CN114434898B - Anti-molten metal heat-insulating fabric and preparation method thereof - Google Patents

Anti-molten metal heat-insulating fabric and preparation method thereof Download PDF

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Publication number
CN114434898B
CN114434898B CN202210127626.3A CN202210127626A CN114434898B CN 114434898 B CN114434898 B CN 114434898B CN 202210127626 A CN202210127626 A CN 202210127626A CN 114434898 B CN114434898 B CN 114434898B
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fabric
flame
stirring
mass
mass ratio
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CN114434898A (en
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黄忠清
金晓峰
李建东
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Jiangsu Xinxin Textile Technology Co ltd
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Jiangsu Xinxin Textile Technology Co ltd
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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • 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
    • 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
    • A41D31/08—Heat resistant; Fire retardant
    • A41D31/085—Heat resistant; Fire retardant using 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
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/02—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose in the form of fibres or filaments
    • 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
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • 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
    • D06M11/73—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 carbon or compounds thereof
    • D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2246—Esters of unsaturated carboxylic acids
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00—Materials for garments
    • A41D2500/50—Synthetic resins or rubbers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • 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
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • 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
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Fluid Mechanics (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention discloses a melting metal-preventing heat-insulating fabric and a preparation method thereof, and relates to the technical field of textiles. The method comprises the steps of firstly spraying and preprocessing pure cotton fabric for the first time to enable the surface to have negative charges; then the carbon nanotubes are pretreated to prepare graphene nanoribbon emulsion, the substrate fabric is subjected to secondary spraying treatment by using an electrospray technology, aerogel is formed by high-pressure auxiliary secondary freeze drying, and the fabric is endowed with heat insulation performance; then, dispensing on the surface of the aerogel to form a high-temperature-resistant adhesive layer, improving the heat insulation property of the fabric, and finally, bonding the flame-retardant layer fabric prepared by blending flame-retardant viscose fibers and wool fibers on the adhesive layer by using a hot-pressing technology to prepare the anti-melting metal heat insulation fabric; the flame-retardant viscose fiber is prepared from viscose fiber, octene trichlorosilane, piperazine, dioxaphosphaphenanthrene oxide and cyclodextrin. The anti-melting metal heat-insulating fabric prepared by the invention has the effects of flame retardance, heat insulation and high-efficiency protection.

Description

Anti-molten metal heat-insulating fabric and preparation method thereof
Technical Field
The invention relates to the technical field of textile, in particular to a melting-metal-preventing heat-insulating fabric and a preparation method thereof.
Background
In working environments where high temperature radiation sources and molten metal splashing exist, such as metallurgy, casting, electric welding, glass and the like, operators must wear protective clothing made of a face fabric for preventing molten metal splashing to protect themselves. For example, when a smelting worker or a welder works under the conditions of high temperature, molten metal splashing and the like, the temperature of liquid aluminum can reach 800 ℃, and the temperature of molten steel can reach 1400 ℃ at most, so that if the protective clothing is incorrectly worn, the body is easily damaged.
Currently, the fabrics used in protective clothing with molten metal splashing prevention function in the market mainly comprise the following types: (1) The flame-retardant cotton fabric is processed by a post-finishing process, has a good fireproof effect, is thick, thick in yarn count, poor in wearing comfort and poor in heat insulation effect, can cause skin allergy after long-time contact, and is required to be fumigated by ammonia gas in the whole flame-retardant process, and has strong pungent smell, and excessive inhalation is harmful to human bodies; (2) The aluminum composite fabric has good heat radiation performance, but the protective clothing has the defect of poor air permeability, so that the protective functionality and the comfort can not meet the requirements; (3) The flame-retardant heat-insulating protective clothing blended by the intrinsic flame-retardant fibers and the common fibers can be used as common flame-retardant protection, cannot be suitable for some special high-temperature working places, and cannot meet the requirements on heat insulation effect and comfort. Based on the above, how to invent a heat-insulating, high-efficiency protective and flame-retardant anti-melting metal fabric is particularly important.
Disclosure of Invention
The invention aims to provide a melting metal-preventing heat-insulating fabric and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the anti-melting metal heat-insulating fabric is characterized by comprising a breathable base fabric, an aerogel layer, an adhesive layer and a flame-retardant layer from bottom to top; the anti-melting metal heat-insulating fabric mainly comprises, by weight, 70-100 parts of pure cotton fabric, 48-65 parts of flame-retardant viscose fiber, 40-50 parts of wool fiber, 46-61 parts of carbon nano-tubes and 50-62 parts of phenolic resin.
Further, the flame-retardant viscose fiber is prepared by reacting octenes trichlorosilane with piperazine and with dioxaphosphene oxide to form a flame retardant, then forming a inclusion compound with cyclodextrin, and then reacting with viscose fiber.
Further, the gram weight of the pure cotton fabric is 180-200 g/m 2.
Further, the preparation method of the anti-melting metal heat-insulating fabric is characterized by mainly comprising the following preparation steps:
(1) Placing pure cotton fabric in a container, spraying negative electrolyte solution with the mass ratio of 0.1-0.3 times that of the pure cotton fabric, namely, poly (4-sodium styrenesulfonate) and deionized water in the negative electrolyte solution being 1:6-1:9, drying for 3-4 hours at room temperature, flushing with deionized water for 4-7 minutes, airing for 1-2 hours at room temperature, placing on a glass plate, electrospraying graphene nanoribbon emulsion, reacting for 3-5 hours in a high-pressure reaction furnace with the temperature of 90-95 ℃ and the pressure of 300-400 MPa, flushing for 20-35 minutes with acetone aqueous solution, freezing for 5-7 hours in a refrigerator with the mass ratio of 1:2-1:3 in the acetone aqueous solution to the deionized water in a freezer dryer, and then freezing for 6-8 hours at the temperature of 1X 10- -3～3×10-3 Pa and 60-50 ℃ in a freeze dryer;
(2) Placing the aerogel fabric in a radio frequency plasma generator, vacuumizing to 8-14 Pa, treating for 5-10 min, placing in a dispensing machine, and dispensing for 2-3 times to obtain a glue layer fabric;
(3) Blending wool fibers and flame-retardant viscose fibers according to a mass ratio of 1:1.2-1:1.3 to obtain flame-retardant layer fabric; and (5) feeding the glue layer fabric and the flame-retardant layer fabric into a hot press to obtain the anti-melting metal heat-insulating fabric.
