CN117944337A - Flame-retardant heat-insulating composite fiber fabric, preparation method thereof and application thereof in fireproof clothes - Google Patents
Flame-retardant heat-insulating composite fiber fabric, preparation method thereof and application thereof in fireproof clothes Download PDFInfo
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Abstract
The invention belongs to the technical field of composite fiber fabrics, and particularly relates to a flame-retardant heat-insulating composite fiber fabric, a preparation method thereof and application thereof in fireproof clothes. The composite fiber fabric provided by the invention comprises a fireproof layer, a heat insulation layer and a comfort layer from outside to inside; the heat insulation layer is prepared from polyacrylonitrile pre-oxidized fibers, carbon fibers and composite coatings; the composite coating comprises modified polyimide and a solvent, wherein the modified polyimide has good heat resistance, hydrophobicity, heat preservation and heat insulation performances and good combination property with a substrate. The heat-insulating layer fabric provided by the invention has excellent waterproof property, heat resistance and heat preservation and insulation properties; the composite fiber fabric obtained by compositing the fireproof layer, the heat insulation layer and the comfortable layer has excellent fireproof, flame-retardant, heat-insulating and heat-insulating effects.
Description
Technical Field
The invention belongs to the technical field of composite fiber fabrics, and particularly relates to a flame-retardant heat-insulating composite fiber fabric, a preparation method thereof and application thereof in fireproof clothes.
Background
The fireproof clothing is one kind of clothing for fireproof and heat protection and has the main function of protecting the wearer from fire, chemical explosion, high temperature, etc. The fireproof suit can prevent harm to human bodies caused by high-temperature environments, effectively improves the safety coefficient of special professionals such as firefighters, ensures the life safety of the firefighters when the firefighters perform tasks, has fire resistance, heat resistance and heat insulation, has toughness and prevents sharp objects from being impacted and collided, and has the performance of preventing the chemical substances from damaging the skin.
CN201610984560.4 provides a fireproof flame-retardant composite fabric, which comprises the following raw materials: colloid, azo cross-linking agent, polyhedral silsesquioxane, polyphenylene sulfide, polyether-ether-ketone, polyamide-imide, phenolic fiber, polyimide and carbon fiber, and the prepared composite fabric has excellent flame retardant property, soft hand feeling, ventilation, washing resistance, wear resistance and good mechanical and thermal properties by adjusting the proportion of raw materials and optimizing the process conditions; CN202210013916.5 provides a composite flame-retardant fabric, which is formed by interweaving aromatic polyamide fiber yarns serving as warp yarns and modified polyimide fiber yarns serving as weft yarns, wherein the modified polyimide fiber is prepared by mixing thermoplastic polyimide resin, a flame retardant, a water repellent and a heat radiating agent; polyimide is added in the composite fabric provided by the invention, is an important polymer material, has excellent comprehensive properties such as excellent mechanical property, insulativity, outstanding thermal stability, chemical corrosion resistance and the like, and has great application potential in many fields, however, the polyimide has rigid molecular chains and strong inter-chain interaction force due to the existence of aromatic heterocycle and polar imine rings, so that the polyimide has the characteristic of insolubility and infusibility, and great difficulty is brought to the molding processing of the material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a flame-retardant heat-insulating composite fiber fabric which has excellent fireproof, flame-retardant and heat-insulating effects; the invention also provides a preparation method of the composite fabric and application of the composite fabric in fireproof clothing.
