacetamide are mixed according to the mass ratio of 1:10 to 1:12, adding pyromellitic dianhydride with the mass of 2.3-2.5 times of that of the p-phenylenediamine, stirring for 2-4 hours at the speed of 1200-1400 r/min, adding 3-bromo-5-nitroaniline with the mass of 0.6-0.8 times of that of the p-phenylenediamine, continuously stirring for 20-24 hours, heating to 70-90 ℃ for 2-4 hours, continuously heating to 110-130 ℃ for 50-70 minutes, heating to 170-190 ℃ for 50-70 minutes, and heating to 240-260 ℃ for 50-70 minutes to obtain the polyimide prepolymer.
Further, the preparation method of the cyano isophthalamide in the step (2) comprises the following steps: at room temperature, m-phenylenediamine and acetone are mixed according to the mass ratio of 1: 90-1: 110, then heating to 89-91 ℃, adding 5-cyano isophthalic acid with the mass 1.4-1.6 times of that of m-phenylenediamine, and continuously stirring for 3.5-4.5 hours to prepare the cyano m-phthalimide.
Further, the preparation method of the acidified carbon nanotubes in the step (2) comprises the following steps: mixing carbon nano tubes and 98% concentrated sulfuric acid according to a mass ratio of 1:210 to 1:230, mixing, ultrasonically oscillating for 25-35 min at 38-47 kHz, then adding concentrated nitric acid with the mass fraction of 68% and the mass of 55-57 times of the carbon nano tube, stirring for 9-11 min at 1200-1400 r/min, heating to 58-62 ℃, continuously stirring for 1.5-2.5 h, adding deionized water with the mass of 98-102 times of the carbon nano tube for dilution, standing for 3.5-4.5 h, vacuum-filtering by using a microporous filter membrane with the aperture of 220nm, washing with deionized water until the pH value of the filtrate is 7, washing with absolute ethyl alcohol for 2-4 times, and baking in an oven at 55-65 ℃ for 40-60 min to obtain the acidified carbon nano tube.
Further, the preparation method of the mixed oxidant in the step (3) comprises the following steps: under the protection of nitrogen, chromium trioxide, methylamine, hydrogen chloride and acetone are mixed according to the mass ratio of 1:0.2:0.3:0.6 to 1:0.3:0.4: and 0.8, uniformly mixing to obtain the mixed oxidant.
Compared with the prior art, the invention has the following beneficial effects:
the radiation-proof breathable fabric prepared by the invention comprises a skin-friendly layer and a radiation-proof layer from bottom to top; firstly, blending and spinning polyimide prepolymer, acidified carbon nano tube and cyano-meta-benzene dicarboxamide, co-twisting and braiding to prepare a radiation-proof layer; then blending and spinning the vitamin A palmitate, the vitamin E polyethylene glycol succinate and the silk fibroin, co-twisting and braiding to prepare a skin-friendly layer; finally, sequentially paving a skin-friendly layer and a radiation-proof layer from bottom to top, and carrying out secondary impregnation by using sodium hydroxide solution and ferric chloride to obtain the radiation-proof breathable fabric, wherein the polyimide prepolymer is prepared by mixing 3-bromo-5-nitroaniline, pyromellitic dianhydride and p-phenylenediamine; the cyano-m-phthalamide is prepared by mixing 5-cyano-m-phthalic acid and m-phenylenediamine.
Firstly, part of bromobenzene on polyimide prepolymer reacts with amino on m-phenylenediamine to form hyperbranched polymer containing triphenylamine, a large number of cavities are left in the radiation-proof layer, cyano groups of m-phenylenediamine are hydrolyzed into carboxyl groups, partial hydroxyl groups on the functionalized carbon nano tubes react and crosslink, nitro groups on polyimide prepolymer are hydrogenated and reduced to form amino groups, partial amino groups react and crosslink with the carboxyl groups on the carbon nano tubes, the carbon nano tubes are firmly dispersed in the radiation-proof fiber, and the water-washing resistance of the radiation-proof layer is enhanced while the air permeability of the radiation-proof layer is enhanced.
Secondly, sodium hydroxide reacts with part of bromobenzene of the radiation-proof layer to form phenol, and under the catalysis of ferric chloride, the phenol reacts with carboxyl on the surface of the skin-friendly layer to form covalent bond crosslinking, so that the skin-friendly layer and the radiation-proof layer are firmly grafted together, and the tear resistance of the radiation-proof breathable fabric is enhanced; the vitamin A palmitate of the skin-friendly layer is hydrolyzed under the action of sodium hydroxide to form vitamin A, an oxidant is introduced to oxidize the vitamin A to form retinol, the density of the retinol is smaller than that of water, the retinol floats upwards through the pore canal of the radiation-proof layer to react with the pore canal of the radiation-proof layer and the amino on the upper surface to form the retinol Huang Xifu alkali, the retinol Huang Xifu alkali reacts with ferric chloride to form the retinol Huang Xifu alkali salt, and the radiation-proof performance of the radiation-proof breathable fabric is enhanced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the method for testing each index of the radiation-proof breathable fabric prepared in the following examples is as follows:
air permeability: the radiation-proof breathable fabrics prepared in the example and the comparative example with the same quality are adopted, and the air permeability is measured according to the GB/T5453 standard.
