Fluorocarbon modified phenolic melt-blown non-woven composite material for fire fighting and preparation

Abstract

The preparation method comprises the following steps: (1) under the action of an initiator, organic silicon resin and fluorine-containing acrylate are subjected to a free radical polymerization reaction and graft copolymerization, and fluorine-containing resin is obtained; (2) dispersing the prepared microcapsule fire extinguishing agent in fluorine-containing resin to obtain a fire extinguishing agent coating; and (3) coating and curing the fire extinguishing agent coating on the phenolic melt-blown non-woven composite material to obtain the fluorocarbon modified phenolic melt-blown non-woven composite material. According to the microcapsule fire extinguishing agent, gelatin and Arabic gum are subjected to complex coacervation to form a capsule wall, a fluorocarbon surfactant, a hydrocarbon surfactant and other materials are compounded to serve as a capsule core, when a fire disaster occurs, a fire extinguishing agent microcapsule is heated to be broken or decomposed, an efficient fluorocarbon fire extinguishing agent is released, and a good fire extinguishing effect is achieved. The fluorocarbon modified phenolic melt-blown non-woven composite material is expected to provide more reliable guarantee for fire safety, and has wide application prospects and important social significance.

Description

Technical Field

[0001] The invention belongs to the field of fire-fighting extinguishing materials, and specifically relates to a fluorocarbon-modified phenolic melt-blown nonwoven composite material for fire-fighting extinguishing and a preparation method thereof. Background Art

[0002] With the rapid development of modern society, fire safety issues have received increasing attention. In many fields such as construction, transportation, and electronics, fires not only cause huge property losses, but also endanger people's lives. Therefore, the development of high-performance fire-fighting materials is crucial to preventing and controlling fires. Common types of fire-fighting materials on the market currently include flame retardants, fire-retardant coatings, and fire blankets. Flame retardants can improve the flame retardant properties of materials, but they are prone to toxicity and pollution, and the flame retardant effect gradually declines, while causing potential harm to human health and the environment. The coating of fire-retardant coatings provides fire protection functions. In actual applications, the adhesion and durability of the coating are difficult to guarantee, and it is prone to cracking, falling off, and other problems, which affect the fire protection effect. Fire blankets can be used to extinguish small fires, but their fire extinguishing capabilities are limited for complex fire scenes.

[0003] As a new type of functional material, phenolic melt-blown nonwoven material has shown certain application potential in the field of fire prevention due to its good thermal insulation performance, high specific surface area and unique fiber structure. Phenolic fiber itself has high heat resistance, is not easy to burn at high temperature, can prevent heat transfer to a certain extent, and provides a basic guarantee for fire prevention. Patent CN115947910A discloses a preparation method and application of silane-modified high-ortho-phenolic resin. The high-ortho-phenolic resin is modified by silanization, and a phenolic melt-blown nonwoven material with excellent thermal insulation performance is obtained through melt spinning, melt blowing and other processes.

[0004] Pure phenolic meltblown nonwoven materials still have some limitations in fire prevention and fire extinguishing. On the one hand, its own flame retardant properties are limited, and it may not be able to effectively prevent the spread of fire when facing a strong fire; on the other hand, it can only play a certain role in heat insulation and delaying combustion, lacks the ability to actively extinguish fires, and is difficult to meet the requirements of modern fire safety for efficient fire extinguishing. Summary of the invention

[0005] The invention discloses a phenolic melt-blown nonwoven composite material for fire extinguishing and a preparation method thereof. By coating a fluorine-containing resin and an easily degradable and highly efficient fluorocarbon microcapsule fire extinguishing agent on the surface of the phenolic melt-blown nonwoven material, the advantages of each component are fully utilized, which not only significantly improves the flame retardant performance of the material, but also gives it the ability of active fire extinguishing.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a fluorocarbon-modified phenolic melt-blown nonwoven composite material for fire extinguishing, comprising the following steps:

[0008] 1) dissolving the organosilicon resin in an anhydrous solvent, adding an initiator, controlling the temperature at 60-90° C. under an inert atmosphere and continuously stirring, adding a fluorinated acrylate dropwise to the mixed solution, maintaining the reaction temperature and continuing stirring for 3-8 hours after the addition is complete, cooling, purifying, and drying to obtain a fluorinated resin;

[0009] 2) dissolving the fluorine-containing resin in an organic solvent, controlling the temperature at 60-80° C., adding a microcapsule fire extinguishing agent, continuously stirring for 1-3 hours, and cooling to obtain a fire extinguishing agent coating;

[0010] 3) coating the fire extinguishing agent coating on the surface of the phenolic melt-blown nonwoven material and curing the coating to obtain a fluorocarbon-modified phenolic melt-blown nonwoven composite material.

[0011] Preferably, in step (1), the silicone resin is methylphenyl silicone resin; the fluorinated acrylate is perfluorobutylethyl acrylate; and the initiator is benzoyl peroxide.

[0012] Preferably, the mass ratio of perfluorobutyl ethyl acrylate to methylphenyl silicone resin is (1-3):1.

[0013] Preferably, in step (2), the mass ratio of the microcapsule fire extinguishing agent to the fluorine-containing resin is 1:(3-5).

[0014] As a preferred embodiment, the preparation of the microcapsule fire extinguishing agent comprises the following steps:

[0015] S1: completely dissolving the foam stabilizer in water, stirring continuously, adding hydrocarbon surfactant, preservative, flame retardant, antifreeze agent and fluorocarbon surfactant in sequence, adjusting the temperature to 50°C until the fluorocarbon surfactant is completely dissolved; cooling, diluting and stirring evenly to obtain a fluorocarbon fire extinguishing agent;

[0016] S2: Dissolve gelatin and gum arabic in water at 50-55°C, mix the two solutions evenly, add the fluorocarbon fire extinguishing agent dropwise thereto, stir, emulsify, and form a primary emulsion;

[0017] S3: Continue stirring, add acetic acid solution to the primary emulsion, adjust the pH value to 4.0-4.5, then add formaldehyde solution, continue stirring and reacting for 1-2 hours after the addition is complete, adjust the pH value to 7-8, dialyze, and dry to obtain a microcapsule fire extinguishing agent. Preferably, the mass ratio of gelatin to gum arabic in step S1 is 1:1.

[0018] Preferably, the raw material components of the fluorocarbon fire extinguishing agent, calculated on a mass basis of 100%, include: 2.5-3.5% fluorocarbon surfactant; 1.5-2.5% hydrocarbon surfactant; 1-2% foam stabilizer; 7-9% flame retardant; 12.5-17.5% antifreeze agent; 0.1-1% preservative; and the balance is water.

[0019] Furthermore, the fluorocarbon surfactant is a perfluorobutyl surfactant, specifically potassium perfluorobutyl sulfonate.

[0020] Furthermore, the hydrocarbon surfactant is sodium dodecylbenzene sulfonate.

[0021] Furthermore, the foam stabilizer is sodium carboxymethyl cellulose.

[0022] Furthermore, the flame retardant is diammonium phosphate.

[0023] Furthermore, the antifreeze agent is propylene glycol.

[0024] Furthermore, the preservative is sodium benzoate.

[0025] Preferably, the total mass of gelatin and gum arabic in step S2 is 5-10% of the fluorocarbon fire extinguishing agent.

[0026] Preferably, in step (3), the amount of the fire extinguishing agent coating relative to the phenolic melt-blown nonwoven material is 150-250 g / m 2 .

[0027] The present invention also provides a fluorocarbon modified phenolic melt-blown nonwoven composite material for fire extinguishing, which is prepared by the above-mentioned preparation method.