Further, the preparation method of the graphene nanoribbon emulsion in the step (1) comprises the following steps:
A. Putting the carbon nanotubes into sulfuric acid with the mass fraction of 70% and the mass fraction of 238-239 times of the carbon nanotubes, carrying out ultrasonic treatment for 30-40 min at 25-35 kHz, stirring for 60-70 min at 200-300 rpm, adding potassium permanganate with the mass of 4-5 times of the carbon nanotubes at 0.09-0.12 g/min, stirring for 60-70 min at the same speed, putting into a water bath kettle at 75 ℃ for reacting for 2-3 h, adding hydrogen peroxide solution with the mass fraction of 72-73 times of the carbon nanotubes, wherein the mass ratio of hydrogen peroxide to ice water in the hydrogen peroxide solution is 3:7, stirring for 30-40 min at the same speed, and washing with deionized water until the pH value of the solution is 6-7 to obtain graphene oxide nanobelt dispersion;
B. Adding graphene oxide nanoribbon dispersion liquid, polyether amine and deionized water into a container according to a mass ratio of 1:2:372-1:2:373, stirring for 5-7 min at 500-600 rpm, adding castor oil with the mass 50.5-51.1 times of that of the graphene oxide nanoribbon dispersion liquid, stirring for 10-13 min at the same speed, and carrying out ultrasonic grinding for 30-40 s at 30-40 kHz to obtain the graphene nanoribbon emulsion.
Further, the spraying speed of the electric spraying in the step (1) is 2.1-3.3 mL/h, the spraying distance is 10-15 cm, the voltage is 7-13 kV, and the spraying time is 10-20 min.
Further, in the step (2), the power of the radio frequency plasma generator is 300-400W, the oxygen flow rate is 15-20 mL/min, and the radio frequency is 11-13 MHz.
Further, the glue dispenser in the step (2) adopts phenolic resin as an adhesive, the glue dispensing frequency is 800-1000 Hz, the glue dispensing speed is 50-60 mm/s, the glue dispensing width is 300-400 mu m, and the glue dispensing temperature is 80-95 ℃.
Further, the pressure of the hot press in the step (3) is 3-5 kg/cm <2 >, the pressing temperature is 120-180 ℃, and the pressing speed is 10-15 m/min.
Further, the preparation method of the flame-retardant viscose fiber in the step (3) comprises the following steps:
a. Adding octene trichlorosilane and toluene into a container according to the mass ratio of 1:3.5-1:4.3, adding piperazine with the mass 1.0-1.5 times of that of the octene trichlorosilane under the stirring of 100-200 rpm, heating to 110-117 ℃, reacting for 4-7 hours, cooling to room temperature, adding ammonia water with the mass fraction 15% with the mass 1.8-2.3 times of that of the octene trichlorosilane, stirring for 38-45 minutes under the stirring of 50-100 rpm, and filtering to obtain piperazine octene silane;
b. Adding the dihydrooxaphosphaphenanthrene oxide and toluene into a container according to the mass ratio of 1:2.5-1:2.7, stirring for 22-30 min at the temperature of 80-85 ℃ and the speed of 50-100 rpm under the nitrogen atmosphere, adding piperazine octene silane mixed solution with the mass ratio of 5.7-6.3 times of the dihydrooxaphosphaphenanthrene oxide, sequentially using tetrahydrofuran and n-hexane to wash for 5-7 times at the temperature of 110 ℃ and the speed of 0.08-0.1 MPa, rotating for 22-35 min at the temperature of 200-300 rpm and the speed of 65-70 ℃ after uniformly stirring, adding azobisisobutyronitrile mixed solution with the mass ratio of 2.7-2.8 times of the dihydrooxaphosphaphenanthrene oxide at the speed of 0.1-0.2 mL/min, reacting for 1:87.1-1:87.9, and drying for 5-7 h at the temperature of 75-80 ℃ after reacting for 16-18 h, and sequentially using tetrahydrofuran and n-hexane to wash for 5-7 times at the temperature of 110 ℃ and 65-70 ℃ to obtain the flame retardant;
c. adding a flame retardant, cyclodextrin and dimethylformamide into a container according to the mass ratio of 1:10:151-1:11:152, uniformly stirring, adding deionized water with the mass 850-900 times of that of the flame retardant at the rate of 0.1-0.2 mL/min, dialyzing in the deionized water for 48-50 h, changing the deionized water every 6h when the molecular weight cut-off of a dialysis bag is 3500, collecting solution in the dialysis bag, sealing, placing, and heating at the temperature of 75-80 ℃ for 46-48 h to obtain a inclusion compound;
d. Adding the inclusion compound, citric acid, sodium hypophosphite and deionized water into a container according to the mass ratio of 1:1:0.5:10-1:1.5:1.0:11, pre-crosslinking for 2-3 hours at 90-95 ℃, adding viscose fiber with the mass 2-3 times of that of the inclusion compound, soaking for 1-2 hours, taking out, pre-baking for 5-7 minutes at 70-80 ℃, and baking for 3-4 minutes at 120-130 ℃ to obtain the flame-retardant viscose fiber.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the fabric through the steps of preparing the flame-retardant viscose fiber, preparing the aerogel layer, preparing the adhesive layer, blending, hot-pressing lamination and the like in sequence, so as to realize the performances of heat insulation, flame retardance and high-efficiency protection.
Firstly, taking pure cotton fabric as breathable and comfortable base fabric, and carrying out first spraying treatment to enable the surface of the base fabric to have negative charges; oxidizing and wall-opening pretreatment of a carbon nano tube to prepare graphene nanoribbon emulsion, carrying out second spraying treatment on a base fabric, atomizing the graphene nanoribbon emulsion into positively charged liquid drops by utilizing electrospray, rapidly and uniformly depositing the positively charged liquid drops on the surface of the base fabric under the action of an electric field force, uniformly enclosing the nanoribbon into a sphere under the action of a force field by high-pressure auxiliary freeze-drying treatment, crosslinking the sphere and the sphere into aerogel with a three-dimensional structure, forming an intercommunicated pore channel structure by utilizing secondary freeze-drying, diffusing and cooling heat input by the surface of the metal liquid drops contacting the fabric along the pore channels of the aerogel, playing a heat dissipation effect, and endowing the fabric with heat insulation performance; then, the plasma oxidation-reduction aerogel layer is utilized to enable the surface to be provided with active groups, a high-temperature resistant adhesive layer is formed on the surface of the aerogel through a dispensing process, the phenolic resin adhesive can react with the active groups of the aerogel and firmly adhere to the surface of the aerogel, and the heat insulation property of the fabric is improved; finally, blending the flame-retardant viscose fiber and the wool fiber to obtain a flame-retardant layer fabric, and attaching the flame-retardant layer fabric to the adhesive-dispensing layer by using a hot-pressing technology to obtain the anti-melting metal heat-insulating fabric.
