High flame-retardant thermal protective fabric and preparation method thereof

Abstract

The application relates to the technical field of functional fabric, and particularly discloses a high-flame-retardant heat-insulating protective fabric and a preparation method thereof. The method comprises the following steps: mixing and weaving aramid fibers and polyester fibers to obtain a base cloth, dipping the base cloth into a silicon dioxide-graphene graft copolymer dispersion liquid, double-dipping and double-rolling, and drying to obtain a flame-retardant heat-insulating layer. The inorganic flame retardant nano silicon dioxide and graphene oxide have good heat-insulating and flame-retardant effects, and the organic flame retardant N,N-bis(2-hydroxyethyl) amino methylene phosphonic acid diethyl ester has a synergistic effect on the base body, so that the flame-retardant heat-insulating property is very high. Cotton fibers and protein fibers are mixed and woven to obtain a comfortable layer. The flame-retardant heat-insulating layer and the comfortable layer are stitched to obtain the high-flame-retardant heat-insulating protective fabric. The obtained fabric is soft and comfortable, has excellent air permeability, and has good comfort, and is an excellent flame-retardant heat-insulating protective fabric.

Description

Technical Field

[0001] This invention relates to the field of functional fabric technology, specifically to a highly flame-retardant heat-insulating protective fabric and its preparation method. Background Technology

[0002] Workers in industries such as firefighting, metallurgy and casting, and electrical engineering often operate in high-temperature environments, potentially exposed to hazards such as hot splashes, intense radiant heat, and burns. To ensure the safety of these workers, specialized flame-retardant and heat-insulating protective clothing is required. The fabrics used to manufacture these protective suits must possess excellent flame-retardant and heat-insulating properties, and must not melt or drip under fire or high-temperature conditions. The fabric must also maintain dimensional stability and exhibit excellent abrasion and tear resistance, effectively extending the service life of the flame-retardant and heat-insulating protective clothing.

[0003] Chinese patent application CN110387740A discloses a method for preparing a graphene-based heat dissipation welding protective clothing fabric and the resulting fabric. The method involves applying a graphene oxide solution to a flame-retardant base fabric, drying it, then performing a reduction treatment and drying again to obtain the graphene-based heat dissipation welding protective clothing fabric. The resulting fabric exhibits good surface heat dissipation performance, flame retardant properties, and the ability to prevent molten metal dripping and heating. However, after repeated washing, the graphene easily detaches, affecting the fabric's performance. Chinese patent CN201640555U discloses a high-temperature resistant composite protective clothing fabric woven from composite flame-retardant yarn. This yarn is composed of a blend of aramid fiber and flame-retardant viscose fiber, wrapped around the outer surface of a glass fiber core yarn. However, this fabric has poor moisture absorption and cannot absorb sweat produced by the body in high-temperature environments, causing severe discomfort. Furthermore, the added glass fiber can be harmful to the human body.

[0004] Therefore, developing a highly hygroscopic, flame-retardant, and heat-insulating protective fabric is of great significance and value. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a highly flame-retardant heat-insulating protective fabric and its preparation method, thereby producing a highly flame-retardant heat-insulating protective fabric with good moisture absorption.

[0006] To achieve the above objectives, this invention discloses a method for preparing a highly flame-retardant heat-insulating protective fabric, comprising the following steps:

[0007] Step 1: Disperse nano-silica (SiO2) into toluene using ultrasound, then add 3-chloropropyltriethoxysilane, stir and mix, and react in an inert gas atmosphere. After the reaction, centrifuge, wash, and dry to obtain chlorosilane-modified silica.

[0008] Step 2: N,N-dimethylformamide, diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate and glycidyl methacrylate are mixed and reacted in an inert gas atmosphere. After the reaction, the mixture is rotary evaporated to obtain a flame-retardant intermediate containing unsaturated double bonds.

[0009] Graphene oxide (GO) was ultrasonically dispersed in an aqueous ethanol solution, and γ-(methacryloyloxy)propyltrimethoxysilane was added. After the reaction, the mixture was centrifuged, washed, and dried to obtain alkenyl-modified graphene oxide.

[0010] Silica modified with chlorosilane was dispersed in an organic solvent, and cuprous chloride (CuCl) was added. After stirring and mixing, alkenyl-modified graphene oxide and a flame-retardant intermediate containing unsaturated double bonds were added. The mixture was reacted in an inert gas atmosphere. After the reaction, the mixture was precipitated, filtered, and dried to obtain a silica-graphene graft copolymer.

[0011] Step 3: Blend aramid fiber and polyester fiber to obtain warp and weft yarns, and weave them to obtain base fabric; disperse silica-graphene graft copolymer in deionized water to obtain silica-graphene graft copolymer dispersion; impregnate the base fabric in silica-graphene graft copolymer dispersion, perform two dips and two treads, and dry to obtain flame-retardant heat insulation layer.

[0012] Cotton fibers and protein fibers are blended to obtain warp and weft yarns, which are then woven to create a comfort layer.

[0013] Using a flame-retardant and heat-insulating layer as the outer layer and a comfort layer as the inner layer, the flame-retardant and heat-insulating layer and the comfort layer are aligned and stacked, and then sewn together to obtain a highly flame-retardant heat-insulating protective fabric.

