A method for preparing a fire-resistant thermal protective fabric

Abstract

The application discloses a preparation method of fireproof and heat-insulating protective fabric and relates to the technical field of textile materials. In the preparation of the fireproof and heat-insulating protective fabric, acetylacetone zirconium and tetraethyl orthosilicate are first spun, the inorganic fiber film is prepared through flat plate collection and high-temperature heating, the modified fiber film is prepared through the reaction of the inorganic fiber film and graphene oxide and the reaction of the modified fiber film and an inorganic mixed solution, the hydrophilic soft segment polymer is prepared through the reaction of polyethylene glycol, toluene diisocyanate and dimethylol propionic acid in sequence, the flame-retardant monomer is prepared through the reaction of phenol and phosphorus oxychloride, the modified carbon nanotube is prepared through the reaction of oxidized carbon nanotubes, the flame-retardant monomer, bisphenol A and p-hydroxybenzoic acid, the modified carbon nanotube film is prepared through the reaction of the modified carbon nanotube, the hydrophilic soft segment polymer and ethylenediamine, and the fireproof and heat-insulating protective fabric is prepared through the hot pressing of the modified carbon nanotube film and the modified fiber film. The fireproof and heat-insulating protective fabric prepared by the application has good water resistance, air permeability and fireproof and heat-insulating properties.

Description

Technical Field

[0001] This invention relates to the field of textile materials technology, specifically to a method for preparing a fire-resistant and heat-insulating protective fabric. Background Technology

[0002] A fire is a disaster caused by uncontrolled combustion in time or space. The new standard defines a fire as uncontrolled combustion in time or space. Among various disasters, fire is one of the most frequent and widespread threats to public safety and social development. Hundreds of thousands of fires occur every year, causing significant property damage and casualties. With social development, people's awareness of fire prevention and their psychological preparedness for self-rescue in the event of a fire are constantly improving. Clothing is the body's first line of defense; therefore, having fire-resistant clothing in a fire is particularly important.

[0003] Most existing fire-resistant fabrics are flame-retardant, which, despite their good flame-retardant effect, can deform and crack, leaving skin exposed at fire scenes and failing to provide adequate protection. The fabric provided by this invention has an outermost layer composed of flexible inorganic fibers and metal hydroxides, which enables the fabric to have good fire resistance at fire scenes, while also being waterproof and breathable. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing fire-resistant and heat-insulating protective fabric, so as to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] A method for preparing a fire-resistant and heat-insulating protective fabric, characterized in that the fire-resistant and heat-insulating protective fabric is obtained by spraying a silane coupling agent onto the surface of a modified carbon nanotube membrane, then laminating it with a modified fiber membrane and hot pressing it.

[0007] As an optimization, the modified carbon nanotube membrane is prepared by reacting polyethylene glycol and toluene diisocyanate, then reacting it with dimethylolpropionic acid to form a hydrophilic soft segment polymer, reacting phenol with excess phosphorus oxychloride to obtain a flame retardant monomer, reacting oxidized carbon nanotubes, flame retardant monomer, bisphenol A, and p-hydroxybenzoic acid to obtain modified carbon nanotubes, and then reacting the modified carbon nanotubes, hydrophilic soft segment polymer, and ethylenediamine before casting.

[0008] As an optimization, the modified fiber membrane is obtained by spinning zirconium acetylacetonate and tetraethyl orthosilicate and collecting it through a flat glass plate. The fiber membrane is then heated at multiple temperatures to obtain an inorganic fiber membrane. The inorganic fiber membrane, graphene oxide, and 3-aminopropyltriethoxysilane are reacted to obtain a pre-modified fiber membrane. The pre-modified fiber membrane is then reacted with an inorganic mixture composed of aluminum nitrate, calcium nitrate, and sodium hydroxide to obtain the final product.

[0009] As an optimization, the preparation method of the fire-resistant and heat-insulating protective fabric includes the following preparation steps:

[0010] (1) Preparation of inorganic fiber membrane: The spinning solution was electrospun, collected with a flat glass plate and peeled off to obtain a fiber membrane with a thickness of 0.8~1mm. The fiber membrane was placed in a muffle furnace and kept at 70~80℃ for 2~3h, 100~120℃ for 20~30min, 200~220℃ for 20~30min, 380~420℃ for 20~30min, 580~620℃ for 20~30min, and 750~850℃ for 2~3h. After cooling, the inorganic fiber membrane was obtained.

[0011] (2) Modification of inorganic fiber membrane: Inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and sodium hydroxide solution with a mass fraction of 8-10% were mixed evenly at a mass ratio of 4:2:1:50-6:3:1:60. The mixture was sonicated at 20-30℃ and 30-40kHz for 35-45 minutes. The mixture was then removed and washed 3-5 times each with pure water and anhydrous ethanol. The mixture was dried at 60-70℃ for 10-12 hours to obtain a pre-modified fiber membrane. The pre-modified fiber membrane and the inorganic mixture were placed in a high-pressure reactor at a mass ratio of 1:20-1:30. The mixture was sonicated at 90-100℃ and 30-40kHz for 20-24 hours. The mixture was then removed and washed 3-5 times with pure water. The mixture was dried at 60-70℃ for 10-12 hours to obtain a modified fiber membrane.