Secondly, the flame-retardant viscose fiber is prepared from viscose fiber, octene trichlorosilane, piperazine, dioxaphosphaphenanthrene oxide and cyclodextrin; after the chloride ion of the octenyl trichlorosilane reacts with the amino of piperazine, the phosphoryl group of the dioxaphosphaphenanthrene oxide reacts with the double bond of the octenyl trichlorosilane to form a flame retardant, and the flame retardant can be quickly carbonized when burnt to form a carbon layer attached to the surface layer of the fabric to isolate combustible gas; in addition, the carbon layer can react with the metal liquid drops to release heat to counteract carbonization heat absorption of the fabric, so that the surface layer temperature of the metal liquid drops is kept unchanged, molten metal is ensured to slide down quickly, and the protective performance of the fabric is improved; the fire retardant is then wrapped with the cyclodextrin hydrophobic cavity to form a wrapped object, the hydroxyl on the surface of the wrapped object reacts with the viscose, the fire retardant is deposited on the surface of the viscose, and the fire retardant, the cyclodextrin and the viscose are crosslinked, so that the fire retardance of the fiber is improved.
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 anti-molten metal heat-insulating fabric manufactured in the following examples is as follows:
Protection performance: the protective effect test is carried out by taking the examples with the same size and the comparative examples, and the surface condition of molten iron and aluminum solution dripping fabric is tested by referring to ISO 9185 evaluation of molten metal splashing resistance of protective clothing materials.
Heat insulation: the heat insulating effect test was performed by taking the same examples as the comparative examples, and the temperature rise of the back surface after 15 drops of molten metal were dropped was measured with reference to GB/T17599.
Flame retardancy: the flame retardant effect test is carried out by taking the examples with the same size and the comparative examples, and the burning performance of the fabric is tested by referring to ISO 15025 test method for flame spread restriction of fireproof insulation of protective clothing.
Example 1
The heat-insulating shell fabric for preventing molten metal mainly comprises the following components in parts by weight: 70 parts of pure cotton fabric, 48 parts of flame-retardant viscose fiber, 40 parts of wool fiber, 46 parts of carbon nano-tubes and 50 parts of phenolic resin.
The preparation method of the anti-melting metal heat-insulating fabric mainly comprises the following preparation steps:
(1) Putting the carbon nanotubes into sulfuric acid with the mass fraction of 70% and the mass fraction of 238 times of the carbon nanotubes, carrying out ultrasonic treatment at 25kHz for 40min, stirring at 200rpm for 70min, adding potassium permanganate with the mass of 4 times of the carbon nanotubes at 0.09g/min, stirring at the same speed for 70min, putting into a water bath kettle at 75 ℃ for reaction for 2h, adding hydrogen peroxide solution with the mass fraction of 72 times of the carbon nanotubes, stirring at the same speed for 40min, and washing with deionized water until the pH value of the solution is 6 to obtain graphene oxide nanobelt dispersion;
(2) Adding graphene oxide nanoribbon dispersion liquid, polyether amine and deionized water into a container according to a mass ratio of 1:2:372, stirring at 500rpm for 7min, adding castor oil with the mass 50.5 times that of the graphene oxide nanoribbon dispersion liquid, stirring at the same speed for 13min, and performing ultrasonic grinding at 30kHz for 40s to obtain graphene nanoribbon emulsion;
(3) Placing pure cotton fabric in a container, spraying negative electrolyte solution with the mass of 0.1 times of that of the pure cotton fabric, wherein the mass ratio of poly (4-sodium styrenesulfonate) to deionized water in the negative electrolyte solution is 1:6, drying for 3 hours at room temperature, washing with deionized water for 4 minutes, airing for 1 hour at room temperature, placing the glass plate on which the graphene nanoribbon emulsion is sprayed, wherein the spraying rate is 2.1mL/h, the spraying distance is 10cm, the voltage is 7kV, the spraying time is 20 minutes, the glass plate is placed in a high-pressure reaction furnace at 90 ℃ and 300MPa, washing with acetone aqueous solution for 20 minutes after reaction for 3 hours, the mass ratio of acetone to deionized water in the acetone aqueous solution is 1:2, freezing for 5 hours in a refrigerator at-10 ℃, and then placing the glass plate in a freeze dryer, freezing for 6 hours at 1X 10 -3 Pa and 60 ℃, and obtaining aerogel fabric;
(4) Placing the aerogel fabric in a radio frequency plasma generator with the power of 300W and the radio frequency of 11MHz, vacuumizing to 8Pa, introducing oxygen, wherein the oxygen flow rate is 15mL/min, treating for 5min, placing in a glue dispenser, adopting phenolic resin as an adhesive, and dispensing at the glue dispensing frequency of 800Hz, the glue dispensing speed of 50mm/s, the glue dispensing width of 300 mu m and the glue dispensing temperature of 80 ℃ for 3 times to obtain a glue layer fabric;
(5) Adding octene trichlorosilane and toluene into a container according to the mass ratio of 1:3.5, adding piperazine with the mass 1.0 times of that of the octene trichlorosilane under the stirring of 100rpm, heating to 110 ℃, cooling to room temperature after reacting for 4 hours, adding 15% ammonia water with the mass 1.8 times of that of the octene trichlorosilane, stirring for 45min under the stirring of 50rpm, and filtering to obtain piperazine octene silane;
(6) Adding the dihydrooxaphosphaphenanthrene oxide and toluene into a container according to the mass ratio of 1:2.5, stirring for 30min at 80 ℃ under nitrogen atmosphere, adding piperazine octene silane mixed solution with the mass ratio of 5.7 times of the dihydrooxaphosphaphenanthrene oxide, wherein the mass ratio of piperazine octene silane to toluene in the piperazine octene silane mixed solution is 1:0.8, stirring uniformly, adding azo diisobutyronitrile mixed solution with the mass ratio of 2.7 times of the dihydrooxaphosphaphenanthrene oxide at 0.1mL/min, wherein the mass ratio of the azo diisobutyronitrile to the toluene in the azo diisobutyronitrile mixed solution is 1:87.1, distilling for 2h at 110 ℃ and 0.08MPa after reacting for 16h, washing for 5 times by tetrahydrofuran and n-hexane in sequence, steaming for 22min at 200rpm and 65 ℃, and drying for 7h at 75 ℃ to obtain the flame retardant;
(7) Adding a flame retardant, cyclodextrin and dimethylformamide into a container according to a mass ratio of 1:10:151, uniformly stirring, adding deionized water with a mass 850 times of that of the flame retardant at 0.1mL/min, dialyzing in the deionized water for 48 hours, changing the molecular weight cut-off of a dialysis bag to 3500, changing the deionized water every 6 hours, collecting solution in the dialysis bag, sealing and placing, and heating at 75 ℃ for 48 hours to obtain a clathrate;
(8) Adding the inclusion compound, citric acid, sodium hypophosphite and deionized water into a container according to the mass ratio of 1:1:0.5:10, pre-crosslinking for 3 hours at 90 ℃, adding viscose fiber with the mass which is 2 times of that of the inclusion compound, soaking for 1 hour, taking out, pre-baking for 7 minutes at 70 ℃, and baking for 4 minutes at 120 ℃ to obtain flame-retardant viscose fiber;
(9) Blending wool fibers and flame-retardant viscose fibers according to the mass ratio of 1:1.2 to obtain flame-retardant layer fabric; and (3) feeding the adhesive layer fabric and the flame-retardant layer fabric into a hot press, wherein the pressure is 3kg/cm 2, the pressing temperature is 120 ℃, and the pressing speed is 10m/min, so as to obtain the anti-melting metal heat-insulating fabric.
