Preparation method of high-temperature-resistant fabric
Through the high-temperature resistant fabric composited with synthetic leather and base cloth, the synergistic effect of boron chlorooxysilane nanosheets and antibacterial agents is solved, and the flame retardant and antibacterial effects are improved.
Patent Information
- Application Number
- CN202510504002.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-01-03
- Publication Date
- 2025-07-11
- Estimated Expiration
- 2044-01-03
AI Technical Summary
Existing fabrics do not have flame retardant and antibacterial effects, are prone to burning and breed microorganisms, affecting human health and the environment.
High-temperature resistant fabrics are used to combine synthetic leather with base cloth. The synthetic leather is made of flame retardant and antibacterial agent. The flame retardant is composed of boron oxysil nanosheets and antibacterial agents. Through the synergistic action of boron oxysil nanosheets and antibacterial agents, the flame retardant and antibacterial properties of the fabric are improved.
The fabric has good flame retardant and antibacterial effects, and can effectively block flammable gases and heat transfer at high temperatures, inhibit bacterial reproduction, and improve human health and environmental safety.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of fabrics, and specifically to a preparation method of a high-temperature resistant fabric. Background Art
[0002] China is the world's largest producer, exporter and consumer of textiles, and its export volume accounts for more than one-fourth of the global export trade. Fabrics are related to all aspects of people's lives. At the same time, with the growth of people's material and cultural needs, there are more and more special function requirements for fabrics, such as flame retardant functions. At present, most fabrics do not have flame retardant functions, and are prone to catch fire and burn when encountering open flames or sparks. The flame spreads quickly and is not easy to extinguish, producing thick smoke and toxic gases, causing huge property losses and casualties.
[0003] In addition, fabrics are a breeding ground for microorganisms such as bacteria and viruses. These microorganisms cause cross-infection through contact with the human body, causing harm to the human body, and can cause allergic adverse reactions such as headache, fever, sore throat, tonsil infection, etc. Moreover, the low-grade fatty acids and volatile compounds produced by the action of dust, human sweat, sebum, etc. adhering to the fabric surface and the resident bacteria and foreign microorganisms on the skin are extremely likely to emit a foul smell, seriously affecting the environment, and long-term contact will affect people's physical health. Therefore, it is particularly important to develop a fabric with flame retardant and antibacterial effects. Summary of the Invention
[0004] The purpose of the present invention is to provide a high-temperature resistant fabric and its preparation method to solve the problems existing in the prior art.
[0005] To solve the above technical problems, the present invention provides the following technical solutions: A high-temperature resistant fabric, wherein the high-temperature resistant fabric is prepared by compounding synthetic leather and a base fabric; the synthetic leather is prepared by mixing a flame retardant, polyvinyl chloride K13S and other additives; the base fabric is a woven fabric with a grammage of 150 g / m 2 ².
[0006] Furthermore, the flame retardant is prepared from chloroboronoxysilane nanosheets and an antibacterial agent; the chloroboronoxysilane nanosheets are prepared from triethoxysilane, graphene oxide, tributyl borate and dichloromethane.
[0007] Furthermore, the antibacterial agent is prepared from 2-(dimethylamino)-5-formylbenzonitrile, pyrrole, 6,6'-di(azido)-6,6'-dideoxy trehalose.
[0008] Furthermore, the other main additives include a plasticizer, a foaming agent, a dispersant and a stabilizer.
[0009] Further, the plasticizer is triphenyl phosphate, o-cresyl phosphate, m-cresyl phosphate or p-cresyl phosphate; the foaming agent is azodicarbonamide; the dispersant is polyethylene wax or paraffin; the stabilizer is calcium stearate or mercaptomethyltin.
