Preparation method and application of composite flame-retardant fabric

Abstract

The invention discloses a preparation method and application of a composite flame-retardant fabric, and relates to the technical field of flame-retardant fabrics. The invention discloses a composite flame-retardant fabric. The flame-retardant flame-retardant composite material is prepared from the following raw materials in parts by weight: 35 to 45 parts of meta-aramid, 25 to 35 parts of a first modified organic phosphorus flame retardant, 10 to 15 parts of a third modified organic phosphorus flame retardant, 20 to 30 parts of first modified organic silicon rubber, 8 to 15 parts of third modified organic silicon rubber, 12 to 18 parts of nano zinc oxide and 4 to 7 parts of octadecyl dimethyl hydroxyethyl ammonium nitrate, the water-based paint is prepared from the following components in parts by weight: 6 to 10 parts of carboxyl-terminated nitrile rubber, 5 to 8 parts of ultra-high molecular weight polyethylene micro powder, 3 to 5 parts of an anti-aging agent, 1 to 3 parts of dicyclohexylcarbodiimide, 0.3 to 1 part of 4-dimethylaminopyridine, 3 to 5 parts of amino silicon oil micro-emulsion, 4 to 7 parts of an organic fluorine waterproof agent, 2 to 4 parts of sodium polyacrylate, 2 to 4 parts of chitosan quaternary ammonium salt, 0.1 to 0.5 part of citric acid and 350 to 550 parts of deionized water. The fabric has various excellent properties such as efficient flame retardance, thermal stability, flexibility and wear resistance, and is low in toxicity, environment-friendly, light, thin, breathable, anti-aging, anti-static and wide in application.

Description

Technical Field

[0001] The present invention relates to the technical field of flame-retardant fabrics, and in particular to a preparation method and application of a composite flame-retardant fabric. Background Art

[0002] In modern life and industrial production, fire hazards pose a constant threat to people's lives and property, and the demand for flame-retardant fabrics continues to grow. Traditional single-ingredient flame-retardant fabrics often have performance shortcomings. For example, while some flame-retardant fabrics offer some flame retardancy, they lack flexibility, making clothing made from them uncomfortable to wear and prone to cracking during activity, limiting their application in the clothing industry. Some fabrics also exhibit poor washability, significantly reducing their flame retardancy after repeated washings, making them unsuitable for long-term use.

[0003] In architectural decoration, fabrics used for curtains, sofa covers, and other items that only have basic decorative functions but lack flame retardancy can easily spread fire and cause serious damage in the event of a fire. Furthermore, with increasing awareness of environmental protection, higher demands are being placed on flame-retardant fabrics, making low-toxic, pollution-free flame-retardant fabrics an urgent market need.

[0004] Furthermore, the widespread use of electronic devices has made anti-static performance a key quality indicator for fabrics. In some electronics production workshops, work clothes without anti-static features can cause accidents due to sparks generated by static electricity. However, some existing fabrics fall short in meeting diverse performance requirements, making them difficult to adapt to complex and diverse application scenarios. Therefore, developing a composite flame-retardant fabric that combines multiple excellent properties while meeting environmental requirements is crucial. This will not only enhance the safety and practicality of various products, but also promote the healthy development of related industries. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the present invention provides a preparation method and application of a composite flame-retardant fabric, which solves the above problems.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: A composite flame-retardant fabric comprises the following raw materials in parts by weight: 35-45 parts of meta-aramid, 25-35 parts of a first modified organophosphorus flame retardant, 10-15 parts of a third modified organophosphorus flame retardant, 20-30 parts of a first modified silicone rubber, 8-15 parts of a third modified silicone rubber, 12-18 parts of nano zinc oxide, 4-7 parts of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, 6-10 parts of carboxyl-terminated nitrile rubber, 5-8 parts of ultra-high molecular weight polyethylene micropowder, 3-5 parts of an anti-aging agent, 1-3 parts of dicyclohexylcarbodiimide, 0.3-1 parts of 4-dimethylaminopyridine, 3-5 parts of amino silicone oil microemulsion, 4-7 parts of an organic fluorine waterproofing agent, 2-4 parts of sodium polyacrylate, 2-4 parts of chitosan quaternary ammonium salt, 0.1-0.5 parts of citric acid, and 350-550 parts of deionized water.

