Fire-resistant heat-insulating protective fabric and preparation method thereof

Abstract

The invention discloses a fire-resistant heat-insulating protective fabric and a preparation method thereof, and relates to the technical field of textile materials. When preparing the fire-resistant heat-insulating protective fabric, the invention first spins zirconium acetylacetonate and ethyl orthosilicate, collects them on a flat plate and heats them at high temperature to obtain an inorganic fiber membrane, reacts the inorganic fiber membrane with graphene oxide and then reacts with an inorganic mixed liquid to obtain a modified fiber membrane, reacts polyethylene glycol with toluene diisocyanate and dihydroxymethyl propionic acid in sequence to obtain a hydrophilic soft segment polymer, reacts phenol with phosphorus oxychloride to obtain a flame retardant monomer, reacts oxidized carbon nanotubes, flame retardant monomers, bisphenol A, and p-hydroxybenzoic acid to obtain modified carbon nanotubes, reacts the modified carbon nanotubes, hydrophilic soft segment polymers, and ethylenediamine to obtain a modified carbon nanotube membrane, and hot presses the modified carbon nanotube membrane and the modified fiber membrane to obtain the fire-resistant heat-insulating protective fabric. The fire-resistant heat-insulating protective fabric prepared by the invention has good waterproofness, air permeability, and fire-resistant heat-insulating properties.

Description

Technical Field

[0001] The invention relates to the technical field of textile materials, in particular to a fire-resistant heat-insulating protective fabric and a preparation method thereof. Background Art

[0002] Fire refers to a disaster caused by burning out of control in time or space. In the new standard, fire is defined as burning out of control in time or space. Among various disasters, fire is one of the most frequent and common major disasters threatening public safety and social development. There are hundreds of thousands of fires every year, causing a large amount of property losses and casualties. With the development of society, people's awareness of fire prevention and psychological quality of self-rescue in the event of a fire are also constantly improving. Clothing is the first line of defense for the human body, so it is particularly important to have a fire-resistant clothing in a fire scene.

[0003] Most of the existing fabrics used for fire prevention are flame retardant. Although they have good flame retardant effects, they can also cause the fabrics to deform and crack, exposing the skin at the fire scene, and cannot achieve good protection effects. The fabric provided by the present invention has an outermost layer composed of flexible inorganic fibers and metal hydroxides, which can make the fabric have good fire resistance at the fire scene and also have waterproof and breathable effects. Summary of the invention

[0004] The object of the present invention is to provide a fire-resistant heat-insulating protective fabric and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

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

[0007] As an optimization, the modified carbon nanotube membrane is prepared by reacting polyethylene glycol and toluene diisocyanate, and then reacting with dihydroxymethylpropionic acid to prepare a hydrophilic soft segment polymer, reacting phenol and excess phosphorus oxychloride to prepare a flame retardant monomer, reacting oxidized carbon nanotubes, flame retardant monomer, bisphenol A, and parahydroxybenzoic acid to prepare modified carbon nanotubes, and reacting modified carbon nanotubes, hydrophilic soft segment polymers, and ethylenediamine to prepare the film by casting.

[0008] As an optimization, the modified fiber membrane is obtained by spinning zirconium acetylacetonate and tetraethyl orthosilicate and collecting the fiber membrane through a flat glass plate, the fiber membrane is 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, and the pre-modified fiber membrane is reacted with an inorganic mixed solution composed of aluminum nitrate, calcium nitrate and sodium hydroxide to obtain the obtained fiber membrane.

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

[0010] (1) Preparation of inorganic fiber membrane: electrospinning the spinning solution, collecting it with a flat glass and peeling it off to obtain a fiber membrane with a thickness of 0.8 to 1 mm, placing the fiber membrane in a muffle furnace, and keeping it at 70 to 80° C. for 2 to 3 h, keeping it at 100 to 120° C. for 20 to 30 min, keeping it at 200 to 220° C. for 20 to 30 min, keeping it at 380 to 420° C. for 20 to 30 min, keeping it at 580 to 620° C. for 20 to 30 min, and keeping it at 750 to 850° C. for 2 to 3 h, and then cooling it to obtain an inorganic fiber membrane;

[0011] (2) Modification of inorganic fiber membrane: The inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and 8-10% sodium hydroxide solution are mixed uniformly in a mass ratio of 4:2:1:50-6:3:1:60, and ultrasonically treated at 20-30°C and 30-40kHz for 35-45min, then taken out and washed with pure water and anhydrous ethanol for 3-5 times, and dried at 60-70°C for 10-12h to obtain a pre-modified fiber membrane; the pre-modified fiber membrane and the inorganic mixed solution are placed in a high-pressure reactor in a mass ratio of 1:20-1:30, and ultrasonically treated at 90-100°C and 30-40kHz for 20-24h, then taken out and washed with pure water for 3-5 times, and dried at 60-70°C for 10-12h to obtain a modified fiber membrane;

