Antibacterial waterproof flame-retardant composite material, preparation method and application of antibacterial waterproof flame-retardant composite material in tent

Abstract

The invention relates to the technical field of composite materials, in particular to an antibacterial waterproof flame-retardant composite material, a preparation method and application of the antibacterial waterproof flame-retardant composite material in tents. The antibacterial waterproof flame-retardant composite material is prepared from the following raw materials in parts by weight: 50 to 100 parts of polyurethane, 1 to 4 parts of lubricant, 1 to 4 parts of compatilizer, 2 to 5 parts of sorbitol oleate polyoxyethylene ether, 15 to 25 parts of filler and 8 to 12 parts of functional additive. The antibacterial waterproof flame-retardant composite material prepared by the invention is applied to a tent, not only has better flame retardance and waterproof performance improvement, but also can adapt to various complex outdoor environments due to the flame retardance, the risk of fire disasters is reduced, the tent can be kept dry under severe weather conditions, and the service life of the tent is prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of composite materials, and in particular to an antibacterial, waterproof and flame-retardant composite material, a preparation method and application thereof in tents. Background Art

[0002] With the popularity of outdoor activities and adventure tourism, tents, as basic outdoor equipment, have increasingly higher performance requirements. Although traditional tent materials are light and easy to build, they have limitations in terms of waterproofing, flame retardancy and antibacterial properties. Rainwater penetration, fire hazards, and the growth of bacteria and mold are common risks in outdoor activities. Therefore, the development of a composite material that combines waterproofing, flame retardancy and antibacterial properties is crucial to improving the safety and comfort of tents.

[0003] Antibacterial, waterproof and flame-retardant composite materials are usually composed of base materials (such as polymers), antibacterial agents, waterproof agents and flame retardants. The base material provides the basic physical properties of the composite material, while the additives give the material specific functions. Antibacterial agents can inhibit the growth of bacteria, mold and algae, and keep the inside of the tent clean; waterproof agents can reduce the surface tension of the material, making it impossible for water droplets to spread on the surface of the material, thereby improving the waterproof performance of the tent; flame retardants can slow down or prevent the spread of flames, improving the fire safety of the tent.

[0004] In terms of preparation methods, the preparation of antibacterial, waterproof and flame-retardant composite materials usually involves mixing the matrix material with functional additives through melt blending, solution mixing or in-situ polymerization. The key is to ensure that the antibacterial agent, waterproof agent and flame retardant are evenly dispersed in the matrix material to achieve the best performance. In addition, the cost-effectiveness, environmental friendliness and durability of the material also need to be considered during the preparation process.

[0005] In tent applications, the use of antibacterial, waterproof and flame-retardant composite materials can significantly improve the performance of tents. This material not only provides better protection and reduces the risks of rain, fire and microbial contamination, but also extends the service life of the tent and improves its stability and reliability in various harsh environments. In addition, with the advancement of technology, this type of composite material is gradually developing in the direction of lightweight, multifunctional and intelligent to meet the needs of higher standards of outdoor equipment.

[0006] Chinese invention patent CN118325324B discloses a high heat-resistant composite material for outdoor tents and its preparation method. The high heat-resistant composite material for outdoor tents is made of the following raw materials: 75-85 parts of fluorosilicone thermoplastic polyurethane elastomer containing benzene rings, 15-25 parts of hyperbranched polyetherimide epoxy compound, 3-5 parts of 3,3'-diamino-4,4'-difluorodiphenyl sulfone, 1-3 parts of 9,9-bis(4-aminophenyl)fluorene, 2-4 parts of 3,5-diamino-1,2,4-triazole, 3-5 parts of 4,4-chloroformylphenyl ether, 2-4 parts of 2,6-pyridinedicarbonyl chloride, 2-4 parts of catalyst, 3-5 parts of coupling agent, 10-20 parts of filler, 0.8-1.5 parts of antioxidant, 1-2 parts of lubricant, 0.3-0.6 parts of compatibilizer, and 3-5 parts of environmentally friendly plasticizer. Although the composite material has high heat resistance, weather resistance and good mechanical properties, the raw materials are complex, difficult to obtain, and too expensive, and its waterproof and antibacterial properties are poor. Summary of the invention

[0007] In view of the above-mentioned deficiencies in the prior art, the present invention provides an antibacterial, waterproof and flame-retardant composite material, a preparation method and application thereof in a tent.