[0007] Furthermore, the modified organophosphorus flame retardant is specifically prepared in the following steps: A1. Add tricresyl phosphate to a three-necked flask, then add toluene as a solvent, stir to dissolve, then slowly dropwise add hydroxyethyl acrylate, simultaneously add p-toluenesulfonic acid, raise the temperature to 105°C, and continue stirring to react for 4.5 hours. After the reaction is completed, cool to room temperature, wash the reaction solution, let it stand to separate, remove the lower aqueous phase, dry the organic phase, filter it, and remove the toluene by distillation under reduced pressure to obtain the first modified organophosphorus flame retardant. A2. The first modified product was added to a three-necked flask, and ethyl acetate was added and stirred to dissolve. Maleic anhydride and benzoyl peroxide were then added, and the temperature was raised to 85° C. and the reaction was continued with stirring for 3.5 hours. After the reaction was completed, the reaction solution was cooled to room temperature, washed, allowed to stand and separated, the lower aqueous phase was removed, the organic phase was dried, filtered, and the ethyl acetate was removed by distillation under reduced pressure to obtain a second modified organophosphorus flame retardant. A3. Place the second modified product into a reactor, add N,N-dimethylacetamide, stir to dissolve, then add 3-mercaptopropyltrimethoxysilane, and continue stirring and reacting at 75°C for 3.5 hours. After the reaction is completed, pour the product into a large amount of deionized water for precipitation, filter, wash, and dry to obtain the third modified organophosphorus flame retardant.

[0008] Furthermore, in the step A1, the ratio of tricresyl phosphate, toluene, hydroxyethyl acrylate, and p-toluenesulfonic acid is 12 g: 35 mL: 4 g: 0.8 g; the stirring speed is 300 r / min; the reaction solution is washed with a 5% sodium carbonate solution; the organic phase is dried over anhydrous sodium sulfate; the pressure during reduced pressure distillation is 1200 Pa and the temperature is 65°C; in the step A2, the ratio of ethyl acetate, maleic anhydride, and benzoyl peroxide is 25 mL : 2.5g:0.4g; stirring speed is 200r / min; washed with 10% mass fraction sodium hydroxide solution; the organic phase is dried over anhydrous magnesium sulfate; the pressure during reduced pressure distillation is 1200Pa and the temperature is 65°C; in the step A3, the amount ratio of N,N-dimethylacetamide and 3-mercaptopropyltrimethoxysilane is 18mL:1.5g; the stirring speed is 200r / min; the solid precipitate is washed with deionized water and dried at 60°C for 6h.

[0009] In the first modification, tricresyl phosphate reacts with hydroxyethyl acrylate under the catalysis of p-toluenesulfonic acid. The hydroxyl groups of hydroxyethyl acrylate react with the reactive groups of tricresyl phosphate, introducing a polymerizable double bond. This modification enhances the flame retardant's ability to bind to the fiber, allowing it to better adhere to the fiber surface or embed into the fiber's internal structure, more effectively exerting its flame retardant properties during combustion. In the second modification, maleic anhydride reacts with the product of the first modification, increasing the polarity of the flame retardant molecule. This increased polarity enhances the flame retardant's interaction with other raw materials, allowing it to better integrate with other ingredients during fabric preparation, further improving overall flame retardancy. In the third modification, 3-mercaptopropyltrimethoxysilane is added to graft siloxane groups onto the flame retardant molecules. Siloxane groups have excellent hydrophilicity and chemical stability, improving the flame retardant's adhesion to the fiber surface, forming a more stable protective film. They also significantly enhance the fabric's water resistance, allowing the flame retardant to remain firmly attached to the fiber even after multiple washes, maintaining stable flame retardancy.

[0010] Furthermore, the modified silicone rubber is specifically prepared in the following steps: B1. Place the silicone rubber in a reaction kettle, add xylene, and stir to swell it. Then add vinyltrimethoxysilane and dibutyltin dilaurate. Raise the temperature to 125°C and stir to react for 4.5 hours. After the reaction is completed, remove the xylene by vacuum distillation to obtain the first modified silicone rubber. B2. Add the first modified product to a reactor, then add cyclohexane, stir and dissolve, then add acrylic acid and azobisisobutyronitrile, raise the temperature to 75°C, and stir to react for 3.5 hours; after the reaction is complete, remove the cyclohexane by distillation under reduced pressure to obtain the second modified silicone rubber; B3. Place the second modified product into a reactor, add acetone, stir and dissolve, then add nano-titanium dioxide and triethylamine, raise the temperature to 65°C, and stir to react for 3.5 hours; after the reaction is completed, filter out the unreacted nano-titanium dioxide, and remove the acetone by vacuum distillation to obtain the third modified silicone rubber.