[0012] (3) Preparation of modified carbon nanotube film: Phenol and phosphorus oxychloride were mixed in a mass ratio of 1:5-1:6, stirred at 90-100°C and 800-1000 r / min for 5-6 h, and allowed to stand at 110-120°C for 2-3 h to obtain a flame retardant monomer; oxidized carbon nanotubes, flame retardant monomer, bisphenol A, anhydrous aluminum chloride, and biphenyl were mixed in a mass ratio of 4:1:1:0.01:40-5:1:1:0.03:50, stirred at 75-85°C and 800-1000 r / min for 20-30 min in a nitrogen atmosphere, heated to 120-130°C and continued to stir for 3-4 h, then heated to 180-200°C and continued to stir for 40-60 min, and then added with 0.05% oxidized carbon nanotube. .1 to 0.2 times of p-hydroxybenzoic acid, and continue to react for 1 to 2 hours, cool to room temperature, filter and wash with pure water and anhydrous ethanol for 3 to 5 times respectively, and dry at 60 to 70°C for 10 to 12 hours to obtain modified carbon nanotubes; the modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone and pure water are mixed uniformly in a mass ratio of 1:1:0.2:1:1:2 to 1:2:0.3:1:2:3, stirred at 40 to 50°C and 800 to 1000 r / min for 60 to 80 minutes, cast on a horizontal glass plate, dried at 30 to 40°C and 100 to 500 Pa for 8 to 10 hours, washed the surface with pure water and anhydrous ethanol for 3 to 5 times and continued to dry for 8 to 10 hours to obtain a modified carbon nanotube film with a thickness of 0.8 to 1 mm;

[0013] (4) Hot pressing: Mix the silane coupling agent and 40-50% ethanol in a mass ratio of 1:15-1:20, stir at 30-40°C, 300-500 r / min for 2-3 minutes, and then heat at 0.1-0.2 g / cm 2 The amount of the modified carbon nanotube membrane is sprayed on one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with the same area. In a nitrogen atmosphere, hot pressing is carried out at 100-120°C and 1-2MPa for 10-15min, and naturally cooled to room temperature to obtain a fire-resistant heat-insulating protective fabric.

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

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

[0016] As an optimization, the inorganic mixed liquid in step (2) is prepared by uniformly mixing aluminum nitrate, calcium nitrate and pure water in a mass ratio of 1:1:10 to 1:1:15, adding a 15-20% sodium hydroxide solution with a mass fraction of 10 to 15 times the mass of aluminum nitrate, 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 the oxidized carbon nanotubes in step (3) is: immersing the carbon nanotubes in concentrated nitric acid with a mass fraction of 60 to 65%, stirring at 70 to 80° C. and 800 to 1000 r / min for 2 to 3 hours, filtering and washing with pure water and anhydrous ethanol for 3 to 5 times each, and drying at 60 to 70° C. for 3 to 4 hours to prepare.

[0018] As an optimization, the preparation method of the hydrophilic soft segment polymer in step (3) is: polyethylene glycol and ethyl acetate are uniformly mixed in a mass ratio of 1:1 to 1:2, toluene diisocyanate is added in an amount of 0.8 to 1.2 times the mass of polyethylene glycol 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 is added in an amount of 0.003 to 0.005 times the mass of polyethylene glycol, the stirring reaction is continued for 2 to 3 h while keeping the conditions unchanged, then dihydroxymethylpropionic acid is added in an amount of 0.3 to 0.5 times the mass of polyethylene glycol, and the mixture is allowed to stand at 20 to 30° C. and 1 to 2 kPa for 6 to 8 h to prepare the hydrophilic soft segment polymer.

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

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

[0021] When preparing the fire-resistant and heat-insulating protective fabric, the present invention first reacts polyethylene glycol and toluene diisocyanate, and then reacts with dihydroxymethyl propionic acid to prepare a hydrophilic soft segment polymer, reacts phenol with an excess of phosphorus oxychloride to prepare a flame retardant monomer, sprays a silane coupling agent on the surface of a modified carbon nanotube film, and then laminates it with a modified fiber film and performs heat pressing to obtain the fabric.

[0022] First, zirconium acetylacetonate and ethyl orthosilicate are spun and collected through a flat glass plate to obtain a fiber membrane, the fiber membrane is 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 and an inorganic mixed solution composed of aluminum nitrate, calcium nitrate and sodium hydroxide are reacted to obtain a modified fiber membrane, the surface of graphene oxide contains a large number of hydrophilic groups such as hydroxyl and carboxyl groups, the metal ions in the inorganic mixed solution are easy to form coordination bonds with these groups and are adsorbed on the surface of graphene oxide, and form layered bimetallic hydrogen hydride, so that the graphene oxide is used as a carrier intercalation, and the graphene oxide Graphene can promote the formation of layered bimetallic hydrogen hydride and improve the degree of bonding between layered bimetallic hydrogen hydride and inorganic fiber membrane. At the same time, graphene oxide as an intercalation layer can transfer the heat of the main body and accelerate the heating of the layered bimetallic hydrogen hydride. The layered bimetallic hydrogen hydride can cool down by removing interlayer water molecules by absorbing heat. At the same time, the microscopic metal oxides formed after dehydration can reflect and scatter thermal radiation, thereby improving the fire-resistant and heat-insulating properties. At the same time, the layered bimetallic hydrogen hydride has abundant hydroxide and intermediate interlayer ions, which makes the modified fiber membrane have good water absorption properties, accelerates the diffusion and desorption of water vapor in the modified carbon nanotube membrane, thereby improving the water vapor permeability.