Tear resistance: the anti-radiation breathable fabric prepared by the example and the comparative example with the same quality is tested for tearing strength according to the GB/T529 standard method.
Resistance to washing with water and radiation protection: the radiation-proof breathable fabric prepared by the example and the comparative example with the same quality is washed with water for 100 times, and the shielding effectiveness before and after washing for 100 times is tested according to GB/T23463.
Example 1
(1) At room temperature, the carbon nano tube and 98% of concentrated sulfuric acid by mass percent are mixed according to the mass ratio of 1:210, mixing, ultrasonically oscillating for 25min at 38kHz, then adding concentrated nitric acid with the mass fraction of 68% and the mass of 55 times of the carbon nano tube, stirring for 9min at 1200r/min, heating to 58 ℃, continuously stirring for 1.5h, adding deionized water with the mass of 98 times of the carbon nano tube for dilution, standing for 3.5h, vacuum-filtering by using a microporous filter membrane with the aperture of 220nm, washing with deionized water until the pH value of the filtrate is 7, washing with absolute ethyl alcohol for 2 times, and drying in a baking oven at 5 ℃ for 40min to obtain the acidified carbon nano tube;
(2) At room temperature, m-phenylenediamine and acetone are mixed according to the mass ratio of 1:90, then heating to 89 ℃, adding 5-cyano isophthalic acid with the mass 1.4 times of that of m-phenylenediamine, and stirring for 3.5 hours at 1200r/min to prepare cyano m-phthalimide;
(3) Under the condition of 0 ℃ and nitrogen protection, p-phenylenediamine and N, N-dimethylacetamide are mixed according to the mass ratio of 1:10, adding pyromellitic dianhydride with the mass of 2.3 times of that of the p-phenylenediamine, stirring for 2 hours at 1200r/min, adding 3-bromo-5-nitroaniline with the mass of 0.6 times of that of the p-phenylenediamine, continuously stirring for 20 hours, then heating to 70 ℃ for 2 hours, continuously heating to 110 ℃ for 50 minutes, then heating to 170 ℃ for 50 minutes, and then heating to 240 ℃ for 50 minutes to obtain a polyimide prepolymer;
(4) At room temperature, calcium chloride, ethanol and deionized water are mixed according to the mass ratio of 1:0.82:1.28, uniformly mixing to prepare a mixed solvent; decocting pupa-removed cocoon in 100 times of 0.5% sodium bicarbonate solution at 100deg.C for 28min, washing with deionized water for 3 times, oven drying at 60deg.C for 1 hr, stirring at 70deg.C for 55min at 1200r/min, naturally cooling to room temperature, and placing into 250-7u dialysis bag at its mass of 100Dialyzing in distilled water for 70h, filtering, freezing at-10deg.C for 12h, and freeze-drying at-55deg.C for 46h under 10Pa to obtain silk fibroin sponge; at 85 ℃, vitamin A palmitate and vitamin E polyethylene glycol succinate are mixed according to the mass ratio of 1:1.8, heating to 85 ℃, preserving heat for 40min, and then adding deionized water with the vitamin A palmitate of 100 ℃ according to the mass ratio of 1:4.5, mixing, stirring for 18min at 1200r/min, then stirring for 110min at room temperature, and then mixing according to the mass ratio of 1:5 adding silk fibroin sponge and deionized water, wherein the mass of silk fibroin is 9 times of that of vitamin A palmitate, continuously stirring for 2h, carrying out electrostatic spinning at a feeding rate of 0.3ml/h under 20kV voltage by using a needle head of 0.21mm, then carrying out side blowing cooling solidification for 25min under the conditions of 10 ℃ and 60% humidity and 0.9m/s wind speed, and carrying out co-twisting and braiding to obtain 200g/m 2 Is a skin-friendly layer of (a);