The technical scheme adopted by the invention for achieving the purpose is as follows:
A flame-retardant heat-insulating composite fiber fabric comprises a fireproof layer, a heat-insulating layer and a comfortable layer from outside to inside; the heat insulation layer is prepared from polyacrylonitrile pre-oxidized fibers, carbon fibers and composite coatings; the composite coating comprises modified polyimide and a solvent; the preparation method of the modified polyimide comprises the following steps:
S1, dispersing (3, 4-dihydro-2H-1, 4-benzoxazine-2-ylmethyl) dimethylamine in 2-methyltetrahydrofuran under the stirring condition, sequentially adding N, N-dimethylcyclohexylamine and 5, 6-epoxyhexyltriethoxysilane, heating to 75-90 ℃, carrying out reflux reaction for 6-9H, cooling to room temperature, carrying out solid-liquid separation, taking liquid, carrying out reduced pressure distillation, and drying to obtain an intermediate;
S2, dispersing 6,6 '-diamino-3, 3' -methylene dibenzoic acid in 2-methyltetrahydrofuran under the stirring condition, sequentially adding p-toluenesulfonic acid and the intermediate obtained in the step S1, heating to 65-80 ℃, carrying out reflux reaction for 5-10h, cooling to room temperature, carrying out solid-liquid separation, taking solid for washing, and drying to obtain modified diamine;
S3, ultrasonically dispersing the modified diamine and the graphene oxide obtained in the step S2 in an ethanol water solution, heating to 60-80 ℃, stirring and reacting for 0.5-1.5h, cooling to room temperature, performing solid-liquid separation, and drying the solid to obtain the modified graphene oxide;
S4, under the nitrogen atmosphere, ultrasonically dispersing the 4,4 '-diaminodiphenylmethane and the modified graphene oxide obtained in the step S3 in N, N-dimethylformamide, adding 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride, stirring for 10-30min, adding a catalyst and a dehydrating agent, stirring and mixing uniformly, heating to 80-200 ℃, stirring and reacting for 10-20h, cooling to room temperature, adding methanol, continuing stirring for 10-20min, carrying out solid-liquid separation, washing and drying solids, and obtaining modified polyimide;
Wherein, the synthetic route of the modified diamine is as follows:
；
。
The polyimide is modified to improve the performance and expand the application field. The flexible groups or functional side chains are introduced into the main chain of the polyimide, so that the regular arrangement of the main chain of the polyimide can be destroyed, the tight stacking of polyimide molecular chains is prevented, the interaction force between molecules is reduced, and the processability and the solubility of the polyimide are improved. The invention firstly takes (3, 4-dihydro-2H-1, 4-benzoxazine-2-methyl) dimethylamine and 5, 6-epoxyhexyl triethoxysilane as raw materials, and prepares an intermediate by ring opening reaction of an epoxy compound; then, using an intermediate and 6,6 '-diamino-3, 3' -methylene dibenzoic acid as raw materials, and preparing modified diamine by esterification reaction; then modifying graphene oxide by using modified diamine as a modifier and utilizing hydrolysis and condensation to obtain modified graphene oxide; finally, 4 '-diaminodiphenylmethane, modified graphene oxide and 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride are taken as raw materials, and the modified polyimide is prepared by polycondensation reaction.
In order to obtain the modified polyimide, improve the heat resistance, hydrophobicity and heat preservation and insulation performance of the modified polyimide, and simultaneously enhance the binding force of the composite coating and a substrate, the molar ratio of the (3, 4-dihydro-2H-1, 4-benzoxazin-2-ylmethyl) dimethylamine to the N, N-dimethylcyclohexylamine to the 5, 6-epoxyhexyltriethoxysilane in the step S1 is 1:0.04-0.06:0.8-1.0,2-methyltetrahydrofuran, and the addition amount of the (3, 4-dihydro-2H-1, 4-benzoxazin-2-ylmethyl) dimethylamine in the step S1 is 0.15-0.35g/mL; the molar ratio of the 6,6 '-diamino-3, 3' -methylene dibenzoic acid to the p-toluenesulfonic acid to the intermediate in the step S2 is 1:0.07-0.09:2.0-2.4,2, and the addition amount of the 6,6 '-diamino-3, 3' -methylene dibenzoic acid in the methyl tetrahydrofuran is 0.2-0.3g/mL; in the step S3, the mass fraction of the ethanol in the ethanol water solution is 70-80%, and the mass ratio of the modified diamine to the graphene oxide to the ethanol water solution is 0.5-0.7:1:16-22; in the step S4, the mass ratio of the 4,4 '-diaminodiphenylmethane to the modified graphene oxide to the 2,2' -difluoromethyl-4, 4', 5' -biphenyltetracarboxylic dianhydride to the N, N-dimethylformamide to the catalyst to the dehydrating agent is 2:0.7-0.9:2.5-3.5:8-10:1-3:2.6-3.4, the catalyst is triethylamine or pyridine, and the dehydrating agent is acetic anhydride and the volume ratio of the N, N-dimethylformamide to the methanol is 1:15-25; the ultrasonic frequencies in the steps S3 and S4 are 30-40kHz, and the ultrasonic time is 20-40min.