[0023] Secondly, the oxidized carbon nanotubes, flame retardant monomers, bisphenol A and p-hydroxybenzoic acid are reacted to obtain modified carbon nanotubes, and the modified carbon nanotubes, hydrophilic soft segment polymers and ethylenediamine are reacted and then cast to obtain modified carbon nanotube membranes. The flame retardant monomers and bisphenol A form hard segment hydrophobic long chains on the surfaces of the oxidized carbon nanotubes, which improve the flame retardancy and increase the hydrophobicity of the modified carbon nanotube membranes. The hydrophilic soft segment polymers can migrate water vapor by adsorption-diffusion-desorption of water molecules, thereby making the modified carbon nanotube membranes waterproof and breathable. The hydrophilic soft segment polymers and the hard segments on the modified carbon nanotubes are cross-linked to give the material good elasticity, and have good supporting and bonding effects on the modified fiber membranes, thereby preventing relative displacement from causing shedding and faults, thereby improving the fire-resistant and heat-insulating properties of the fire-resistant and heat-insulating protective fabrics. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the fire-resistant and heat-insulating protective fabrics prepared in the following examples 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, place the modified carbon nanotube film face up and fix it horizontally on a glass plate with double-sided tape, 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] Air permeability: The fire-resistant heat-insulating protective fabrics obtained in each embodiment and the comparative example materials were taken with the same size, shape and thickness, and the water vapor permeability was tested and recorded for 24 hours according to GB / T 1037 standard.

[0028] Fire-resistant and heat-insulating performance: The fire-resistant and heat-insulating protective fabrics obtained in each embodiment and the comparative material are taken in the same size, shape and thickness, placed at the same fire source and position, with the modified fiber membrane facing the fire source and the same starting temperature. 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 uniformly in a mass ratio of 10:1:10, stirred at 20°C and 800 r / min for 3 h, and then 0.8 times the mass of zirconium acetylacetonate of tetraethyl orthosilicate was added and stirred for 10 h to prepare a spinning solution; the spinning solution was subjected to electrostatic spinning at a perfusion rate of 1 ml / h, a collection distance of 18 cm, a voltage of 22 kV, a drum speed of 50 r / min, an ambient temperature of 20°C, and an ambient humidity of 40% RH, and the solution was collected with a flat glass and peeled off to obtain a fiber membrane with a thickness of 0.9 mm. The fiber membrane was placed in a muffle furnace and kept at 70°C for 3 h, 100°C for 30 min, 200°C for 30 min, 380°C for 30 min, 580°C for 30 min, and 750°C for 3 h in sequence, and then cooled to obtain an inorganic fiber membrane;

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

[0032] (3) Preparation of modified carbon nanotube membrane: polyethylene glycol and ethyl acetate were mixed in a mass ratio of 1:1, and toluene diisocyanate (0.8 times the mass of polyethylene glycol) was added in a nitrogen atmosphere, and stirred at 60°C, 500 r / min for 30 min. Then, dibutyltin dilaurate (0.003 times the mass of polyethylene glycol) was added, and the stirring reaction was continued for 3 h while keeping the conditions unchanged. Then, dihydroxymethylpropionic acid (0.3 times the mass of polyethylene glycol) was added, and the mixture was stirred at 20°C, 1 kPa static pressure. The carbon nanotubes were immersed in 60% concentrated nitric acid, stirred at 70°C and 800 r / min for 3 h, filtered and washed with pure water and anhydrous ethanol for 3 times, and dried at 60°C for 3 h to obtain oxidized carbon nanotubes; phenol and phosphorus oxychloride were mixed in a mass ratio of 1:5, stirred at 90°C and 800 r / min for 6 h, and allowed to stand at 110°C for 3 h to obtain flame retardant monomers; oxidized carbon nanotubes and flame retardant monomers were mixed in a mass ratio of 1:5, stirred at 90°C and 800 r / min for 6 h, and allowed to stand at 110°C for 3 h to obtain flame retardant monomers; The monomer, bisphenol A, anhydrous aluminum chloride and biphenyl were mixed uniformly in a mass ratio of 4:1:1:0.01:40, stirred and reacted at 75°C and 800r / min in a nitrogen atmosphere for 30min, heated to 120°C and continued to stir and react for 4h, then heated to 180°C and continued to stir and react for 40min, then 0.1 times the mass of the oxidized carbon nanotubes of p-hydroxybenzoic acid was added, and the reaction was continued for 2h, cooled to room temperature, filtered and washed 3 times with pure water and anhydrous ethanol respectively, and then The modified carbon nanotubes were prepared by drying at 60°C for 12 hours; the modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone and pure water were mixed uniformly in a mass ratio of 1:1:0.2:1:1:2, stirred at 40°C and 800r / min for 80 minutes, cast on a horizontal glass plate, dried at 30°C and 100Pa for 10 hours, and the surface was cleaned with pure water and anhydrous ethanol for 3 times and then continued to dry for 8 hours to obtain a 0.9mm thick modified carbon nanotube film;