[0028] The bond energy of the Si-O bond in the main chain of the silicone resin can reach 452 kJ / mol. After phenyl modification, the temperature of 5% thermal weight loss is increased from 350°C to 450°C. When it encounters high temperature, it decomposes rapidly to generate a SiO glassy layer and a carbonized layer, forming a dense thermal insulation barrier to prevent heat transfer. In step (1) of the present technical solution, under the action of an initiator, the silicone resin and the fluorine-containing acrylate undergo free radical polymerization, and undergo grafting or copolymerization to form a fluorine-containing resin. The introduction of fluorine-containing groups further reduces the surface energy of the material, provides better hydrophobicity and chemical stability, and forms a dense protective film on the surface of the substrate to prevent oxygen from contacting the material, slowing down the combustion process and helping to prevent the spread of the fire.

[0029] When encountering a fire, the microcapsule fire extinguishing agent is ruptured or decomposed by heat, releasing the fire extinguishing agent. In step (2) of the present technical solution, the microcapsule fire extinguishing agent is evenly dispersed in the fluorine-containing resin. The film-forming property of the fluorine-containing resin can prevent the microcapsules from agglomerating, and a stable microcapsule fire extinguishing agent coating is formed under the interaction of the interface. As a fireproof material, the fluorine-containing resin and the microcapsule fire extinguishing agent have a synergistic effect. The fire extinguishing substance released by the microcapsule fire extinguishing agent forms a covering layer such as foam on the surface of the burning object, and acts together with the carbonized layer formed by the fluorine-containing resin to form a more effective isolation layer, which better prevents continuous combustion; on the other hand, the fluorine-containing resin decomposes at high temperature to produce active substances such as fluorine-containing free radicals, which capture the active hydrogen free radicals generated during the combustion process, thereby interrupting the combustion chain reaction and actively suppressing combustion.

[0030] In step (3) of the present technical solution, the fluorine-containing resin is used as a carrier to fix the microcapsule fire extinguishing agent on the surface of the phenolic melt-blown nonwoven material, so that the microcapsule fire extinguishing agent is evenly distributed on the surface of the phenolic melt-blown nonwoven material. The fluorocarbon surfactant and other ingredients therein can reduce the surface tension, so that the fire extinguishing agent can be better spread on the surface of the burning object and isolate oxygen.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) The present invention obtains a phenolic melt-blown nonwoven fire extinguishing material with excellent comprehensive performance by coating a fluorine-containing resin and an easily degradable and highly efficient fluorocarbon microcapsule fire extinguishing agent on the surface of a phenolic melt-blown nonwoven material. The material gives full play to the advantages of the fluorine-containing resin and the fluorocarbon microcapsule fire extinguishing agent, not only significantly improves the flame retardant properties of the material, but also has the ability to actively extinguish fires, can provide more reliable protection for fire safety, and has broad application prospects and important social significance.

[0033] (2) The present invention uses methylphenyl silicone resin and perfluorobutyl ethyl acrylate as main raw materials to react to obtain a fluorine-containing resin with excellent hydrophobicity and chemical stability. The fluorine-containing resin can form a dense protective film on the surface of the material to prevent oxygen from contacting the material and slow down the combustion process. At the same time, its low surface energy characteristics also help to prevent the spread of flames.

[0034] (3) A highly efficient fluorocarbon microcapsule fire extinguishing agent is provided, which is fixed on the surface of a phenolic melt-blown nonwoven material. When a fire occurs, the fire extinguishing agent microcapsules are ruptured or decomposed by heat, releasing highly efficient fluorocarbon fire extinguishing agent, thereby achieving a better fire extinguishing effect. DETAILED DESCRIPTION

[0035] The technical solution of the present invention will be clearly and completely described below 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. Unless otherwise stated, all technical and scientific terms used herein have the same meanings as those of ordinary skill in the art of the present invention generally understand. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which will be apparent to those skilled in the art.

[0036] The phenolic melt-blown nonwoven material used in the present invention is a melt-blown nonwoven material (thickness 3 mm) prepared according to Example 3 in patent CN118835389A; the methylphenyl silicone resin used in Examples 1-6 and Comparative Examples 1 and 2 is SH-9602 purchased from Hubei Longsheng Sihai New Materials Co., Ltd., and the methyl silicone resin used in Example 7 is methyl silicone resin SH-021 purchased from the same manufacturer.