[0014] Preferably, in step one: the mass ratio of nano-silica, toluene, and 3-chloropropyltriethoxysilane is 100:8000-12000:85-105; the reaction conditions are: reaction at 100-110℃ for 18-24h; centrifugation conditions are: centrifugation at 6000-8000r / min for 12-15min; and drying conditions are: drying at 60℃ for 12-18h.

[0015] Preferably, in step two, the mass ratio of N,N-dimethylformamide, diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate, and glycidyl methacrylate is 1500-1800:100:50-60, and the reaction conditions are 65-75℃ for 36-42 hours.

[0016] Preferably, in step two, the mass ratio of graphene oxide, aqueous ethanol solution, and γ-(methacryloyloxy)propyltrimethoxysilane is 100:9000-9500:75-105, and the reaction conditions are 60-65℃ for 24-30 hours.

[0017] Preferably, in step two, the mass ratio of chlorosilane-modified silica, organic solvent, cuprous chloride, alkenyl-modified graphene oxide, and flame-retardant intermediate containing unsaturated double bonds is 100:3500-6000:1-2:1-1.5:5-9, and the reaction conditions are 90-95℃ for 2-3 hours.

[0018] Preferably, the organic solvent in step four includes at least one of xylene, N,N-dimethylformamide, and toluene.

[0019] Preferably, in step three: the mass ratio of aramid fiber to polyester fiber is 100:60-70, and the basis weight of the base fabric is 190-240 g / m². 2 The mass ratio of warp to weft yarns in the base fabric is 100:78-85, and the mass ratio of silica-graphene graft copolymer to deionized water is 3-8:100.

[0020] Preferably, in step three: the immersion conditions are immersion at 60-75℃ for 35-45 minutes, and the drying conditions are drying at 90-95℃ for 15-18 minutes.

[0021] Preferably, in step three: the mass ratio of cotton fiber to protein fiber is 100:35-55, and the weight of the comfort layer is 102-150 g / m². 2 The mass ratio of warp to weft yarns in the comfort layer is 100:65-72.

[0022] Preferably, a high flame-retardant heat-insulating protective fabric is prepared using the above-described method for preparing high flame-retardant heat-insulating protective fabric.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] In this invention, 3-chloropropyltriethoxysilane is used to modify nano-silica, introducing chlorosilane-modified silica onto the surface of nano-silica to obtain chlorosilane-modified silica. The hydroxyl groups on N,N-bis(2-hydroxyethyl)aminomethylenephosphonate diethyl ester and the epoxy groups on glycidyl methacrylate react to obtain a flame-retardant intermediate containing unsaturated double bonds. γ-(methacryloyloxy)propyltrimethoxysilane is then used to modify graphene oxide to obtain alkenyl-modified graphene oxide. The alkenyl-modified graphene oxide and the flame-retardant intermediate containing unsaturated double bonds undergo a polymerization reaction under the action of the initiator chlorosilane-modified silica and the catalyst cuprous chloride to obtain a silica-graphene graft copolymer. A aramid fiber and polyester fiber are blended and woven to obtain a base fabric. The base fabric is then impregnated in a silica-graphene graft copolymer dispersion, subjected to two dips and two nips, and dried to obtain a flame-retardant and heat-insulating layer. The silica-graphene graft copolymer in the dispersion contains a large number of active groups, which can form an interaction force with the groups on the base fabric, improving the adhesion of the silica-graphene graft copolymer and making it less likely to fall off after washing. Cotton fiber and protein fiber are blended and woven to obtain a comfort layer. The flame-retardant and heat-insulating layer and the comfort layer are sewn together to obtain a highly flame-retardant heat-insulating protective fabric.

[0025] In this invention, the aramid and polyester fibers in the flame-retardant and heat-insulating layer possess ultra-high strength, stable chemical structure, and are not easily damaged. Aramid fibers exhibit no dripping during combustion, good softness, and low shrinkage, while polyester fibers possess excellent toughness, are not easily damaged, and have good elasticity and heat resistance. The two fibers are blended to obtain yarn, which is then woven into a base fabric. This fabric is impregnated in a silica-graphene graft copolymer dispersion, subjected to two dips and two nips, and dried to obtain a flame-retardant and heat-insulating layer with excellent flame-retardant and heat-insulating properties. Nano-silica is a common reinforcing inorganic filler that effectively improves the mechanical properties and thermal stability of the matrix. It is also an effective flame-retardant synergist. Nano-silica and graphene dispersed on the surface of the base fabric effectively improve the thermal stability, high-temperature resistance, and density of the carbon layer during combustion, blocking the transfer of heat between the inside and outside of the matrix while slowing down the release of pyrolysis products. The synergistic effect of these two components significantly enhances the flame-retardant capability of the matrix. Introducing 3-chloropropyltriethoxysilane onto the surface of nano-silica allows the chlorine atoms to act not only as initiators for subsequent reactions but also to react with the free radicals HO· from matrix decomposition during combustion to generate halogen free radicals Cl·, which then react with polymer chains to produce HCl. This effectively interrupts the reaction between HO· and oxygen, and the low content of HCl makes it virtually harmless to the human body. The product also contains silicon. Silicon was also introduced onto the surface of graphene oxide, further enhancing the density of the char layer during combustion. The modification effectively prevents the aggregation of nano-silica and graphene oxide, and the inorganic flame retardant provides excellent heat insulation. The phosphorus element in the organic flame retardant N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester generates PO· free radicals during combustion, which can capture ·OH and H· free radicals in the flame, interrupt the combustion chain reaction, reduce the heat released by combustion, and at the same time generate phosphoric acid-containing substances, promoting char formation on the matrix surface. The formed char layer is more dense, preventing heat conduction and further inhibiting the continuation of the combustion reaction. The nitrogen element it contains generates non-flammable gases during combustion, effectively diluting the oxygen concentration required for combustion and reducing the elements required for the combustion reaction.