[0012] (3) Preparation of modified carbon nanotube membrane: Phenol and phosphorus oxychloride were mixed evenly at a mass ratio of 1:5~1:6, stirred at 90~100℃ and 800~1000r / min for 5~6h, and then allowed to stand at 110~120℃ for 2~3h to obtain flame retardant monomer; carbon nanotube oxide, flame retardant monomer, bisphenol A, anhydrous aluminum trichloride, and biphenyl were mixed evenly at a mass ratio of 4:1:1:0.01:40~5:1:1:0.03:50, stirred at 75~85℃ and 800~1000r / min for 20~30min in a nitrogen atmosphere, heated to 120~130℃ and stirred for 3~4h, then heated to 180~200℃ and stirred for 40~60min, and then carbon nanotube oxide was added at a mass ratio of 0. Add 0.1-0.2 times the amount of p-hydroxybenzoic acid and continue the reaction for 1-2 hours. Cool to room temperature, filter, and wash 3-5 times each with pure water and anhydrous ethanol. Dry at 60-70℃ for 10-12 hours to obtain modified carbon nanotubes. Mix the modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone, and pure water in a mass ratio of 1:1:0.2:1:1:2~1:2:0.3:1:2:3 until homogeneous. Stir at 800-1000 r / min for 60-80 minutes at 40-50℃. Cast the mixture onto a horizontal glass plate and dry at 100-500 Pa at 30-40℃ for 8-10 hours. Wash the surface 3-5 times with pure water and anhydrous ethanol and continue drying for 8-10 hours to obtain a modified carbon nanotube film with a thickness of 0.8-1 mm.

[0013] (4) Hot pressing: Mix the silane coupling agent and 40-50% ethanol at a mass ratio of 1:15-1:20, stir at 30-40℃ and 300-500 r / min for 2-3 min, and then press at 0.1-0.2 g / cm³. 2 A certain amount of material is sprayed onto one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with an equal area. In a nitrogen atmosphere, it is hot-pressed at 100~120℃ and 1~2MPa for 10~15min, and then naturally cooled to room temperature to obtain a fire-resistant and heat-insulating protective fabric.

[0014] As an optimization, the spinning solution in step (1) is prepared by mixing zirconium acetylacetonate, polyethylene oxide and acetone in a mass ratio of 10:1:10~20:1:20, stirring at 20~30℃ and 800~1000r / min for 2~3h, and then adding 0.8~1.2 times the mass of zirconium acetylacetonate orthosilicate and stirring for 10~12h.

[0015] As an optimization, the electrospinning process parameters in step (1) are: injection speed 1~1.5ml / h, collection distance 18~20cm, voltage 22~28kV, roller speed 50~70r / min, ambient temperature 20~30℃, and ambient humidity 40~45%RH.

[0016] As an optimization, the inorganic mixture in step (2) is prepared by mixing aluminum nitrate, calcium nitrate and pure water in a mass ratio of 1:1:10 to 1:1:15, then adding 10 to 15 times the mass of aluminum nitrate and 15 to 20% sodium hydroxide solution, and stirring at 20 to 30°C and 800 to 1000 r / min for 20 to 30 minutes.

[0017] As an optimization, the preparation method of carbon nanotubes in step (3) is as follows: immerse carbon nanotubes in concentrated nitric acid with a mass fraction of 60-65%, stir at 70-80℃ and 800-1000r / min for 2-3h, filter and wash with pure water and anhydrous ethanol 3-5 times each, and dry at 60-70℃ for 3-4h to prepare the product.

[0018] As an optimization, the preparation method of the hydrophilic soft segment polymer in step (3) is as follows: polyethylene glycol and ethyl acetate are mixed evenly at a mass ratio of 1:1 to 1:2. Toluene diisocyanate at a mass ratio of 0.8 to 1.2 times that of polyethylene glycol is added in a nitrogen atmosphere, and stirred at 60 to 70°C and 300 to 500 r / min for 25 to 30 min. Then, dibutyltin dilaurate at a mass ratio of 0.003 to 0.005 times that of polyethylene glycol is added. The reaction is continued under the same conditions for 2 to 3 h. Then, dimethylolpropionic acid at a mass ratio of 0.3 to 0.5 times that of polyethylene glycol is added. The mixture is then allowed to stand at 20 to 30°C and 1 to 2 kPa for 6 to 8 h to prepare the polymer.

[0019] As an optimization, the silane coupling agent in step (4) is of type Z-6040.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] In preparing the fire-resistant and heat-insulating protective fabric, the present invention first reacts polyethylene glycol and toluene diisocyanate, then reacts them with dimethylolpropionic acid to form a hydrophilic soft segment polymer, reacts phenol with excess phosphorus oxychloride to obtain a flame-retardant monomer, sprays a silane coupling agent on the surface of a modified carbon nanotube membrane, and then laminates it with a modified fiber membrane and hot-presses it to obtain the final product.

[0022] First, zirconium acetylacetonate and tetraethyl orthosilicate are spun into fibers and collected by a flat glass plate to obtain a fiber membrane. The fiber membrane is then heated at multiple temperatures to obtain an inorganic fiber membrane. A pre-modified fiber membrane is prepared by reacting the inorganic fiber membrane, graphene oxide, and 3-aminopropyltriethoxysilane. The pre-modified fiber membrane is then reacted with an inorganic mixture composed of aluminum nitrate, calcium nitrate, and sodium hydroxide to obtain a modified fiber membrane. The surface of graphene oxide contains a large number of hydrophilic groups such as hydroxyl and carboxyl groups. Metal ions in the inorganic mixture readily form complex bonds with these groups and are adsorbed onto the surface of graphene oxide, forming layered bimetallic hydrides. This allows graphene oxide to act as a carrier for intercalation. Graphene can promote the formation of layered bimetallic hydrides and improve the bonding between layered bimetallic hydrides and inorganic fiber membranes. At the same time, graphene oxide, as an intercalation layer, can transfer heat from the host and accelerate the heating of layered bimetallic hydrides. Layered bimetallic hydrides can absorb heat and remove interlayer water molecules to cool down. Meanwhile, the microscopic metal oxides formed after dehydration can reflect and scatter thermal radiation, thereby improving fire resistance and heat insulation performance. In addition, layered bimetallic hydrides have abundant hydroxide ions and interlayer ions, which give the modified fiber membrane good water absorption performance, accelerate the diffusion and desorption of water vapor in the modified carbon nanotube membrane, and thus improve water vapor permeability.