(5) Under the protection of nitrogen, polyimide prepolymer, cyano-isophthalamide, potassium carbonate and copper bromide are mixed according to the mass ratio of 1:0.3:0.2: mixing 0.09, heating to 160deg.C, stirring at 1200r/min for 11.5 hr, adding chloroform 1 times of polyimide prepolymer mass, filtering, steaming at 10Pa and 70deg.C for 30min at 2000r/min, adding nano nickel 0.02 times of polyimide prepolymer mass and deionized water 2 times of polyimide prepolymer mass, mixing uniformly, and stirring at 110deg.C and 1.5MPa for 3m 3 Introducing hydrogen gas with the mass of polyimide prepolymer being 1 time, continuously stirring for 1.5 hours, then cooling to 90 ℃, adding sulfuric acid solution with the mass fraction of 0.1 time of the mass of polyimide prepolymer being 70%, continuously stirring for 2 hours, then cooling to 70 ℃, adding acidified carbon nano tubes with the mass fraction of 0.4 time of the polyimide prepolymer, dropwise adding concentrated sulfuric acid with the mass fraction of 0.08 time of the polyimide prepolymer being 98% at 40 drops/min, continuously stirring for 2 hours, placing into a spinning box at 300 ℃, spinning at the spinning speed of 800m/min, using a screw extruder, performing side-blowing cooling curing for 25 minutes at the temperature of 10 ℃ and the humidity of 60% and the wind speed of 0.9m/s, and then co-twisting and braiding to obtain 200g/m 2 Is arranged on the radiation-proof layer;
(6) Under the protection of nitrogen, chromium trioxide, methylamine, hydrogen chloride and acetone are mixed according to the mass ratio of 1:0.2:0.3:0.6, uniformly mixing to prepare a mixed oxidant; under the condition of room temperature and nitrogen protection, paving a skin-friendly layer and a radiation-proof layer from bottom to top, immersing the skin-friendly layer and the radiation-proof layer in 10% sodium hydroxide solution by mass fraction, enabling the sodium hydroxide solution to be flush with the radiation-proof layer, heating to 85 ℃, performing ultrasonic treatment for 0.3h at 40kHz, dropwise adding 6% hydrochloric acid solution by mass fraction to adjust pH to 7 at 40 drops/min, then adding a mixed oxidant with 0.2 times of the skin-friendly layer by mass fraction, continuing ultrasonic treatment for 40min, performing microwave treatment for 80min under 2400MHz and 700W microwave conditions, fishing out, washing with acetone for 2 times, putting into a 58 ℃ oven for baking for 40min, immersing the skin-friendly layer and the radiation-proof layer into 6% ferric chloride ethanol solution, continuing ultrasonic treatment for 60min at 80 ℃, standing for 30min, fishing out, washing with deionized water and ethanol for 2 times, and putting into the 58 ℃ oven for baking for 2h to obtain the radiation-proof breathable fabric.
Example 2
(1) At room temperature, the carbon nano tube and 98% of concentrated sulfuric acid by mass percent are mixed according to the mass ratio of 1:220, carrying out ultrasonic oscillation for 30min at 42kHz, then adding concentrated nitric acid with the mass fraction of 68% and the mass of 56 times of the carbon nano tube, stirring for 10min at 1300r/min, heating to 60 ℃, continuing stirring for 2h, adding deionized water with the mass of 100 times of the carbon nano tube, diluting, standing for 4h, carrying out vacuum suction filtration by using a microporous filter membrane with the aperture of 220nm, washing with deionized water until the pH value of the filtrate is 7, then washing with absolute ethyl alcohol for 3 times, and putting into a baking oven at 60 ℃ for 50min to obtain the acidified carbon nano tube;
(2) At room temperature, m-phenylenediamine and acetone are mixed according to the mass ratio of 1:100, then heating to 90 ℃, adding 5-cyano isophthalic acid with the mass 1.5 times of that of m-phenylenediamine, and stirring for 4 hours at 1300r/min to prepare cyano m-phthalamide;
(3) Under the condition of 2 ℃ and nitrogen protection, p-phenylenediamine and N, N-dimethylacetamide are mixed according to the mass ratio of 1:11, adding pyromellitic dianhydride with the mass of 2.4 times of that of the p-phenylenediamine, stirring for 3 hours at 1300r/min, adding 3-bromo-5-nitroaniline with the mass of 0.7 times of that of the p-phenylenediamine, continuously stirring for 22 hours, then heating to 80 ℃ for 3 hours, continuously heating to 120 ℃ for 60 minutes, then heating to 180 ℃ for 60 minutes, and then heating to 250 ℃ for 60 minutes to prepare the polyimide prepolymer;