[0008] In order to solve the above technical problems, the technical solution adopted by the present invention is:

[0009] An antibacterial, waterproof and flame-retardant composite material is composed of the following raw materials in parts by weight: 50-100 parts by weight of polyurethane, 1-4 parts by weight of lubricant, 1-4 parts by weight of compatibilizer, 2-5 parts by weight of sorbitan oleate polyoxyethylene ether, 15-25 parts by weight of filler and 8-12 parts by weight of functional additive.

[0010] The lubricant is at least one of zinc stearate, ethylene bis stearamide and oleamide.

[0011] The compatibilizer is at least one of maleic anhydride, acrylic acid and polypropylene grafted maleic anhydride.

[0012] The filler is any one of titanium dioxide, lanthanum oxide, calcium carbonate, diatomaceous earth and wollastonite.

[0013] The performance of the antibacterial, waterproof and flame-retardant composite materials used in existing tents may gradually decline under long-term ultraviolet radiation, extreme climate conditions and frequent use, or the material surface may still be easily stained with stains and dust, affecting the appearance and cleaning, even if it has antibacterial properties. Therefore, it is necessary to add functional additives with better performance to the antibacterial, waterproof and flame-retardant tent composite materials, so as to achieve antibacterial, waterproof and flame-retardant properties, improve the service life of the tent, adapt to various complex outdoor environments, reduce the risk of fire, and ensure the safety of users.

[0014] The preparation method of the functional additive is as follows:

[0015] The silane-modified oligomer, bis(4-carboxyphenyl)phenylphosphine oxide, sodium hydroxide and solvent are mixed and heated, 1-allyl-3-methylimidazole chloride is added and the mixture is continuously stirred, triethylamine and N,N-dimethylformamide are added and heated for reaction to obtain a functional additive.

[0016] Titanium dioxide has high chemical stability and is not easy to react with other chemicals, which allows the tent material to maintain stable performance in various environments. It can be an effective ultraviolet (UV) absorber, which can absorb and scatter ultraviolet rays, protect the tent material from UV degradation, and extend the service life of the tent; at the same time, the photocatalytic properties of titanium dioxide can also produce active oxygen species, which can kill or inhibit the growth of bacteria, mold and algae, and provide antibacterial effects. Therefore, using titanium dioxide as a filler is the best choice.

[0017] In the present invention, the addition of functional additives can effectively improve the flame retardant and waterproof properties of the tent. In terms of flame retardant properties: the silane-modified oligomer and bis(4-carboxyphenyl)phenylphosphine oxide in the functional additives can quickly form a stable carbon layer at high temperature as flame retardants, isolate oxygen and heat, decompose to produce phosphoric acid during combustion, catalyze carbonization reaction, form a dense carbon layer, effectively protect the tent material from being penetrated by flames, and slow down the thermal decomposition rate of the material. The addition of 1-allyl-3-methylimidazole chloride can reduce the heat release rate of the material and reduce the heat generated during combustion, thereby reducing the risk of fire, thereby improving the flame retardant properties of the tent. In terms of waterproof properties: the addition of perfluoropolyether carboxylic acid and silane coupling agent can change the surface properties of the material, increase the surface energy, and make it difficult for water molecules to spread on the surface of the material. Through the grafting modification of the silane coupling agent, the binding force between the hydrophobic layer and the base material is enhanced. The acryloxy group in the silane coupling agent reacts with the hydroxyl group on the surface of the material to form a hydrophobic layer, which enhances the waterproof performance of the tent, the durability of the waterproof layer and the water washability.

[0018] Preferably, the preparation method of the functional additive is as follows:

[0019] Mixing perfluoropolyether carboxylic acid and hydrofluoroether and stirring; then adding oxalyl chloride and heating to react; then adding N,N-dimethylformamide and silane coupling agent and stirring at room temperature to obtain silane-modified oligomer;

[0020] Mix bis(4-carboxyphenyl)phenylphosphine oxide, sodium hydroxide and a solvent, heat and stir to react, then add 1-allyl-3-methylimidazole chloride, continue stirring to obtain a flame retardant;

[0021] The silane-modified oligomer, the flame retardant, triethylamine and N,N-dimethylformamide are heated to react to obtain a functional additive.