[0023] Secondly, modified carbon nanotubes are prepared by reacting carbon oxide nanotubes, flame-retardant monomers, bisphenol A, and p-hydroxybenzoic acid. Modified carbon nanotubes are then prepared by reacting the modified carbon nanotubes, hydrophilic soft-segment polymers, and ethylenediamine, followed by casting to obtain a modified carbon nanotube membrane. The flame-retardant monomers and bisphenol A form hard-segment hydrophobic long chains on the surface of the carbon oxide nanotubes, improving flame retardancy and increasing the hydrophobicity of the modified carbon nanotube membrane. Furthermore, the hydrophilic soft-segment polymer can facilitate the migration of water vapor through adsorption-diffusion-desorption of water molecules, thus making the modified carbon nanotube membrane waterproof and breathable. The cross-linking of the hydrophilic soft-segment polymer with the hard-segment phase on the modified carbon nanotubes gives the material good elasticity, providing excellent support and adhesion for the modified fiber membrane, preventing relative displacement and detachment or delamination, thereby improving the fire-resistant and heat-insulating performance of the fire-resistant and heat-insulating protective fabric. Detailed Implementation

[0024] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0025] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The test methods for various indicators of the fire-resistant and heat-insulating protective fabric produced in the following embodiments are as follows:

[0026] Waterproof performance: Take the fire-resistant and heat-insulating protective fabrics obtained in each embodiment and the comparative material of the same size, shape and thickness, fix the modified carbon nanotube film with the modified carbon nanotube film facing up and flat on a glass plate with double-sided tape, place it horizontally, and drop the same volume of pure water on the surface in the same environmental atmosphere. Tilt the glass plate until the water droplets of each component material roll, and record the rolling angle.

[0027] Breathability: The fire-resistant and heat-insulating protective fabrics obtained in each embodiment were made with the same size, shape and thickness as the comparative material, and the water vapor transmission rate was tested and recorded for 24 hours in accordance with GB / T 1037 standard.

[0028] Fire resistance and heat insulation performance: The fire-resistant and heat-insulating protective fabrics obtained in each embodiment and the comparative material are of the same size, shape and thickness, placed in the same position with the same fire source, with the modified fiber membrane facing the fire source and the initial temperature the same. After ten minutes, the temperature change on the other side is measured.

[0029] Example 1

[0030] (1) Preparation of inorganic fiber membrane: Zirconium acetylacetonate, polyethylene oxide and acetone were mixed evenly in a mass ratio of 10:1:10 and stirred at 20℃ and 800r / min for 3h. Then, 0.8 times the mass of tetraethyl orthosilicate of zirconium acetylacetonate was added and stirred for another 10h to prepare a spinning solution. The spinning solution was electrospun at an injection speed of 1ml / h, a collection distance of 18cm, a voltage of 22kV, a roller speed of 50r / min, an ambient temperature of 20℃ and an ambient humidity of 40%RH. After collection with a flat glass plate, the fiber membrane with a thickness of 0.9mm was obtained. The fiber membrane was placed in a muffle furnace and kept at 70℃ for 3h, 100℃ for 30min, 200℃ for 30min, 380℃ for 30min, 580℃ for 30min and 750℃ for 3h. After cooling, the inorganic fiber membrane was obtained.

[0031] (2) Modification of inorganic fiber membrane: Inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and sodium hydroxide solution with a mass fraction of 8-10% were mixed evenly at a mass ratio of 4:2:1:50. The mixture was ultrasonicated at 30 kHz for 45 min at 20 ℃. The mixture was then removed and washed three times each with pure water and anhydrous ethanol. The mixture was dried at 60 ℃ for 12 h to obtain a pre-modified fiber membrane. Aluminum nitrate, calcium nitrate, and pure water were mixed evenly at a mass ratio of 1:1:10. Then, 10 times the mass of aluminum nitrate and 20% sodium hydroxide solution with a mass fraction of 20% were added. The mixture was stirred at 800 r / min for 30 min at 20 ℃ to obtain an inorganic mixture. The pre-modified fiber membrane and the inorganic mixture were placed in a high-pressure reactor at a mass ratio of 1:20. The mixture was ultrasonicated at 30 kHz for 24 h at 90 ℃. The mixture was then removed and washed three times with pure water. The mixture was dried at 60 ℃ for 12 h to obtain a modified fiber membrane.