[0033] (4) Hot pressing: Mix Z-6040 silane coupling agent and 40% ethanol in a mass ratio of 1:15, stir at 30°C, 300 r / min for 3 min, and then heat at 0.1 g / cm 2 The amount of the modified carbon nanotube membrane was sprayed on one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with the same area. In a nitrogen atmosphere, it was hot-pressed at 100°C and 1MPa for 15 minutes and 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 uniformly in a mass ratio of 15:1:15, stirred at 25°C and 900 r / min for 2.5 h, and then 1 times the mass of zirconium acetylacetonate of tetraethyl orthosilicate was added and stirred for 11 h to prepare a spinning solution; the spinning solution was electrospun at a perfusion rate of 1.2 ml / h, a collection distance of 19 cm, a voltage of 25 kV, a drum speed of 60 r / min, an ambient temperature of 25°C, and an ambient humidity of 42% RH, and the solution was collected with a flat glass and peeled off to obtain a fiber membrane with a thickness of 0.9 mm. The fiber membrane was placed in a muffle furnace and kept at 75°C for 2.5 h, 110°C for 25 min, 210°C for 25 min, 400°C for 25 min, 600°C for 25 min, and 800°C for 2.5 h in sequence, and then cooled to obtain an inorganic fiber membrane;

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

[0037] (3) Preparation of modified carbon nanotube membrane: polyethylene glycol and ethyl acetate were mixed at a mass ratio of 1:1.5, and toluene diisocyanate (1 times the mass of polyethylene glycol) was added in a nitrogen atmosphere, and stirred at 65°C, 400 r / min for 28 min. Then, dibutyltin dilaurate (0.004 times the mass of polyethylene glycol) was added, and the stirring reaction was continued for 2.5 h while keeping the conditions unchanged. Then, dihydroxymethylpropionic acid (0.4 times the mass of polyethylene glycol) was added, and the mixture was allowed to stand at 25°C, 1.5 kPa for 7 min. h, to obtain a hydrophilic soft segment polymer; immerse the carbon nanotubes in 62% concentrated nitric acid by mass, stir and react at 75°C, 900r / min for 2.5h, filter and wash with pure water and anhydrous ethanol 4 times each, and dry at 65°C for 3.5h to obtain oxidized carbon nanotubes; mix phenol and phosphorus oxychloride in a mass ratio of 1:5, stir and react at 95°C, 900r / min for 5.5h, and stand at 115°C for 2.5h to obtain a flame retardant monomer; oxidized carbon nanotubes and flame retardant The monomer, bisphenol A, anhydrous aluminum chloride and biphenyl were mixed evenly in a mass ratio of 4.5:1:1:0.01:45, stirred and reacted at 80°C and 900r / min in a nitrogen atmosphere for 25min, heated to 125°C and continued to stir and react for 3.5h, then heated to 190°C and continued to stir and react for 50min, then 0.15 times the mass of the oxidized carbon nanotubes of p-hydroxybenzoic acid was added, and the reaction was continued for 1.5h, cooled to room temperature, filtered and washed 4 times with pure water and anhydrous ethanol respectively , dried at 65°C for 11h to obtain modified carbon nanotubes; the modified 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 900r / min for 70min, cast on a horizontal glass plate, dried at 35°C and 300Pa for 9h, the surface was washed with pure water and anhydrous ethanol for 4 times and then dried for 9h to obtain a 0.9mm thick modified carbon nanotube film;

[0038] (4) Hot pressing: Mix Z-6040 silane coupling agent and 45% ethanol in a mass ratio of 1:18, stir at 35°C, 400 r / min for 2.5 min, and then heat at 0.15 g / cm 2 The amount of the modified carbon nanotube membrane was sprayed on one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with the same area. In a nitrogen atmosphere, it was hot-pressed at 110°C and 1.5MPa for 12min and naturally cooled 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 uniformly in a mass ratio of 20:1:20, stirred at 30°C and 1000 r / min for 2 h, and then 1.2 times the mass of zirconium acetylacetonate of tetraethyl orthosilicate was added and stirred for 12 h to prepare a spinning solution; the spinning solution was subjected to electrostatic spinning at a perfusion rate of 1.5 ml / h, a collection distance of 20 cm, a voltage of 28 kV, a drum speed of 70 r / min, an ambient temperature of 30°C, and an ambient humidity of 45% RH, and the solution was collected with a flat glass and then peeled off to obtain a fiber membrane with a thickness of 0.9 mm. The fiber membrane was placed in a muffle furnace and kept at 80°C for 2 h, 120°C for 20 min, 220°C for 20 min, 420°C for 20 min, 620°C for 20 min, and 850°C for 2 h in sequence, and then cooled to obtain an inorganic fiber membrane;