[0022] Specific reaction mechanism: S1: Mix perfluoropolyether carboxylic acid and solvent hydrofluoroether to form a uniform solution, add oxalyl chloride (an acylating agent) to the above solution, and at 50-70°C, oxalyl chloride and perfluoropolyether carboxylic acid undergo acylation reaction to form an amide bond, and remove the reaction solvent hydrofluoroether by reduced pressure distillation to obtain an intermediate product, and then add a silane coupling agent to the reaction system, which can react with the terminal groups of perfluoropolyether carboxylic acid to form a silane-modified oligomer.

[0023] S2: Bis(4-carboxyphenyl)phenylphosphine oxide is reacted with sodium hydroxide to form a salt, and 1-allyl-3-methylimidazole chloride is added as a cross-linking agent to react with the salt to form a compound with a flame retardant effect.

[0024] S3: Mix the silane-modified oligomer and the flame retardant to form a uniform solution, use triethylamine as a catalyst to promote the reaction between the silane-modified oligomer and the flame retardant, and dry to obtain the final functional additive.

[0025] In the above mechanism, the silane coupling agent plays a key bridging role in the preparation process. The active groups it contains (such as acryloxy, carboxyl allylamide, triethoxysilyl, etc.) can react with the corresponding groups in perfluoropolyether carboxylic acid and flame retardant to form stable chemical bonds. This modification not only improves the surface properties of the material, such as water resistance and flame retardancy, but also enhances the mechanical properties and durability of the material.

[0026] The functional additive prepared by the present invention can give the composite material excellent waterproof and flame retardant properties while maintaining other physical properties of the material, which is very important for improving the performance of outdoor equipment such as tents.

[0027] Furthermore, the preparation method of the functional additive is as follows:

[0028] S1, 15-30 parts by weight of perfluoropolyether carboxylic acid and 40-70 parts by weight of hydrofluoroether are mixed, and stirred at 300-500 rpm for 5-15 min; then 1-3 parts by weight of oxalyl chloride are added, and the mixture is reacted at 50-70° C. and 200-400 rpm for 8-15 h, and the hydrofluoroether solvent is removed by reduced pressure distillation; then 40-80 parts by weight of N,N-dimethylformamide and 8-12 parts by weight of silane coupling agent are added, and the mixture is stirred at room temperature and 400-800 rpm for 8-15 h; the N,N-dimethylformamide solvent is removed by reduced pressure distillation to obtain a silane-modified oligomer;

[0029] S2, 8-14 parts by weight of bis(4-carboxyphenyl)phenylphosphine oxide, 1-3 parts by weight of sodium hydroxide, 10-30 parts by weight of water and 30-60 parts by weight of N,N-dimethylformamide are mixed, and the mixture is stirred at 50-70° C. and 400-800 rpm for 3-6 hours, and then 5-10 parts by weight of 1-allyl-3-methylimidazole chloride are added, and stirring is continued for 4-8 hours, the organic phase is separated, and water is removed by rotary evaporation to obtain a flame retardant;

[0030] S3. React 16-26 parts by weight of the above-mentioned silane-modified oligomer, 8-14 parts by weight of the above-mentioned flame retardant, 0.2-1 parts by weight of triethylamine and 60-120 parts by weight of N,N-dimethylformamide at 50-70° C. and 300-500 rpm for 1-4 hours, distill under reduced pressure, and dry to obtain a functional additive.

[0031] The silane coupling agent is any one of N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, 3-[3-carboxyallylamide]propyltriethoxysilane, and [3-(triethoxysilyl)propyl]carbamic acid 2-propynyl ester.

[0032] The preparation method of the antibacterial, waterproof and flame-retardant composite material comprises the following steps: putting polyurethane, lubricant, compatibilizer, sorbitan oleate polyoxyethylene ether, filler and functional additive into an internal mixer, mixing at 140-180°C for 8-15 minutes, extruding and granulating to obtain the antibacterial, waterproof and flame-retardant composite material.

[0033] Application of the antibacterial, waterproof and flame-retardant composite material in tents.