(4) At room temperature, calcium chloride, ethanol and deionized water are mixed according to the mass ratio of 1:0.83:1.29, uniformly mixing to prepare a mixed solvent; boiling pupa-removed silkworm cocoons in a sodium bicarbonate solution with the mass fraction of 0.5% which is 150 times of that of the silkworm cocoons for 3 times at 100 ℃ and 30min each time, then fishing out and washing with deionized water for 4 times, drying for 2h at 60 ℃, stirring for 60min at 1300r/min in a mixed solvent at 70 ℃, naturally cooling to room temperature, putting into a 250-7u dialysis bag, dialyzing for 72h in distilled water with the mass fraction of 150 times of that of the silkworm cocoons, filtering, freezing for 13h at-5 ℃, and then freezing and drying for 48h at 15Pa and-50 ℃ to obtain silk fibroin sponge; at 85 ℃, vitamin A palmitate and vitamin E polyethylene glycol succinate are mixed according to the mass ratio of 1:2, mixing, heating to 85 ℃, preserving heat for 50min, and then adding deionized water with the vitamin A palmitate of 100 ℃ according to the mass ratio of 1:5, mixing, stirring for 20min at 1300r/min, then stirring for 120min at room temperature, and then mixing according to the mass ratio of 1:6 adding silk fibroin sponge and deionized water, wherein the mass of silk fibroin is 10 times of that of vitamin A palmitate, continuously stirring for 3h, carrying out electrostatic spinning at a feeding rate of 0.3ml/h and a voltage of 20kV by using a needle head of 0.21mm, then carrying out side blowing cooling solidification for 30min under the conditions of 15 ℃ and humidity of 70% and wind speed of 1.1m/s, and then co-twisting and braiding to obtain 220g/m 2 Is a skin-friendly layer of (a);
(5) Under the protection of nitrogen, polyimide prepolymer, cyano-isophthalamide, potassium carbonate and copper bromide are mixed according to the mass ratio of 1:0.4:0.3: mixing 0.1, heating to 170deg.C, stirring at 1300r/min for 12 hr, adding chloroform 2 times of polyimide prepolymer mass, filtering, steaming at 15Pa and 75deg.C for 40min at 2500r/min, adding nano nickel 0.03 times of polyimide prepolymer mass and deionized water 2.5 times of polyimide prepolymer mass, mixing uniformly, and stirring at 130deg.C and 1.75MPa for 4m 3 Introducing hydrogen with the mass of 1.5 times of that of the polyimide prepolymer, continuously stirring for 2 hours, then cooling to 100 ℃, adding sulfuric acid solution with the mass fraction of 0.2 times of that of the polyimide prepolymer being 70%, continuously stirring for 3 hours, cooling to 80 ℃, and adding acidified carbon nano tubes with the mass of 0.5 times of that of the polyimide prepolymerAdding 98% concentrated sulfuric acid with a mass fraction of 0.09 times of that of polyimide prepolymer dropwise at a speed of 50 drops/min, continuously stirring for 3h, placing into a spinning box at 350 ℃, spinning at a spinning speed of 900m/min by using a screw extruder, cooling and solidifying for 30min by side air blowing at a temperature of 15 ℃ at a humidity of 70% and a wind speed of 1.1m/s, and then co-twisting and braiding to obtain 220g/m of polyimide 2 Is arranged on the radiation-proof layer;
(6) Under the protection of nitrogen, chromium trioxide, methylamine, hydrogen chloride and acetone are mixed according to the mass ratio of 1:0.25:0.35:0.7, uniformly mixing to prepare a mixed oxidant; under the conditions of room temperature and nitrogen protection, paving a skin-friendly layer and a radiation-proof layer from bottom to top, immersing the skin-friendly layer and the radiation-proof layer in 10% sodium hydroxide solution by mass fraction, enabling the sodium hydroxide solution to be flush with the radiation-proof layer, heating to 85 ℃, performing ultrasonic treatment for 0.4h at 50kHz, dropwise adding 8% hydrochloric acid solution by mass fraction to adjust pH to 7 at 50 drops/min, adding a mixed oxidant with 0.3 times of the skin-friendly layer by mass fraction, continuing ultrasonic treatment for 50min, performing microwave treatment for 90min at 2450MHz and 800W, fishing out, washing with acetone for 3 times, putting into a 60 ℃ oven for baking for 50min, immersing the skin-friendly layer and the radiation-proof layer into 7% ferric chloride ethanol solution by mass fraction, continuing ultrasonic treatment for 70min at 80 ℃, standing for 40min, fishing out, washing with deionized water and ethanol for 3 times, and putting into the 60 ℃ oven for baking for 3h to obtain the radiation-proof breathable fabric.