[0037] Preparation of fluorocarbon fire extinguishing agent: taking 70% of the total water volume, adding 1-2% sodium carboxymethyl cellulose into the water at 150rpm, stirring until completely dissolved; then sequentially adding 1.5-2.5% sodium dodecylbenzene sulfonate, 0.1-1% sodium benzoate, 7-9% ammonium dihydrogen phosphate, 12.5-17.5% propylene glycol, stirring continuously for 15 minutes each time a raw material is added; finally adding 2.5-3.5% potassium perfluorobutyl sulfonate, heating to 50°C while stirring until the potassium perfluorobutyl sulfonate is completely dissolved; cooling to room temperature, adding the remaining water to make the total mass of the raw materials reach 100%; stirring for another 45 minutes to obtain the fluorocarbon fire extinguishing agent.

[0038] Preparation Example 1 of Microcapsule Fire Extinguishing Agent

[0039] Fluorocarbon fire extinguishing agent component content: 2.5% potassium perfluorobutyl sulfonate, 1.5% sodium dodecylbenzene sulfonate, 1% sodium carboxymethyl cellulose, 7% diammonium phosphate, 12.5% ​​propylene glycol, 0.1% sodium benzoate, and the balance is water.

[0040] 2.5 g of gelatin and 2.5 g of gum arabic were added to 25 mL of water respectively, stirred at 50°C until completely dissolved, and then the two solutions were mixed evenly, 100 g of fluorocarbon fire extinguishing agent was added dropwise thereto, stirred at 800 rpm for 20 min, and then stirred at 10000 rpm for emulsification for 10 min to form a primary emulsion;

[0041] Under stirring at 200 rpm, add 10 wt % acetic acid aqueous solution to the primary emulsion of step S1 to adjust the pH value to 4.0, then add 0.65 g 37 wt % formaldehyde aqueous solution while stirring, continue stirring and react for 1 hour after the addition is complete, then adjust the pH value to 7 with 5 wt % sodium hydroxide aqueous solution, spray dry, and obtain a microcapsule fire extinguishing agent.

[0042] Preparation Example 2 of Microcapsule Fire Extinguishing Agent

[0043] Fluorocarbon fire extinguishing agent component content: 3.5% potassium perfluorobutyl sulfonate, 2.5% sodium dodecylbenzene sulfonate, 2% sodium carboxymethyl cellulose, 9% diammonium phosphate, 17.5% propylene glycol, 1% sodium benzoate, and the balance is water.

[0044] 5 g of gelatin and 5 g of gum arabic were added to 50 mL of water respectively, stirred at 55°C until completely dissolved, and then the two solutions were mixed evenly, 100 g of fluorocarbon fire extinguishing agent was added dropwise thereto, stirred at 1000 rpm for 15 min, and then stirred at 12000 rpm for emulsification for 5 min to form a primary emulsion;

[0045] Under stirring at 200 rpm, add 10 wt % acetic acid aqueous solution to the primary emulsion of step S1 to adjust the pH value to 4.5, then add 1.5 g 37 wt % formaldehyde aqueous solution, stirring while adding, and continue stirring and reacting for 2 h after the addition is completed, then adjust the pH value to 8 with 5 wt % sodium hydroxide aqueous solution, spray dry, and obtain a microcapsule fire extinguishing agent.

[0046] Preparation Example 3 of Microcapsule Fire Extinguishing Agent

[0047] Fluorocarbon fire extinguishing agent component content: 3% potassium perfluorobutyl sulfonate, 1.5% sodium dodecylbenzene sulfonate, 1.5% sodium carboxymethyl cellulose, 8% diammonium phosphate, 15% propylene glycol, 0.5% sodium benzoate, and the balance is water.