[0032] (3) Preparation of modified carbon nanotube membrane: Polyethylene glycol and ethyl acetate were mixed evenly at a mass ratio of 1:1. Toluene diisocyanate (0.8 times the mass of polyethylene glycol) was added under a nitrogen atmosphere and stirred at 60°C and 500 r / min for 30 min. Then, dibutyltin dilaurate (0.003 times the mass of polyethylene glycol) was added and stirred for 3 h under the same conditions. Finally, dimethylolpropionic acid (0.3 times the mass of polyethylene glycol) was added and the mixture was stirred at 20°C and 1 kPa. After 8 hours, a hydrophilic soft segment polymer was obtained. Carbon nanotubes were immersed in 60% concentrated nitric acid and stirred at 70°C and 800 rpm for 3 hours. The mixture was filtered and washed three times each with pure water and anhydrous ethanol, and dried at 60°C for 3 hours to obtain carbon oxide nanotubes. Phenol and phosphorus oxychloride were mixed evenly at a mass ratio of 1:5 and stirred at 90°C and 800 rpm for 6 hours. The mixture was then allowed to stand at 110°C for 3 hours to obtain a flame-retardant monomer. The carbon oxide nanotubes and the flame-retardant monomer were then combined. The monomer, bisphenol A, anhydrous aluminum trichloride, and biphenyl were mixed uniformly in a mass ratio of 4:1:1:0.01:40. The mixture was stirred at 75°C and 800 rpm for 30 min under a nitrogen atmosphere. The temperature was then raised to 120°C and the stirring continued for 4 h. The temperature was then raised to 180°C and the stirring continued for another 40 min. Finally, 0.1 times the mass of carbon oxide nanotubes of p-hydroxybenzoic acid was added, and the reaction continued for 2 h. The mixture was cooled to room temperature, filtered, and washed three times each with pure water and anhydrous ethanol. Modified carbon nanotubes were prepared by drying at 60℃ for 12 hours. The modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone and pure water were mixed evenly in a mass ratio of 1:1:0.2:1:1:2. The mixture was stirred at 800 r / min for 80 min at 40℃ and cast onto a horizontal glass plate. The mixture was dried at 30℃ and 100 Pa for 10 hours. The surface was washed three times with pure water and anhydrous ethanol and then dried for another 8 hours to obtain a modified carbon nanotube film with a thickness of 0.9 mm.

[0033] (4) Hot pressing: Mix Z-6040 silane coupling agent and 40% ethanol at a mass ratio of 1:15, stir at 30℃ and 300r / min for 3min, and then press with 0.1g / cm 2 A certain amount of material is sprayed onto one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with an equal area. In a nitrogen atmosphere, it is hot-pressed at 100°C and 1MPa for 15 minutes, and then naturally cooled to room temperature to obtain a fire-resistant and heat-insulating protective fabric.

[0034] Example 2

[0035] (1) Preparation of inorganic fiber membrane: Zirconium acetylacetonate, polyethylene oxide and acetone were mixed evenly in a mass ratio of 15:1:15 and stirred at 25℃ and 900r / min for 2.5h. Then, tetraethyl orthosilicate with a mass of 1 times that of zirconium acetylacetonate was added and stirred for 11h to prepare a spinning solution. The spinning solution was electrospun at an injection speed of 1.2ml / h, a collection distance of 19cm, a voltage of 25kV, a roller speed of 60r / min, an ambient temperature of 25℃ and an ambient humidity of 42%RH. After collection with a flat glass plate, the fiber membrane with a thickness of 0.9mm was obtained. The fiber membrane was placed in a muffle furnace and kept at 75℃ for 2.5h, 110℃ for 25min, 210℃ for 25min, 400℃ for 25min, 600℃ for 25min and 800℃ for 2.5h. After cooling, the inorganic fiber membrane was obtained.

[0036] (2) Modification of inorganic fiber membrane: Inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and sodium hydroxide solution with a mass fraction of 8-10% were mixed evenly at a mass ratio of 5:2.5:1:55. The mixture was ultrasonicated at 35 kHz for 40 min at 25 ℃. The mixture was then removed and washed 4 times each with pure water and anhydrous ethanol. The mixture was dried at 65 ℃ for 11 h to obtain a pre-modified fiber membrane. Aluminum nitrate, calcium nitrate, and pure water were mixed evenly at a mass ratio of 1:1:12. Then, 12 times the mass of aluminum nitrate and 18% sodium hydroxide solution with a mass fraction of 18% were added. The mixture was stirred at 900 r / min for 25 min at 25 ℃ to obtain an inorganic mixture. The pre-modified fiber membrane and the inorganic mixture were placed in a high-pressure reactor at a mass ratio of 1:25. The mixture was ultrasonicated at 35 kHz for 22 h at 95 ℃. The mixture was then removed and washed 4 times with pure water. The mixture was dried at 65 ℃ for 11 h to obtain a modified fiber membrane.

[0037] (3) Preparation of modified carbon nanotube membrane: Polyethylene glycol and ethyl acetate were mixed evenly at a mass ratio of 1:1.5. Toluene diisocyanate with a mass of 1 times that of polyethylene glycol was added under a nitrogen atmosphere, and the mixture was stirred at 65°C and 400 r / min for 28 min. Then, dibutyltin dilaurate with a mass of 0.004 times that of polyethylene glycol was added, and the mixture was stirred and reacted for 2.5 h under the same conditions. Then, dimethylolpropionic acid with a mass of 0.4 times that of polyethylene glycol was added, and the mixture was allowed to stand at 25°C and 1.5 kPa for 7 h. h, a hydrophilic soft segment polymer was prepared; carbon nanotubes were immersed in 62% concentrated nitric acid and stirred at 75℃ and 900 r / min for 2.5 h, filtered and washed 4 times each with pure water and anhydrous ethanol, and dried at 65℃ for 3.5 h to obtain carbon oxide nanotubes; phenol and phosphorus oxychloride were mixed evenly at a mass ratio of 1:5, stirred at 95℃ and 900 r / min for 5.5 h, and allowed to stand at 115℃ for 2.5 h to obtain a flame retardant monomer; carbon oxide nanotubes, flame retardant... The monomer, bisphenol A, anhydrous aluminum trichloride, and biphenyl were mixed evenly in a mass ratio of 4.5:1:1:0.01:45. The mixture was stirred at 80°C and 900 rpm for 25 min under a nitrogen atmosphere. The temperature was then raised to 125°C and the stirring continued for 3.5 h. The temperature was then raised to 190°C and the stirring continued for 50 min. Finally, 0.15 times the mass of carbon oxide nanotubes of p-hydroxybenzoic acid was added, and the reaction continued for 1.5 h. The mixture was cooled to room temperature, filtered, and washed four times each with pure water and anhydrous ethanol. Modified carbon nanotubes were prepared by drying at 65℃ for 11 hours. Modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone, and pure water were mixed evenly in a mass ratio of 1:1:0.25:1:1.5:2.5. The mixture was stirred at 45℃ and 900 r / min for 70 minutes. The mixture was then cast onto a horizontal glass plate and dried at 35℃ and 300 Pa for 9 hours. The surface was washed four times with pure water and anhydrous ethanol and then dried for another 9 hours to obtain a modified carbon nanotube film with a thickness of 0.9 mm.