[0011] Furthermore, in step B1, the amount ratio of silicone rubber, xylene, vinyltrimethoxysilane, and dibutyltin dilaurate is 10g:25mL:2.5g:0.25g; the stirring speed is 300r / min; the pressure of the reduced pressure distillation is 10kPa, and the temperature is 80°C; in step B2, the amount ratio of cyclohexane, acrylic acid, and azobisisobutyronitrile is 18mL:1.5g:0.15g; the stirring speed is 300r / min; the pressure of the reduced pressure distillation is 0.02MPa, and the temperature is 65°C; in step B3, the amount ratio of acetone, nano-titanium dioxide, and triethylamine is 12mL:0.8g:0.15g; the stirring speed is 300r / min; the pressure of the reduced pressure distillation is 0.05MPa, and the temperature is 40°C.

[0012] In the first modification, vinyltrimethoxysilane reacts with silicone rubber under the catalysis of dibutyltin dilaurate, introducing reactive vinyl groups into the silicone rubber's molecular chain. This vinyl group significantly enhances the reactivity of the silicone rubber with other monomers, allowing it to react more fully with other raw materials in subsequent blending reactions, forming a tighter network structure and thus improving the overall performance of the fabric. In the second modification, acrylic acid reacts with the first-modified product under the initiation of azobisisobutyronitrile, further increasing the number of reactive sites in the silicone rubber. These additional reactive sites enable the silicone rubber to form more chemical bonds when blended with other ingredients, significantly improving the fabric's flexibility and elasticity, making it less susceptible to breakage during stretching and bending, and more comfortable to wear. In the third modification, nano-titanium dioxide and triethylamine are added, uniformly dispersing the nano-titanium dioxide throughout the silicone rubber. Nano-titanium dioxide has good photocatalytic and UV resistance properties, which not only enhances the weather resistance and anti-aging properties of silicone rubber, but also gives the fabric self-cleaning ability; triethylamine, as a catalyst, promotes the combination of nano-titanium dioxide and silicone rubber, ensuring that nano-titanium dioxide exists stably in the rubber system and continues to exert its functions.

[0013] Furthermore, the anti-aging agent is a mixture of ultraviolet absorber UV-531 and antioxidant 1076 in a ratio of 1:1.

[0014] A method for preparing a composite flame-retardant fabric specifically comprises the following steps: S1. Add deionized water to the reactor, start stirring, add sodium polyacrylate and nano zinc oxide in sequence, stir for 30-40 minutes, and then ultrasonically disperse for 10-20 minutes to form a uniform milky white dispersion; S2. Add meta-aramid, the first modified organophosphorus flame retardant, the first modified silicone rubber, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, carboxyl-terminated nitrile rubber, ultra-high molecular weight polyethylene powder, antioxidant, dicyclohexylcarbodiimide and 4-dimethylaminopyridine to the above dispersion, raise the temperature to 80-90° C., stir and react for 5-7 hours to form a preliminary polymer system; S3. After the blending reaction is completed, the temperature is lowered to 60°C, and the third modified organophosphorus flame retardant, the third modified silicone rubber, the amino silicone oil microemulsion, the organofluorine waterproofing agent, and the chitosan quaternary ammonium salt are added to the system in sequence. The reaction is continued for 1-2 hours, and then cooling water is introduced to cool the system to 25°C. Citric acid is added dropwise to adjust the pH value of the system to 6-7; S4. The post-treated material is filtered through a filter and transferred to a degassing tank. It is degassed under vacuum for 2 hours to obtain a uniform, bubble-free spinning solution. The spinning solution is transported to the spinning equipment and extruded through a spinneret. The spinneret stream vertically enters the coagulation bath to complete the coagulation process. The formed nascent fibers immediately enter a multi-stage countercurrent washing device for cleaning; then they are stretched and finally dried at 105°C for 3 hours to obtain a composite flame-retardant fabric.

[0015] Furthermore, in the step S1, the stirring speed is 300 r / min; in the step S2, the heating rate is 2°C / min, and the stirring speed is 400-500 r / min.

[0016] Furthermore, in the S4 step, the material is filtered through a 200-mesh stainless steel filter; the vacuum degree of the degassing process is -0.09 MPa; the coagulation bath is an 18 wt.% sodium chloride aqueous solution at 15°C, and the spun fiber passes through the coagulation bath at a speed of 8 m / min; the water washing temperature is maintained at 60°C, and the total washing time is 10 min; and the fiber is stretched at a stretching ratio of 3.5 times.

[0017] The invention discloses an application of a composite flame-retardant fabric, wherein the fabric is at least applied to clothes, hats, curtains and sofa covers.