Example 2
The heat-insulating shell fabric for preventing molten metal mainly comprises the following components in parts by weight: 85 parts of pure cotton fabric, 52.5 parts of flame-retardant viscose fiber, 42 parts of wool fiber, 53 parts of carbon nano-tubes and 55 parts of phenolic resin.
The preparation method of the anti-melting metal heat-insulating fabric mainly comprises the following preparation steps:
(1) Placing the carbon nanotubes in sulfuric acid with the mass fraction of 70% and the mass fraction of 238.65 times of the carbon nanotubes, carrying out ultrasonic treatment at 32kHz for 33min, stirring at 260rpm for 65min, adding potassium permanganate with the mass of 4.67 times of the carbon nanotubes at 0.10g/min, stirring at the same speed for 65min, placing in a water bath kettle at 75 ℃ for 2.53h, adding a hydrogen peroxide solution with the mass fraction of 72.51 times of the carbon nanotubes, wherein the mass ratio of the hydrogen peroxide to ice water in the hydrogen peroxide solution is 3:7, stirring at the same speed for 36min, and washing with deionized water until the pH of the solution is 6.5 to obtain graphene oxide nanobelt dispersion;
(2) Adding graphene oxide nanoribbon dispersion liquid, polyether amine and deionized water into a container according to a mass ratio of 1:2:372.77, stirring for 6min at 550rpm, adding castor oil with the mass 50.8 times that of the graphene oxide nanoribbon dispersion liquid, stirring for 12min at the same speed, and performing ultrasonic grinding for 36s at 33kHz to obtain graphene nanoribbon emulsion;
(3) Placing pure cotton fabric in a container, spraying negative electrolyte solution with the mass of 0.21 times of that of the pure cotton fabric, wherein the mass ratio of poly (4-sodium styrene sulfonate) to deionized water in the negative electrolyte solution is 1:7, drying for 3.5 hours at room temperature, washing with deionized water for 6 minutes, airing for 1.5 hours at room temperature, placing on a glass plate, electrically spraying graphene nanoribbon emulsion with the spraying rate of 2.8mL/h, the spraying distance of 13cm and the voltage of 9kV, the spraying time of 16 minutes, washing with acetone aqueous solution for 30 minutes in a high-pressure reaction furnace with the temperature of 93 ℃ and 355MPa after the reaction for 4 hours, freezing with the mass ratio of acetone and deionized water in the acetone aqueous solution for 1:2.55 in a refrigerator with the temperature of-9 ℃, and then placing in a freeze dryer for 7 hours at the temperature of 2.1X10 -3 Pa and the temperature of minus 56 ℃, and obtaining the aerogel fabric;
(4) Placing the aerogel fabric in a radio frequency plasma generator with the power of 350W and the radio frequency of 12MHz, vacuumizing to 9Pa, introducing oxygen, and placing the aerogel fabric in a glue dispenser with the flow rate of 18mL/min, treating for 8min, wherein the glue dispenser adopts phenolic resin as an adhesive, the glue dispensing frequency is 900Hz, the glue dispensing speed is 56mm/s, the glue dispensing width is 348 mu m, the glue dispensing temperature is 90 ℃, and the glue dispensing is performed for 3 times to obtain the glue layer fabric;
(5) Adding octene trichlorosilane and toluene into a container according to the mass ratio of 1:3.77, adding piperazine with the mass of 1.32 times of that of the octene trichlorosilane under the stirring of 160rpm, heating to 115 ℃, cooling to room temperature after the reaction is carried out for 6 hours, adding ammonia water with the mass fraction of 15% and the mass of 2.07 times of that of the octene trichlorosilane, stirring for 40 minutes under the stirring of 80rpm, and filtering to obtain piperazine octene silane;
(6) Adding the dihydrooxaphosphaphenanthrene oxide and toluene into a container according to the mass ratio of 1:2.68, stirring for 27min at 83 ℃ under nitrogen atmosphere, adding piperazine octene silane mixed solution with the mass ratio of 6.14 times of the dihydrooxaphosphaphenanthrene oxide into the container, stirring uniformly, adding azo diisobutyronitrile mixed solution with the mass ratio of 2.77 times of the dihydrooxaphosphaphenanthrene oxide into the container at 0.15mL/min, distilling for 3h at 110 ℃ and 0.09MPa after reacting for 17h, washing for 6 times by tetrahydrofuran and n-hexane sequentially, steaming for 33min at 270rpm and 69 ℃, and drying for 6h at 77 ℃ to obtain the flame retardant;
(7) Adding a flame retardant, cyclodextrin and dimethylformamide into a container according to the mass ratio of 1:10.25:151.63, uniformly stirring, adding deionized water with the mass 898 times of that of the flame retardant at 0.15mL/min, dialyzing in the deionized water for 49 hours, changing the molecular weight cut-off of a dialysis bag into 3500 every 6 hours, collecting solution in the dialysis bag, sealing and placing, and heating at 77 ℃ for 47 hours to obtain a inclusion complex;
(8) Adding the inclusion compound, citric acid, sodium hypophosphite and deionized water into a container according to the mass ratio of 1:1.39:0.71:10.76, pre-crosslinking for 2.5 hours at 93 ℃, adding viscose fiber with the mass 2.57 times of that of the inclusion compound, soaking for 1.5 hours, taking out, pre-baking for 6 minutes at 76 ℃, and baking for 4 minutes at 126 ℃ to obtain flame-retardant viscose fiber;
(9) Blending wool fibers and flame-retardant viscose fibers according to the mass ratio of 1:1.25 to obtain flame-retardant layer fabric; and (3) feeding the adhesive layer fabric and the flame-retardant layer fabric into a hot press, wherein the pressure is 4kg/cm 2, the pressing temperature is 169 ℃, and the pressing speed is 13m/min, so as to obtain the anti-melting metal heat-insulating fabric.