[0038] (4) Hot pressing: Mix Z-6040 silane coupling agent and 45% ethanol at a mass ratio of 1:18, stir at 35℃ and 400r / min for 2.5min, and then press at 0.15g / cm 2 A certain amount of material is sprayed onto one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with an equal area. The mixture is then hot-pressed at 110°C and 1.5MPa for 12 minutes in a nitrogen atmosphere and allowed to cool naturally to room temperature to obtain a fire-resistant and heat-insulating protective fabric.

[0039] Example 3

[0040] (1) Preparation of inorganic fiber membrane: Zirconium acetylacetonate, polyethylene oxide and acetone were mixed evenly in a mass ratio of 20:1:20 and stirred at 30℃ and 1000r / min for 2h. Then, 1.2 times the mass of tetraethyl orthosilicate of zirconium acetylacetonate was added and stirred for 12h to prepare a spinning solution. The spinning solution was electrospun at an injection speed of 1.5ml / h, a collection distance of 20cm, a voltage of 28kV, a roller speed of 70r / min, an ambient temperature of 30℃ and an ambient humidity of 45%RH. After collection with a flat glass plate, the fiber membrane with a thickness of 0.9mm was obtained. The fiber membrane was placed in a muffle furnace and kept at 80℃ for 2h, 120℃ for 20min, 220℃ for 20min, 420℃ for 20min, 620℃ for 20min and 850℃ for 2h. After cooling, the inorganic fiber membrane was obtained.

[0041] (2) Modification of inorganic fiber membrane: Inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and sodium hydroxide solution with a mass fraction of 8-10% were mixed evenly at a mass ratio of 6:3:1:60. The mixture was ultrasonicated at 30℃ and 40kHz for 35 min. The mixture was then removed and washed 5 times each with pure water and anhydrous ethanol. The mixture was dried at 70℃ for 10 h to obtain a pre-modified fiber membrane. Aluminum nitrate, calcium nitrate, and pure water were mixed evenly at a mass ratio of 1:1:15. Then, 15 times the mass of aluminum nitrate and 15% sodium hydroxide solution with a mass fraction of 15% were added. The mixture was stirred at 30℃ and 1000r / min for 20 min to obtain an inorganic mixture. The pre-modified fiber membrane and the inorganic mixture were placed in a high-pressure reactor at a mass ratio of 1:30. The mixture was ultrasonicated at 100℃ and 40kHz for 20 h. The mixture was then removed and washed 5 times with pure water. The mixture was dried at 70℃ for 10 h to obtain a modified fiber membrane.

[0042] (3) Preparation of modified carbon nanotube membrane: Polyethylene glycol and ethyl acetate were mixed evenly at a mass ratio of 1:2. Toluene diisocyanate (1.2 times the mass of polyethylene glycol) was added under a nitrogen atmosphere and stirred at 70°C and 500 r / min for 25 min. Then, dibutyltin dilaurate (0.005 times the mass of polyethylene glycol) was added, and the reaction was continued under the same conditions for 3 h. Then, dimethylolpropionic acid (0.5 times the mass of polyethylene glycol) was added and the mixture was allowed to stand at 30°C and 2 kPa for 6 h. h, a hydrophilic soft segment polymer was prepared; carbon nanotubes were immersed in 65% concentrated nitric acid, stirred at 80℃ and 1000 r / min for 2 h, filtered and washed 5 times each with pure water and anhydrous ethanol, and dried at 70℃ for 3 h to obtain carbon oxide nanotubes; phenol and phosphorus oxychloride were mixed evenly at a mass ratio of 1:6, stirred at 100℃ and 1000 r / min for 5 h, and allowed to stand at 120℃ for 2 h to prepare a flame retardant monomer; carbon oxide nanotubes, flame retardant The monomer, bisphenol A, anhydrous aluminum trichloride, and biphenyl were mixed evenly in a mass ratio of 5:1:1:0.03:50. The mixture was stirred at 85°C and 1000 rpm for 20 min under a nitrogen atmosphere. The temperature was then raised to 130°C and the stirring continued for 4 h. The temperature was then raised to 200°C and the stirring continued for 40 min. Finally, 0.2 times the mass of carbon oxide nanotubes of p-hydroxybenzoic acid was added, and the reaction continued for 2 h. The mixture was cooled to room temperature, filtered, and washed five times each with pure water and anhydrous ethanol. Modified carbon nanotubes were prepared by drying at 70℃ for 10 hours. The modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone, and pure water were mixed evenly in a mass ratio of 1:2:0.3:1:2:3. The mixture was stirred at 50℃ and 1000 r / min for 60 min, and then cast onto a horizontal glass plate. The mixture was dried at 40℃ and 500 Pa for 8 hours. The surface was washed 5 times with pure water and anhydrous ethanol, and then dried for another 10 hours to obtain a modified carbon nanotube film with a thickness of 0.9 mm.