[0034] Beneficial effects of the present invention:

[0035] The present invention provides an antibacterial, waterproof and flame-retardant composite material, a preparation method and application thereof in a tent. When applied in a tent, the composite material not only has better flame retardant and waterproof performance, but also has flame retardant performance that enables it to adapt to various complex outdoor environments, reduces the risk of fire, and ensures the safety of users. The improved waterproof performance enables the tent to remain dry even in adverse weather conditions, thereby extending the service life of the tent. The preparation method of the present invention is simple, the raw materials are readily available, the cost is low, and it is suitable for wide promotion. DETAILED DESCRIPTION

[0036] The above content of the present invention is further described in detail below in conjunction with specific implementation modes, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following embodiments.

[0037] Introduction of some raw materials in this application:

[0038] Polyurethane was purchased from Sansheng Trading Co., Ltd., Shunde District, Foshan City, model PU3109.

[0039] Polypropylene grafted with maleic anhydride was purchased from Shanghai Yisufa New Materials Co., Ltd. with the brand number QB516.

[0040] Sorbitol oleate polyoxyethylene ether was purchased from Hai'an Petrochemical Plant, Jiangsu Province, with the item number T-85.

[0041] Perfluoropolyether carboxylic acid was purchased from Shanghai MacLean Biochemical Technology Co., Ltd., with a molecular weight of 3000 g / mol.

[0042] Example 1

[0043] The antibacterial, waterproof and flame-retardant composite material is composed of the following raw materials in parts by weight: 70 parts by weight of polyurethane, 2 parts by weight of zinc stearate, 2 parts by weight of polypropylene grafted maleic anhydride, 3 parts by weight of sorbitan oleate polyoxyethylene ether, 17 parts by weight of titanium dioxide and 10 parts by weight of functional additives.

[0044] The preparation method of the functional additive is as follows:

[0045] S1, 20 parts by weight of perfluoropolyether carboxylic acid and 50 parts by weight of hydrofluoroether are mixed, and stirred at 400 rpm for 10 min; then 2 parts by weight of oxalyl chloride are added, and the mixture is reacted at 60° C. and 300 rpm for 10 h, and the hydrofluoroether solvent is removed by distillation under reduced pressure; then 50 parts by weight of N,N-dimethylformamide and 10 parts by weight of N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane are added, and the mixture is stirred at room temperature and 600 rpm for 12 h; the N,N-dimethylformamide solvent is removed by distillation under reduced pressure to obtain a silane-modified oligomer;

[0046] S2, 10 parts by weight of bis(4-carboxyphenyl)phenylphosphine oxide, 2 parts by weight of sodium hydroxide, 20 parts by weight of water and 40 parts by weight of N,N-dimethylformamide were mixed, stirred at 60°C and 600 rpm for 4 hours, and then 8 parts by weight of 1-allyl-3-methylimidazole chloride were added, and stirring was continued for 6 hours, the organic phase was separated, and water was removed by rotary evaporation to obtain a flame retardant;

[0047] S3. React 20 parts by weight of the above-mentioned silane-modified oligomer, 10 parts by weight of the above-mentioned flame retardant, 0.5 parts by weight of triethylamine and 80 parts by weight of N,N-dimethylformamide at 60° C. and 400 rpm for 2 hours, distill under reduced pressure, and dry to obtain a functional additive.

[0048] The preparation method of the antibacterial, waterproof and flame-retardant composite material comprises the following steps: putting polyurethane, lubricant, compatibilizer, sorbitan oleate polyoxyethylene ether, filler and functional additive into an internal mixer, performing internal mixing at 160° C. for 10 minutes, and extruding and granulating to obtain the antibacterial, waterproof and flame-retardant composite material.

[0049] Example 2

[0050] The antibacterial, waterproof and flame-retardant composite material is composed of the following raw materials in parts by weight: 50 parts by weight of polyurethane, 1 part by weight of zinc stearate, 1 part by weight of polypropylene grafted maleic anhydride, 2 parts by weight of sorbitan oleate polyoxyethylene ether, 15 parts by weight of titanium dioxide and 8 parts by weight of functional additives.