[0010] Further, a preparation method of a high-temperature resistant fabric includes the following preparation steps: (1) Mix tetracyanoporphyrin, 6,6'-diazido-6,6'-dideoxy trehalose, cuprous bromide, hexamethylenetriamine, and N,N-dimethylformamide according to a mass ratio of 9:5:1:11:3 to 11:7:3:15:3, react at 50-60°C under a nitrogen atmosphere for 2-4 h, freeze in liquid nitrogen for 30-60 s, add n-hexane until precipitation is complete, filter, wash with deionized water 3-5 times, and vacuum dry at -0.08 MPa and 50-60°C for 12 h to obtain an antibacterial agent; (2) Mix chloroborosilicate nanosheets, antibacterial agent, deionized water, and N,N-dimethylformamide according to a mass ratio of 20:1:10:10 to 30:3:20:10, react at 200-300 rpm and 110-150°C for 2-4 h, then wash with absolute ethanol and deionized water 3-5 times in sequence to obtain a flame retardant; (3) Mix polyvinyl chloride K13S, flame retardant, foaming agent, plasticizer, stabilizer, and dispersant according to a mass ratio of 60:5:1:40:0.5:3 to 80:15:3:60:0.5:5, knead at 20-40 rpm and 120-140°C for 0.5-1.5 h, rough roll at a steam pressure of 0.5-0.7 MPa and a roll gap of 3 mm for 3-5 min, refine at a steam pressure of 0.4-0.6 MPa and a roll gap of 2 mm for 3-5 min, and then calender at 120-160°C to form a synthetic leather with a thickness of 0.1-0.3 mm; bond the synthetic leather to a base cloth and perform foaming and embossing treatment at a pressure of 0.2-0.4 MPa and 180-200°C to obtain a high-temperature resistant fabric.
[0011] Further, the preparation method of the tetracyanoporphyrin in step (1) is as follows: Mix 2-(dimethylamino)-5-formylbenzonitrile and propionic acid according to a mass ratio of 0.6:20 to 0.8:20, stir at 200-300 rpm and 80-140°C for 3-5 min, then add pyrrole with a mass 0.8-1.0 times that of 2-(dimethylamino)-5-formylbenzonitrile and acetic anhydride with a mass 2-3 times that of 2-(dimethylamino)-5-formylbenzonitrile, continue to react for 20-60 min, cool to room temperature, add methanol with a mass 10-20 times that of 2-(dimethylamino)-5-formylbenzonitrile, let stand for 12 h, filter, and vacuum dry at -0.08 MPa and 50-60°C for 12 h to obtain tetracyanoporphyrin.
[0012] Further, the preparation method of the chloroborosiloxane nanosheets in step (2) is as follows: in an atmosphere of nitrogen / oxygen mixed gas at 700-800 °C, the volume ratio of nitrogen to oxygen in the nitrogen / oxygen mixed gas is 1:3. After preheating the intermediate product 2 for 20-40 min, the temperature is raised to 900-1000 °C, and tributyl borate with a mass 0.1-0.3 times that of the intermediate product 2 and dichloromethane with a mass 0.05-0.07 times that of the intermediate product 2 are sequentially sprayed onto the intermediate product 2, and the reaction continues for 20-40 min to obtain the chloroborosiloxane nanosheets.
[0013] Further, the preparation method of the intermediate product 2 is as follows: the intermediate product 1 and ammonia water are mixed at a mass ratio of 1:20-1:30, reacted at 200-300 rpm for 24-32 h, centrifugally washed 3-5 times with deionized water at 15000 rpm, and freeze-dried at a vacuum degree of 50 Pa and -10 to -30 °C for 15-25 h to obtain the intermediate product 2.
[0014] Further, the preparation method of the intermediate product 1 is as follows: graphene oxide and N,N-dimethylformamide are mixed at a mass ratio of 0.1:40-0.3:40, ultrasonicated at 500-800 W for 1 h, then triethoxysilane with a mass 1.1-1.3 times that of N,N-dimethylformamide and azobisisobutyronitrile with a mass 0.006-0.008 times that of N,N-dimethylformamide are added, reacted at 100-200 rpm and 60-80 °C for 24-32 h, centrifuged at 15000 rpm for 5-10 min, the precipitate is taken, centrifugally washed 3-5 times with N,N-dimethylformamide at 15000 rpm, and the precipitate is taken to obtain the intermediate product 1.
[0015] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: After the synthetic leather is prepared by mixing a flame retardant, polyvinyl chloride and other auxiliaries in the present invention and then bonded to a base fabric to obtain a high-temperature resistant fabric, the flame retardant is prepared from triethoxysilane, graphene oxide, tributyl borate, dichloromethane and an antibacterial agent, and has antibacterial and flame retardant effects.
[0016] First, the antibacterial agent is prepared from 2-(dimethylamino)-5-formylbenzonitrile, pyrrole, and 6,6'-diazido-6,6'-dideoxytrehalose; the aldehyde group in 2-(dimethylamino)-5-formylbenzonitrile condenses with pyrrole to prepare tetracyanoporphyrin, which can generate reactive oxygen under light irradiation and act on microorganisms, resulting in the death of microorganisms, thereby making the fabric have antibacterial effect; tetracyanoporphyrin reacts with the azide group in 6,6'-diazido-6,6'-dideoxytrehalose through the cyano group to form a triazole structure, and bridges and polymerizes to form a network structure. The triazole structure can inhibit the reproduction of bacteria, and at the same time, cooperate with the network structure to enhance the conjugated system of porphyrin, improve the photocatalytic activity of the porphyrin structure, and enhance the antibacterial effect.