Preferably, the fireproof layer is made of polyacrylonitrile pre-oxidized fiber, ceramic fiber and carbon fiber in a blending mode, the mass ratio of the polyacrylonitrile pre-oxidized fiber to the ceramic fiber to the carbon fiber is 50-60:15-20:10-20, the density of the fireproof layer surface is 300-350g/m 2, and the thickness is 1.2-1.8mm; the comfort layer is made of aramid fiber non-woven fabric, the density of the comfort layer surface is 250-280g/m 2, and the thickness is 0.8-1.3mm; the preparation method of the heat insulation layer comprises the following steps: blending polyacrylonitrile pre-oxidized fiber and carbon fiber to prepare a blended layer; uniformly mixing the modified polyimide with a solvent to obtain a composite coating; uniformly coating the composite coating on the surface of the blended layer, and drying to obtain the composite coating, wherein the mass ratio of the polyacrylonitrile pre-oxidized fiber to the carbon fiber is 55-65:15-25, the mass ratio of the modified polyimide to the solvent is 1:8-15, the solvent is N-methylpyrrolidone, and the coating amount of the composite coating is 2-4mL/cm 2; the density of the heat insulation layer is 250-300g/m 2, and the thickness is 2.2-2.7mm.
The invention also provides a preparation method of the flame-retardant heat-insulating composite fiber fabric, which is prepared by quilting and sewing the fireproof layer, the heat-insulating layer and the comfort layer.
The flame-retardant heat-insulating composite fiber fabric is applied to fireproof clothing.
The invention has the following beneficial effects:
the preparation method comprises the steps of sequentially carrying out ring opening reaction and esterification reaction on epoxy compounds to obtain modified diamine, then modifying graphene oxide by using the modified diamine to obtain modified graphene oxide, and finally initiating polycondensation reaction of the modified graphene oxide, 4 '-diaminodiphenylmethane and 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride to obtain modified polyimide, wherein benzoxazine, siloxane and trifluoromethyl are introduced into a polyimide side chain; the introduction of benzoxazine and trifluoromethyl can obviously improve the heat resistance of polyimide; the introduction of siloxane can not only improve the hydrophobicity of polyimide and the waterproofness of the composite coating, but also enhance the binding force of the composite coating and the blending layer and improve the stability and durability of the fabric; in addition, the modified graphene oxide is used as an inorganic filler, and the inorganic nano particles and the organic high molecular polymer are combined in a chemical grafting mode, so that the defects of insufficient compatibility and dispersibility of the inorganic nano particles are overcome, and the heat preservation and heat insulation performance of the composite material can be effectively improved while the heat resistance of polyimide is not influenced.
Mixing the modified polyimide with a solvent to obtain a composite coating, and uniformly coating the composite coating on the surface of the blended layer to prepare a heat-insulating layer, wherein the heat-insulating layer fabric has excellent waterproof property, heat resistance and heat preservation and heat insulation performance; the composite fiber fabric obtained by compositing the fireproof layer, the heat insulation layer and the comfortable layer has excellent fireproof, flame-retardant, heat-insulating and heat-insulating effects.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application. The raw materials used in the following examples are all common commercial products.