Example 3
(1) At room temperature, the carbon nano tube and 98% of concentrated sulfuric acid by mass percent are mixed according to the mass ratio of 1:230, mixing, ultrasonically oscillating for 35min at 47kHz, then adding concentrated nitric acid with the mass fraction of 68% and the mass fraction of 57 times of the carbon nano tubes, stirring for 11min at 1400r/min, heating to 62 ℃, continuously stirring for 2.5h, adding deionized water with the mass of 102 times of the carbon nano tubes for dilution, standing for 4.5h, vacuum-filtering by using a microporous filter membrane with the aperture of 220nm, washing with deionized water until the pH value of the filtrate is 7, washing with absolute ethyl alcohol for 4 times, and drying in a drying oven at 65 ℃ for 60min to obtain acidified carbon nano tubes;
(2) At room temperature, m-phenylenediamine and acetone are mixed according to the mass ratio of 1:110, then heating to 91 ℃, adding 5-cyano isophthalic acid with the mass 1.6 times of that of m-phenylenediamine, and stirring for 4.5 hours at 1400r/min to prepare cyano m-phthalimide;
(3) Under the condition of 4 ℃ and nitrogen protection, p-phenylenediamine and N, N-dimethylacetamide are mixed according to the mass ratio of 1:12, adding pyromellitic dianhydride with the mass of 2.5 times of that of the p-phenylenediamine, stirring for 4 hours at 1400r/min, adding 3-bromo-5-nitroaniline with the mass of 0.8 times of that of the p-phenylenediamine, continuously stirring for 24 hours, then heating to 90 ℃ for 4 hours, continuously heating to 130 ℃ for 70 minutes, then heating to 190 ℃ for 70 minutes, and then heating to 260 ℃ for 70 minutes to prepare the polyimide prepolymer;
(4) At room temperature, calcium chloride, ethanol and deionized water are mixed according to the mass ratio of 1:0.84:1.3, uniformly mixing to prepare a mixed solvent; boiling pupa-removed silkworm cocoons in 200 times of 0.5% sodium bicarbonate solution at 100 ℃ for 3 times at 32min, then fishing out, washing with deionized water for 5 times, baking at 60 ℃ for 3h, stirring at 1400r/min in a 70 ℃ mixed solvent for 65min, naturally cooling to room temperature, putting into a 250-7u dialysis bag, dialyzing for 74h in 200 times of distilled water, filtering, freezing at 0 ℃ for 14h, and freeze-drying at 20 Pa-45 ℃ for 50h to obtain silk fibroin sponge; at 85 ℃, vitamin A palmitate and vitamin E polyethylene glycol succinate are mixed according to the mass ratio of 1:2.2, mixing, heating to 85 ℃, preserving heat for 60min, and then adding deionized water with the vitamin A palmitate of 100 ℃ according to the mass ratio of 1:5.5, mixing, stirring for 22min at 1400r/min, then stirring for 130min at room temperature, and then mixing according to the mass ratio of 1:7 adding silk fibroin sponge and deionized water, wherein the mass of silk fibroin is 11 times of that of vitamin A palmitate, continuously stirring for 4 hours, carrying out electrostatic spinning at a feeding rate of 0.3ml/h and a voltage of 20kV by using a needle head of 0.21mm, then carrying out side blowing cooling and solidification for 35 minutes under the conditions of 20 ℃ and humidity of 80% and wind speed of 1.3m/s, and then co-twisting and braiding to obtain 240g/m 2 Is a skin-friendly layer of (a);
(5) Under the protection of nitrogen, polyimide prepolymer, cyano-isophthalamide, potassium carbonate and copper bromide are mixed according to the mass ratio of 1:0.5:0.4: mixing 0.11, heating to 180deg.C, stirring at 1400r/min for 12.5 hr, adding chloroform 3 times of polyimide prepolymer mass, filtering, and heating to 20Pa and 80deg.CSteaming for 50min at 3000r/min, adding nano nickel with the mass of 0.04 times of that of polyimide prepolymer and deionized water with the mass of 3 times of that of polyimide prepolymer, mixing uniformly, and heating at 150deg.C under 2MPa for 5m 3 Introducing hydrogen with the mass of polyimide prepolymer being 2 times, continuously stirring for 2.5 hours, then cooling to 110 ℃, adding sulfuric acid solution with the mass fraction of 0.3 times of the mass of the polyimide prepolymer being 70%, continuously stirring for 4 hours, then cooling to 90 ℃, adding acidified carbon nano tubes with the mass fraction of 0.6 times of the polyimide prepolymer, dropwise adding concentrated sulfuric acid with the mass fraction of 0.1 times of the polyimide prepolymer being 98% at 60 drops/min, continuously stirring for 4 hours, placing into a spinning box at 400 ℃, spinning at the spinning speed of 1000m/min, using a screw extruder, performing side-blowing cooling curing for 35 minutes at the temperature of 20 ℃ and the humidity of 80% and the wind speed of 1.3m/s, and then co-twisting and braiding to obtain 240g/m 2 Is arranged on the radiation-proof layer;
(6) Under the protection of nitrogen, chromium trioxide, methylamine, hydrogen chloride and acetone are mixed according to the mass ratio of 1:0.3:0.4:0.8, uniformly mixing to prepare a mixed oxidant; under the condition of room temperature and nitrogen protection, paving a skin-friendly layer and a radiation-proof layer from bottom to top, immersing the skin-friendly layer and the radiation-proof layer in 10% sodium hydroxide solution by mass fraction, enabling the sodium hydroxide solution to be flush with the radiation-proof layer, heating to 85 ℃, performing ultrasonic treatment for 0.5h at 60kHz, dropwise adding 10% hydrochloric acid solution by mass fraction to adjust pH to 7 at 60 drops/min, adding a mixed oxidant with 0.4 times of the skin-friendly layer by mass fraction, continuing ultrasonic treatment for 60min, performing microwave treatment for 100min at 2500MHz and 900W, fishing out, washing for 4 times by acetone, putting into a 62 ℃ oven for baking for 60min, immersing the skin-friendly layer and the radiation-proof layer into 8% ferric chloride ethanol solution, continuing ultrasonic treatment for 80min at 80 ℃, standing for 50min, fishing out, washing for 4 times by deionized water and ethanol, and putting into the 62 ℃ oven for baking for 4h, thus obtaining the radiation-proof breathable fabric.