[0017] Secondly, after triethoxysilane hydrolyzes and surface polymerizes in graphene oxide to form a silica layer, under the action of high temperature and oxygen, graphene oxide decomposes. At the same time, tributyl borate and dichloromethane are sprayed to dope boron and chlorine into the silica to form chloroborosilicate nanosheets, which can improve the high temperature resistance of the material through the high heat resistance of the borosilicate structure, the barrier effect of the sheet structure and the restriction of molecular chain movement. During combustion, boric acid can be generated to promote the dehydration and carbonization of oxygen-containing groups, and through cross-linking and condensation with silicon and boron, a three-dimensional network structure carbon layer with a silicon-carbon-boron structure is formed to block flammable gases and heat transfer, thereby making the fabric have flame retardant effect; the chlorine group in the chloroborosilicate nanosheet reacts with the tertiary amine in the antibacterial agent to form a quaternary ammonium structure, which enhances the antibacterial effect and can decompose by heat during combustion to form ammonia to expand the carbon layer, further enhancing the barrier effect of the carbon layer and enhancing the flame retardant effect; in addition, the flame retardant can react with the chlorine group in polyvinyl chloride through hydroxyl groups to curb the dehydrochlorination reaction of polyvinyl chloride and improve the high temperature resistance of the fabric. Specific implementation mode
[0018] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.
[0019] In order to more clearly illustrate the method provided by the present invention, the following examples are used for detailed description. The test methods for each index of the high temperature resistant fabric produced in the following examples are as follows: Antibacterial effect: Take the examples and comparative examples of equal size and measure the antibacterial rate in a dark environment and under the irradiation of an 808 laser with an intensity of 0.3 watts per square centimeter according to QB / T4715; High temperature resistance effect: Take the same-sized examples and comparative examples, dry them at 60 °C for 12 hours, and then use a thermogravimetric analyzer to test the 5% thermal decomposition temperature of the fabric under a nitrogen atmosphere, with a flow rate of 50 mL per minute and a heating rate of 10 °C per minute. Flame retardant effect: Take equal-sized examples and comparative examples, and evaluate the flame retardant grade by testing the burning time and burning phenomenon of the fabric according to UL94.
[0020] Example 1 (1) Mix 2-(dimethylamino)-5-formylbenzonitrile and propionic acid at a mass ratio of 0.6:20, stir at 200 rpm and 80 °C for 3 min, then add pyrrole 0.8 times the mass of 2-(dimethylamino)-5-formylbenzonitrile and acetic anhydride 2 times the mass of 2-(dimethylamino)-5-formylbenzonitrile, continue to react for 20 min, cool to room temperature, add methanol 10 times the mass of 2-(dimethylamino)-5-formylbenzonitrile, let stand for 12 h, filter, and vacuum dry at -0.08 MPa and 50 °C for 12 h to obtain tetracyanoporphyrin. (2) Mix tetracyanoporphyrin, 6,6'-diazido-6,6'-dideoxytrehalose, cuprous bromide, hexamethylenetriamine, and N,N-dimethylformamide at a mass ratio of 9:5:1:11:3, react at 50 °C under a nitrogen atmosphere for 2 h, freeze in liquid nitrogen for 30 s, then add n-hexane until precipitation is complete, filter, wash with deionized water 3 times, and vacuum dry at -0.08 MPa and 50 °C for 12 h to obtain the antibacterial agent. (3) Mix graphene oxide and N,N-dimethylformamide at a mass ratio of 0.1:40, sonicate at 500 W for 1 h, then add triethoxysilane 1.1 times the mass of N,N-dimethylformamide and azobisisobutyronitrile 0.006 times the mass of N,N-dimethylformamide, react at 100 rpm and 60 °C for 24 h, centrifuge at 15000 rpm for 5 min, take the precipitate, wash the precipitate with N,N-dimethylformamide by centrifugation 3 times at 15000 rpm, take the precipitate to obtain Intermediate Product 1; Mix Intermediate Product 1 and ammonia water at a mass ratio of 1:20, react at 200 rpm for 24 h, wash the precipitate with deionized water by centrifugation 3 times at 15000 rpm, and freeze-dry at a vacuum of 50 Pa and -30 °C for 15 h to obtain Intermediate Product 2; Under a nitrogen / oxygen mixed gas atmosphere at 700 °C, the volume ratio of nitrogen to oxygen in the nitrogen / oxygen mixed gas is 1:3. After preheating