[0018] The present invention provides a preparation method and application of a composite flame-retardant fabric, which has the following beneficial effects: 1. Excellent flame retardancy: By subjecting the organophosphorus flame retardant to triple modification and rationally combining it with flame retardant ingredients such as meta-aramid, the organophosphorus flame retardant decomposes at high temperatures to produce substances such as phosphoric acid and metaphosphoric acid when the fabric burns. These substances have a strong dehydrating effect, carbonizing the fiber surface to form a dense char layer. This char layer isolates oxygen and heat, preventing further spread of flames, significantly improving the fabric's flame retardancy and providing reliable protection for the safety of people and property.

[0019] 2. Excellent Overall Physical Properties: After undergoing three modifications, silicone rubber synergizes with other raw materials to significantly improve the fabric's physical properties. The vinyl introduced in the first modification enhances reactivity, allowing it to better bond with other ingredients. The increased active sites in the second modification improve the fabric's flexibility and elasticity, making it more comfortable and less prone to deformation during wear and use. The addition of nano-titanium dioxide in the third modification enhances weather resistance and aging resistance. Combined with the enhanced wear resistance of ultra-high molecular weight polyethylene micropowder and the increased toughness of carboxyl-terminated nitrile rubber, the fabric possesses excellent overall physical properties, meeting the needs of diverse application scenarios.

[0020] 3. Environmental and Safety: This composite flame-retardant fabric utilizes low-toxic, environmentally friendly raw materials, posing no harm to humans or the environment during production and use. Meta-aramid inherently possesses excellent stability and low toxicity; the modified organophosphorus flame retardant and silicone rubber are modified without introducing harmful heavy metals or highly toxic substances. Furthermore, the fabric does not produce significant amounts of toxic and harmful gases during combustion, minimizing secondary fire hazards and meeting modern society's stringent environmental and safety requirements.

[0021] 4. Wide Range of Applications: The fabric boasts numerous excellent properties, including high flame retardancy, thermal stability, flexibility, wear resistance, washability, low toxicity, environmental friendliness, lightweight, anti-aging, breathability, and anti-static properties, resulting in broad application prospects across multiple sectors. In the apparel sector, it can be used to produce firefighter uniforms, work clothes, and children's clothing, ensuring personnel safety in challenging environments. In architectural decoration, it can be used in curtains, sofa covers, carpets, and other interior decoration materials, enhancing the safety of interior decoration materials. In industries such as electronic equipment manufacturing, its anti-static properties make it suitable for work clothes and packaging materials, effectively preventing static damage to electronic components and providing a high-performance material option for the development of various industries. DETAILED DESCRIPTION

[0022] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0023] Example 1: Preparation of composite flame retardant fabrics. The specific preparation steps are as follows: S1. Add 350 parts of deionized water to a reactor, stir at 300 r / min, add 2 parts of sodium polyacrylate and 12 parts of nano zinc oxide in sequence, stir for 30 minutes, and then ultrasonically disperse for 10 minutes to form a uniform milky white dispersion; S2. Add 35 parts of meta-aramid, 25 parts of the first modified organophosphorus flame retardant, 20 parts of the first modified silicone rubber, 4 parts of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, 6 parts of carboxyl-terminated nitrile rubber, 5 parts of ultra-high molecular weight polyethylene powder, 3 parts of antioxidant, 1 part of dicyclohexylcarbodiimide and 0.3 parts of 4-dimethylaminopyridine to the above dispersion, heat the mixture to 80°C at a heating rate of 2°C / min, stir the mixture at a speed of 400 r / min for 5-7 hours to form a preliminary polymer system; S3. After the blending reaction is completed, the temperature is lowered to 60°C, and 10 parts of the third modified organophosphorus flame retardant, 8 parts of the third modified silicone rubber, 3 parts of amino silicone oil microemulsion, 4 parts of organic fluorine waterproofing agent, and 2 parts of chitosan quaternary ammonium salt are added to the system in sequence. The reaction is continued for 1 hour, and then cooling water is introduced to lower the temperature to 25°C, and citric acid is added dropwise to adjust the pH value of the system to 6; S4. The post-treated material is filtered through a 200-mesh stainless steel filter, transferred to a degassing tank, and degassed at a vacuum degree of -0.09 MPa for 2 hours to obtain a uniform, bubble-free spinning solution. The spinning solution is transported to the spinning equipment and extruded through a spinneret. The spinneret stream vertically enters a coagulation bath of 18 wt.% sodium chloride aqueous solution at 15°C. The spun fibers pass through the coagulation bath at a speed of 8 m / min to complete the coagulation process. The formed spun fibers immediately enter a multi-stage countercurrent washing device for cleaning. The washing temperature is maintained at 60°C, and the total washing time is 10 minutes. The fibers are then stretched at a stretching ratio of 3.5 times, and finally dried at 105°C for 3 hours to obtain a composite flame-retardant fabric.