[0026] In this invention, the cotton fibers in the comfort layer contain a large number of hydrophilic hydroxyl groups, which make the skin feel soft and not stiff and have excellent heat resistance. The protein fibers have good skin affinity, breathability and moisture-wicking function. The two fibers are blended to obtain yarn, and then woven to obtain the comfort layer as the inner layer. The fabric is soft and comfortable, and has excellent breathability, which avoids stuffiness for workers during wear and provides good comfort. The fabric obtained after hot pressing has high flame retardancy and heat insulation properties, making it an excellent protective fabric. Attached Figure Description

[0027] Figure 1 This is a flowchart of the preparation of highly flame-retardant heat-insulating protective fabric in this invention;

[0028] Figure 2This is a flowchart of the preparation of silica-graphene graft copolymer in this invention;

[0029] Figure 3 This is a schematic diagram of the structure of chlorosilane-modified silicon dioxide prepared in this invention;

[0030] Figure 4 This is a schematic diagram of the structure of the flame-retardant intermediate containing unsaturated double bonds prepared in this invention. Detailed Implementation

[0031] 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. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0032] Example 1

[0033] A method for preparing a highly flame-retardant heat-insulating protective fabric includes the following steps:

[0034] (1) Nano silica was ultrasonically dispersed in toluene, and then 3-chloropropyltriethoxysilane was added and stirred. The mixture was heated under reflux in an argon atmosphere at a temperature of 100°C for 24 hours. The mass ratio of nano silica, toluene and 3-chloropropyltriethoxysilane was 100:8000:85. After the reaction was completed, the mixture was centrifuged at a speed of 6000 r / min for 15 minutes. The mixture was washed with anhydrous ethanol and dried under vacuum at 60°C for 12 hours to obtain chlorosilane-modified silica.

[0035] (2) N,N-dimethylformamide, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester and glycidyl methacrylate were mixed evenly in a mass ratio of 1500:100:50, heated, and reacted in a nitrogen atmosphere at 65°C for 42 h. After the reaction was completed, the mixture was rotary evaporated to obtain a flame-retardant intermediate containing unsaturated double bonds.

[0036] (3) Graphene oxide was ultrasonically dispersed in a 95wt% ethanol aqueous solution. After uniform dispersion, γ-(methacryloyloxy)propyltrimethoxysilane was added and stirred. The mixture was reacted at 60℃ for 30h. The mass ratio of graphene oxide, 95wt% ethanol aqueous solution and γ-(methacryloyloxy)propyltrimethoxysilane was 100:9000:75. After the reaction was completed, the mixture was centrifuged at a speed of 6000r / min for 10min. The mixture was then washed with anhydrous ethanol and deionized water until neutral. The mixture was then vacuum dried at 60℃ for 12h to obtain alkenyl-modified graphene oxide.

[0037] (4) Disperse chlorosilane-modified silica in organic solvent N,N-dimethylformamide, add cuprous chloride, stir and mix evenly, add alkenyl-modified graphene oxide and flame-retardant intermediate containing unsaturated double bonds, stir and mix in an argon atmosphere, and react at 90°C for 3 hours. The mass ratio of chlorosilane-modified silica, organic solvent N,N-dimethylformamide, cuprous chloride, alkenyl-modified graphene oxide and flame-retardant intermediate containing unsaturated double bonds is 100:3500:1:1:5. After the reaction is completed, precipitate in methanol and dry at 60°C for 12 hours to obtain silica-graphene graft copolymer.

[0038] (5) S1. A yarn is obtained by blending aramid fiber and polyester fiber in a mass ratio of 100:60. The yarn is used as warp and weft yarns respectively, and the base fabric is woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:78, and the weight of the base fabric is 190 g / m². 2 ;

[0039] S2. The silica-graphene graft copolymer is dispersed in deionized water, wherein the mass ratio of silica-graphene graft copolymer to deionized water is 3:100, to obtain a silica-graphene graft copolymer dispersion.

[0040] S3. The base fabric is immersed in a silica-graphene graft copolymer dispersion for 35 minutes at a temperature of 75°C. The mass ratio of the base fabric to the silica-graphene graft copolymer dispersion is 100:600. The fabric is then dipped and rolled twice, and dried at 90°C for 18 minutes to obtain a flame-retardant and heat-insulating layer. This flame-retardant and heat-insulating layer is used as the outer layer.