Comparative example 1
Comparative example 1 differs from example 2 only in that a polyimide prepolymer was not prepared, and only cyano isophthalamide and acidified carbon nanotubes were used to prepare a radiation protective layer. The remaining preparation steps were the same as in example 2.
Comparative example 2
Comparative example 2 differs from example 2 only in that cyano isophthalamide was not prepared, and only polyimide prepolymer and acidified carbon nanotubes were used to prepare the radiation protective layer. The remaining preparation steps were the same as in example 2.
Comparative example 3
Comparative example 3 differs from example 2 in that the radiation protective breathable fabric was prepared using only the radiation protective layer without the skin friendly layer. The remaining preparation steps were the same as in example 2.
Comparative example 4
Comparative example 4 differs from example 2 in that in step (6), only sodium hydroxide solution was used for impregnation to prepare a radiation-proof breathable fabric. The remaining preparation steps were the same as in example 2.
Comparative example 5
Comparative example 5 differs from example 2 in that in step (6), only iron chloride was used for impregnation to produce a radiation-protective breathable fabric. The remaining preparation steps were the same as in example 2.
Effect example
The following table 1 shows the analysis results of the breathability, laundering resistance, tear resistance, and radiation protection of the radiation protective breathable fabrics made using examples 1 to 3 of the present invention and comparative examples 1 to 5.
TABLE 1
From table 1, it can be found that the radiation-proof breathable fabrics prepared in examples 1, 2 and 3 have good breathability, washability, tear resistance and radiation resistance; from comparison of experimental data of examples 1, 2 and 3 and comparative example 1, it can be found that the radiation-proof layer is prepared by using polyimide prepolymer, hyperbranched polymer containing triphenylamine can be formed, and subsequent preparation of the radiation-proof breathable fabric can form Huang Xifu alkali salt, so that the prepared radiation-proof breathable fabric has stronger air permeability, washing resistance, tear resistance and radiation resistance; from the experimental data of examples 1, 2 and 3 and comparative example 2, it can be found that the radiation-proof layer prepared by using cyano-isophthalamide can form hyperbranched polymer containing triphenylamine, and the prepared radiation-proof breathable fabric has stronger air permeability and water resistance; from the experimental data of examples 1, 2 and 3 and comparative example 3, it can be found that the radiation-proof breathable fabric prepared by using the skin-friendly layer can form a Huang Xifu alkali salt, and the prepared radiation-proof breathable fabric has stronger radiation resistance; from the experimental data of examples 1, 2, 3 and comparative example 4, it can be found that sodium hydroxide is used for preparing the radiation-proof breathable fabric, and Huang Xifu alkali salt can be formed, so that the prepared radiation-proof breathable fabric has stronger tear resistance and radiation resistance; from the experimental data of examples 1, 2 and 3 and comparative example 5, it can be found that the anti-radiation breathable fabric prepared by using ferric chloride can form Huang Xifu alkali salt, and the prepared anti-radiation breathable fabric has stronger tear resistance and radiation resistance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The radiation-proof breathable fabric is characterized by being obtained by paving a skin-friendly layer and a radiation-proof layer from bottom to top in sequence and performing secondary dip rolling by using sodium hydroxide solution and ferric chloride.
2. The radiation-proof breathable fabric according to claim 1, wherein the skin-friendly layer is obtained by blending, spinning, co-twisting and braiding of vitamin A palmitate, vitamin E polyethylene glycol succinate and silk fibroin.
3. The radiation-proof breathable fabric according to claim 1, wherein the radiation-proof layer is formed by spinning, co-twisting and braiding polyimide prepolymer, acidified carbon nanotubes and cyano-isophthalamide.
4. The radiation-proof breathable fabric according to claim 3, wherein the polyimide prepolymer is prepared by mixing 3-bromo-5-nitroaniline, pyromellitic dianhydride and p-phenylenediamine.
5. The radiation-proof breathable fabric according to claim 3, wherein the cyano-isophthalamide is prepared by mixing 5-cyano-isophthalic acid and m-phenylenediamine.