Example 1
A preparation method of modified polyimide comprises the following steps:
S1, dispersing (3, 4-dihydro-2H-1, 4-benzoxazine-2-ylmethyl) dimethylamine in 2-methyltetrahydrofuran under the stirring condition of 180rpm, sequentially adding N, N-dimethylcyclohexylamine and 5, 6-epoxyhexyltriethoxysilane, heating to 80 ℃, carrying out reflux reaction for 7 hours, cooling to room temperature, carrying out solid-liquid separation, taking liquid, carrying out reduced pressure distillation to remove 2-methyltetrahydrofuran, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain an intermediate, wherein the molar ratio of (3, 4-dihydro-2H-1, 4-benzoxazine-2-ylmethyl) dimethylamine to N, N-dimethylcyclohexylamine to 5, 6-epoxyhexyltriethoxysilane is 1:0.05:0.9, and the adding amount of (3, 4-dihydro-2H-1, 4-benzoxazine-2-ylmethyl) dimethylamine in 2-methyltetrahydrofuran is 0.2g/mL;
S2, dispersing 6,6 '-diamino-3, 3' -methylene dibenzoic acid in 2-methyltetrahydrofuran under the stirring condition of 180rpm, sequentially adding p-toluenesulfonic acid and an intermediate obtained in the step S1, heating to 70 ℃, carrying out reflux reaction for 8 hours, cooling to room temperature, carrying out solid-liquid separation, taking solids, sequentially washing with dichloromethane and deionized water, and carrying out vacuum drying at 60 ℃ for 48 hours to obtain modified diamine, wherein the molar ratio of 6,6 '-diamino-3, 3' -methylene dibenzoic acid to p-toluenesulfonic acid to the intermediate is 1:0.08:2.2, the adding amount of 6 '-diamino-3, 3' -methylene dibenzoic acid in 2-methyltetrahydrofuran is 0.25g/mL, and the volume ratio of dichloromethane to deionized water is 1:1;
S3, ultrasonically dispersing the modified diamine and graphene oxide (with the thickness of 0.55-1.2nm and the diameter of 0.5-3 mu m, the content of more than 99wt% and purchased from Zhongkesheng technology Co., ltd.) obtained in the step S2 into an ethanol water solution, heating to 70 ℃, reacting for 1h under the stirring condition of 180rpm, cooling to room temperature, carrying out solid-liquid separation, taking a solid, and vacuum drying at 60 ℃ for 12h to obtain the modified graphene oxide, wherein the mass fraction of ethanol in the ethanol water solution is 75%, the mass ratio of the modified diamine to the graphene oxide to the ethanol water solution is 0.6:1:20, the ultrasonic frequency is 35kHz, and the ultrasonic time is 25min;
S4, under the nitrogen atmosphere, carrying out ultrasonic dispersion on the 4,4 '-diaminodiphenylmethane and the modified graphene oxide obtained in the step S3 in N, N-dimethylformamide, adding 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride, reacting for 20min under the stirring condition of 200rpm, adding a catalyst and a dehydrating agent, stirring and uniformly mixing, respectively stirring and reacting for 2h at three positions of 80 ℃ and 120 ℃ and 180 ℃, then stirring and reacting for 10h at 200 ℃, cooling to room temperature, adding methanol (the volume ratio of methanol to N, N-dimethylformamide is 1:20), continuing stirring for 15min, carrying out solid-liquid separation, taking solid, washing by methanol, and carrying out vacuum drying at 120 ℃ for 12h to obtain the modified polyimide, wherein the mass ratio of the 4,4 '-diaminodiphenylmethane, the modified graphene oxide, the 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride, the N, N-dimethylformamide, the catalyst and the dehydrating agent is 2:0.8:3.1:9 kHz, the ultrasonic frequency of the catalyst is 35:3 kHz, and the ultrasonic frequency of the dehydrating agent is 30min;
wherein the nuclear magnetic result of the modified diamine is ：1H NMR(300MHz,DMSO-d6) δ 7.72（s,2H）,7.05（d,2H）,6.90（d,2H）,6.74-6.80（m,12H）,4.50-4.53（m,2H）,3.82-3.85（m,16H）,3.58-3.62（m,4H）,2.85-2.88（m,4H）,2.75（s,6H）,2.59-2.63（m,4H）,2.18（s,6H）,1.65-1.69（m,4H）,1.20-1.25（m,26H）,0.56（t,4H）.