Intermediate Product 2 for 20 min, raise the temperature to 900 °C, and sequentially spray tributyl borate 0.1 times the mass of Intermediate Product 2 and dichloromethane 0.05 times the mass of Intermediate Product 2 onto Intermediate Product 2, and continue to react for 20 min to obtain chloroborosiloxane nanosheets. (4) Mix chloroborosilicate nanosheets, antibacterial agent, deionized water, and N,N-dimethylformamide at a mass ratio of 20:1:10:10. After reacting at 200 rpm and 110 °C for 2 h, wash with absolute ethanol and deionized water three times in sequence to obtain a flame retardant. (5) Mix polyvinyl chloride K13S, flame retardant, azodicarbonamide, triphenyl phosphate, calcium stearate, and polyethylene wax at a mass ratio of 60:5:1:40:0.5:3. After kneading at 20 rpm and 120 °C for 0.5 h, rough roll for 3 min at a steam pressure of 0.5 MPa and a roll gap of 3 mm, refine for 3 min at a steam pressure of 0.4 MPa and a roll gap of 2 mm, and then calender at 120 - 160 °C to obtain a synthetic leather with a thickness of 0.1 mm. Bond the synthetic leather to the base fabric and perform foaming and embossing treatments at a pressure of 0.2 MPa and 180 °C to obtain a high-temperature resistant fabric.
[0021] Example 2 (1) Mix 2-(dimethylamino)-5-formylbenzonitrile and propionic acid at a mass ratio of 0.7:20. After stirring at 250 rpm and 110 °C for 4 min, add pyrrole with a mass 0.9 times that of 2-(dimethylamino)-5-formylbenzonitrile and acetic anhydride with a mass 2.5 times that of 2-(dimethylamino)-5-formylbenzonitrile, and continue to react for 40 min. Cool to room temperature, add methanol with a mass 15 times that of 2-(dimethylamino)-5-formylbenzonitrile, let stand for 12 h, filter, and vacuum dry at -0.08 MPa and 55 °C for 12 h to obtain tetracyanoporphyrin. (2) Mix tetracyanoporphyrin, 6,6'-di(azido)-6,6'-dideoxytrehalose, cuprous bromide, hexamethylenetriamine, and N,N-dimethylformamide at a mass ratio of 10:6:2:13:3. React in a nitrogen atmosphere at 55 °C for 3 h, freeze in liquid nitrogen for 45 s, add n-hexane until precipitation is complete, filter, wash with deionized water four times, and vacuum dry at -0.08 MPa and 55 °C for 12 h to obtain an antibacterial agent. (3)Graphene oxide and N,N-dimethylformamide were mixed at a mass ratio of 0.2:40. After ultrasonic treatment at 650W for 1h, triethoxysilane which is 1.2 times the mass of N,N-dimethylformamide and azobisisobutyronitrile which is 0.007 times the mass of N,N-dimethylformamide were added. After reacting at 150rpm and 70°C for 29h, centrifugation was carried out at 15000rpm for 7.5min, and the precipitate was taken. The precipitate was centrifugally washed 4 times with N,N-dimethylformamide at 15000rpm, and the precipitate was taken to obtain Intermediate Product 1; Intermediate Product 1 and ammonia water were mixed at a mass ratio of 1:25. After reacting at 250rpm for 29h, centrifugal washing was carried out 4 times with deionized water at 15000rpm, and freeze-dried at -20°C with a vacuum degree of 50Pa for 20h to obtain Intermediate Product 2; in an atmosphere of nitrogen / oxygen mixture gas at 750°C, the volume ratio of nitrogen to oxygen in the nitrogen / oxygen mixture gas is 1:3. After preheating Intermediate Product 2 for 30min, the temperature was raised to 950°C, tributyl borate which is 0.2 times the mass of Intermediate Product 2 and dichloromethane which is 0.06 times the mass of Intermediate Product 2 were successively sprayed onto Intermediate Product 2, and the reaction was continued for 30min to obtain chloroborosiloxane nanosheets; (4)Chloroborosiloxane nanosheets, antibacterial agent, deionized water, and N,N-dimethylformamide were mixed at a mass ratio of 25:2:15:10. After reacting at 250rpm and 130°C for 3h, washing was carried out 4 times successively with absolute ethanol and deionized water to obtain a flame retardant; (5)Polyvinyl chloride K13S, flame retardant, azodicarbonamide, p-tolyl phosphate, calcium stearate, and polyethylene wax were mixed at a mass ratio of 70:10:2:50:0.5:4. After kneading at 30rpm and 130°C for 1h, rough kneading was carried out for 4min at a steam pressure of 0.6MPa and a roll gap of 3mm, and refining was carried out for 4min at a steam pressure of 0.5MPa and a roll gap of 2mm. Then, calendering was carried out at 120 - 160°C to obtain a synthetic leather with a thickness of 0.2mm; the synthetic leather was laminated on the base cloth, and foaming and embossing treatments were carried out at a pressure of 0.3MPa and 190°C to prepare a high-temperature resistant fabric.