[0041] (6) The comfort layer is made of a blend of cotton and protein fibers in a mass ratio of 100:35. The yarn is used as both warp and weft yarns and woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:65, and the weight of the comfort layer is 102 g / m². 2 The comfort layer is used as the inner layer;

[0042] (7) After aligning and stacking the flame-retardant heat insulation layer and the comfort layer, sew them together with polyester sewing thread to obtain a highly flame-retardant heat insulation protective fabric.

[0043] Example 2

[0044] A method for preparing a highly flame-retardant heat-insulating protective fabric includes the following steps:

[0045] (1) Nano silica was ultrasonically dispersed in toluene, and then 3-chloropropyltriethoxysilane was added and stirred. The mixture was heated under reflux in an argon atmosphere at a temperature of 105°C for 20 h. The mass ratio of nano silica, toluene and 3-chloropropyltriethoxysilane was 100:9500:92. After the reaction was completed, the mixture was centrifuged at a speed of 7000 r / min for 14 min. The mixture was washed with anhydrous ethanol and dried under vacuum at 60°C for 15 h to obtain chlorosilane-modified silica.

[0046] (2) N,N-dimethylformamide, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester and glycidyl methacrylate were mixed evenly in a mass ratio of 1600:100:54, heated, and reacted in a nitrogen atmosphere at 70°C for 38 hours. After the reaction was completed, the mixture was rotary evaporated to obtain a flame-retardant intermediate containing unsaturated double bonds.

[0047] (3) Graphene oxide was ultrasonically dispersed in a 95wt% ethanol aqueous solution. After uniform dispersion, γ-(methacryloyloxy)propyltrimethoxysilane was added and stirred. The mixture was reacted at 62℃ for 26h. The mass ratio of graphene oxide, 95wt% ethanol aqueous solution and γ-(methacryloyloxy)propyltrimethoxysilane was 100:9200:85. After the reaction was completed, the mixture was centrifuged at a speed of 6000r / min for 10min. The mixture was then washed with anhydrous ethanol and deionized water until neutral. The mixture was then vacuum dried at 60℃ for 12h to obtain alkenyl-modified graphene oxide.

[0048] (4) Disperse chlorosilane-modified silica in organic solvent N,N-dimethylformamide, add cuprous chloride, stir and mix evenly, then add alkenyl-modified graphene oxide and flame-retardant intermediate containing unsaturated double bonds, stir and mix in an argon atmosphere, and react at 92°C for 2.5 h. The mass ratio of chlorosilane-modified silica, organic solvent N,N-dimethylformamide, cuprous chloride, alkenyl-modified graphene oxide and flame-retardant intermediate containing unsaturated double bonds is 100:4500:1.4:1.2:6.5. After the reaction is completed, precipitate in methanol and dry at 65°C for 10 h to obtain silica-graphene graft copolymer;

[0049] (5) S1. A yarn is obtained by blending aramid fiber and polyester fiber in a mass ratio of 100:62. The yarn is used as warp and weft yarns respectively, and the base fabric is woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:80, and the weight of the base fabric is 205 g / m². 2 ;

[0050] S2. The silica-graphene graft copolymer is dispersed in deionized water, wherein the mass ratio of silica-graphene graft copolymer to deionized water is 5:100, to obtain a silica-graphene graft copolymer dispersion.

[0051] S3. The base fabric is immersed in a silica-graphene graft copolymer dispersion for 38 minutes at a temperature of 70°C. The mass ratio of the base fabric to the silica-graphene graft copolymer dispersion is 100:680. The fabric is then dipped and rolled twice, and dried at 92°C for 16 minutes to obtain a flame-retardant and heat-insulating layer. This flame-retardant and heat-insulating layer is used as the outer layer.

[0052] (6) The comfort layer is made of a blend of cotton and protein fibers in a mass ratio of 100:42. The yarn is used as both warp and weft yarns and woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:68, and the weight of the comfort layer is 120 g / m². 2 The comfort layer is used as the inner layer;

[0053] (7) After aligning and stacking the flame-retardant heat insulation layer and the comfort layer, sew them together with polyester sewing thread to obtain a highly flame-retardant heat insulation protective fabric.

[0054] Example 3

[0055] A method for preparing a highly flame-retardant heat-insulating protective fabric includes the following steps:

[0056] (1) Nano silica was ultrasonically dispersed in toluene, and then 3-chloropropyltriethoxysilane was added and stirred. The mixture was heated under reflux in an argon atmosphere at a temperature of 105°C for 22 hours. The mass ratio of nano silica, toluene and 3-chloropropyltriethoxysilane was 100:11000:100. After the reaction was completed, the mixture was centrifuged at a speed of 7000 r / min for 14 minutes. The mixture was washed with anhydrous ethanol and dried under vacuum at 60°C for 16 hours to obtain chlorosilane-modified silica.