[0051] The preparation method of the functional additive is as follows:

[0052] S1, 15 parts by weight of perfluoropolyether carboxylic acid and 40 parts by weight of hydrofluoroether are mixed, and stirred at 300 rpm for 5 min; then 1 part by weight of oxalyl chloride is added, and the mixture is reacted at 50° C. and 200 rpm for 8 h, and the hydrofluoroether solvent is removed by distillation under reduced pressure; then 40 parts by weight of N,N-dimethylformamide and 8 parts by weight of N-(3-acryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane are added, and the mixture is stirred at room temperature and 400 rpm for 8 h; the N,N-dimethylformamide solvent is removed by distillation under reduced pressure to obtain a silane-modified oligomer;

[0053] S2, 8 parts by weight of bis(4-carboxyphenyl)phenylphosphine oxide, 1 part by weight of sodium hydroxide, 10 parts by weight of water and 30 parts by weight of N,N-dimethylformamide were mixed, stirred at 50°C and 400rpm for 3h, and then 5 parts by weight of 1-allyl-3-methylimidazole chloride were added, and stirring was continued for 4h, the organic phase was separated, and water was removed by rotary evaporation to obtain a flame retardant;

[0054] S3. React 16 parts by weight of the above-mentioned silane-modified oligomer, 8 parts by weight of the above-mentioned flame retardant, 0.2 parts by weight of triethylamine and 60 parts by weight of N,N-dimethylformamide at 50° C. and 300 rpm for 1 hour, distill under reduced pressure, and dry to obtain a functional additive.

[0055] The preparation method of the antibacterial, waterproof and flame-retardant composite material comprises the following steps: putting polyurethane, lubricant, compatibilizer, sorbitan oleate polyoxyethylene ether, filler and functional additive into an internal mixer, performing internal mixing at 140° C. for 8 minutes, and extruding and granulating to obtain the antibacterial, waterproof and flame-retardant composite material.

[0056] Example 3

[0057] The antibacterial, waterproof and flame-retardant composite material is composed of the following raw materials in parts by weight: 100 parts by weight of polyurethane, 4 parts by weight of zinc stearate, 4 parts by weight of polypropylene grafted maleic anhydride, 5 parts by weight of sorbitan oleate polyoxyethylene ether, 25 parts by weight of titanium dioxide and 12 parts by weight of functional additives.

[0058] The preparation method of the functional additive is as follows:

[0059] S1, 30 parts by weight of perfluoropolyether carboxylic acid and 70 parts by weight of hydrofluoroether are mixed, and stirred at 500 rpm for 15 min; then 3 parts by weight of oxalyl chloride are added, and the mixture is reacted at 70° C. and 400 rpm for 15 h, and the hydrofluoroether solvent is removed by distillation under reduced pressure; then 80 parts by weight of N,N-dimethylformamide and 12 parts by weight of N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane are added, and the mixture is stirred at room temperature and 800 rpm for 15 h; the N,N-dimethylformamide solvent is removed by distillation under reduced pressure to obtain a silane-modified oligomer;

[0060] S2, 14 parts by weight of bis(4-carboxyphenyl)phenylphosphine oxide, 3 parts by weight of sodium hydroxide, 30 parts by weight of water and 60 parts by weight of N,N-dimethylformamide were mixed, stirred at 70°C and 800 rpm for 6 hours, and then 10 parts by weight of 1-allyl-3-methylimidazole chloride were added, and stirring was continued for 8 hours, the organic phase was separated, and water was removed by rotary evaporation to obtain a flame retardant;

[0061] S3. React 26 parts by weight of the above-mentioned silane-modified oligomer, 14 parts by weight of the above-mentioned flame retardant, 1 part by weight of triethylamine and 120 parts by weight of N,N-dimethylformamide at 70° C. and 500 rpm for 4 hours, distill under reduced pressure, and dry to obtain a functional additive.

[0062] The preparation method of the antibacterial, waterproof and flame-retardant composite material comprises the following steps: putting polyurethane, lubricant, compatibilizer, sorbitan oleate polyoxyethylene ether, filler and functional additive into an internal mixer, performing internal mixing at 180° C. for 15 minutes, and extruding and granulating to obtain the antibacterial, waterproof and flame-retardant composite material.

[0063] Comparative Example 1

[0064] The antibacterial, waterproof and flame-retardant composite material is composed of the following raw materials in parts by weight: 70 parts by weight of polyurethane, 2 parts by weight of zinc stearate, 2 parts by weight of polypropylene grafted maleic anhydride, 3 parts by weight of sorbitan oleate polyoxyethylene ether, 17 parts by weight of titanium dioxide and 10 parts by weight of functional additives.