[0022] Example 3 (1)2-(Dimethylamino)-5-formylbenzonitrile and propionic acid were mixed at a mass ratio of 0.8:20. After stirring at 300rpm and 140°C for 5min, pyrrole which is 1.0 times the mass of 2-(Dimethylamino)-5-formylbenzonitrile and acetic anhydride which is 3 times the mass of 2-(Dimethylamino)-5-formylbenzonitrile were added. The reaction was continued for 60min, cooled to room temperature, methanol which is 20 times the mass of 2-(Dimethylamino)-5-formylbenzonitrile was added, allowed to stand for 12h, filtered, and vacuum dried at -0.08MPa and 60°C for 12h to obtain tetracyanoporphyrin; (2) Mix tetracyanoporphyrin, 6,6'-diazido-6,6'-dideoxytrehalose, cuprous bromide, hexamethylenetriamine, and N,N-dimethylformamide in a mass ratio of 11:7:3:15:3. React under a nitrogen atmosphere at 60 °C for 4 h. After freezing in liquid nitrogen for 60 s, add n-hexane until precipitation is complete. Filter, wash with deionized water 5 times, and vacuum dry at -0.08 MPa and 60 °C for 12 h to obtain the antibacterial agent; (3) Mix graphene oxide and N,N-dimethylformamide in a mass ratio of 0.3:40. After ultrasonic treatment at 800 W for 1 h, add triethoxysilane which is 1.3 times the mass of N,N-dimethylformamide and azobisisobutyronitrile which is 0.008 times the mass of N,N-dimethylformamide. React at 200 rpm and 80 °C for 32 h. After centrifugation at 15000 rpm for 10 min, take the precipitate and wash it 5 times by centrifugation with N,N-dimethylformamide at 15000 rpm. Take the precipitate to obtain Intermediate Product 1; Mix Intermediate Product 1 and ammonia water in a mass ratio of 1:30. React at 300 rpm for 32 h. After centrifugation and washing 5 times with deionized water at 15000 rpm, freeze-dry at a vacuum degree of 50 Pa and -30 °C for 25 h to obtain Intermediate Product 2; In an atmosphere of nitrogen / oxygen mixed gas at 800 °C, where the volume ratio of nitrogen to oxygen in the nitrogen / oxygen mixed gas is 1:3, preheat Intermediate Product 2 for 40 min and then raise the temperature to 1000 °C. Sprinkle tributyl borate which is 0.3 times the mass of Intermediate Product 2 and dichloromethane which is 0.07 times the mass of Intermediate Product 2 on Intermediate Product 2 in sequence and continue to react for 40 min to obtain chloroborosiloxane nanosheets; (4) Mix chloroborosiloxane nanosheets, antibacterial agent, deionized water, and N,N-dimethylformamide in a mass ratio of 30:3:20:10. React at 300 rpm and 150 °C for 4 h. Then wash with anhydrous ethanol and deionized water 5 times in sequence to obtain the flame retardant; (5) Mix polyvinyl chloride K13S, flame retardant, azodicarbonamide, tricresyl phosphate, mercaptomethyltin, and paraffin in a mass ratio of 80:15:3:60:0.5:5. Knead at 40 rpm and 140 °C for 1.5 h. Then carry out rough kneading for 5 min under a steam pressure of 0.7 MPa and a roll gap of 3 mm, and carry out refining for 5 min under a steam pressure of 0.6 MPa and a roll gap of 2 mm. Then carry out calendering at 120 - 160 °C to obtain a synthetic leather with a thickness of 0.3 mm; Bond the synthetic leather to the base fabric and carry out foaming and embossing treatment at a pressure of 0.4 MPa and 200 °C to obtain the high-temperature resistant fabric.