[0057] (2) N,N-dimethylformamide, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester and glycidyl methacrylate were mixed evenly in a mass ratio of 1700:100:58, heated, and reacted in a nitrogen atmosphere at 70°C for 40 h. After the reaction was completed, the mixture was rotary evaporated to obtain a flame-retardant intermediate containing unsaturated double bonds.

[0058] (3) Graphene oxide was ultrasonically dispersed in a 95wt% ethanol aqueous solution. After uniform dispersion, γ-(methacryloyloxy)propyltrimethoxysilane was added and stirred. The mixture was reacted at 62℃ for 28h. The mass ratio of graphene oxide, 95wt% ethanol aqueous solution and γ-(methacryloyloxy)propyltrimethoxysilane was 100:9400:95. After the reaction was completed, the mixture was centrifuged at a speed of 6000r / min for 10min. The mixture was then washed with anhydrous ethanol and deionized water until neutral. The mixture was then vacuum dried at 60℃ for 12h to obtain alkenyl-modified graphene oxide.

[0059] (4) Disperse chlorosilane-modified silica in organic solvent N,N-dimethylformamide, add cuprous chloride, stir and mix evenly, add alkenyl-modified graphene oxide and flame-retardant intermediate containing unsaturated double bonds, stir and mix in an argon atmosphere, and react at 92°C for 2.5 h. The mass ratio of chlorosilane-modified silica, organic solvent N,N-dimethylformamide, cuprous chloride, alkenyl-modified graphene oxide and flame-retardant intermediate containing unsaturated double bonds is 100:5500:1.8:1.4:8. After the reaction is completed, precipitate in methanol and dry at 75°C for 11 h to obtain silica-graphene graft copolymer;

[0060] (5) S1. A yarn is obtained by blending aramid fiber and polyester fiber in a mass ratio of 100:68. The yarn is used as warp and weft yarns respectively, and the base fabric is woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:82, and the weight of the base fabric is 225 g / m². 2 ;

[0061] S2. The silica-graphene graft copolymer is dispersed in deionized water, wherein the mass ratio of silica-graphene graft copolymer to deionized water is 7:100, to obtain a silica-graphene graft copolymer dispersion.

[0062] S3. The base fabric is immersed in a silica-graphene graft copolymer dispersion for 42 minutes at a temperature of 65°C. The mass ratio of the base fabric to the silica-graphene graft copolymer dispersion is 100:750. The fabric is then dipped and rolled twice, and dried at 92°C for 17 minutes to obtain a flame-retardant and heat-insulating layer. This flame-retardant and heat-insulating layer is used as the outer layer.

[0063] (6) The comfort layer is made of a blend of cotton and protein fibers in a mass ratio of 100:50. The yarn is used as both warp and weft yarns and woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:70, and the weight of the comfort layer is 135 g / m². 2 The comfort layer is used as the inner layer;

[0064] (7) After aligning and stacking the flame-retardant heat insulation layer and the comfort layer, sew them together with polyester sewing thread to obtain a highly flame-retardant heat insulation protective fabric.

[0065] Example 4

[0066] A method for preparing a highly flame-retardant heat-insulating protective fabric includes the following steps:

[0067] (1) Nano silica was ultrasonically dispersed in toluene, and then 3-chloropropyltriethoxysilane was added and stirred. The mixture was heated under reflux in an argon atmosphere at a temperature of 110°C for 18 hours. The mass ratio of nano silica, toluene and 3-chloropropyltriethoxysilane was 100:12000:105. After the reaction was completed, the mixture was centrifuged at a speed of 8000 r / min for 12 minutes. The mixture was washed with anhydrous ethanol and dried under vacuum at 60°C for 18 hours to obtain chlorosilane-modified silica.

[0068] (2) N,N-dimethylformamide, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester and glycidyl methacrylate were mixed evenly in a mass ratio of 1800:100:60, heated, and reacted in a nitrogen atmosphere at 75°C for 36 h. After the reaction was completed, the mixture was rotary evaporated to obtain a flame-retardant intermediate containing unsaturated double bonds.

[0069] (3) Graphene oxide was ultrasonically dispersed in a 95wt% ethanol aqueous solution. After uniform dispersion, γ-(methacryloyloxy)propyltrimethoxysilane was added and stirred. The mixture was reacted at 65℃ for 24h. The mass ratio of graphene oxide, 95wt% ethanol aqueous solution and γ-(methacryloyloxy)propyltrimethoxysilane was 100:9500:105. After the reaction was completed, the mixture was centrifuged at a speed of 6000r / min for 10min. The mixture was then washed with anhydrous ethanol and deionized water until neutral. The mixture was then vacuum dried at 60℃ for 12h to obtain alkenyl-modified graphene oxide.

[0070] (4) Disperse chlorosilane-modified silica in organic solvent N,N-dimethylformamide, add cuprous chloride, stir and mix evenly, add alkenyl-modified graphene oxide and flame-retardant intermediate containing unsaturated double bonds, stir and mix in an argon atmosphere, and react at 95°C for 2 hours. The mass ratio of chlorosilane-modified silica, organic solvent N,N-dimethylformamide, cuprous chloride, alkenyl-modified graphene oxide and flame-retardant intermediate containing unsaturated double bonds is 100:6000:2:1.5:9. After the reaction is completed, precipitate in methanol and dry at 80°C for 9 hours to obtain silica-graphene graft copolymer.