[0065] The preparation method of the functional additive is as follows:

[0066] S1, 10 parts by weight of bis(4-carboxyphenyl)phenylphosphine oxide, 2 parts by weight of sodium hydroxide, 20 parts by weight of water and 40 parts by weight of N,N-dimethylformamide were mixed, stirred at 60°C and 600 rpm for 4 hours, then 8 parts by weight of 1-allyl-3-methylimidazole chloride were added, stirring was continued for 6 hours, the organic phase was separated, and water was removed by rotary evaporation to obtain a flame retardant;

[0067] S2. React 20 parts by weight of N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, 10 parts by weight of the above flame retardant, 0.5 parts by weight of triethylamine and 80 parts by weight of N,N-dimethylformamide at 60°C and 400 rpm for 2 hours, distill under reduced pressure, and dry to obtain a functional additive.

[0068] The preparation method of the antibacterial, waterproof and flame-retardant composite material comprises the following steps: putting polyurethane, lubricant, compatibilizer, sorbitan oleate polyoxyethylene ether, filler and functional additive into an internal mixer, performing internal mixing at 160° C. for 10 minutes, and extruding and granulating to obtain the antibacterial, waterproof and flame-retardant composite material.

[0069] Comparative Example 2

[0070] The antibacterial, waterproof and flame-retardant composite material is composed of the following raw materials in parts by weight: 70 parts by weight of polyurethane, 2 parts by weight of zinc stearate, 2 parts by weight of polypropylene grafted maleic anhydride, 3 parts by weight of sorbitan oleate polyoxyethylene ether, 17 parts by weight of titanium dioxide and 10 parts by weight of functional additives.

[0071] The preparation method of the functional additive is as follows:

[0072] S1, 20 parts by weight of perfluoropolyether carboxylic acid and 50 parts by weight of hydrofluoroether are mixed, and stirred at 400 rpm for 10 min; then 2 parts by weight of oxalyl chloride are added, and the mixture is reacted at 60° C. and 300 rpm for 10 h, and the hydrofluoroether solvent is removed by distillation under reduced pressure; then 50 parts by weight of N,N-dimethylformamide and 10 parts by weight of 3-[3-carboxyallylamide]propyltriethoxysilane are added, and the mixture is stirred at room temperature and 600 rpm for 12 h; the N,N-dimethylformamide solvent is removed by distillation under reduced pressure to obtain a silane-modified oligomer;

[0073] S2, 10 parts by weight of bis(4-carboxyphenyl)phenylphosphine oxide, 2 parts by weight of sodium hydroxide, 20 parts by weight of water and 40 parts by weight of N,N-dimethylformamide were mixed, stirred at 60°C and 600 rpm for 4 hours, and then 8 parts by weight of 1-allyl-3-methylimidazole chloride were added, and stirring was continued for 6 hours, the organic phase was separated, and water was removed by rotary evaporation to obtain a flame retardant;

[0074] S3. React 20 parts by weight of the above-mentioned silane-modified oligomer, 10 parts by weight of the above-mentioned flame retardant, 0.5 parts by weight of triethylamine and 80 parts by weight of N,N-dimethylformamide at 60° C. and 400 rpm for 2 hours, distill under reduced pressure, and dry to obtain a functional additive.

[0075] The preparation method of the antibacterial, waterproof and flame-retardant composite material comprises the following steps: putting polyurethane, lubricant, compatibilizer, sorbitan oleate polyoxyethylene ether, filler and functional additive into an internal mixer, performing internal mixing at 160° C. for 10 minutes, and extruding and granulating to obtain the antibacterial, waterproof and flame-retardant composite material.

[0076] Comparative Example 3

[0077] The antibacterial, waterproof and flame-retardant composite material is composed of the following raw materials in parts by weight: 70 parts by weight of polyurethane, 2 parts by weight of zinc stearate, 2 parts by weight of polypropylene grafted maleic anhydride, 3 parts by weight of sorbitan oleate polyoxyethylene ether, 17 parts by weight of titanium dioxide and 10 parts by weight of functional additives.