A flame-retardant heat-insulating composite fiber fabric comprises a fireproof layer, a heat-insulating layer and a comfortable layer from outside to inside; the fireproof layer is formed by blending polyacrylonitrile pre-oxidized fiber (with the thickness of 1.5D, the compressive strength of 40MPa and the specific gravity of 1.37g/cm, which are purchased from Guangdong Kadun New Material Co., ltd.), ceramic fiber (the ceramic fiber is aluminum silicate fiber, the compressive strength of 450MPa, the heat conductivity coefficient of 0.002, the use temperature of 1200 ℃ is purchased from Lingshu county Jia Shu building materials processing Co., ltd.) and carbon fiber (with the thickness of 7 μm, the density of 1.75g/cm 3, which is purchased from Shenzha Tuling New Material Co., ltd.), wherein the mass ratio of the polyacrylonitrile pre-oxidized fiber, the ceramic fiber and the carbon fiber is 55:17:15, the fireproof layer density is 330g/m 2, and the thickness is 1.5mm; the preparation method of the heat insulation layer comprises the following steps: blending polyacrylonitrile pre-oxidized fiber and carbon fiber to prepare a blended layer; uniformly mixing the modified polyimide with a solvent to obtain a composite coating; uniformly coating the composite coating on the surface of the blended layer, and drying to obtain the composite coating; wherein the mass ratio of the polyacrylonitrile pre-oxidized fiber to the carbon fiber is 60:20, the mass ratio of the modified polyimide to the solvent is 1:12, the solvent is N-methylpyrrolidone, and the coating amount of the composite coating is 3mL/cm 2; the density of the heat insulation layer is 280g/m 2, and the thickness is 2.5mm; the comfort layer is an aramid nonwoven fabric, and the aramid nonwoven fabric comprises the following components in parts by weight: 95 parts of aramid 1313 and 5 parts of aramid 1414 (aramid 1313, length 51mm, strength 4.6cN/dtex, thickness 1.5D, aramid 1414, length 51mm, strength 16cN/dtex, thickness 1.5D), comfort layer density 260g/m 2, thickness 1.1mm.
A preparation method of a flame-retardant heat-insulating composite fiber fabric is characterized in that the flame-retardant heat-insulating composite fiber fabric is prepared by quilting and sewing a fireproof layer, a heat-insulating layer and a comfort layer.
Example 2
A modified polyimide was prepared as described in example 1, except that: in the step S4, the mass ratio of the 4,4 '-diaminodiphenylmethane to the modified graphene oxide to the 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride to the N, N-dimethylformamide to the catalyst to the dehydrating agent is 2:0.7:2.6:9:1.8:3. Flame-retardant heat-insulating composite fiber fabric and preparation method thereof are prepared according to the method described in example 1.
Example 3
A modified polyimide was prepared as described in example 1, except that: in the step S4, the mass ratio of the 4,4 '-diaminodiphenylmethane to the modified graphene oxide to the 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride to the N, N-dimethylformamide to the catalyst to the dehydrating agent is 2:0.9:3.3:9:2.5:3.2. Flame-retardant heat-insulating composite fiber fabric and preparation method thereof are prepared according to the method described in example 1.
Example 4
A flame-retardant heat-insulating composite fiber fabric comprises a fireproof layer, a heat-insulating layer and a comfortable layer from outside to inside; the fireproof layer is formed by blending polyacrylonitrile pre-oxidized fiber (with the thickness of 1.5D, the compressive strength of 40MPa and the specific gravity of 1.37g/cm, which are purchased from Guangdong Kadun New Material Co., ltd.), ceramic fiber (the ceramic fiber is aluminum silicate fiber, the compressive strength of 450MPa, the heat conductivity coefficient of 0.002, the use temperature of 1200 ℃ is purchased from Lingshu county Jia Shu building materials processing Co., ltd.) and carbon fiber (with the thickness of 7 μm, the density of 1.75g/cm 3, which is purchased from Shenzha Tuling New Material Co., ltd.), wherein the mass ratio of the polyacrylonitrile pre-oxidized fiber, the ceramic fiber and the carbon fiber is 50:20:20, the fireproof layer density is 350g/m 2, and the thickness is 1.5mm; the preparation method of the heat insulation layer comprises the following steps: blending polyacrylonitrile pre-oxidized fiber and carbon fiber to prepare a blended layer; uniformly mixing the modified polyimide prepared in the embodiment 1 with a solvent to obtain a composite coating; uniformly coating the composite coating on the surface of the blended layer, and drying to obtain the composite coating; wherein the mass ratio of the polyacrylonitrile pre-oxidized fiber to the carbon fiber is 60:20, the mass ratio of the modified polyimide to the solvent is 1:12, the solvent is N-methylpyrrolidone, and the coating amount of the composite coating is 2mL/cm 2; the density of the heat insulation layer is 280g/m 2, and the thickness is 2.5mm; the comfort layer is an aramid nonwoven fabric, and the aramid nonwoven fabric comprises the following components in parts by weight: 95 parts of aramid 1313 and 5 parts of aramid 1414 (aramid 1313, length 51mm, strength 4.6cN/dtex, thickness 1.5D, aramid 1414, length 51mm, strength 16cN/dtex, thickness 1.5D), comfort layer density 260g/m 2, thickness 1.1mm.