[0023] Comparative Example 1 The difference between Comparative Example 1 and Example 2 is only that step (1) is absent, and step (2) is changed to: Mix 2-(dimethylamino)-5-formylbenzonitrile, 6,6'-di(azido)-6,6'-dideoxytrehalose, cuprous bromide, hexamethyltriethylenetetramine, and N,N-dimethylformamide in a mass ratio of 10:6:2:13:3, react at 55 °C for 3 h under a nitrogen atmosphere, after freezing with liquid nitrogen for 45 s, add n-hexane until precipitation is complete, filter, wash 4 times with deionized water, and vacuum dry at -0.08 MPa and 55 °C for 12 h to obtain the antibacterial agent. The remaining steps are the same as in Example 2.
[0024] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is only that step (2) is absent, and step (1) is changed to: Mix 2-(dimethylamino)-5-formylbenzonitrile and propionic acid in a mass ratio of 0.7:20, stir at 250 rpm and 110 °C for 4 min, then add pyrrole 0.9 times the mass of 2-(dimethylamino)-5-formylbenzonitrile and acetic anhydride 2.5 times the mass of 2-(dimethylamino)-5-formylbenzonitrile, continue to react for 40 min, cool to room temperature, add methanol 15 times the mass of 2-(dimethylamino)-5-formylbenzonitrile, stand for 12 h, filter, and vacuum dry at -0.08 MPa and 55 °C for 12 h to obtain the antibacterial agent. The remaining steps are the same as in Example 2.
[0025] Comparative Example 3 (1) Mix 2-(dimethylamino)-5-formylbenzonitrile and propionic acid in a mass ratio of 0.7:20, stir at 250 rpm and 110 °C for 4 min, then add pyrrole 0.9 times the mass of 2-(dimethylamino)-5-formylbenzonitrile and acetic anhydride 2.5 times the mass of 2-(dimethylamino)-5-formylbenzonitrile, continue to react for 40 min, cool to room temperature, add methanol 15 times the mass of 2-(dimethylamino)-5-formylbenzonitrile, stand for 12 h, filter, and vacuum dry at -0.08 MPa and 55 °C for 12 h to obtain tetracyanoporphyrin; (2) Mix tetracyanoporphyrin, 6,6'-di(azido)-6,6'-dideoxytrehalose, cuprous bromide, hexamethyltriethylenetetramine, and N,N-dimethylformamide in a mass ratio of 10:6:2:13:3, react at 55 °C for 3 h under a nitrogen atmosphere, after freezing with liquid nitrogen for 45 s, add n-hexane until precipitation is complete, filter, wash 4 times with deionized water, and vacuum dry at -0.08 MPa and 55 °C for 12 h to obtain the antibacterial agent; (3)Graphene oxide and N,N-dimethylformamide were mixed at a mass ratio of 0.2:40. After ultrasonic treatment at 650 W for 1 h, triethoxysilane with a mass 1.2 times that of N,N-dimethylformamide and azobisisobutyronitrile with a mass 0.007 times that of N,N-dimethylformamide were added. After reacting at 150 rpm and 70 °C for 29 h, centrifugation was carried out at 15,000 rpm for 7.5 min. The precipitate was taken, and then centrifugally washed 4 times with N,N-dimethylformamide at 15,000 rpm. The precipitate was taken to obtain Intermediate Product 1; Intermediate Product 1 and ammonia water were mixed at a mass ratio of 1:25. After reacting at 250 rpm for 29 h, centrifugally washed 4 times with deionized water at 15,000 rpm, and freeze-dried at a vacuum degree of 50 Pa and -20 °C for 20 h to obtain Intermediate Product 2; In an atmosphere of nitrogen / oxygen mixed gas at 750 °C, the volume ratio of nitrogen to oxygen in the nitrogen / oxygen mixed gas was 1:3. After preheating Intermediate Product 2 for 30 min, the temperature was raised to 950 °C and the reaction was continued for 30 min to obtain silica nanosheets; (4)Silica nanosheets, antibacterial agent, deionized water, and N,N-dimethylformamide were mixed at a mass ratio of 25:2:15:10. After reacting at 250 rpm and 130 °C for 3 h, washed 4 times with anhydrous ethanol and deionized water in sequence to obtain the flame retardant; (5)Polyvinyl chloride K13S, flame retardant, azodicarbonamide, p-tolyl phosphate, calcium stearate, and polyethylene wax were mixed at a mass ratio of 70:10:2:50:0.5:4. After kneading at 30 rpm and 130 °C for 1 h, rough kneading was carried out at a steam pressure of 0.6 MPa and a roll gap of 3 mm for 4 min, and refining was carried out at a steam pressure of 0.5 MPa and a roll gap of 2 mm for 4 min. Then, calendering was carried out at 120 - 160 °C to obtain a synthetic leather with a thickness of 0.2 mm; The synthetic leather was laminated on the base cloth, and foaming and embossing treatments were carried out at a pressure of 0.3 MPa and 190 °C to obtain the high-temperature resistant fabric.