[0024] Example 2: Preparation of composite flame-retardant fabrics. The specific preparation steps are as follows: S1. Add 550 parts of deionized water to a reactor, stir at 300 r / min, add 4 parts of sodium polyacrylate and 18 parts of nano zinc oxide in sequence, stir for 40 minutes, and then ultrasonically disperse for 20 minutes to form a uniform milky white dispersion; S2. Add 45 parts of meta-aramid, 35 parts of the first modified organophosphorus flame retardant, 30 parts of the first modified silicone rubber, 7 parts of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, 10 parts of carboxyl-terminated nitrile rubber, 8 parts of ultra-high molecular weight polyethylene powder, 5 parts of anti-aging agent, 3 parts of dicyclohexylcarbodiimide and 1 part of 4-dimethylaminopyridine to the above dispersion, heat the mixture to 90°C at a heating rate of 2°C / min, stir the mixture at a speed of 500 r / min for 7 hours to form a preliminary polymer system; S3. After the blending reaction is completed, the temperature is lowered to 60°C, and 15 parts of the third modified organophosphorus flame retardant, 15 parts of the third modified silicone rubber, 5 parts of amino silicone oil microemulsion, 7 parts of organic fluorine waterproofing agent, and 4 parts of chitosan quaternary ammonium salt are added to the system in sequence, and the reaction is continued for 2 hours. Then, cooling water is introduced to cool the system to 25°C, and citric acid is added dropwise to adjust the pH value of the system to 7; S4. The post-treated material is filtered through a 200-mesh stainless steel filter, transferred to a degassing tank, and degassed at a vacuum degree of -0.09 MPa for 2 hours to obtain a uniform, bubble-free spinning solution. The spinning solution is transported to the spinning equipment and extruded through a spinneret. The spinneret stream vertically enters a coagulation bath of 18 wt.% sodium chloride aqueous solution at 15°C. The spun fibers pass through the coagulation bath at a speed of 8 m / min to complete the coagulation process. The formed spun fibers immediately enter a multi-stage countercurrent washing device for cleaning. The washing temperature is maintained at 60°C, and the total washing time is 10 minutes. The fibers are then stretched at a stretching ratio of 3.5 times, and finally dried at 105°C for 3 hours to obtain a composite flame-retardant fabric.

[0025] Example 3: Preparation of composite flame-retardant fabrics. The specific preparation steps are as follows: S1. Add 450 parts of deionized water to a reactor, stir at 300 r / min, add 3 parts of sodium polyacrylate and 15 parts of nano zinc oxide in sequence, stir for 35 minutes, and then ultrasonically disperse for 15 minutes to form a uniform milky white dispersion; S2. Add 40 parts of meta-aramid, 30 parts of the first modified organophosphorus flame retardant, 25 parts of the first modified silicone rubber, 5 parts of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, 8 parts of carboxyl-terminated nitrile rubber, 6 parts of ultra-high molecular weight polyethylene powder, 4 parts of antioxidant, 2 parts of dicyclohexylcarbodiimide and 0.5 parts of 4-dimethylaminopyridine to the above dispersion, heat to 85° C. at a heating rate of 2° C. / min, stir at a speed of 450 r / min for 6 h to form a preliminary polymer system; S3. After the blending reaction is completed, the temperature is lowered to 60°C, and 12 parts of the third modified organophosphorus flame retardant, 11 parts of the third modified silicone rubber, 4 parts of amino silicone oil microemulsion, 5 parts of organic fluorine waterproofing agent, and 3 parts of chitosan quaternary ammonium salt are added to the system in sequence, and the reaction is continued for 1.5 hours. Then, cooling water is introduced to cool the system to 25°C, and citric acid is added dropwise to adjust the pH value of the system to 7; S4. The post-treated material is filtered through a 200-mesh stainless steel filter, transferred to a degassing tank, and degassed at a vacuum degree of -0.09 MPa for 2 hours to obtain a uniform, bubble-free spinning solution. The spinning solution is transported to the spinning equipment and extruded through a spinneret. The spinneret stream vertically enters a coagulation bath of 18 wt.% sodium chloride aqueous solution at 15°C. The spun fibers pass through the coagulation bath at a speed of 8 m / min to complete the coagulation process. The formed spun fibers immediately enter a multi-stage countercurrent washing device for cleaning. The washing temperature is maintained at 60°C, and the total washing time is 10 minutes. The fibers are then stretched at a stretching ratio of 3.5 times, and finally dried at 105°C for 3 hours to obtain a composite flame-retardant fabric.