[0041] (2) Modification of inorganic fiber membrane: The inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and sodium hydroxide solution with a mass fraction of 8-10% were mixed in a mass ratio of 6:3:1:60, and ultrasonicated at 30°C and 40kHz for 35 minutes. The mixture was taken out and washed with pure water and anhydrous ethanol for 5 times each, and dried at 70°C for 10 hours to obtain a pre-modified fiber membrane. Aluminum nitrate, calcium nitrate, and pure water were mixed in a mass ratio of 1:1:15, and a sodium hydroxide solution with a mass fraction of 15% that is 15 times the mass of aluminum nitrate was added. The mixture was stirred at 30°C and 1000 r / min for 20 minutes to obtain an inorganic mixed solution. The pre-modified fiber membrane and the inorganic mixed solution were placed in a high-pressure reactor in a mass ratio of 1:30, and ultrasonicated at 100°C and 40kHz for 20 hours. The mixture was taken out and washed with pure water for 5 times, and dried at 70°C for 10 hours 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 in a nitrogen atmosphere, and stirred at 70°C, 500 r / min for 25 min, then dibutyltin dilaurate (0.005 times the mass of polyethylene glycol) was added, and the stirring reaction was continued for 3 h while keeping the conditions unchanged, then dihydroxymethylpropionic acid (0.5 times the mass of polyethylene glycol) was added, and the mixture was allowed to stand at 30°C, 2 kPa for 6 h. h, to obtain a hydrophilic soft segment polymer; immerse the carbon nanotubes in 65% concentrated nitric acid, stir and react at 80°C, 1000r / min for 2h, filter and wash with pure water and anhydrous ethanol 5 times each, and dry at 70°C for 3h to obtain oxidized carbon nanotubes; mix phenol and phosphorus oxychloride in a mass ratio of 1:6, stir and react at 100°C, 1000r / min for 5h, and stand at 120°C for 2h to obtain a flame retardant monomer; oxidized carbon nanotubes and flame retardant The monomer, bisphenol A, anhydrous aluminum chloride and biphenyl were mixed in a mass ratio of 5:1:1:0.03:50, stirred at 85°C and 1000r / min in a nitrogen atmosphere for 20min, heated to 130°C and continued to stir for 4h, then heated to 200°C and continued to stir for 40min, then p-hydroxybenzoic acid (0.2 times the mass of the oxidized carbon nanotubes) was added, and the reaction was continued for 2h, cooled to room temperature, filtered and washed with pure water and anhydrous ethanol 5 times each, and then heated to 130°C and continued to stir for 40min. The modified carbon nanotubes were prepared by drying at 70°C for 10 hours; the modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone and pure water were mixed uniformly in a mass ratio of 1:2:0.3:1:2:3, stirred at 50°C and 1000 r / min for 60 minutes, cast on a horizontal glass plate, dried at 40°C and 500 Pa for 8 hours, and the surface was cleaned with pure water and anhydrous ethanol for 5 times and then dried for 10 hours to obtain a 0.9 mm thick modified carbon nanotube film;

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

[0044] Comparative Example 1

[0045] The preparation method of the fire-resistant heat-insulating protective fabric of Comparative Example 1 is different from that of Example 2 only in step (2), and step (2) is modified as follows: aluminum nitrate, calcium nitrate and pure water are mixed uniformly at a mass ratio of 1:1:12, and then a sodium hydroxide solution with a mass fraction of 18% and a mass fraction of 12 times the mass of aluminum nitrate is added, and stirred at 25°C and 900r / min for 25min to obtain an inorganic mixed solution; the inorganic fiber membrane and the inorganic mixed solution are placed in a high-pressure reactor at a mass ratio of 1:25, and ultrasonically reacted at 95°C and 35kHz for 22h, taken out and washed with pure water 4 times, and dried at 65°C for 11h to obtain a modified fiber membrane. The remaining steps are the same as those of Example 2.

[0046] Comparative Example 2

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

[0048] Comparative Example 3

[0049] The preparation method of the fire-resistant heat-insulating protective fabric of Comparative Example 3 is different from that of Example 2 only in step (3). Step (3) is modified as follows: polyethylene glycol and ethyl acetate are uniformly mixed at a mass ratio of 1:1.5, toluene diisocyanate is added in a nitrogen atmosphere at 1 times the mass of polyethylene glycol, and stirred at 65°C, 400r / min for 28min, then dibutyltin dilaurate is added at 0.004 times the mass of polyethylene glycol, the stirring reaction is continued for 2.5h while keeping the conditions unchanged, then dihydroxymethylpropionic acid is added at 0.4 times the mass of polyethylene glycol, and the mixture is allowed to stand at 25°C, 1.5kPa for 7h to obtain a hydrophilic soft segment polymer; the carbon nanotubes are immersed in the mixture. In concentrated nitric acid with a mass fraction of 62%, the reaction was stirred at 75°C and 900r / min for 2.5h, filtered and washed with pure water and anhydrous ethanol 4 times each, and dried at 65°C for 3.5h to obtain oxidized carbon nanotubes; the oxidized 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 900r / min for 70min, cast on a horizontal glass plate, dried at 35°C and 300Pa for 9h, washed the surface with pure water and anhydrous ethanol 4 times, and then continued to dry for 9h to obtain a 0.9mm thick modified carbon nanotube film. The remaining steps are the same as in Example 2.