[0071] (5) S1. A yarn is obtained by blending aramid fiber and polyester fiber in a mass ratio of 100:70. The yarn is used as warp and weft yarns respectively, and the base fabric is woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:85, and the weight of the base fabric is 240 g / m². 2 ;

[0072] S2. The silica-graphene graft copolymer is dispersed in deionized water, wherein the mass ratio of silica-graphene graft copolymer to deionized water is 8:100, to obtain a silica-graphene graft copolymer dispersion.

[0073] S3. The base fabric is immersed in a silica-graphene graft copolymer dispersion for 45 minutes at a temperature of 60°C. The mass ratio of the base fabric to the silica-graphene graft copolymer dispersion is 100:800. The fabric is then dipped and rolled twice, and dried at 95°C for 15 minutes to obtain a flame-retardant and heat-insulating layer. This flame-retardant and heat-insulating layer is used as the outer layer.

[0074] (6) The comfort layer is made of a blend of cotton and protein fibers in a mass ratio of 100:55. The yarn is used as both warp and weft yarns and woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:72, and the weight of the comfort layer is 150 g / m². 2 The comfort layer is used as the inner layer;

[0075] (7) After aligning and stacking the flame-retardant heat insulation layer and the comfort layer, sew them together with polyester sewing thread to obtain a highly flame-retardant heat insulation protective fabric.

[0076] Comparative Example 1

[0077] A method for preparing a highly flame-retardant heat-insulating protective fabric includes the following steps:

[0078] (1) Nano silica was ultrasonically dispersed in toluene, and then 3-chloropropyltriethoxysilane was added and stirred. The mixture was heated under reflux in an argon atmosphere at a temperature of 110°C for 18 hours. The mass ratio of nano silica, toluene and 3-chloropropyltriethoxysilane was 100:12000:105. After the reaction was completed, the mixture was centrifuged at a speed of 8000 r / min for 12 minutes. The mixture was washed with anhydrous ethanol and dried under vacuum at 60°C for 18 hours to obtain chlorosilane-modified silica.

[0079] (2) N,N-dimethylformamide, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester and glycidyl methacrylate were mixed evenly in a mass ratio of 1800:100:60, heated, and reacted in a nitrogen atmosphere at 75°C for 36 h. After the reaction was completed, the mixture was rotary evaporated to obtain a flame-retardant intermediate containing unsaturated double bonds.

[0080] (3) Disperse chlorosilane-modified silica in organic solvent N,N-dimethylformamide, add cuprous chloride, stir and mix evenly, add flame retardant intermediate containing unsaturated double bonds, stir and mix in an argon atmosphere, and react at 95°C for 2 hours. The mass ratio of chlorosilane-modified silica, organic solvent N,N-dimethylformamide, cuprous chloride and flame retardant intermediate containing unsaturated double bonds is 100:6000:2:10.5. After the reaction is completed, precipitate in methanol and dry at 80°C for 9 hours to obtain silica graft copolymer;

[0081] (4) S1. A yarn is obtained by blending aramid fiber and polyester fiber in a mass ratio of 100:70. The yarn is used as warp and weft yarns respectively, and the base fabric is woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:85, and the weight of the base fabric is 240 g / m². 2 ;

[0082] S2. Disperse the silica graft copolymer in deionized water, wherein the mass ratio of silica graft copolymer to deionized water is 8:100, to obtain a silica graft copolymer dispersion.

[0083] S3. The base fabric is immersed in a silica graft copolymer dispersion for 45 minutes at a temperature of 60°C. The mass ratio of the base fabric to the silica graft copolymer dispersion is 100:800. The fabric is then dipped and rolled twice, and dried at 95°C for 15 minutes to obtain a flame-retardant and heat-insulating layer. This flame-retardant and heat-insulating layer is used as the outer layer.

[0084] (5) The comfort layer is made of a blend of cotton and protein fibers in a mass ratio of 100:55. The yarn is used as both warp and weft yarns and woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:72, and the weight of the comfort layer is 150 g / m². 2 The comfort layer is used as the inner layer;

[0085] (6) After aligning and stacking the flame-retardant heat insulation layer and the comfort layer, sew them together with polyester sewing thread to obtain a highly flame-retardant heat insulation protective fabric.

[0086] Comparative Example 2

[0087] A method for preparing a highly flame-retardant heat-insulating protective fabric includes the following steps:

[0088] (1) Nano silica was ultrasonically dispersed in toluene, and then 3-chloropropyltriethoxysilane was added and stirred. The mixture was heated under reflux in an argon atmosphere at a temperature of 110°C for 18 hours. The mass ratio of nano silica, toluene and 3-chloropropyltriethoxysilane was 100:12000:105. After the reaction was completed, the mixture was centrifuged at a speed of 8000 r / min for 12 minutes. The mixture was washed with anhydrous ethanol and dried under vacuum at 60°C for 18 hours to obtain chlorosilane-modified silica.