[0048] 4 g of gelatin and 4 g of gum arabic were added to 40 mL of water respectively, stirred at 50°C until completely dissolved, and then the two solutions were mixed evenly, 100 g of fluorocarbon fire extinguishing agent was added dropwise thereto, stirred at 900 rpm for 15 min, and then stirred at 11000 rpm for emulsification for 7.5 min to form a primary emulsion;

[0049] Under stirring at 200 rpm, add 10 wt % acetic acid aqueous solution to the primary emulsion of step S1 to adjust the pH value to 4.5, then add 1 g of 37 wt % formaldehyde aqueous solution while stirring, continue stirring and react for 1.5 h after the addition is complete, then adjust the pH value to 7.5 with 5 wt % sodium hydroxide aqueous solution, spray dry, and obtain a microcapsule fire extinguishing agent.

[0050] Preparation Example 4 of Microcapsule Fire Extinguishing Agent

[0051] The preparation method and steps are the same as those in Preparation Example 3, except that the amount of gelatin and gum arabic are both 6 g.

[0052] Preparation Example 5 of Microcapsule Fire Extinguishing Agent

[0053] The preparation method and steps are the same as those of Preparation Example 3, except that an equal mass of gelatin is used instead of gum arabic.

[0054] Preparation Example 6 of Microcapsule Fire Extinguishing Agent

[0055] The preparation method and steps are the same as those of Preparation Example 3, except that the amount of sodium dodecylbenzenesulfonate used is 3%.

[0056] Example 1

[0057] The preparation method of the fluorocarbon modified phenolic melt-blown nonwoven composite material comprises the following steps:

[0058] (1) 100 g of methylphenyl silicone resin was added to a container, 500 mL of anhydrous tetrahydrofuran was poured in, and the methylphenyl silicone resin was stirred until it was dissolved, 0.5 g of initiator BPO was added thereto, and the stirring was continued. Then nitrogen was introduced to ensure that the reaction system was in an oxygen-free environment, the temperature was raised to 60° C., and 100 g of perfluorobutyl ethyl acrylate was added thereto dropwise. During the dropping process, the reaction temperature was kept stable at about 60° C. After the dropping was completed, the reaction temperature was maintained and the stirring reaction was continued for 8 h, and the reaction was cooled to room temperature, and the solvent was evaporated by heating, purified, and dried to obtain a fluorine-containing resin;

[0059] (2) 30 g of the microcapsule fire extinguishing agent obtained in Preparation Example 1 was dispersed in 150 mL of toluene to form a suspension, and 90 g of the fluorine-containing resin was dissolved in 200 mL of toluene and stirred until dissolved. Under stirring conditions of 60° C. and 250 rpm, the suspension of the microcapsule fire extinguishing agent was added to the solution of the fluorine-containing resin and stirred for 1 hour. After the reaction was completed, the solvent was removed and the mixture was cooled to room temperature to obtain a fire extinguishing agent coating;

[0060] (3) Apply the fire extinguishing agent coating of step (2) on the surface of the phenolic melt-blown nonwoven material (the amount is 150g / m 2 ), and cured at 120°C for 2h to obtain a fluorocarbon modified phenolic melt-blown nonwoven composite material.

[0061] Example 2

[0062] The preparation method of the fluorocarbon modified phenolic melt-blown nonwoven composite material comprises the following steps:

[0063] (1) 100 g of methylphenyl silicone resin was added to a container, 800 mL of anhydrous tetrahydrofuran was poured in, and the methylphenyl silicone resin was stirred until it was dissolved, 0.7 g of initiator BPO was added thereto, and the stirring was continued. Then nitrogen was introduced to ensure that the reaction system was in an oxygen-free environment, the temperature was raised to 80° C., and 300 g of perfluorobutyl ethyl acrylate was added thereto dropwise. During the addition, the reaction temperature was controlled to be stable at about 80° C. After the addition was completed, the reaction temperature was maintained and the stirring reaction was continued for 2 h, and the reaction was cooled to room temperature, and the solvent was heated to evaporate, purified, and dried to obtain a fluorine-containing resin;

[0064] (2) 30 g of the microcapsule fire extinguishing agent obtained in Preparation Example 2 was dispersed in 150 mL of toluene to form a suspension, and 150 g of the fluorine-containing resin was dissolved in 300 mL of toluene and stirred until dissolved. Under stirring conditions of 80° C. and 250 rpm, the suspension of the microcapsule fire extinguishing agent was added to the solution of the fluorine-containing resin and stirred for 3 h. After the reaction was completed, the solvent was removed and the mixture was cooled to room temperature to obtain a fire extinguishing agent coating;

[0065] (3) Apply the fire extinguishing agent coating of step (2) on the surface of the phenolic melt-blown nonwoven material (in an amount of 250 g / m 2 ), and cured at 120°C for 2h to obtain a phenolic melt-blown nonwoven composite material.