[0026] Example 4: Preparation of modified organophosphorus flame retardant. The specific preparation steps are as follows: A1. Add 12 g of tricresyl phosphate to a three-necked flask, then add 35 mL of toluene as a solvent, stir at 300 r / min to dissolve it, then slowly dropwise add 4 g of hydroxyethyl acrylate, and simultaneously add 0.8 g of p-toluenesulfonic acid. Raise the temperature to 105°C and continue stirring to react for 4.5 hours. After the reaction is completed, cool to room temperature, wash the reaction solution with 5% by mass sodium carbonate solution, let it stand to separate, remove the lower aqueous phase, dry the organic phase with anhydrous sodium sulfate, filter, and remove the toluene by vacuum distillation at a pressure of 1200 Pa and a temperature of 65°C to obtain a first modified organophosphorus flame retardant. A2. The first modified product was added to a three-necked flask, and 25 mL of ethyl acetate was added. The mixture was stirred at 200 r / min to dissolve. Then, 2.5 g of maleic anhydride and 0.4 g of benzoyl peroxide were added. The temperature was raised to 85°C and the reaction was continued with stirring for 3.5 hours. After the reaction was completed, the mixture was cooled to room temperature and washed with a 10% sodium hydroxide solution. The mixture was allowed to stand for separation and the lower aqueous phase was removed. The organic phase was dried over anhydrous magnesium sulfate and filtered. The ethyl acetate was removed by reduced pressure distillation at a pressure of 1200 Pa and a temperature of 65°C to obtain a second modified organophosphorus flame retardant. A3. The second modified product was placed in a reactor, 18 mL of N,N-dimethylacetamide was added, and the mixture was stirred at 200 r / min to dissolve. Then, 1.5 g of 3-mercaptopropyltrimethoxysilane was added and the mixture was stirred and reacted at 75°C for 3.5 h. After the reaction, the product was poured into a large amount of deionized water for precipitation, filtered, washed with deionized water, and dried at 60°C for 6 h to obtain the third modified organophosphorus flame retardant.

[0027] Example 5, preparation of modified silicone rubber, the specific preparation steps are as follows: B1. Place 10 g of silicone rubber in a reactor, add 25 mL of xylene, stir to swell it, then add 2.5 g of vinyltrimethoxysilane and 0.25 g of dibutyltin dilaurate, raise the temperature to 125° C., and stir at 300 r / min for 4.5 h. After the reaction is complete, remove the xylene by vacuum distillation at a pressure of 10 kPa and a temperature of 80° C. to obtain the first modified silicone rubber; B2. The first modified product was added to a reactor, and 18 mL of cyclohexane was added and stirred to dissolve. Then, 1.5 g of acrylic acid and 0.15 g of azobisisobutyronitrile were added, and the temperature was raised to 75° C. and stirred at 300 r / min for 3.5 h. After the reaction was completed, the cyclohexane was removed by reduced pressure distillation at a pressure of 0.02 MPa and a temperature of 65° C. to obtain a second modified silicone rubber. B3. The second modified product was placed in a reactor, 12 mL of acetone was added, and the mixture was stirred to dissolve. Then, 0.8 g of nano-titanium dioxide and 0.15 g of triethylamine were added. The temperature was raised to 65°C, and the mixture was stirred at 300 r / min for 3.5 h. After the reaction was completed, the unreacted nano-titanium dioxide was removed by filtration, and the acetone was removed by reduced pressure distillation at a pressure of 0.05 MPa and a temperature of 40°C to obtain the third modified silicone rubber.

[0028] Comparative Example 1: Preparation of composite flame retardant fabrics, the specific preparation steps are as follows: The remaining steps remained unchanged, except that the modified organophosphorus flame retardant in Example 2 was replaced by an untreated organophosphorus flame retardant to prepare a composite flame-retardant fabric.

[0029] Comparative Example 2: preparing a composite flame-retardant fabric, the specific steps are as follows: The remaining steps remained unchanged, except that the modified silicone rubber in Example 2 was replaced by silicone rubber without any treatment to prepare a composite flame-retardant fabric.