[0089] (2) Graphene oxide was ultrasonically dispersed in a 95wt% ethanol aqueous solution. After uniform dispersion, γ-(methacryloyloxy)propyltrimethoxysilane was added and stirred. The mixture was reacted at 65℃ for 24h. The mass ratio of graphene oxide, 95wt% ethanol aqueous solution and γ-(methacryloyloxy)propyltrimethoxysilane was 100:9500:105. After the reaction was completed, the mixture was centrifuged at a speed of 6000r / min for 10min. The mixture was then washed with anhydrous ethanol and deionized water until neutral. The mixture was then vacuum dried at 60℃ for 12h to obtain alkenyl-modified graphene oxide.

[0090] (3) S1. A blend of aramid fiber and polyester fiber in a mass ratio of 100:70 is used to obtain yarn. The yarn is used as warp and weft yarns respectively, and the base fabric is woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:85, and the weight of the base fabric is 240 g / m². 2 ;

[0091] S2. Disperse chlorosilane-modified silica, alkenyl-modified graphene oxide, and diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate in deionized water, wherein the mass ratio of chlorosilane-modified silica, alkenyl-modified graphene oxide, diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate, and deionized water is 7.2:0.1:0.7:100, to obtain a flame-retardant dispersion;

[0092] S3. The base fabric is immersed in the flame retardant dispersion for 45 minutes at a temperature of 60°C. The mass ratio of the base fabric to the flame retardant dispersion is 100:800. After two dips and two rolls, the fabric is dried at 95°C for 15 minutes to obtain a flame retardant and heat insulation layer. The flame retardant and heat insulation layer is used as the outer layer.

[0093] (4) The comfort layer is made of a blend of cotton and protein fibers in a mass ratio of 100:55. The yarn is used as both warp and weft yarns and woven using a shuttle weaving process. The mass ratio of warp to weft yarn is 100:72, and the weight of the comfort layer is 150 g / m². 2 The comfort layer is used as the inner layer;

[0094] (5) After aligning and stacking the flame-retardant heat insulation layer and the comfort layer, sew them together with polyester sewing thread to obtain a highly flame-retardant heat insulation protective fabric.

[0095] The nano-silica used in the embodiments and comparative examples of this invention was purchased from Nanjing Baoket New Materials Co., Ltd., product model PST-Q02, with a primary particle size of 20 nm and a specific surface area of ​​200 m². 2 / g; Graphene oxide was purchased from Hangzhou Zhitai Purification Technology Co., Ltd. The graphene oxide was a single layer with an average thickness of 0.5-1.2nm and a diameter of 4-7μm; Aramid fiber (AF) was purchased from DuPont, USA, and was 1500D, 1670detx; Polyester fiber was purchased from Jiangsu Sanlian New Material Co., Ltd., with a fineness of 50D / 144F; Silk fiber was purchased from Shengzhou Xiehe Silk Co., Ltd.; Polyester sewing thread was purchased from Dongguan Dachang Thread Factory Co., Ltd., specification: 20S / 2; Other reagents were commercially available.

[0096] The high flame-retardant heat-insulating protective fabrics prepared in Examples 1-4 and Comparative Examples 1-2 were used as samples for performance testing, and the tests are as follows:

[0097] (1) Flame retardant performance test: The test standard GB / T 5454-1997 "Oxygen Index Method for Burning Performance Tests of Textiles" was adopted. The test sample was clamped in the test sample holder and placed vertically inside the combustion cylinder. In the upward flow of oxygen and nitrogen gas, the upper end of the test sample was ignited, and its combustion characteristics were observed. The afterflame time or damage length was compared with the specified limit value. Through a series of tests at different oxygen concentrations, the lowest oxygen concentration value expressed as oxygen volume fraction for sustaining combustion can be determined. The samples corresponding to Examples 1-4 and Comparative Examples 1-2 were washed 50 times. After washing, the flame retardant performance test was carried out again. The test method was the same as before washing.

[0098] (2) Air permeability test: The air permeability of the sample was measured using the Fraser method of ISO9237, and the measuring pressure was 125 Pa.

[0099] (3) Moisture absorption performance test: The samples were tested in accordance with the national standard GB / T 21655.1-2008 "Evaluation of moisture absorption and quick-drying properties of textiles - Part 1: Single combination test method";

[0100] The performance test results are shown in Table 1:

[0101] Table 1

[0102]

[0103] According to the test results in Table 1, the fabrics corresponding to Examples 1-4 have excellent flame-retardant properties. After 50 washes, they still maintain good flame-retardant efficacy, while also exhibiting good breathability and water absorption. The flame-retardant and heat-insulating layer of the protective fabric contains inorganic flame retardants such as nano-silica and graphene oxide, which have excellent heat-insulating and flame-retardant effects. The phosphorus and nitrogen elements contained in the organic flame retardant N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester both play a flame-retardant role during the combustion of the matrix. The cotton fibers in the comfort layer contain a large number of hydrophilic hydroxyl groups, making them soft and non-stiff against the skin and possessing excellent heat resistance. The protein fibers have excellent skin-friendliness, breathability, and moisture-wicking properties, making the protective fabric soft, comfortable, and highly breathable. In Comparative Example 1, no alkenyl-modified graphene oxide was added, resulting in a certain reduction in flame retardant performance, but with little impact on air permeability and moisture absorption. In Comparative Example 2, no polymerization reaction was carried out, and the flame retardant dispersion was obtained by direct mixing. After treating the base fabric, the dispersion was poor, which had a certain impact on air permeability and moisture absorption. Moreover, after multiple washings, the flame retardant was prone to falling off, and the flame retardant effect was greatly reduced.