Example 3
The heat-insulating shell fabric for preventing molten metal mainly comprises the following components in parts by weight: 100 parts of pure cotton fabric, 65 parts of flame-retardant viscose fiber, 50 parts of wool fiber, 61 parts of carbon nano-tubes and 62 parts of phenolic resin.
The preparation method of the anti-melting metal heat-insulating fabric mainly comprises the following preparation steps:
(1) Placing the carbon nanotubes in sulfuric acid with the mass fraction of 70% and the mass of 239 times of the carbon nanotubes, carrying out ultrasonic treatment at 35kHz for 30min, stirring at 300rpm for 60min, adding potassium permanganate with the mass of 5 times of the carbon nanotubes at 0.12g/min, stirring at the same speed for 60min, placing in a water bath kettle at 75 ℃ for reaction for 3h, adding hydrogen peroxide solution with the mass fraction of 73 times of the carbon nanotubes, wherein the mass ratio of the hydrogen peroxide solution to ice water is 3:7, stirring at the same speed for 30min, and washing with deionized water until the pH value of the solution is 7 to obtain graphene oxide nanobelt dispersion;
(2) Adding graphene oxide nanoribbon dispersion liquid, polyether amine and deionized water into a container according to a mass ratio of 1:2:373, stirring at 600rpm for 5min, adding castor oil with the mass 51.1 times of that of the graphene oxide nanoribbon dispersion liquid, stirring at the same speed for 10min, and performing ultrasonic grinding at 40kHz for 30s to obtain graphene nanoribbon emulsion;
(3) Placing pure cotton fabric in a container, spraying negative electrolyte solution with the mass of 0.3 times of that of the pure cotton fabric, wherein the mass ratio of poly (4-sodium styrenesulfonate) to deionized water in the negative electrolyte solution is 1:9, drying for 4 hours at room temperature, washing with deionized water for 7 minutes, airing for 2 hours at room temperature, placing the glass plate on which the graphene nanoribbon emulsion is sprayed, wherein the spraying rate is 3.3mL/h, the spraying distance is 15cm, the voltage is 13kV, the spraying time is 20 minutes, the glass plate is placed in a high-pressure reaction furnace with the temperature of 95 ℃ and 400MPa, washing with acetone aqueous solution for 35 minutes after reaction for 5 hours, the mass ratio of acetone to deionized water in the acetone aqueous solution is 1:3, freezing for 7 hours in a refrigerator with the temperature of minus 8 ℃, and then placing the glass plate in a freeze dryer, freezing for 8 hours at the temperature of 3X 10 -3 Pa and 50 ℃;
(4) Placing the aerogel fabric in a radio frequency plasma generator with power of 400W and radio frequency of 13MHz, vacuumizing to 14Pa, introducing oxygen, wherein the oxygen flow rate is 20mL/min, treating for 10min, placing in a glue dispenser, adopting phenolic resin as an adhesive, dispensing at a glue dispensing frequency of 1000Hz, a glue dispensing speed of 60mm/s, a glue dispensing width of 400 mu m, and a glue dispensing temperature of 95 ℃ for 2 times to obtain a glue layer fabric;
(5) Adding octene trichlorosilane and toluene into a container according to the mass ratio of 1:4.3, adding piperazine with the mass 1.5 times of that of the octene trichlorosilane under the stirring of 200rpm, heating to 117 ℃, reacting for 7 hours, cooling to room temperature, adding ammonia water with the mass 15% with the mass 2.3 times of that of the octene trichlorosilane, stirring for 38 minutes under the stirring of 100rpm, and filtering to obtain piperazine octene silane;
(6) Adding the dihydrooxaphosphaphenanthrene oxide and toluene into a container according to the mass ratio of 1:2.7, stirring for 22min at the temperature of 85 ℃ under the nitrogen atmosphere, adding piperazine octene silane mixed solution with the mass ratio of 6.3 times of the dihydrooxaphosphaphenanthrene oxide, wherein the mass ratio of piperazine octene silane to toluene in the piperazine octene silane mixed solution is 1:0.9, stirring uniformly, adding azo diisobutyronitrile mixed solution with the mass ratio of 2.8 times of the dihydrooxaphosphaphenanthrene oxide at 0.2mL/min, wherein the mass ratio of the azo diisobutyronitrile to the toluene in the azo diisobutyronitrile mixed solution is 1:87.9, distilling for 4h at the temperature of 110 ℃ and the pressure of 0.1MPa after reacting for 18h, washing for 7 times by tetrahydrofuran and n-hexane in sequence, steaming for 22min at the temperature of 70 ℃ and drying for 5h at the temperature of 80 ℃ to obtain the flame retardant;
(7) Adding a flame retardant, cyclodextrin and dimethylformamide into a container according to the mass ratio of 1:11:152, uniformly stirring, adding deionized water with the mass 900 times of that of the flame retardant at 0.2mL/min, dialyzing in the deionized water for 50 hours, changing the molecular weight cut-off of a dialysis bag to 3500, changing the deionized water every 6 hours, collecting the solution in the dialysis bag, sealing and placing, and heating at 80 ℃ for 48 hours to obtain a clathrate;
(8) Adding the inclusion compound, citric acid, sodium hypophosphite and deionized water into a container according to the mass ratio of 1:1.5:1.0:11, pre-crosslinking for 2 hours at 95 ℃, adding viscose fiber with the mass 3 times of that of the inclusion compound, soaking for 2 hours, taking out, pre-baking for 5 minutes at 80 ℃, and baking for 3 minutes at 130 ℃ to obtain flame-retardant viscose fiber;
(9) Blending wool fibers and flame-retardant viscose fibers according to the mass ratio of 1:1.3 to obtain flame-retardant layer fabric; and (3) feeding the adhesive layer fabric and the flame-retardant layer fabric into a hot press, wherein the pressure is 5kg/cm 2, the pressing temperature is 180 ℃, and the pressing speed is 15m/min, so as to obtain the anti-melting metal heat-insulating fabric.