6. The preparation method of the radiation-proof breathable fabric is characterized by comprising the following preparation steps of:
(1) At room temperature, calcium chloride, ethanol and deionized water are mixed according to the mass ratio of 1:0.82:1.28 to 1:0.84:1.3, uniformly mixing to prepare a mixed solvent; boiling pupa removed cocoons in sodium bicarbonate solution with the mass fraction of 0.5% of 100-200 times of that of the cocoons for 3 times at 100 ℃ for 28-32 min each time, then fishing out, washing with deionized water for 3-5 times, baking at 60 ℃ for 1-3 h, stirring at 1200-1400 r/min in a mixed solvent at 70 ℃ for 55-65 min, naturally cooling to room temperature, putting into a 250-7u dialysis bag, dialyzing in distilled water with the mass fraction of 100-200 times of that of the cocoons for 70-74 h, filtering, freezing at-10-0 ℃ for 12-14 h, and then freezing and drying at 10-20 Pa and-55-45 ℃ for 46-50 h to obtain silk fibroin sponge; at 85 ℃, vitamin A palmitate and vitamin E polyethylene glycol succinate are mixed according to the mass ratio of 1:1.8 to 1:2.2, mixing, heating to 85 ℃, preserving heat for 40-60 min, and then adding deionized water with the vitamin A palmitate of 100 ℃ according to the mass ratio of 1:4.5 to 1:5.5 mixing, stirring for 18-22 min at 1200-1400 r/min, then continuously stirring for 110-130 min at room temperature, and then mixing according to massRatio 1:5 to 1:7 adding silk fibroin sponge and deionized water, wherein the mass of the silk fibroin is 9-11 times of that of vitamin A palmitate, continuously stirring for 2-4 h, carrying out electrostatic spinning at a voltage of 20kV and a liquid feeding rate of 0.3ml/h, then carrying out cross-blowing cooling solidification for 25-35 min under the conditions of 10-20 ℃ and humidity of 60-80% and wind speed of 0.9-1.3 m/s, and then co-twisting and braiding to obtain 200-240 g/m 2 Is a skin-friendly layer of (a);
(2) Under the protection of nitrogen, polyimide prepolymer, cyano-isophthalamide, potassium carbonate and copper bromide are mixed according to the mass ratio of 1:0.3:0.2: 0.09-1: 0.5:0.4: mixing 0.11, heating to 160-180 ℃, stirring for 11.5-12.5 h at 1200-1400 r/min, adding chloroform with the mass of 1-3 times of polyimide prepolymer, filtering, steaming for 30-50 min at 2000-3000 r/min at 10-20 Pa and 70-80 ℃, adding nano nickel with the mass of 0.02-0.04 times of polyimide prepolymer and deionized water with the mass of 2-3 times of polyimide prepolymer, uniformly mixing, and steaming for 3-5 m at 110-150 ℃ and 1.5-2 MPa 3 Introducing hydrogen with the mass of 1-2 times of the polyimide prepolymer per hour, continuously stirring for 1.5-2.5 hours, then cooling to 90-110 ℃, adding sulfuric acid solution with the mass fraction of 0.1-0.3 times of the polyimide prepolymer, continuously stirring for 2-4 hours, cooling to 70-90 ℃, adding acidified carbon nano tubes with the mass fraction of 0.4-0.6 times of the polyimide prepolymer, dripping concentrated sulfuric acid with the mass fraction of 0.08-0.1 times of the polyimide prepolymer at 40-60 drops/min, continuously stirring for 2-4 hours, placing into a spinning box at 300-400 ℃, spinning at the spinning speed of 800-1000 m/min, using a screw extruder for spinning, carrying out side blowing cooling and solidification for 25-35 minutes under the conditions of 10-20 ℃ with the humidity of 60-80% and the wind speed of 0.9-1.3 m/s, and then co-twisting and braiding to obtain 200-240 g/m 2 Is arranged on the radiation-proof layer;
(3) Under the condition of room temperature and nitrogen protection, paving a skin-friendly layer and a radiation-proof layer from bottom to top, immersing the skin-friendly layer and the radiation-proof layer in 10% sodium hydroxide solution by mass fraction, flushing the sodium hydroxide solution with the radiation-proof layer, heating the solution to 85 ℃, performing ultrasonic treatment for 0.3-0.5 h at 40-60 kHz, dripping 6-10% hydrochloric acid solution by mass fraction at 40-60 drops/min to adjust the pH value to 7, adding a mixed oxidant which is 0.2-0.4 times of the skin-friendly layer, continuing ultrasonic treatment for 40-60 min, performing microwave treatment for 80-100 min at 2400-2500 MHz and 700-900W, fishing out, washing for 2-4 times by acetone, placing the fabric into an oven for drying for 40-60 min at 58-62 ℃, then immersing the fabric into 6-8% ferric chloride ethanol solution, continuing ultrasonic treatment for 60-80 min at 80 ℃, standing for 30-50 min, fishing out, washing the fabric by deionized water and ethanol for 2-4 times, and placing the fabric into the oven for 2-4 h to obtain the radiation-proof breathable fabric.