[0030] Performance Testing The composite flame-retardant fabrics prepared in Examples 1-3 exhibit excellent comprehensive properties. In terms of flame retardancy, they exhibit a short vertical combustion damage length and a high limiting oxygen index, effectively resisting fire. They also exhibit outstanding physical and mechanical properties, with good tensile strength and elongation at break, and excellent flexibility and strength. They also exhibit excellent abrasion resistance and a low coefficient of dynamic friction. They also exhibit excellent washability, maintaining a high level of flame retardancy after multiple washes. They also possess good antistatic properties and low surface resistivity, as well as excellent aging resistance and a high UV protection factor. Furthermore, the fabrics offer excellent environmental performance, with no detectable formaldehyde levels.

[0031] In comparison, Comparative Examples 1-2, due to the use of unmodified raw materials, exhibit significant deficiencies in most of the aforementioned properties. This clearly demonstrates that modifying raw materials and adopting a reasonable formulation are key to improving the performance of composite flame-retardant fabrics and are of great significance in meeting the stringent requirements for fabrics in various fields.

[0032] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A composite flame-retardant fabric, characterized by: The invention comprises the following raw materials in parts by weight: 35-45 parts of meta-aramid, 25-35 parts of a first modified organic phosphorus flame retardant, 10-15 parts of a third modified organic phosphorus flame retardant, 20-30 parts of a first modified organic silicone rubber, 8-15 parts of a third modified organic silicone rubber, 12-18 parts of nano zinc oxide, 4-7 parts of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, 6-10 parts of carboxyl-terminated nitrile rubber, 5-8 parts of ultra-high molecular weight polyethylene micropowder, 3-5 parts of an anti-aging agent, 1-3 parts of dicyclohexylcarbodiimide, 0.3-1 parts of 4-dimethylaminopyridine, 3-5 parts of amino silicone oil microemulsion, 4-7 parts of an organic fluorine waterproofing agent, 2-4 parts of sodium polyacrylate, 2-4 parts of chitosan quaternary ammonium salt, 0.1-0.5 parts of citric acid, and 350-550 parts of deionized water.

2. The composite flame-retardant fabric according to claim 1, characterized in that: The modified organophosphorus flame retardant is specifically prepared in the following steps: A1. Add tricresyl phosphate to a three-necked flask, then add toluene as a solvent, stir to dissolve, then slowly dropwise add hydroxyethyl acrylate, simultaneously add p-toluenesulfonic acid, raise the temperature to 105°C, and continue stirring to react for 4.5 hours. After the reaction is completed, cool to room temperature, wash the reaction solution, let it stand to separate, remove the lower aqueous phase, dry the organic phase, filter it, and remove the toluene by distillation under reduced pressure to obtain the first modified organophosphorus flame retardant. A2. The first modified product was added to a three-necked flask, and ethyl acetate was added and stirred to dissolve. Maleic anhydride and benzoyl peroxide were then added, and the temperature was raised to 85° C. and the reaction was continued with stirring for 3.5 hours. After the reaction was completed, the reaction solution was cooled to room temperature, washed, allowed to stand and separated, the lower aqueous phase was removed, the organic phase was dried, filtered, and the ethyl acetate was removed by distillation under reduced pressure to obtain a second modified organophosphorus flame retardant. A3. Place the second modified product into a reactor, add N,N-dimethylacetamide, stir to dissolve, then add 3-mercaptopropyltrimethoxysilane, and continue stirring and reacting at 75°C for 3.5 hours. After the reaction is completed, pour the product into a large amount of deionized water for precipitation, filter, wash, and dry to obtain the third modified organophosphorus flame retardant.

3. The composite flame-retardant fabric according to claim 2, characterized in that: In step A1, the amount ratio of tricresyl phosphate, toluene, hydroxyethyl acrylate, and p-toluenesulfonic acid is 12g:35mL:4g:0.8g; the stirring speed is 300r / min; the reaction solution is washed with a 5% sodium carbonate solution; the organic phase is dried over anhydrous sodium sulfate; the pressure during reduced pressure distillation is 1200Pa and the temperature is 65°C; in step A2, the amount ratio of ethyl acetate, maleic anhydride, and benzoyl peroxide is 25mL:2.5g:0.4g; the stirring speed is 200r / min; the reaction solution is washed with a 10% sodium hydroxide solution; the organic phase is dried over anhydrous magnesium sulfate; the pressure during reduced pressure distillation is 1200Pa and the temperature is 65°C; in step A3, the amount ratio of N,N-dimethylacetamide and 3-mercaptopropyltrimethoxysilane is 18mL:1.5g; the stirring speed is 200r / min; the solid precipitate is washed with deionized water and dried at 60°C for 6h.