A method for preparing a flame retardant and heat insulating composite fiber fabric was prepared according to the method described in example 1.
Example 5
A flame-retardant heat-insulating composite fiber fabric comprises a fireproof layer, a heat-insulating layer and a comfortable layer from outside to inside; the fireproof layer is formed by blending polyacrylonitrile pre-oxidized fiber (with the thickness of 1.5D, the compressive strength of 40MPa and the specific gravity of 1.37g/cm, which are purchased from Guangdong Kadun New Material Co., ltd.), ceramic fiber (the ceramic fiber is aluminum silicate fiber, the compressive strength of 450MPa, the heat conductivity coefficient of 0.002, the use temperature of 1200 ℃ is purchased from Lingshu county Jia Shu building materials processing Co., ltd.) and carbon fiber (with the thickness of 7 μm, the density of 1.75g/cm 3, which is purchased from Shenzha Tuling New Material Co., ltd.), wherein the mass ratio of the polyacrylonitrile pre-oxidized fiber, the ceramic fiber and the carbon fiber is 60:15:15, the fireproof layer density is 310g/m 2, and the thickness is 1.5mm; the preparation method of the heat insulation layer comprises the following steps: blending polyacrylonitrile pre-oxidized fiber and carbon fiber to prepare a blended layer; uniformly mixing the modified polyimide prepared in the embodiment 1 with a solvent to obtain a composite coating; uniformly coating the composite coating on the surface of the blended layer, and drying to obtain the composite coating; wherein the mass ratio of the polyacrylonitrile pre-oxidized fiber to the carbon fiber is 60:20, the mass ratio of the modified polyimide to the solvent is 1:12, the solvent is N-methylpyrrolidone, and the coating amount of the composite coating is 4mL/cm 2; the density of the heat insulation layer is 280g/m 2, and the thickness is 2.5mm; the comfort layer is an aramid nonwoven fabric, and the aramid nonwoven fabric comprises the following components in parts by weight: 95 parts of aramid 1313 and 5 parts of aramid 1414 (aramid 1313, length 51mm, strength 4.6cN/dtex, thickness 1.5D, aramid 1414, length 51mm, strength 16cN/dtex, thickness 1.5D), comfort layer density 260g/m 2, thickness 1.1mm.
A method for preparing a flame retardant and heat insulating composite fiber fabric was prepared according to the method described in example 1.
Comparative example 1
A modified polyimide was prepared as described in example 1, except that: in the step S4, the mass ratio of the 4,4 '-diaminodiphenylmethane to the modified graphene oxide to the 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride to the N, N-dimethylformamide to the catalyst to the dehydrating agent is 2:0.4:2.5:9:1.7:2.8. Flame-retardant heat-insulating composite fiber fabric and preparation method thereof are prepared according to the method described in example 1.
Comparative example 2
A modified polyimide was prepared as described in example 1, except that: steps S1, S2, S3 are omitted, and the modified graphene oxide in step S4 is replaced with graphene oxide. Flame-retardant heat-insulating composite fiber fabric and preparation method thereof are prepared according to the method described in example 1.