[0078] The preparation method of the functional additive is as follows:

[0079] S1, 20 parts by weight of perfluoropolyether carboxylic acid and 50 parts by weight of hydrofluoroether are mixed, and stirred at 400 rpm for 10 min; then 2 parts by weight of oxalyl chloride are added, and the mixture is reacted at 60° C. and 300 rpm for 10 h, and the hydrofluoroether solvent is removed by distillation under reduced pressure; then 50 parts by weight of N,N-dimethylformamide and 10 parts by weight of N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane are added, and the mixture is stirred at room temperature and 600 rpm for 12 h; the N,N-dimethylformamide solvent is removed by distillation under reduced pressure to obtain a silane-modified oligomer;

[0080] S2. React 20 parts by weight of the above-mentioned silane-modified oligomer, 10 parts by weight of bis(4-carboxyphenyl)phenylphosphine oxide, 0.5 parts by weight of triethylamine and 80 parts by weight of N,N-dimethylformamide at 60° C. and 400 rpm for 2 hours, distill under reduced pressure, and dry to obtain a functional additive.

[0081] The preparation method of the antibacterial, waterproof and flame-retardant composite material comprises the following steps: putting polyurethane, lubricant, compatibilizer, sorbitan oleate polyoxyethylene ether, filler and functional additive into an internal mixer, performing internal mixing at 160° C. for 10 minutes, and extruding and granulating to obtain the antibacterial, waterproof and flame-retardant composite material.

[0082] Test Example 1

[0083] Oxygen index test: Adopt the national standard GB / T2406.2-2009 "Plastic Oxygen Index Method Determination"

[0084] Burning behavior Part 2: Room temperature test》Method A was used for testing; Sample shape: Type II. Before the test, the antibacterial, waterproof and flame-retardant composite material was conditioned at a temperature of 23°C and a humidity of 50% for 90 h. The test sample had a length of 100 mm, a width of 10 mm and a thickness of 10 mm. Six parallel groups were used to take the average value. The test results are shown in Table 1.

[0085] Table 1 Flame retardancy test results of antibacterial, waterproof and flame retardant composite materials

[0086] Oxygen index (%) Example 1 35.8 Example 2 32.7 Example 3 33.6 Comparative Example 1 28.1 Comparative Example 2 31.6 Comparative Example 3 25.7

[0087] Test Example 2

[0088] Water contact angle test: The prepared antibacterial, waterproof and flame-retardant composite material was fixed on a glass slide by double-sided tape. 5 μL of water was measured at five locations of each sample at room temperature using a contact angle meter (Powereach JC2000D1) and the water contact angle was obtained by calculating the average value. The results are shown in Table 2.

[0089] Table 2 Waterproof performance test of antibacterial, waterproof and flame retardant composite materials

[0090] Water contact angle Example 1 153.8° Example 2 148.2° Example 3 150.1° Comparative Example 1 63.2° Comparative Example 2 139.1° Comparative Example 3 131.6°

[0091] From the above results, it can be seen that the antibacterial, waterproof and flame-retardant composite material prepared by the present invention has good flame-retardant and waterproof effects, and also has antibacterial effects, and can be widely used in tent materials to extend the service life of the tent and enable it to adapt to various complex outdoor environments.

[0092] Comparing the results of Example 1 with Comparative Examples 1 and 3, it can be seen that the addition of functional additives significantly improves the flame retardant and waterproof properties of the tent material. The silane-modified oligomer and bis(4-carboxylphenyl)phenylphosphine oxide in the functional additives are flame retardants, organic flame retardants, containing phosphorus heterocycles and amino groups. During the combustion of the matrix, the phosphorus heterocycles will generate acidic substances such as phosphoric acid and phosphorous acid, promote the carbonization of the matrix, and prevent the combustion reaction from proceeding. The PO· free radicals generated during the combustion process can capture ·OH and H· free radicals in the flame, interrupt the combustion chain reaction, and reduce the heat released by the combustion. At the same time, a large amount of nitrogen-containing non-combustible gas will be generated, which can isolate oxygen and heat, effectively dilute the concentration of oxygen in the combustion system, prevent the flame from penetrating the material, and further improve the flame retardant effect. The silicon element introduced during the reaction process can further increase the density of the carbon layer. The carbon layer will also further stably decompose during the combustion process, slowing down the thermal decomposition rate of the material. At the same time, the addition of 1-allyl-3-methylimidazole chloride helps the material reduce the heat release rate during combustion, reduces the heat generated during combustion, further reduces the risk of fire, and effectively improves the flame retardant properties of the tent material as a whole. In addition, the introduction of perfluoropolyether carboxylic acid and silane coupling agent improves the hydrophobicity of the material by reducing the surface energy of the material, making it difficult for water molecules to spread on the surface of the material. The acryloxy group in the silane coupling agent can react with the hydroxyl group on the surface of the substrate to form a stable chemical bond, enhancing the bonding force between the waterproof layer and the substrate, thereby improving the durability and washability of the waterproof layer. This modification gives the tent material a more durable waterproof performance in complex outdoor environments.