[0026] Comparative Example 4 (1) Graphene oxide and N,N-dimethylformamide were mixed at a mass ratio of 0.2:40. After ultrasonic treatment at 650 W for 1 h, triethoxysilane which is 1.2 times the mass of N,N-dimethylformamide and azobisisobutyronitrile which is 0.007 times the mass of N,N-dimethylformamide were added. After reacting at 150 rpm and 70 °C for 29 h, centrifugation was carried out at 15000 rpm for 7.5 min. The precipitate was taken, and then centrifugally washed 4 times with N,N-dimethylformamide at 15000 rpm. The precipitate was taken to obtain Intermediate Product 1; Intermediate Product 1 and ammonia water were mixed at a mass ratio of 1:25. After reacting at 250 rpm for 29 h, centrifugally washed 4 times with deionized water at 15000 rpm, and freeze-dried at a vacuum degree of 50 Pa and -20 °C for 20 h to obtain Intermediate Product 2; In an atmosphere of nitrogen / oxygen mixed gas at 750 °C, the volume ratio of nitrogen to oxygen in the nitrogen / oxygen mixed gas is 1:3. After preheating Intermediate Product 2 for 30 min, the temperature was raised to 950 °C. Tributyl borate which is 0.2 times the mass of Intermediate Product 2 and dichloromethane which is 0.06 times the mass of Intermediate Product 2 were successively sprayed onto Intermediate Product 2, and the reaction was continued for 30 min to obtain chloroborosiloxane nanosheets; (2) Polyvinyl chloride K13S, flame retardant, azodicarbonamide, p-tolyl phosphate, calcium stearate, and polyethylene wax were mixed at a mass ratio of 70:10:2:50:0.5:4. After kneading at 30 rpm and 130 °C for 1 h, rough kneading was carried out at a steam pressure of 0.6 MPa and a roll gap of 3 mm for 4 min, and refining was carried out at a steam pressure of 0.5 MPa and a roll gap of 2 mm for 4 min. Then calendering was carried out at 120 - 160 °C to obtain a synthetic leather with a thickness of 0.2 mm; The synthetic leather was laminated on a base cloth, and foaming and embossing treatments were carried out at a pressure of 0.3 MPa and 190 °C to prepare a high-temperature resistant fabric.
[0027] Effect Example Table 1 below gives the performance analysis results of the high-temperature resistant fabrics using Examples 1 - 3 and Comparative Examples 1 - 4 of the present invention.
[0028] Table 1 From the comparison of the antibacterial rate data between the examples and the comparative examples in Table 1, it can be found that the fabric has good antibacterial performance. Tetracyanoporphyrin is prepared by condensing the aldehyde group in 2-(dimethylamino)-5-formylbenzonitrile with pyrrole, which can generate reactive oxygen under light irradiation and act on microorganisms, resulting in the death of microorganisms, thereby making the fabric have antibacterial effect; the further reaction of tetracyanoporphyrin with 6,6'-diazido-6,6'-dideoxy trehalose bridges the cyanoporphyrin through a triazole structure, enhancing the conjugated system of the porphyrin structure, and synergistically improving the antibacterial effect of the fabric with the inhibitory reproduction effect of the triazole structure. The antibacterial agent reacts with chloroborosilicate nanosheets to form a quaternary ammonium structure, which can further improve the antibacterial effect; from the comparison of the flame retardant grade and 5% thermal decomposition temperature data between the examples and the comparative examples in Table 1, it can be found that the fabric has good flame retardant performance. Tri-n-butyl borate and dichloromethane are sprayed on the graphene oxide nanosheets coated with silica under high temperature and oxygen to prepare chloroborosilicate nanosheets. The high heat resistance, barrier property of the nanosheets and their restriction on the molecular chain movement improve the high temperature resistance of the material. At the same time, during combustion, it can promote the carbonization and crosslinking of the material to form a three-dimensional network carbon layer with a silicon-carbon-boron structure, blocking the combustible gas and heat transfer, thereby making the fabric have a flame retardant effect. The further reaction of chloroborosilicate nanosheets with the antibacterial agent introduces a quaternary ammonium structure, which can be decomposed by heat during combustion to form ammonia gas to expand the carbon layer, further enhancing the barrier effect of the carbon layer and increasing the flame retardant effect. In addition, the flame retardant can react with polyvinyl chloride to curb the dehydrochlorination reaction of polyvinyl chloride and improve the high temperature resistance of the fabric.