[0050] Comparative Example 4

[0051] The preparation method of the fire-resistant heat-insulating protective fabric of Comparative Example 4 is different from that of Example 2 only in step (3). Step (3) is modified as follows: immersing the carbon nanotubes in concentrated nitric acid with a mass fraction of 62%, stirring and reacting at 75°C and 900 r / min for 2.5 hours, filtering and washing with pure water and anhydrous ethanol 4 times each, and drying at 65°C for 3.5 hours to obtain oxidized carbon nanotubes; mixing phenol and phosphorus oxychloride in a mass ratio of 1:5, stirring and reacting at 95°C and 900 r / min for 5.5 hours, and standing at 115°C for 2.5 hours to obtain a flame retardant monomer; mixing the oxidized carbon nanotubes, flame retardant monomer, bisphenol A, anhydrous aluminum chloride, and biphenyl in a mass ratio of 4.5:1:1:0.01:45, and drying in a nitrogen atmosphere at 80°C and 900 r / min. nStir and react for 25 minutes, heat to 125°C and continue to stir and react for 3.5 hours, heat to 190°C and continue to stir and react for 50 minutes, then add 0.15 times the mass of the oxidized carbon nanotubes p-hydroxybenzoic acid, and continue to react for 1.5 hours, cool to room temperature, filter, wash with pure water and anhydrous ethanol 4 times each, and dry at 65°C for 11 hours to obtain modified carbon nanotubes; modify carbon nanotubes, ethylenediamine, triethylamine, acetone, and pure water are mixed uniformly in a mass ratio of 1:1:0.25:1:1.5:2.5, stir at 45°C, 900r / min for 70 minutes, cast on a horizontal glass plate, dry at 35°C, 300Pa for 9 hours, wash the surface with pure water and anhydrous ethanol 4 times, and continue to dry for 9 hours to obtain a 0.9mm thick modified carbon nanotube film. The remaining steps are the same as in Example 2.

[0052] Comparative Example 5

[0053] (1) Preparation of inorganic fiber membrane: zirconium acetylacetonate, polyethylene oxide and acetone were mixed uniformly in a mass ratio of 15:1:15, stirred at 25°C and 900 r / min for 2.5 h, and then 1 times the mass of zirconium acetylacetonate of tetraethyl orthosilicate was added and stirred for 11 h to prepare a spinning solution; the spinning solution was electrospun at a perfusion rate of 1.2 ml / h, a collection distance of 19 cm, a voltage of 25 kV, a drum speed of 60 r / min, an ambient temperature of 25°C, and an ambient humidity of 42% RH, and the solution was collected with a flat glass and peeled off to obtain a fiber membrane with a thickness of 0.9 mm. The fiber membrane was placed in a muffle furnace and kept at 75°C for 2.5 h, 110°C for 25 min, 210°C for 25 min, 400°C for 25 min, 600°C for 25 min, and 800°C for 2.5 h in sequence, and then cooled to obtain an inorganic fiber membrane;

[0054] (2) Preparation of modified carbon nanotube membrane: polyethylene glycol and ethyl acetate were mixed uniformly at a mass ratio of 1:1.5, and toluene diisocyanate (1 times the mass of polyethylene glycol) was added in a nitrogen atmosphere, and stirred at 65°C, 400 r / min for 28 min, and then dibutyltin dilaurate (0.004 times the mass of polyethylene glycol) was added, and the stirring reaction was continued for 2.5 h while keeping the conditions unchanged, and then dihydroxymethylpropionic acid (0.4 times the mass of polyethylene glycol) was added, and the mixture was allowed to stand at 25°C, 1.5 kPa for 7 h to obtain a hydrophilic soft segment polymer; the carbon nanotubes were immersed in 62% concentrated nitric acid at 75 ℃, 900r / min stirring reaction for 2.5h, filtered and washed with pure water and anhydrous ethanol 4 times each, dried at 65℃ for 3.5h to obtain oxidized carbon nanotubes; oxidized 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℃, 900r / min for 70min, cast on a horizontal glass plate, dried at 35℃, 300Pa for 9h, washed the surface with pure water and anhydrous ethanol 4 times and continued to dry for 9h to obtain a 0.9mm thick modified carbon nanotube film;

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

[0056] Effect example

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

[0058] Table 1

[0059]

[0060] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 1, it can be found that the fire-resistant heat-insulating protective fabric prepared by the present invention has good waterproof performance, air permeability and fire-resistant heat-insulating performance.