[0093] Comparing the results of Example 1 and Comparative Example 2, it can be seen that the use of N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane significantly improves the waterproof effect, compared with 3-[3-carboxyallyl amide] propyl triethoxysilane. The reason is that the acryloxy group in N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane has a high reactivity and can undergo a cross-linking reaction with hydroxyl groups or other active groups on the surface of the material to form a stable chemical bond. This high reactivity helps to generate a uniform and dense waterproof layer on the surface of the material, thereby enhancing the waterproof performance. In addition, the molecular structure of N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane contains multiple reactive functional groups: acryloxy, hydroxyl and amino. These multi-functional group characteristics enable it to form a strong chemical bond with different substrates, enhancing the adhesion and stability between the waterproof layer and the substrate.

Claims

1. An antibacterial, waterproof and flame-retardant composite material, characterized in that: The invention is composed of the following raw materials in parts by weight: 50-100 parts by weight of polyurethane, 1-4 parts by weight of lubricant, 1-4 parts by weight of compatibilizer, 2-5 parts by weight of sorbitol oleate polyoxyethylene ether, 15-25 parts by weight of filler and 8-12 parts by weight of functional additive.

2. The antibacterial, waterproof and flame-retardant composite material according to claim 1, characterized in that: The lubricant is at least one of zinc stearate, ethylene bis stearamide and oleamide.

3. The antibacterial, waterproof and flame-retardant composite material according to claim 1, characterized in that: The compatibilizer is at least one of maleic anhydride, acrylic acid and polypropylene grafted maleic anhydride.

4. The antibacterial, waterproof and flame-retardant composite material according to claim 1, characterized in that: The filler is any one of titanium dioxide, lanthanum oxide, calcium carbonate, diatomaceous earth and wollastonite.

5. The antibacterial, waterproof and flame-retardant composite material according to claim 1, characterized in that: The preparation method of the functional additive is as follows: The silane-modified oligomer, bis(4-carboxyphenyl)phenylphosphine oxide, sodium hydroxide and solvent are mixed and heated, 1-allyl-3-methylimidazole chloride is added and the mixture is continuously stirred, triethylamine and N,N-dimethylformamide are added and heated for reaction to obtain a functional additive.

6. The antibacterial, waterproof and flame-retardant composite material according to claim 5, characterized in that: The preparation method of the functional additive is as follows: Mixing perfluoropolyether carboxylic acid and hydrofluoroether and stirring; then adding oxalyl chloride and heating to react; then adding N,N-dimethylformamide and silane coupling agent and stirring at room temperature to obtain silane-modified oligomer; Mix bis(4-carboxyphenyl)phenylphosphine oxide, sodium hydroxide and a solvent, heat and stir to react, then add 1-allyl-3-methylimidazole chloride, continue stirring to obtain a flame retardant; The silane-modified oligomer, the flame retardant, triethylamine and N,N-dimethylformamide are heated to react to obtain a functional additive.

7. The antibacterial, waterproof and flame-retardant composite material according to claim 6, characterized in that: The silane coupling agent is any one of N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, 3-[3-carboxyallylamide]propyltriethoxysilane, and [3-(triethoxysilyl)propyl]carbamic acid 2-propynyl ester.

8. The antibacterial, waterproof and flame-retardant composite material according to claim 6, characterized in that: The solvent consists of water and N,N-dimethylformamide.

9. The method for preparing the antibacterial, waterproof and flame-retardant composite material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: putting polyurethane, lubricant, compatibilizer, sorbitol oleate polyoxyethylene ether, filler and functional additive into an internal mixer for internal mixing, and extruding and granulating to obtain the antibacterial, waterproof and flame-retardant composite material.

10. Use of the antibacterial, waterproof and flame-retardant composite material according to any one of claims 1 to 8 in a tent.