[0043] (4) Hot pressing: Mix Z-6040 silane coupling agent and 45% ethanol at a mass ratio of 1:20, stir at 40℃ and 500r / min for 2min, and then press with 0.2g / cm 2 A certain amount of material is sprayed onto one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with an equal area. In a nitrogen atmosphere, it is hot-pressed at 100~120℃ and 1~2MPa for 10~15min, and then naturally cooled to room temperature to obtain a fire-resistant and heat-insulating protective fabric.

[0044] Comparative Example 1

[0045] The preparation method of the fire-resistant and heat-insulating protective fabric in Comparative Example 1 differs from that in Example 2 only in step (2). Step (2) is modified as follows: aluminum nitrate, calcium nitrate, and pure water are mixed evenly at a mass ratio of 1:1:12, and then 12 times the mass of aluminum nitrate is added to a sodium hydroxide solution with a mass fraction of 18%. The mixture is stirred at 25°C and 900 r / min for 25 min to obtain an inorganic mixture. The inorganic fiber membrane and the inorganic mixture are placed in a high-pressure reactor at a mass ratio of 1:25 and ultrasonically reacted at 95°C and 35 kHz for 22 h. The membrane is then removed, washed four times with pure water, and dried at 65°C for 11 h to obtain a modified fiber membrane. The remaining steps are the same as in Example 2.

[0046] Comparative Example 2

[0047] The preparation method of the fire-resistant and heat-insulating protective fabric in Comparative Example 2 differs from that in Example 2 only in step (2). Step (2) is modified as follows: Inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and sodium hydroxide solution with a mass fraction of 8-10% are mixed evenly at a mass ratio of 5:2.5:1:55, sonicated at 25°C and 35kHz for 40 minutes, removed and washed 4 times each with pure water and anhydrous ethanol, and dried at 65°C for 11 hours to obtain the modified fiber membrane. The remaining steps are the same as in Example 2.

[0048] Comparative Example 3

[0049] The preparation method of the fire-resistant and heat-insulating protective fabric of Comparative Example 3 differs from that of Example 2 only in step (3). Step (3) is modified as follows: polyethylene glycol and ethyl acetate are mixed evenly at a mass ratio of 1:1.5. Toluene diisocyanate with a mass of 1 times that of polyethylene glycol is added in a nitrogen atmosphere and stirred at 65°C and 400 r / min for 28 min. Then, dibutyltin dilaurate with a mass of 0.004 times that of polyethylene glycol is added. The reaction is continued for 2.5 h with the conditions unchanged. Then, dimethylolpropionic acid with a mass of 0.4 times that of polyethylene glycol is added and the mixture is allowed to stand at 25°C and 1.5 kPa for 7 h to obtain a hydrophilic soft segment polymer. Carbon nanotubes are then immersed in the mixture. In 62% concentrated nitric acid, the mixture was stirred at 75°C and 900 rpm for 2.5 h. After filtration, the mixture was washed four times each with pure water and anhydrous ethanol, and dried at 65°C for 3.5 h to obtain carbon nanotubes. Carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone, and pure water were mixed uniformly in a mass ratio of 1:1:0.25:1:1.5:2.5, stirred at 45°C and 900 rpm for 70 min, and cast onto a horizontal glass plate. The mixture was dried at 35°C and 300 Pa for 9 h, and the surface was washed four times with pure water and anhydrous ethanol, followed by further drying for 9 h to obtain a 0.9 mm thick modified carbon nanotube film. The remaining steps were the same as in Example 2.

[0050] Comparative Example 4

[0051] The preparation method of the fire-resistant and heat-insulating protective fabric of Comparative Example 4 differs from that of Example 2 only in step (3). Step (3) is modified as follows: carbon nanotubes are immersed in concentrated nitric acid with a mass fraction of 62%, stirred at 75°C and 900 r / min for 2.5 h, filtered, and washed 4 times each with pure water and anhydrous ethanol, and dried at 65°C for 3.5 h to obtain carbon nanotube oxide; phenol and phosphorus oxychloride are mixed evenly at a mass ratio of 1:5, stirred at 95°C and 900 r / min for 5.5 h, and allowed to stand at 115°C for 2.5 h to obtain flame-retardant monomer; carbon nanotube oxide, flame-retardant monomer, bisphenol A, anhydrous aluminum trichloride, and biphenyl are mixed evenly at a mass ratio of 4.5:1:1:0.01:45, and stirred at 80°C and 900 r / min in a nitrogen atmosphere. The mixture was stirred for 25 min, heated to 125°C and stirred for 3.5 h, then heated to 190°C and stirred for 50 min. 0.15 times the mass of the carbon nanotubes (p-hydroxybenzoic acid) was added, and the reaction continued for 1.5 h. The mixture was cooled to room temperature, filtered, and washed four times each with pure water and anhydrous ethanol. It was then dried at 65°C for 11 h to obtain modified carbon nanotubes. The modified carbon nanotubes, ethylenediamine, triethylamine, acetone, and pure water were mixed uniformly in a mass ratio of 1:1:0.25:1:1.5:2.5, stirred at 900 rpm for 70 min at 45°C, and cast onto a horizontal glass plate. The mixture was dried at 35°C and 300 Pa for 9 h, washed four times with pure water and anhydrous ethanol, and dried for another 9 h to obtain a 0.9 mm thick modified carbon nanotube film. The remaining steps were performed in Example 2.