[0061] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1, it can be found that the water vapor permeability of Examples 1, 2, and 3 is higher than that of Comparative Example 1, and the temperature change is lower, which indicates that the inorganic fiber membrane reacts with the graphene oxide first. The surface of the graphene oxide contains a large number of hydrophilic groups such as hydroxyl groups and carboxyl groups. The metal ions in the inorganic mixed solution are easy to form coordination bonds with these groups and are adsorbed on the surface of the graphene oxide, thereby acting as a carrier intercalation layer, promoting the formation of layered bimetallic hydrogen hydride and improving the degree of combination of the layered bimetallic hydrogen hydride and the inorganic fiber membrane. At the same time, the graphene oxide intercalation layer can transfer the heat of the main body and perform the layered bimetallic hydrogen hydride. Heating is performed to accelerate the removal of water molecules between the layers, thereby improving the water vapor permeability and fire-resistant and heat-insulating properties of the fire-resistant and heat-insulating protective fabric; from the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2, it can be found that the water vapor permeability of Examples 1, 2, and 3 is higher than that of Comparative Example 2, and the temperature change is lower, which shows that the modification of the inorganic mixed liquid can form a layered bimetallic hydrogen hydride, which contains more hydroxide and intermediate interlayer ions, has good water absorption performance, and promotes the migration and diffusion of water vapor by the modified carbon nanotube film, thereby improving the water vapor permeability of the fire-resistant and heat-insulating protective fabric, and the layered bimetallic hydrogen hydride can By absorbing heat and removing interlayer water molecules to cool down, the microscopic metal oxides formed after dehydration can reflect and scatter thermal radiation, thereby improving the fire-resistant and heat-insulating properties of the fire-resistant and heat-insulating protective fabric; from the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3, it can be found that the rolling angles of Examples 1, 2, 3 are larger than those of Comparative Example 3, which shows that the oxidized carbon nanotubes are modified so that the flame retardant monomer and bisphenol A form hard segment hydrophobic long chains on the surface of the oxidized carbon nanotubes, thereby improving the flame retardancy and increasing the hydrophobicity of the modified carbon nanotube film, thereby improving the waterproof performance of the fire-resistant and heat-insulating protective fabric; from Examples 1, 2, 3 and Comparative Example 4 By comparing the experimental data, it can be found that Examples 1, 2, and 3 have higher water vapor permeability and lower temperature variation than Comparative Example 4, which indicates that a hydrophilic soft segment polymer is used in the preparation process of the modified carbon nanotube membrane. The hydrophilic soft segment polymer can migrate water vapor by adsorption-diffusion-desorption of water molecules, thereby improving the water vapor permeability of the fire-resistant and heat-insulating protective fabric. In addition, the hydrophilic soft segment polymer and the hard segment on the modified carbon nanotubes are cross-linked to give the material good elasticity, and have a good supporting and bonding effect on the modified fiber membrane, preventing relative displacement and shedding and faulting, thereby improving the fire-resistant and heat-insulating properties of the fire-resistant and heat-insulating protective fabric.

[0062] It will be apparent to those skilled in the art that the 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 the spirit or essential features of the invention. 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, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for preparing a fire-resistant, heat-insulating and protective fabric, characterized in that: The fire-resistant heat-insulating protective fabric is prepared by spraying a silane coupling agent on the surface of a modified carbon nanotube film, laminating it with a modified fiber film, and then hot pressing it; the modified carbon nanotube film is prepared by reacting polyethylene glycol and toluene diisocyanate, and then reacting it with dihydroxymethyl propionic acid to prepare a hydrophilic soft segment polymer, reacting phenol with an excess of phosphorus oxychloride to prepare a flame retardant monomer, reacting oxidized carbon nanotubes, flame retardant monomers, bisphenol A, and p-hydroxybenzoic acid to prepare modified carbon nanotubes, and reacting the modified carbon nanotubes, hydrophilic soft segment polymer, and ethylenediamine to prepare the fabric by casting; The modified fiber membrane is obtained by spinning zirconium acetylacetonate and tetraethyl orthosilicate and collecting the fiber membrane through a flat glass plate, heating the fiber membrane at multiple temperatures to obtain an inorganic fiber membrane, reacting the inorganic fiber membrane, graphene oxide and 3-aminopropyltriethoxysilane to obtain a pre-modified fiber membrane, and reacting the pre-modified fiber membrane with an inorganic mixed solution consisting of aluminum nitrate, calcium nitrate and sodium hydroxide.