Comparative example 1
The heat-insulating shell fabric for preventing molten metal mainly comprises the following components in parts by weight: 85 parts of pure cotton fabric, 73 parts of wool fabric, 53 parts of carbon nano-tubes and 55 parts of phenolic resin.
The preparation method of the anti-melting metal heat-insulating fabric mainly comprises the following preparation steps:
(1) Placing the carbon nanotubes in sulfuric acid with the mass fraction of 70% and the mass fraction of 238.65 times of the carbon nanotubes, carrying out ultrasonic treatment at 32kHz for 33min, stirring at 260rpm for 65min, adding potassium permanganate with the mass of 4.67 times of the carbon nanotubes at 0.10g/min, stirring at the same speed for 65min, placing in a water bath kettle at 75 ℃ for 2.53h, adding a hydrogen peroxide solution with the mass fraction of 72.51 times of the carbon nanotubes, wherein the mass ratio of the hydrogen peroxide to ice water in the hydrogen peroxide solution is 3:7, stirring at the same speed for 36min, and washing with deionized water until the pH of the solution is 6.5 to obtain graphene oxide nanobelt dispersion;
(2) Adding graphene oxide nanoribbon dispersion liquid, polyether amine and deionized water into a container according to a mass ratio of 1:2:372.77, stirring for 6min at 550rpm, adding castor oil with the mass 50.8 times that of the graphene oxide nanoribbon dispersion liquid, stirring for 12min at the same speed, and performing ultrasonic grinding for 36s at 33kHz to obtain graphene nanoribbon emulsion;
(3) Placing pure cotton fabric in a container, spraying negative electrolyte solution with the mass of 0.3 times of that of the pure cotton fabric, wherein the mass ratio of poly (4-sodium styrene sulfonate) to deionized water in the negative electrolyte solution is 1:9, drying for 3.5 hours at room temperature, washing with deionized water for 6 minutes, airing for 1.5 hours at room temperature, placing on a glass plate, electrically spraying graphene nanoribbon emulsion with the spraying rate of 2.8mL/h, the spraying distance of 13cm and the voltage of 9kV, the spraying time of 16 minutes, washing with acetone aqueous solution for 30 minutes in a high-pressure reaction furnace with the temperature of 93 ℃ and 355MPa after the reaction for 4 hours, freezing with the mass ratio of acetone and deionized water in the acetone aqueous solution for 1:2.55 in a refrigerator with the temperature of-9 ℃, and then placing in a freeze dryer for 7 hours at the temperature of 2.1X10 -3 Pa and the temperature of minus 56 ℃, and obtaining the aerogel fabric;
(4) Placing the aerogel fabric in a radio frequency plasma generator with the power of 350W and the radio frequency of 12MHz, vacuumizing to 9Pa, introducing oxygen, and placing the aerogel fabric in a glue dispenser with the flow rate of 18mL/min, treating for 8min, wherein the glue dispenser adopts phenolic resin as an adhesive, the glue dispensing frequency is 900Hz, the glue dispensing speed is 56mm/s, the glue dispensing width is 348 mu m, the glue dispensing temperature is 90 ℃, and the glue dispensing is performed for 3 times to obtain the glue layer fabric;
(5) And (3) feeding the glue layer fabric and the wool fabric into a hot press, wherein the pressure is 4kg/cm 2, the pressing temperature is 169 ℃, and the pressing speed is 13m/min, so that the anti-melting metal heat-insulating fabric is obtained.
Comparative example 2
The recipe for comparative example 2 was the same as that of example 2. The preparation method of the anti-molten metal heat-insulating fabric is different from that of the embodiment 2 only in that the step (3) is modified as follows: soaking pure cotton fabric in graphene nanobelt emulsion with the mass of 2 times that of the pure cotton fabric for 190min, fishing out, reacting in a high-pressure reaction furnace at 93 ℃ and 355MPa for 4h, washing with acetone aqueous solution for 30min, freezing in a refrigerator at-9 ℃ for 6h with the mass ratio of acetone to deionized water being 1:2.55, and then placing in a freeze dryer, freezing at 2.1X10 -3 Pa and 56 ℃ for 7h to obtain aerogel fabric. The remaining preparation steps were the same as in example 2.
Comparative example 3
The recipe for comparative example 3 was the same as in example 2. The preparation method of the anti-molten metal heat-insulating fabric is different from that of the embodiment 2 only in that the step (3) is modified as follows: placing pure cotton fabric in a container, spraying negative electrolyte solution with the mass of 1.13 times of that of the pure cotton fabric, wherein the mass ratio of poly (4-sodium styrene sulfonate) to deionized water in the negative electrolyte solution is 1:280, drying for 3.5 hours at room temperature, washing for 6 minutes with deionized water, airing for 1.5 hours at room temperature, placing the pure cotton fabric on a glass plate, electrically spraying graphene nanoribbon emulsion with the spraying rate of 2.8mL/h, the spraying distance of 13cm and the voltage of 9kV, freezing for 6 hours in a refrigerator at the temperature of minus 9 ℃, then placing the pure cotton fabric in a freeze dryer, and freezing for 7 hours at the temperature of 2.1X10 -3 Pa and minus 56 ℃ to obtain aerogel fabric. The remaining preparation steps were the same as in example 2.
Comparative example 4
The heat-insulating shell fabric for preventing molten metal mainly comprises the following components in parts by weight: 85 parts of pure cotton fabric, 73 parts of wool fabric, 53 parts of carbon nano-tubes and 55 parts of phenolic resin.