[0104] Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the patent coverage of the present invention.

Claims

1. A method of making a high flame resistant thermal protective fabric, characterized in that, The method comprises the following steps: Step one, dispersing nano-silica into toluene, adding 3-chloropropyl triethoxysilane, stirring and mixing, and reacting in an inert gas atmosphere; after the reaction, centrifuging, washing, and drying to obtain chlorosilane-modified silica; Step two, mixing N,N-dimethylformamide, N,N-bis(2-hydroxyethyl) aminomethylene phosphonic acid diethyl ester, and glycidyl methacrylate, and reacting in an inert gas atmosphere; after the reaction, rotary evaporation to obtain a flame-retardant intermediate containing an unsaturated double bond; Dispersing graphene oxide into an ethanol aqueous solution, adding γ-(methacryloyloxy) propyl trimethoxysilane, and reacting; after the reaction, centrifuging, washing, and drying to obtain alkenyl-modified graphene oxide; Dispersing chlorosilane-modified silica into an organic solvent, adding cuprous chloride, stirring and mixing, and then adding alkenyl-modified graphene oxide and the flame-retardant intermediate containing an unsaturated double bond, and reacting in an inert gas atmosphere; after the reaction, precipitating, filtering, and drying to obtain a silica-graphene graft copolymer; Step three, mixing aramid fibers and polyester fibers to obtain warp and weft yarns, and weaving to obtain a base cloth; dispersing the silica-graphene graft copolymer into deionized water to obtain a silica-graphene graft copolymer dispersion liquid; placing the base cloth in the silica-graphene graft copolymer dispersion liquid for dipping, double-dipping and double-rolling, and drying to obtain a flame-retardant thermal insulation layer; Mixing cotton fibers and protein fibers to obtain warp and weft yarns, and weaving to obtain a comfortable layer; Taking the flame-retardant thermal insulation layer as an outer layer and the comfortable layer as an inner layer, aligning and stacking the flame-retardant thermal insulation layer and the comfortable layer, and sewing to obtain a high-flame-retardant thermal insulation protective fabric.

2. The method of claim 1, wherein the flame resistant thermal protective fabric is prepared by the steps of: In the step one, the mass ratio of nano-silica, toluene and 3-chloropropyl triethoxysilane is 100:8000-12000:85-105, and the reaction condition is 100-110℃ for 18-24h.

3. A process for the preparation of high flame resistant thermal protective fabric according to claim 1, characterized in that, In the step two, the mass ratio of N,N-dimethylformamide, N,N-bis(2-hydroxyethyl) aminomethylene phosphonic acid diethyl ester and glycidyl methacrylate is 1500-1800:100:50-60, and the reaction condition is 65-75℃ for 36-42h.

4. The process for preparing a high flame resistant thermal protective fabric according to claim 1, characterized in that, In the step two, the mass ratio of graphene oxide, an ethanol aqueous solution and γ-(methacryloyloxy) propyl trimethoxysilane is 100:9000-9500:75-105, and the reaction condition is 60-65℃ for 24-30h.

5. The method of claim 1, wherein the flame resistant thermal protective fabric is prepared by the steps of: In the step two, the mass ratio of chlorosilane-modified silica, an organic solvent, cuprous chloride, alkenyl-modified graphene oxide and the flame-retardant intermediate containing an unsaturated double bond is 100:3500-6000:1-2:1-1.5:5-9, and the reaction condition is 90-95℃ for 2-3h.

6. The process for preparing a high flame resistant thermal protective fabric according to claim 5, wherein, The organic solvent comprises at least one of xylene, N,N-dimethylformamide and toluene.

7. The method for preparing a high flame-retardant heat-insulating protective fabric according to claim 1, characterized in that, In the third step, the mass ratio of aramid fiber and polyester fiber is 100:60-70, the gram weight of the base fabric is 190-240 g / m 2 , the mass ratio of warp yarn and weft yarn in the base fabric is 100:78-85, and the mass ratio of silica-graphene graft copolymer and deionized water is 3-8:

100.

8. The process for preparing a high flame resistant thermal protective fabric according to claim 1, wherein, In the step three, the dipping condition is 60-75℃ for 35-45min, and the drying condition is 90-95℃ for 15-18min.

9. The method for preparing a high flame-retardant heat-insulating protective fabric according to claim 1, characterized in that, In the third step, the mass ratio of cotton fiber and protein fiber is 100:35-55, the gram weight of the comfort layer is 102-150 g / m 2 , and the mass ratio of warp yarn and weft yarn in the comfort layer is 100:65-72.

10. A high flame resistant thermal protective fabric prepared by the method of any of claims 1-9.

Images