7. The method for preparing the radiation-proof breathable fabric according to claim 6, wherein the preparation method of the polyimide prepolymer in the step (2) is as follows: under the conditions of 0-4 ℃ and nitrogen protection, p-phenylenediamine and N, N-dimethylacetamide are mixed according to the mass ratio of 1:10 to 1:12, adding pyromellitic dianhydride with the mass of 2.3-2.5 times of that of the p-phenylenediamine, stirring for 2-4 hours at the speed of 1200-1400 r/min, adding 3-bromo-5-nitroaniline with the mass of 0.6-0.8 times of that of the p-phenylenediamine, continuously stirring for 20-24 hours, heating to 70-90 ℃ for 2-4 hours, continuously heating to 110-130 ℃ for 50-70 minutes, heating to 170-190 ℃ for 50-70 minutes, and heating to 240-260 ℃ for 50-70 minutes to obtain the polyimide prepolymer.
8. The method for preparing the radiation-proof breathable fabric according to claim 6, wherein the method for preparing the cyano-isophthalamide in the step (2) is as follows: at room temperature, m-phenylenediamine and acetone are mixed according to the mass ratio of 1: 90-1: 110, then heating to 89-91 ℃, adding 5-cyano isophthalic acid with the mass 1.4-1.6 times of that of m-phenylenediamine, and continuously stirring for 3.5-4.5 hours to prepare the cyano m-phthalimide.
9. The method for preparing a radiation-proof breathable fabric according to claim 6, wherein the method for preparing the acidified carbon nanotubes in the step (2) comprises the following steps: mixing carbon nano tubes and 98% concentrated sulfuric acid according to a mass ratio of 1:210 to 1:230, mixing, ultrasonically oscillating for 25-35 min at 38-47 kHz, then adding concentrated nitric acid with the mass fraction of 68% and the mass of 55-57 times of the carbon nano tube, stirring for 9-11 min at 1200-1400 r/min, heating to 58-62 ℃, continuously stirring for 1.5-2.5 h, adding deionized water with the mass of 98-102 times of the carbon nano tube for dilution, standing for 3.5-4.5 h, vacuum-filtering by using a microporous filter membrane with the aperture of 220nm, washing with deionized water until the pH value of the filtrate is 7, washing with absolute ethyl alcohol for 2-4 times, and baking in an oven at 55-65 ℃ for 40-60 min to obtain the acidified carbon nano tube.
10. The method for preparing the radiation-proof breathable fabric according to claim 6, wherein the method for preparing the mixed oxidant in the step (3) is as follows: under the protection of nitrogen, chromium trioxide, methylamine, hydrogen chloride and acetone are mixed according to the mass ratio of 1:0.2:0.3:0.6 to 1:0.3:0.4: and 0.8, uniformly mixing to obtain the mixed oxidant.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875835A (en) * 2011-07-12 2013-01-16 中国科学院化学研究所 Polyimide porous film and preparation method thereof
CN104846555A (en) * 2015-05-07 2015-08-19 东华大学 Preparation method of gelatin nanofiber membrane capable of synergistically releasing vitamin A and vitamin E
CN109370396A (en) * 2018-08-31 2019-02-22 王雪峰 A kind of preparation method of high intensity radiation shielding coating
CN209454304U (en) * 2018-12-27 2019-10-01 南通海盟实业股份有限公司 A new type of anti-radiation elastic skin-friendly composite fabric
CN209454292U (en) * 2018-11-12 2019-10-01 惠州市金豪成无纺布有限公司 A kind of environmental protection fiber cotton that gas permeability is strong
CN111420706A (en) * 2020-03-25 2020-07-17 上海大学 Cu2O/Bi2O2CO3Preparation method and application of semiconductor heterojunction composite silk fibroin fibrous membrane
CN113665201A (en) * 2021-07-09 2021-11-19 浙江众华家纺集团有限公司 Fragrant anti-radiation textile fabric

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875835A (en) * 2011-07-12 2013-01-16 中国科学院化学研究所 Polyimide porous film and preparation method thereof
CN104846555A (en) * 2015-05-07 2015-08-19 东华大学 Preparation method of gelatin nanofiber membrane capable of synergistically releasing vitamin A and vitamin E
CN109370396A (en) * 2018-08-31 2019-02-22 王雪峰 A kind of preparation method of high intensity radiation shielding coating
CN209454292U (en) * 2018-11-12 2019-10-01 惠州市金豪成无纺布有限公司 A kind of environmental protection fiber cotton that gas permeability is strong
CN209454304U (en) * 2018-12-27 2019-10-01 南通海盟实业股份有限公司 A new type of anti-radiation elastic skin-friendly composite fabric
CN111420706A (en) * 2020-03-25 2020-07-17 上海大学 Cu2O/Bi2O2CO3Preparation method and application of semiconductor heterojunction composite silk fibroin fibrous membrane
CN113665201A (en) * 2021-07-09 2021-11-19 浙江众华家纺集团有限公司 Fragrant anti-radiation textile fabric

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
盛祝波, 工程科技Ⅰ辑/间苯二甲酰胺类化合物的设计、合成及其生物活性研究, 15 February 2022 (2022-02-15), pages 9 - 12 *
金壮编著: "服装品质管理实用手册", 31 August 2005, 中国纺织出版社, pages: 126 - 129 *

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