[0066] Example 3

[0067] The preparation method of the fluorocarbon modified phenolic melt-blown nonwoven composite material comprises the following steps:

[0068] (1) 100 g of methylphenyl silicone resin was added to a container, 700 mL of anhydrous tetrahydrofuran was poured in, and the methylphenyl silicone resin was stirred until it was dissolved, 0.6 g of initiator BPO was added thereto, and the stirring was continued. Then nitrogen was introduced to ensure that the reaction system was in an oxygen-free environment, the temperature was raised to 70° C., and 200 g of perfluorobutyl ethyl acrylate was added thereto dropwise. During the dropping process, the reaction temperature was controlled to be stable at about 70° C. After the dropping was completed, the reaction temperature was maintained and the stirring reaction was continued for 6 hours, and the reaction was cooled to room temperature, and the solvent was evaporated by heating, purified, and dried to obtain a fluorine-containing resin;

[0069] (2) 30 g of the microcapsule fire extinguishing agent obtained in Preparation Example 3 was dispersed in 150 mL of toluene to form a suspension, and 120 g of the fluorine-containing resin was dissolved in 200 mL of toluene and stirred until dissolved. The suspension of the microcapsule fire extinguishing agent was added to the solution of the fluorine-containing resin at 70° C. and 250 rpm, and the stirring was maintained for 2 h. After the reaction was completed, the solvent was removed and the mixture was cooled to room temperature to obtain a fire extinguishing agent coating;

[0070] (3) Apply the fire extinguishing agent coating of step (2) on the surface of the phenolic melt-blown nonwoven material (the amount is 200g / m 2), and cured at 120°C for 2h to obtain a phenolic melt-blown nonwoven composite material.

[0071] Example 4

[0072] The preparation method of the fluorocarbon modified phenolic melt-blown nonwoven composite material is the same as that of Example 3, except that the amount of perfluorobutyl ethyl acrylate used in step (1) is 85 g.

[0073] Example 5

[0074] The preparation method of the fluorocarbon modified phenolic melt-blown nonwoven composite material is the same as that of Example 3, except that the amount of perfluorobutyl ethyl acrylate used in step (1) is 320 g.

[0075] Example 6

[0076] The preparation method of the fluorocarbon modified phenolic melt-blown nonwoven composite material is the same as that of Example 3, except that the amount of the microcapsule fire extinguishing agent used in step (2) is 60 g.

[0077] Example 7

[0078] The preparation method of the fluorocarbon modified phenolic melt-blown nonwoven composite material is the same as that of Example 3, except that an equal mass of methyl silicone resin is used instead of methylphenyl silicone resin.

[0079] Comparative Example 1

[0080] A method for preparing a phenolic melt-blown nonwoven composite material without fluorine-containing resin loading comprises the following steps:

[0081] (1) 30 g of the microcapsule fire extinguishing agent obtained in Preparation Example 3 was dispersed in 150 mL of toluene to form a suspension, and 120 g of methylphenyl silicone resin was dissolved in 200 mL of toluene and stirred until dissolved. The suspension of the microcapsule fire extinguishing agent was added to the solution of the methylphenyl silicone resin at 70° C. and 250 rpm, and the stirring was maintained for 2 h. After the reaction was completed, the solvent was removed and the mixture was cooled to room temperature to obtain a fire extinguishing agent coating;

[0082] (2) Apply the fire extinguishing agent coating of step (2) on the surface of the phenolic melt-blown nonwoven material (in an amount of 200 g / m 2 ), and cured at 120°C for 2h to obtain a phenolic melt-blown nonwoven composite material.