[0052] Comparative Example 5

[0053] (1) Preparation of inorganic fiber membrane: Zirconium acetylacetonate, polyethylene oxide and acetone were mixed evenly in a mass ratio of 15:1:15 and stirred at 25℃ and 900r / min for 2.5h. Then, tetraethyl orthosilicate with a mass of 1 times that of zirconium acetylacetonate was added and stirred for 11h to prepare a spinning solution. The spinning solution was electrospun at an injection speed of 1.2ml / h, a collection distance of 19cm, a voltage of 25kV, a roller speed of 60r / min, an ambient temperature of 25℃ and an ambient humidity of 42%RH. After collection with a flat glass plate, the fiber membrane with a thickness of 0.9mm was obtained. The fiber membrane was placed in a muffle furnace and kept at 75℃ for 2.5h, 110℃ for 25min, 210℃ for 25min, 400℃ for 25min, 600℃ for 25min and 800℃ for 2.5h. After cooling, the inorganic fiber membrane was obtained.

[0054] (2) Preparation of modified carbon nanotube membrane: Polyethylene glycol and ethyl acetate were mixed evenly at a mass ratio of 1:1.5. Toluene diisocyanate with a mass ratio of 1:1.5 of polyethylene glycol was added under a nitrogen atmosphere and stirred at 65°C and 400 r / min for 28 min. Then, dibutyltin dilaurate with a mass ratio of 0.004:1 of polyethylene glycol was added and the reaction was continued under the same conditions for 2.5 h. Then, dimethylolpropionic acid with a mass ratio of 0.4:1 of polyethylene glycol was added and the mixture was allowed to stand at 25°C and 1.5 kPa for 7 h to obtain a hydrophilic soft segment polymer. The carbon nanotubes were immersed in 62% concentrated nitric acid and stirred at 75°C. The mixture was stirred at 900 rpm for 2.5 h at ℃, filtered, and washed 4 times each with pure water and anhydrous ethanol. It was then dried at 65℃ for 3.5 h to obtain carbon nanotubes. Carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone, and pure water were mixed evenly in a mass ratio of 1:1:0.25:1:1.5:2.5. The mixture was stirred at 900 rpm for 70 min at 45℃, cast onto a horizontal glass plate, and dried at 300 Pa at 35℃ for 9 h. The surface was washed 4 times with pure water and anhydrous ethanol, and then dried for another 9 h to obtain a modified carbon nanotube film with a thickness of 0.9 mm.

[0055] (3) Hot pressing: Mix Z-6040 silane coupling agent and 45% ethanol at a mass ratio of 1:18, stir at 35℃ and 400r / min for 2.5min, and then press at 0.15g / cm 2 A certain amount of material was sprayed onto one side of the modified carbon nanotube membrane, and then bonded to an inorganic fiber membrane of equal area. The membrane was then hot-pressed at 110°C and 1.5MPa for 12 minutes in a nitrogen atmosphere and allowed to cool naturally to room temperature to obtain a fire-resistant and heat-insulating protective fabric.

[0056] Example of effect

[0057] Table 1 below shows the performance analysis results of the waterproof performance, air permeability and fire-resistant and heat-insulating performance of the fire-resistant and heat-insulating protective fabrics of Examples 1-3 and Comparative Examples 1-5 of the present invention.

[0058] Table 1

[0059]

[0060] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 1 reveals that the fire-resistant and heat-insulating protective fabric prepared by this invention has good waterproof, breathable, and fire-resistant and heat-insulating properties.

[0061] A comparison of the experimental data from Examples 1, 2, and 3 with Comparative Example 1 reveals that Examples 1, 2, and 3 exhibit higher water vapor permeability and lower temperature variation compared to Comparative Example 1. This indicates that the inorganic fiber membrane first reacts with graphene oxide. The surface of graphene oxide contains a large number of hydrophilic groups such as hydroxyl and carboxyl groups. Metal ions in the inorganic mixture readily form complex bonds with these groups and are adsorbed onto the surface of graphene oxide, thus acting as a carrier for intercalation. This promotes the formation of layered bimetallic hydrides and enhances the bonding between the layered bimetallic hydrides and the inorganic fiber membrane. Simultaneously, the graphene oxide intercalation can transfer heat from the host and further enhance the adhesion of the layered bimetallic hydrides to the inorganic fiber membrane. Heating accelerates the removal of water molecules between layers, thereby improving the water vapor transmission rate and fire insulation performance of the fire-resistant and heat-insulating protective fabric. A comparison of experimental data from Examples 1, 2, and 3 and Comparative Example 2 reveals that Examples 1, 2, and 3 exhibit higher water vapor transmission rates and lower temperature variations compared to Comparative Example 2. This indicates that modification with the inorganic mixture can form layered bimetallic hydrides. These layered bimetallic hydrides contain a large number of hydroxide ions and interlayer ions, possessing excellent water absorption properties. This promotes the migration and diffusion of water vapor through the modified carbon nanotube membrane, thereby improving the water vapor transmission rate of the fire-resistant and heat-insulating protective fabric. Furthermore, the layered bimetallic hydrides can... By absorbing heat and removing interlayer water molecules for cooling, the microscopic metal oxides formed after dehydration can reflect and scatter thermal radiation, thereby improving the fire resistance and heat insulation performance of the fire-resistant and heat-insulating protective fabric. A comparison of experimental data from Examples 1, 2, and 3 and Comparative Example 3 reveals that Examples 1, 2, and 3 exhibit a larger roll-off angle compared to Comparative Example 3. This indicates that modification of carbon nanotubes allows flame-retardant monomers and bisphenol A to form hard-segment hydrophobic long chains on the surface of the carbon nanotubes, improving flame retardancy and increasing the hydrophobicity of the modified carbon nanotube film, thus enhancing the waterproof performance of the fire-resistant and heat-insulating protective fabric. From Examples 1, 2, and 3 and Comparative Example 4... The experimental data comparison revealed that Examples 1, 2, and 3 had higher water vapor transmission rates and lower temperature variations compared to Comparative Example 4. This indicates that the use of hydrophilic soft-segment polymers in the preparation of modified carbon nanotube membranes allows water vapor to migrate through adsorption-diffusion-desorption of water molecules, thereby improving the water vapor transmission rate of the fire-resistant and heat-insulating protective fabric. Furthermore, the cross-linking of the hydrophilic soft-segment polymers with the hard-segment phases on the modified carbon nanotubes gives the material good elasticity, providing excellent support and adhesion for the modified fiber membrane, preventing relative displacement and detachment or delamination, thus improving the fire-resistant and heat-insulating performance of the fire-resistant and heat-insulating protective fabric.