4. The composite flame-retardant fabric according to claim 1, characterized in that: The modified silicone rubber is specifically prepared in the following steps: B1. Place the silicone rubber in a reaction kettle, add xylene, and stir to swell it. Then add vinyltrimethoxysilane and dibutyltin dilaurate. Raise the temperature to 125°C and stir to react for 4.5 hours. After the reaction is completed, remove the xylene by vacuum distillation to obtain the first modified silicone rubber. B2. Add the first modified product to a reactor, then add cyclohexane, stir and dissolve, then add acrylic acid and azobisisobutyronitrile, raise the temperature to 75°C, and stir to react for 3.5 hours; after the reaction is complete, remove the cyclohexane by distillation under reduced pressure to obtain the second modified silicone rubber; B3. Place the second modified product into a reactor, add acetone, stir and dissolve, then add nano-titanium dioxide and triethylamine, raise the temperature to 65°C, and stir to react for 3.5 hours; after the reaction is completed, filter out the unreacted nano-titanium dioxide, and remove the acetone by vacuum distillation to obtain the third modified silicone rubber.

5. The composite flame-retardant fabric according to claim 4, characterized in that: In step B1, the amount ratio of silicone rubber, xylene, vinyltrimethoxysilane, and dibutyltin dilaurate is 10g:25mL:2.5g:0.25g; the stirring speed is 300r / min; the pressure of the reduced pressure distillation is 10kPa, and the temperature is 80°C; in step B2, the amount ratio of cyclohexane, acrylic acid, and azobisisobutyronitrile is 18mL:1.5g:0.15g; the stirring speed is 300r / min; the pressure of the reduced pressure distillation is 0.02MPa, and the temperature is 65°C; in step B3, the amount ratio of acetone, nano-titanium dioxide, and triethylamine is 12mL:0.8g:0.15g; the stirring speed is 300r / min; the pressure of the reduced pressure distillation is 0.05MPa, and the temperature is 40°C.

6. The composite flame-retardant fabric according to claim 1, characterized in that: The anti-aging agent is a mixture of ultraviolet absorber UV-531 and antioxidant 1076 in a ratio of 1:

1.

7. A method for preparing a composite flame-retardant fabric, characterized in that: The specific steps include: S1. Add deionized water to the reactor, start stirring, add sodium polyacrylate and nano zinc oxide in sequence, stir for 30-40 minutes, and then ultrasonically disperse for 10-20 minutes to form a uniform milky white dispersion; S2. Add meta-aramid, the first modified organophosphorus flame retardant, the first modified silicone rubber, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, carboxyl-terminated nitrile rubber, ultra-high molecular weight polyethylene powder, antioxidant, dicyclohexylcarbodiimide and 4-dimethylaminopyridine to the above dispersion, raise the temperature to 80-90° C., stir and react for 5-7 hours to form a preliminary polymer system; S3. After the blending reaction is completed, the temperature is lowered to 60°C, and the third modified organophosphorus flame retardant, the third modified silicone rubber, the amino silicone oil microemulsion, the organofluorine waterproofing agent, and the chitosan quaternary ammonium salt are added to the system in sequence. The reaction is continued for 1-2 hours, and then cooling water is introduced to cool the system to 25°C. Citric acid is added dropwise to adjust the pH value of the system to 6-7; S4. The post-treated material is filtered through a filter and transferred to a degassing tank. It is degassed under vacuum for 2 hours to obtain a uniform, bubble-free spinning solution. The spinning solution is transported to the spinning equipment and extruded through a spinneret. The spinneret stream vertically enters the coagulation bath to complete the coagulation process. The formed nascent fibers immediately enter a multi-stage countercurrent washing device for cleaning; then they are stretched and finally dried at 105°C for 3 hours to obtain a composite flame-retardant fabric.

8. The method for preparing a composite flame-retardant fabric according to claim 7, characterized in that: In the step S1, the stirring speed is 300 r / min; in the step S2, the heating rate is 2°C / min, and the stirring speed is 400-500 r / min.

9. The method for preparing a composite flame-retardant fabric according to claim 7, characterized in that: In the S4 step, the material is filtered through a 200-mesh stainless steel filter; the vacuum degree during the degassing process is -0.09 MPa; the coagulation bath is an 18 wt.% sodium chloride aqueous solution at 15° C., and the spun fiber passes through the coagulation bath at a speed of 8 m / min; the water washing temperature is maintained at 60° C., and the total washing time is 10 min; and the fiber is stretched at a draw ratio of 3.5 times.

10. An application of the composite flame-retardant fabric according to any one of claims 1 to 9, characterized in that: The fabric is at least applied to clothes, hats, curtains and sofa covers.

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