2. The method for preparing a fire-resistant heat-insulating protective fabric according to claim 1, characterized in that: The preparation method of the fire-resistant heat-insulating protective fabric comprises the following preparation steps: (1) Preparation of inorganic fiber membrane: The spinning solution is subjected to electrostatic spinning, and the spinning solution is collected with a flat glass and then peeled off to obtain a fiber membrane with a thickness of 0.8-1 mm. The fiber membrane is placed in a muffle furnace and kept at 70-80°C for 2-3 h, 100-120°C for 20-30 min, 200-220°C for 20-30 min, 380-420°C for 20-30 min, 580-620°C for 20-30 min, and 750-850°C for 2-3 h. After cooling, the inorganic fiber membrane is obtained. (2) Modification of inorganic fiber membrane: The inorganic fiber membrane, graphene oxide, 3-aminopropyltriethoxysilane, and 8-10% sodium hydroxide solution were mixed in a mass ratio of 4:2:1:50-6:3:1:60, and ultrasonicated at 20-30°C and 30-40kHz for 35-45min. The membrane was taken out and washed with pure water and anhydrous ethanol for 3-5 times respectively, and dried at 60-70°C for 10-12h to obtain a pre-modified fiber membrane. The pre-modified fiber membrane and the inorganic mixed liquid are placed in a high-pressure reactor at a mass ratio of 1:20-1:30, and ultrasonically reacted at 90-100°C and 30-40kHz for 20-24 hours, then taken out and washed with pure water for 3-5 times, and dried at 60-70°C for 10-12 hours to obtain a modified fiber membrane; (3) Preparation of modified carbon nanotube membrane: Phenol and phosphorus oxychloride were mixed at a mass ratio of 1:5-1:6, stirred at 90-100°C and 800-1000 r / min for 5-6 h, and allowed to stand at 110-120°C for 2-3 h to obtain a flame retardant monomer; oxidized carbon nanotubes, flame retardant monomer, bisphenol A, anhydrous aluminum chloride, and biphenyl were mixed at a mass ratio of 4:1:1:0.01:40-5:1:1:0.03:50, and stirred at 75-120°C in a nitrogen atmosphere. 85°C, 800-1000r / min, stirring and reacting for 20-30min, heating to 120-130°C, stirring and reacting for 3-4h, heating to 180-200°C, stirring and reacting for 40-60min, adding 0.1-0.2 times the mass of the oxidized carbon nanotubes of p-hydroxybenzoic acid, and continuing to react for 1-2h, cooling to room temperature, filtering, washing with pure water and anhydrous ethanol for 3-5 times respectively, and drying at 60-70°C for 10-12h to obtain modified carbon nanotubes; The modified carbon nanotubes, hydrophilic soft segment polymer, ethylenediamine, triethylamine, acetone and pure water were mixed uniformly in a mass ratio of 1:1:0.2:1:1:2~1:2:0.3:1:2:3, stirred at 40~50℃, 800~1000r / min for 60~80min, cast on a horizontal glass plate, dried at 30~40℃, 100~500Pa for 8~10h, washed the surface with pure water and anhydrous ethanol for 3~5 times and then continued to dry for 8~10h to obtain a modified carbon nanotube film with a thickness of 0.8~1mm; (4) Hot pressing: Mix the silane coupling agent and 40-50% ethanol in a mass ratio of 1:15-1:20, stir at 30-40°C, 300-500 r / min for 2-3 min, and then heat at 0.1-0.2 g / cm 2 The amount of the modified carbon nanotube membrane is sprayed on one side of the modified carbon nanotube membrane, and then bonded to the modified fiber membrane with the same area. In a nitrogen atmosphere, hot pressing is carried out at 100-120°C and 1-2MPa for 10-15min, and then naturally cooled to room temperature to obtain a fire-resistant heat-insulating protective fabric.

3. The method for preparing a fire-resistant heat-insulating protective fabric according to claim 2, characterized in that: The spinning solution in step (1) is prepared by uniformly mixing zirconium acetylacetonate, polyethylene oxide and acetone in a mass ratio of 10:1:10-20:1:20, stirring at 20-30°C and 800-1000 r / min for 2-3 hours, and then adding 0.8-1.2 times the mass of zirconium acetylacetonate of tetraethyl orthosilicate and continuing to stir for 10-12 hours.

4. The method for preparing a fire-resistant heat-insulating protective fabric according to claim 2, characterized in that: The process parameters of the electrospinning in step (1) are: injection speed 1~1.5ml / h, collection distance 18~20cm, voltage 22~28kV, drum speed 50~70r / min, ambient temperature 20~30℃, and ambient humidity 40~45%RH.

5. The method for preparing a fire-resistant heat-insulating protective fabric according to claim 2, characterized in that: The inorganic mixed solution in step (2) is prepared by uniformly mixing aluminum nitrate, calcium nitrate and pure water in a mass ratio of 1:1:10 to 1:1:15, adding a 15-20% sodium hydroxide solution which is 10-15 times the mass of the aluminum nitrate, and stirring at 20-30° C. and 800-1000 r / min for 20-30 min.

6. The method for preparing a fire-resistant heat-insulating protective fabric according to claim 2, characterized in that: The preparation method of the oxidized carbon nanotubes in step (3) is as follows: immersing the carbon nanotubes in concentrated nitric acid with a mass fraction of 60-65%, stirring at 70-80°C and 800-1000 r / min for 2-3 hours, filtering and washing with pure water and anhydrous ethanol for 3-5 times respectively, and drying at 60-70°C for 3-4 hours to prepare the carbon nanotubes.

7. The method for preparing a fire-resistant, heat-insulating and protective fabric according to claim 2, characterized in that: The preparation method of the hydrophilic soft segment polymer in step (3) is as follows: polyethylene glycol and ethyl acetate are uniformly mixed in a mass ratio of 1:1 to 1:2, toluene diisocyanate is added in an amount of 0.8 to 1.2 times the mass of the polyethylene glycol 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 is added in an amount of 0.003 to 0.005 times the mass of the polyethylene glycol, the stirring reaction is continued for 2 to 3 h while keeping the conditions unchanged, then dihydroxymethylpropionic acid is added in an amount of 0.3 to 0.5 times the mass of the polyethylene glycol, and the mixture is allowed to stand at 20 to 30° C. and 1 to 2 kPa for 6 to 8 h to prepare the hydrophilic soft segment polymer.

8. The method for preparing a fire-resistant, heat-insulating and protective fabric according to claim 2, characterized in that: The model of the silane coupling agent in step (4) is Z-6040.

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