[0029] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be construed as limiting the claimed claim.
Claims
1. A method for preparing a high-temperature resistant fabric, characterized in that, It includes the following preparation steps: (1) Mix 2-(dimethylamino)-5-formylbenzonitrile and propionic acid at a mass ratio of 0.7:
20. After stirring at 250 rpm and 110 °C for 4 min, add pyrrole 0.9 times the mass of 2-(dimethylamino)-5-formylbenzonitrile and acetic anhydride 2.5 times the mass of 2-(dimethylamino)-5-formylbenzonitrile, and continue the reaction for 40 min. Cool to room temperature, add methanol 15 times the mass of 2-(dimethylamino)-5-formylbenzonitrile, let stand for 12 h, filter, and vacuum dry at -0.08 MPa and 55 °C for 12 h to obtain tetracyanoporphyrin; (2) Mix tetracyanoporphyrin, 6,6'-diazido-6,6'-dideoxytrehalose, cuprous bromide, hexamethylenetriamine, and N,N-dimethylformamide at a mass ratio of 10:6:2:13:
3. React at 55 °C in a nitrogen atmosphere for 3 h. After freezing in liquid nitrogen for 45 s, add n-hexane until precipitation is complete, filter, wash 4 times with deionized water, and vacuum dry at -0.08 MPa and 55 °C for 12 h to obtain the antibacterial agent; (3) Mix graphene oxide and N,N-dimethylformamide at a mass ratio of 0.2:
40. After ultrasonic treatment at 650 W for 1 h, add triethoxysilane 1.2 times the mass of N,N-dimethylformamide and azobisisobutyronitrile 0.007 times the mass of N,N-dimethylformamide, and react at 150 rpm and 70 °C for 29 h. Then centrifuge at 15000 rpm for 7.5 min, take the precipitate, and centrifuge and wash 4 times with N,N-dimethylformamide at 15000 rpm, take the precipitate to obtain intermediate product 1; Mix intermediate product 1 and ammonia water at a mass ratio of 1:25, react at 250 rpm for 29 h, then centrifuge and wash 4 times with deionized water at 15000 rpm, and freeze-dry at a vacuum of 50 Pa and -20 °C for 20 h to obtain intermediate product 2; In a nitrogen / oxygen mixed gas atmosphere at 750 °C, the volume ratio of nitrogen to oxygen in the nitrogen / oxygen mixed gas is 1:
3. After preheating intermediate product 2 for 30 min, raise the temperature to 950 °C, and sequentially spray tributyl borate 0.2 times the mass of intermediate product 2 and dichloromethane 0.06 times the mass of intermediate product 2 onto intermediate product 2, and continue the reaction for 30 min to obtain chloroborosiloxane nanosheets; (4) Mix chloroborosiloxane nanosheets, antibacterial agent, deionized water, and N,N-dimethylformamide at a mass ratio of 25:2:15:
10. React at 250 rpm and 130 °C for 3 h, then wash 4 times with absolute ethanol and deionized water in sequence to obtain the flame retardant; (5) Mix polyvinyl chloride K13S, flame retardant, azodicarbonamide, p-cresyl phosphate, calcium stearate, and polyethylene wax in a mass ratio of 70:10:2:50:0.5:
4. After kneading at 30 rpm and 130 °C for 1 h, rough knead for 4 min under a steam pressure of 0.6 MPa and a roll gap of 3 mm, refine for 4 min under a steam pressure of 0.5 MPa and a roll gap of 2 mm, and then calender at 120 - 160 °C to obtain a synthetic leather with a thickness of 0.2 mm. Bond the synthetic leather to the base fabric and perform foaming and embossing treatments at a pressure of 0.3 MPa and 190 °C to produce a high-temperature resistant fabric.