The thermal insulation layers prepared in examples 1-3 and comparative examples 1-2, and the composite fiber fabrics prepared in examples 1-5 and comparative examples 1-2 were subjected to the relevant performance test. Contact angle testing was performed using a K100 fully automatic surface tensiometer from Kruss, germany; the adhesive force test of the composite coating is carried out by adopting a QFH paint film cross-cut tester according to GB/T9286-1998 cross-cut test of paint films of colored paint and varnish; the abrasion resistance test is carried out by adopting a JM-1 type paint film abrasion resistance tester according to GB1768- (79) 88 paint film abrasion resistance test method, and the abrasion loss of a test sample is tested; the thermal stability test is carried out according to GA10-2014 fire fighter fire protection suit, and the dimensional change rate of the test sample is tested; thermal insulation performance test according to GB/T11048-2018 (measurement of thermal resistance and wet resistance under physiological comfort steady-state condition of textiles (evaporation hot plate method)) rule, the Crohn value of a sample is measured; the test sample is washed for 30 times and then subjected to flame retardant performance test, the limiting oxygen index of the test sample is tested according to the specification of GB/T5454-1997 oxygen index method of textile combustion performance test method, and the test sample is tested according to the specification of GB/T5455-2014 determination of damage length, smoldering and smoldering time in the vertical direction of textile combustion performance; the above test was repeated three times to average, and the test results are shown in tables 1 and 2. As can be seen from Table 1, compared with comparative examples 1-2, the thermal insulation layer fabric prepared in examples 1-3 has better hydrophobicity, thermal stability, thermal insulation performance, coating adhesion and wear resistance, and as can be seen from the coating adhesion and wear resistance data, the modified polyimide is used as a raw material to prepare the composite coating, so that the binding force between the coating and a substrate can be effectively improved, and the stability and durability of the material can be improved. As can be seen from Table 2, compared with comparative examples 1-2, the composite fiber fabrics prepared in examples 1-5 are excellent in comprehensive performance, have limiting oxygen indexes of 57% or more, have Crohn values of 1.155m 2 & C/W or more, and have flame-retardant property, smoldering time and damage length of 0, and the composite fiber fabrics prepared in examples 1-5 are excellent in flame retardant property and heat insulation property.
TABLE 1 results of insulation layer related Performance test
Table 2 test results of composite fiber fabric related properties
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The flame-retardant heat-insulating composite fiber fabric is characterized by comprising a fireproof layer, a heat-insulating layer and a comfortable layer from outside to inside; the heat insulation layer is prepared from polyacrylonitrile pre-oxidized fibers, carbon fibers and composite coatings; the composite coating comprises modified polyimide and a solvent; the preparation method of the modified polyimide comprises the following steps:
S1, dispersing (3, 4-dihydro-2H-1, 4-benzoxazine-2-ylmethyl) dimethylamine in 2-methyltetrahydrofuran under the stirring condition, sequentially adding N, N-dimethylcyclohexylamine and 5, 6-epoxyhexyltriethoxysilane, heating to 75-90 ℃, carrying out reflux reaction for 6-9H, cooling to room temperature, carrying out solid-liquid separation, taking liquid, carrying out reduced pressure distillation, and drying to obtain an intermediate, wherein the structural formula of the intermediate is as follows: ；
S2, dispersing 6,6 '-diamino-3, 3' -methylene dibenzoic acid in 2-methyltetrahydrofuran under the stirring condition, sequentially adding p-toluenesulfonic acid and the intermediate obtained in the step S1, heating to 65-80 ℃, carrying out reflux reaction for 5-10h, cooling to room temperature, carrying out solid-liquid separation, taking solid for washing, and drying to obtain modified diamine, wherein the structural formula of the modified diamine is as follows: ；
S3, ultrasonically dispersing the modified diamine and the graphene oxide obtained in the step S2 in an ethanol water solution, heating to 60-80 ℃, stirring and reacting for 0.5-1.5h, cooling to room temperature, performing solid-liquid separation, and drying the solid to obtain the modified graphene oxide;
S4, under the nitrogen atmosphere, ultrasonically dispersing the 4,4 '-diaminodiphenylmethane and the modified graphene oxide obtained in the step S3 in N, N-dimethylformamide, adding 2,2' -difluoromethyl-4, 4', 5' -biphenyl tetracarboxylic dianhydride, stirring for 10-30min, adding a catalyst and a dehydrating agent, stirring and mixing uniformly, heating to 80-200 ℃, stirring and reacting for 10-20h, cooling to room temperature, adding methanol, continuing stirring for 10-20min, carrying out solid-liquid separation, washing and drying solids, and obtaining the modified polyimide.