The preparation method of the anti-melting metal heat-insulating fabric mainly comprises the following preparation steps:
(1) Placing the carbon nanotubes in sulfuric acid with the mass fraction of 70% and the mass fraction of 238.65 times of the carbon nanotubes, carrying out ultrasonic treatment at 32kHz for 33min, stirring at 260rpm for 65min, adding potassium permanganate with the mass of 4.67 times of the carbon nanotubes at 0.10g/min, stirring at the same speed for 65min, placing in a water bath kettle at 75 ℃ for 2.53h, adding a hydrogen peroxide solution with the mass fraction of 72.51 times of the carbon nanotubes, wherein the mass ratio of the hydrogen peroxide to ice water in the hydrogen peroxide solution is 3:7, stirring at the same speed for 36min, and washing with deionized water until the pH of the solution is 6.5 to obtain graphene oxide nanobelt dispersion;
(2) Adding graphene oxide nanoribbon dispersion liquid, polyether amine and deionized water into a container according to a mass ratio of 1:2:372.77, stirring for 6min at 550rpm, adding castor oil with the mass 50.8 times that of the graphene oxide nanoribbon dispersion liquid, stirring for 12min at the same speed, and performing ultrasonic grinding for 36s at 33kHz to obtain graphene nanoribbon emulsion;
(3) Soaking pure cotton fabric in graphene nanobelt emulsion with the mass 2 times of that of the pure cotton fabric for 190min, fishing out, freezing in a refrigerator at-9 ℃ for 6h, then placing in a freeze dryer, and freezing at 2.1X10 -3 Pa and at-56 ℃ for 7h to obtain aerogel fabric;
(4) Placing the aerogel fabric in a radio frequency plasma generator with the power of 350W and the radio frequency of 12MHz, vacuumizing to 9Pa, introducing oxygen, and placing the aerogel fabric in a glue dispenser with the flow rate of 18mL/min, treating for 8min, wherein the glue dispenser adopts phenolic resin as an adhesive, the glue dispensing frequency is 900Hz, the glue dispensing speed is 56mm/s, the glue dispensing width is 348 mu m, the glue dispensing temperature is 90 ℃, and the glue dispensing is performed for 3 times to obtain the glue layer fabric;
(5) And (3) feeding the glue layer fabric and the wool fabric into a hot press, wherein the pressure is 4kg/cm 2, the pressing temperature is 169 ℃, and the pressing speed is 13m/min, so that the anti-melting metal heat-insulating fabric is obtained.
Effect example
The following table 1 shows the results of performance analysis of the anti-molten metal heat insulating facings using examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
From comparison of experimental data of examples 1,2 and 3 and comparative example 4, it can be found that flame-retardant viscose fibers are used in the product, a carbon layer is rapidly formed when the flame-retardant viscose fibers meet fire, the fabric is protected, the fabric is prevented from burning, the fabric has flame retardance, and meanwhile, the formed carbon layer promotes molten metal drops to rapidly slide down, so that the protective performance of the fabric is improved; in addition, a porous graphene aerogel layer is introduced into the fabric to rapidly spread heat, so that the fabric achieves the effects of rapid cooling and heat insulation; from the comparison of experimental data of examples 1,2 and 3 and comparative example 1, it can be found that octene trichlorosilane, piperazine and dioxaphosphorite oxide are utilized to form a nitrogen-phosphorus-silicon flame retardant, when molten metal with fire or high heat is encountered, the flame retardant is quickly carbonized to isolate combustible gas, so that the fabric has flame retardant effect, and simultaneously, heat is released in the carbon layer forming process to counteract carbonization heat absorption of the fabric, thereby ensuring quick sliding of the molten metal and improving the protection property of the fabric; from comparison of experimental data of examples 1,2 and 3 with comparative example 2, it can be found that if the breathable base fabric is directly soaked in the graphene nanoribbon emulsion, the graphene nanoribbon has fewer surface active groups and cannot react with the breathable base fabric, so that fewer graphene nanoribbons are grafted on the surface of the base fabric, and the heat insulation property of the fabric is affected; from comparison of experimental data of examples 1,2 and 3 and comparative example 3, it can be found that, in the aerogel preparation process, high-pressure pretreatment is assisted, so that the nanobelts are uniformly surrounded into spheres, the spheres are crosslinked into a three-dimensional structure, the pore channels are mutually communicated, the heat dissipation path is improved, and the heat insulation performance of the fabric is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (6)

1. The anti-melting metal heat-insulating fabric is characterized by comprising a breathable base fabric, an aerogel layer, an adhesive layer and a flame-retardant layer from bottom to top; the anti-melting metal heat-insulating fabric mainly comprises, by weight, 70-100 parts of pure cotton fabric, 48-65 parts of flame-retardant viscose fiber, 40-50 parts of wool fiber, 46-61 parts of carbon nano-tubes and 50-62 parts of phenolic resin;
the preparation method of the anti-melting metal heat-insulating fabric comprises the following preparation steps:
(1) Placing pure cotton fabric in a container, spraying negative electrolyte solution with the mass ratio of 0.1-0.3 times that of the pure cotton fabric, namely, poly (4-sodium styrenesulfonate) and deionized water in the negative electrolyte solution being 1:6-1:9, drying for 3-4 hours at room temperature, flushing with deionized water for 4-7 minutes, airing for 1-2 hours at room temperature, placing on a glass plate, electrospraying graphene nanoribbon emulsion, reacting for 3-5 hours in a high-pressure reaction furnace with the temperature of 90-95 ℃ and the pressure of 300-400 MPa, flushing for 20-35 minutes with acetone aqueous solution, freezing for 5-7 hours in a refrigerator with the mass ratio of 1:2-1:3 in the acetone aqueous solution to the deionized water in a freezer dryer, and then freezing for 6-8 hours at the temperature of 1X 10- -3～3×10-3 Pa and 60-50 ℃ in a freeze dryer;
(2) Placing the aerogel fabric in a radio frequency plasma generator, vacuumizing to 8-14 Pa, treating for 5-10 min, placing in a dispensing machine, and dispensing for 2-3 times to obtain a glue layer fabric;
(3) Blending wool fibers and flame-retardant viscose fibers according to a mass ratio of 1:1.2-1:1.3 to obtain flame-retardant layer fabric; feeding the glue layer fabric and the flame-retardant layer fabric into a hot press to obtain a melting metal-preventing heat-insulating fabric;