[0062] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A method for preparing a fire-resistant and heat-insulating protective fabric, characterized in that: The preparation steps include the following: (1) Preparation of inorganic fiber membrane: Zirconium acetylacetonate, polyethylene oxide and acetone were mixed evenly in a mass ratio of 15:1:15 and stirred at 25℃ and 900r / min for 2.5h. Then, tetraethyl orthosilicate with a mass of 1 times that of zirconium acetylacetonate was added and stirred for 11h to prepare a spinning solution. The spinning solution was electrospun at a pouring speed of 1.2ml / h, a collection distance of 19cm, a voltage of 25kV, a drum speed of 60r / min, an ambient temperature of 25℃ and an ambient humidity of 42%RH. After collection with a flat glass plate, the fiber membrane with a thickness of 0.9mm was obtained. The fiber membrane was placed in a muffle furnace and kept at 75℃ for 2.5h, 110℃ for 25min, 210℃ for 25min, 400℃ for 25min, 600℃ for 25min and 800℃ for 2.5h. After cooling, the inorganic fiber membrane was obtained. (2) Modification of inorganic fiber membrane: Inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and sodium hydroxide solution with a mass fraction of 8-10% were mixed evenly at a mass ratio of 5:2.5:1:

55. The mixture was ultrasonicated at 35 kHz for 40 min at 25 ℃. The mixture was then removed and washed 4 times each with pure water and anhydrous ethanol. The mixture was dried at 65 ℃ for 11 h to obtain a pre-modified fiber membrane. Aluminum nitrate, calcium nitrate, and pure water were mixed evenly at a mass ratio of 1:1:

12. Then, 12 times the mass of aluminum nitrate and 18% sodium hydroxide solution with a mass fraction of 18% were added. The mixture was stirred at 900 r / min for 25 min at 25 ℃ to obtain an inorganic mixture. The pre-modified fiber membrane and the inorganic mixture were placed in a high-pressure reactor at a mass ratio of 1:

25. The mixture was ultrasonicated at 35 kHz for 22 h at 95 ℃. The mixture was then removed and washed 4 times with pure water. The mixture was dried at 65 ℃ for 11 h to obtain a modified fiber membrane. (3) Preparation of modified carbon nanotube membrane: Polyethylene glycol and ethyl acetate were mixed evenly at a mass ratio of 1:1.

5. Toluene diisocyanate with a mass of 1 times that of polyethylene glycol was added under a nitrogen atmosphere, and the mixture was stirred at 65°C and 400 r / min for 28 min. Then, dibutyltin dilaurate with a mass of 0.004 times that of polyethylene glycol was added, and the mixture was stirred and reacted for 2.5 h under the same conditions. Then, dimethylolpropionic acid with a mass of 0.4 times that of polyethylene glycol was added, and the mixture was allowed to stand at 25°C and 1.5 kPa for 7 h. h, a hydrophilic soft segment polymer was prepared; carbon nanotubes were immersed in 62% concentrated nitric acid and stirred at 75℃ and 900 r / min for 2.5 h, filtered and washed 4 times each with pure water and anhydrous ethanol, and dried at 65℃ for 3.5 h to obtain carbon oxide nanotubes; phenol and phosphorus oxychloride were mixed evenly at a mass ratio of 1:5, stirred at 95℃ and 900 r / min for 5.5 h, and allowed to stand at 115℃ for 2.5 h to obtain a flame retardant monomer; carbon oxide nanotubes, flame retardant... The monomer, bisphenol A, anhydrous aluminum trichloride, and biphenyl were mixed evenly in a mass ratio of 4.5:1:1:0.01:

45. The mixture was stirred at 80°C and 900 rpm for 25 min under a nitrogen atmosphere. The temperature was then raised to 125°C and the stirring continued for 3.5 h. The temperature was then raised to 190°C and the stirring continued for 50 min. Finally, 0.15 times the mass of carbon oxide nanotubes of p-hydroxybenzoic acid was added, and the reaction continued for 1.5 h. The mixture was cooled to room temperature, filtered, and washed four times each with pure water and anhydrous ethanol. Modified carbon nanotubes were prepared by drying at 65℃ for 11 hours. Modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone, and pure water were mixed evenly in a mass ratio of 1:1:0.25:1:1.5:2.

5. The mixture was stirred at 45℃ and 900 r / min for 70 minutes. The mixture was then cast onto a horizontal glass plate and dried at 35℃ and 300 Pa for 9 hours. The surface was washed four times with pure water and anhydrous ethanol and then dried for another 9 hours to obtain a modified carbon nanotube film with a thickness of 0.9 mm. (4) Hot pressing: Mix Z-6040 silane coupling agent and 45% ethanol at a mass ratio of 1:18, stir at 35℃ and 400r / min for 2.5min, and then press at 0.15g / cm 2 A certain amount of material is sprayed onto one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with an equal area. The mixture is then hot-pressed at 110°C and 1.5MPa for 12 minutes in a nitrogen atmosphere and allowed to cool naturally to room temperature to obtain a fire-resistant and heat-insulating protective fabric.

Images