2. The flame-retardant and heat-insulating composite fiber fabric according to claim 1, wherein the molar ratio of (3, 4-dihydro-2H-1, 4-benzoxazin-2-ylmethyl) dimethylamine, N-dimethylcyclohexylamine and 5, 6-epoxyhexyltriethoxysilane in the step S1 is 1:0.04-0.06:0.8-1.0,2-methyltetrahydrofuran, and the addition amount of (3, 4-dihydro-2H-1, 4-benzoxazin-2-ylmethyl) dimethylamine is 0.15-0.35g/mL.
3. The flame-retardant and heat-insulating composite fiber fabric according to claim 1, wherein in the step S2, the molar ratio of 6,6 '-diamino-3, 3' -methylenedibenzoic acid, p-toluenesulfonic acid and intermediates is 1:0.07-0.09:2.0-2.4,2-methyltetrahydrofuran, and the addition amount of 6,6 '-diamino-3, 3' -methylenedibenzoic acid is 0.2-0.3g/mL.
4. The flame-retardant and heat-insulating composite fiber fabric according to claim 1, wherein in the step S3, the mass fraction of ethanol in the ethanol aqueous solution is 70-80%, and the mass ratio of the modified diamine to the graphene oxide to the ethanol aqueous solution is 0.5-0.7:1:16-22.
5. The flame-retardant and heat-insulating composite fiber fabric according to claim 1, wherein in the step S4, the mass ratio of 4,4 '-diaminodiphenylmethane to modified graphene oxide to 2,2' -difluoromethyl-4, 4', 5' -biphenyltetracarboxylic dianhydride to N, N-dimethylformamide to a catalyst to a dehydrating agent is 2:0.7-0.9:2.5-3.5:8-10:1-3:2.6-3.4, the catalyst is triethylamine or pyridine, the dehydrating agent is acetic anhydride, and the volume ratio of N, N-dimethylformamide to methanol is 1:15-25; the ultrasonic frequencies in the steps S3 and S4 are 30-40kHz, and the ultrasonic time is 20-40min.
6. The flame-retardant and heat-insulating composite fiber fabric according to claim 1, wherein the fireproof layer is formed by blending polyacrylonitrile pre-oxidized fibers, ceramic fibers and carbon fibers, wherein the mass ratio of the polyacrylonitrile pre-oxidized fibers to the ceramic fibers to the carbon fibers is 50-60:15-20:10-20, the fireproof layer has a density of 300-350g/m 2 and a thickness of 1.2-1.8mm; the comfort layer is made of aramid non-woven fabric, the density of the comfort layer surface is 250-280g/m 2, and the thickness is 0.8-1.3mm.
7. The flame-retardant and heat-insulating composite fiber fabric according to claim 1, wherein the preparation method of the heat-insulating layer is as follows: blending polyacrylonitrile pre-oxidized fiber and carbon fiber to prepare a blended layer; uniformly mixing the modified polyimide with a solvent to obtain a composite coating; and uniformly coating the composite coating on the surface of the blending layer, and drying to obtain the composite coating.
8. The flame-retardant and heat-insulating composite fiber fabric according to claim 7, wherein the mass ratio of the polyacrylonitrile pre-oxidized fiber to the carbon fiber is 55-65:15-25, the mass ratio of the modified polyimide to the solvent is 1:8-15, the solvent is N-methylpyrrolidone, and the coating amount of the composite coating is 2-4mL/cm 2; the density of the heat insulation layer is 250-300g/m 2, and the thickness is 2.2-2.7mm.
9. The method for preparing the flame-retardant and heat-insulating composite fiber fabric according to any one of claims 1 to 8, which is characterized by being prepared by quilting and sewing a fireproof layer, a heat-insulating layer and a comfort layer.
10. Use of a flame retardant and heat insulating composite fiber fabric according to any one of claims 1-8 in fire protection clothing.
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