the preparation method of the graphene nanoribbon emulsion comprises the following steps:
A. Putting the carbon nanotubes into sulfuric acid with the mass fraction of 70% and the mass fraction of 238-239 times of the carbon nanotubes, carrying out ultrasonic treatment for 30-40 min at 25-35 kHz, stirring for 60-70 min at 200-300 rpm, adding potassium permanganate with the mass of 4-5 times of the carbon nanotubes at 0.09-0.12 g/min, stirring for 60-70 min at the same speed, putting into a water bath kettle at 75 ℃ for reacting for 2-3 h, adding hydrogen peroxide solution with the mass fraction of 72-73 times of the carbon nanotubes, wherein the mass ratio of hydrogen peroxide to ice water in the hydrogen peroxide solution is 3:7, stirring for 30-40 min at the same speed, and washing with deionized water until the pH value of the solution is 6-7 to obtain graphene oxide nanobelt dispersion;
B. Adding graphene oxide nanoribbon dispersion liquid, polyether amine and deionized water into a container according to a mass ratio of 1:2:372-1:2:373, stirring for 5-7 min at 500-600 rpm, adding castor oil with the mass 50.5-51.1 times of that of the graphene oxide nanoribbon dispersion liquid, stirring for 10-13 min at the same speed, and carrying out ultrasonic grinding for 30-40 s at 30-40 kHz to obtain graphene nanoribbon emulsion;
The preparation method of the flame-retardant viscose fiber comprises the following steps:
a. Adding octene trichlorosilane and toluene into a container according to the mass ratio of 1:3.5-1:4.3, adding piperazine with the mass 1.0-1.5 times of that of the octene trichlorosilane under the stirring of 100-200 rpm, heating to 110-117 ℃, reacting for 4-7 hours, cooling to room temperature, adding ammonia water with the mass fraction 15% with the mass 1.8-2.3 times of that of the octene trichlorosilane, stirring for 38-45 minutes under the stirring of 50-100 rpm, and filtering to obtain piperazine octene silane;
b. Adding the dihydrooxaphosphaphenanthrene oxide and toluene into a container according to the mass ratio of 1:2.5-1:2.7, stirring for 22-30 min at the temperature of 80-85 ℃ and the speed of 50-100 rpm under the nitrogen atmosphere, adding piperazine octene silane mixed solution with the mass ratio of 5.7-6.3 times of the dihydrooxaphosphaphenanthrene oxide, sequentially using tetrahydrofuran and n-hexane to wash for 5-7 times at the temperature of 110 ℃ and the speed of 0.08-0.1 MPa, rotating for 22-35 min at the temperature of 200-300 rpm and the speed of 65-70 ℃ after uniformly stirring, adding azobisisobutyronitrile mixed solution with the mass ratio of 2.7-2.8 times of the dihydrooxaphosphaphenanthrene oxide at the speed of 0.1-0.2 mL/min, reacting for 1:87.1-1:87.9, and drying for 5-7 h at the temperature of 75-80 ℃ after reacting for 16-18 h, and sequentially using tetrahydrofuran and n-hexane to wash for 5-7 times at the temperature of 110 ℃ and 65-70 ℃ to obtain the flame retardant;
c. adding a flame retardant, cyclodextrin and dimethylformamide into a container according to the mass ratio of 1:10:151-1:11:152, uniformly stirring, adding deionized water with the mass 850-900 times of that of the flame retardant at the rate of 0.1-0.2 mL/min, dialyzing in the deionized water for 48-50 h, changing the deionized water every 6h when the molecular weight cut-off of a dialysis bag is 3500, collecting solution in the dialysis bag, sealing, placing, and heating at the temperature of 75-80 ℃ for 46-48 h to obtain a inclusion compound;
d. Adding the inclusion compound, citric acid, sodium hypophosphite and deionized water into a container according to the mass ratio of 1:1:0.5:10-1:1.5:1.0:11, pre-crosslinking for 2-3 hours at 90-95 ℃, adding viscose fiber with the mass 2-3 times of that of the inclusion compound, soaking for 1-2 hours, taking out, pre-baking for 5-7 minutes at 70-80 ℃, and baking for 3-4 minutes at 120-130 ℃ to obtain the flame-retardant viscose fiber.
2. The anti-melting metal heat insulation fabric according to claim 1, wherein the gram weight of the pure cotton fabric in the step (1) is 180-200 g/m 2.
3. The anti-molten metal heat-insulating fabric according to claim 1, wherein the electrospraying in the step (1) has a spraying rate of 2.1-3.3 mL/h, a spraying distance of 10-15 cm, a voltage of 7-13 kV and a spraying time of 10-20 min.
4. The anti-melting metal heat insulation fabric according to claim 1, wherein the power of the radio frequency plasma generator in the step (2) is 300-400W, the oxygen flow rate is 15-20 mL/min, and the radio frequency is 11-13 MHz.
5. The anti-melting metal heat insulation fabric as claimed in claim 1, wherein the glue dispenser in the step (2) adopts phenolic resin as an adhesive, the glue dispensing frequency is 800-1000 Hz, the glue dispensing speed is 50-60 mm/s, the glue dispensing width is 300-400 μm, and the glue dispensing temperature is 80-95 ℃.
6. The heat-insulating shell fabric for preventing molten metal according to claim 1, wherein the pressure of the hot press in the step (3) is 3-5 kg/cm 2, the pressing temperature is 120-180 ℃, and the pressing speed is 10-15 m/min.
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Publication number Priority date Publication date Assignee Title
CN110978683A (en) * 2019-12-18 2020-04-10 翁菀蕾 High-temperature-resistant double-layer metal melting splashing-preventing fabric and processing technology thereof
CN112497861A (en) * 2020-05-07 2021-03-16 刘家浩 Long-acting flame-retardant anti-piercing anti-radiation composite fabric

Family Cites Families (5)

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CN105542229B (en) * 2016-03-02 2018-05-25 广东工业大学 A kind of more gradient function microcapsules titanium phosphate fire retardants and preparation method thereof
CN206703633U (en) * 2017-05-09 2017-12-05 上海伊贝纳纺织品有限公司 A kind of fusion proof metal splash composite material
US20200362180A1 (en) * 2017-05-11 2020-11-19 Premendra Pratap SINGH Thermal insulating and fire protecting materials and process of their development
CN109909895A (en) * 2019-02-25 2019-06-21 常州市奥普泰克光电科技有限公司 A kind of preparation method of multiple grinding piece
CN111450808A (en) * 2020-04-13 2020-07-28 东华理工大学 Phosphonic acid functionalized polymer/graphene nanoribbon composite aerogel and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110978683A (en) * 2019-12-18 2020-04-10 翁菀蕾 High-temperature-resistant double-layer metal melting splashing-preventing fabric and processing technology thereof
CN112497861A (en) * 2020-05-07 2021-03-16 刘家浩 Long-acting flame-retardant anti-piercing anti-radiation composite fabric

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