[0083] Comparative Example 2

[0084] A method for preparing a phenolic melt-blown nonwoven composite material without microcapsules comprises the following steps:

[0085] (1) 100 g of methylphenyl silicone resin was added to a container, 700 mL of anhydrous tetrahydrofuran was poured in, and the methylphenyl silicone resin was stirred until it was dissolved, 0.6 g of initiator BPO was added thereto, and the stirring was continued. Then nitrogen was introduced to ensure that the reaction system was in an oxygen-free environment, the temperature was raised to 70° C., and 200 g of perfluorobutyl ethyl acrylate was added thereto dropwise. During the dropping process, the reaction temperature was controlled to be stable at about 70° C. After the dropping was completed, the reaction temperature was maintained and the stirring reaction was continued for 6 hours, and the reaction was cooled to room temperature, and the solvent was evaporated by heating, purified, and dried to obtain a fluorine-containing resin;

[0086] (3) Coating the fluorine-containing resin of step (1) on the surface of the phenolic melt-blown nonwoven material (in an amount of 200 g / m 2 ), and cured at 120°C for 2h to obtain a phenolic melt-blown nonwoven composite material.

[0087] Performance Testing

[0088] (1) Encapsulation rate: Take 10.0g (m0) of the microcapsule fire extinguishing agent samples of Preparation Examples 1-6 and put them into beakers respectively, add 50mL of deionized water, stir at room temperature for 2h to make the fire extinguishing agent fully dissolved in water; centrifuge and transfer the supernatant to another beaker; repeat the above extraction and separation operations 3 times, and combine all the supernatants. Use high performance liquid chromatography to determine the content of the fire extinguishing agent components in the supernatant, and calculate the total mass of the unencapsulated fire extinguishing agent (m1). Encapsulation rate (%) = 100% × (m0 × the sum of the mass fractions of the various components of the fluorocarbon fire extinguishing agent - m1) / m0 × the sum of the mass fractions of the various components of the fluorocarbon fire extinguishing agent. Each group was tested three times and the average value was taken.

[0089] (2) Stability: 5.0 g of each of the microcapsule fire extinguishing agents of Preparation Examples 1-6 were placed in beakers and placed in the following environments for 90 days: (1) Normal temperature and humidity environment: indoor environment at 25°C and relative humidity of 50%; (2) High temperature and high humidity environment: environment at 50°C and relative humidity of 80%; (3) Low temperature and dry environment: environment at -10°C and relative humidity of 30%; the encapsulation efficiency was tested according to the above method.

[0090] (3) Burst temperature: The burst temperature of the microcapsule fire extinguishing agent of Preparation Examples 1-6 was tested using TG.

[0091] The specific test results are shown in Table 1.

[0092]

[0093] Table 1

[0094] (4) Fire extinguishing performance: The phenolic melt-blown nonwoven composite materials prepared in each embodiment and comparative example were tested for fire extinguishing performance using an infrared thermometer. The flame size and sample height were fixed. The samples were attached to a perforated steel plate and placed downward at 1.5 cm from the outer flame. The flame temperature was about 800°C. One site was selected for each group of samples. Each group was tested three times. The time for the flame to go out was recorded and the average value was taken. The specific test results are shown in Table 2.

[0095]

[0096] Table 2

[0097] As shown in Table 1, the fire extinguishing agent microcapsules obtained in Preparation Examples 1-3 have a high encapsulation rate, excellent stability under different environments, and a rupture temperature of about 220° C. Compared with Preparation Example 3, the amount of raw materials used in Preparation Examples 4-6 was changed, which would affect the coating of the fire extinguishing agent components by the wall material, resulting in different degrees of decrease in the encapsulation rate and rupture temperature.

[0098] As shown in Table 2, the phenolic melt-blown nonwoven composite materials prepared in Examples 1-3 have excellent fire extinguishing effects. Compared with Example 3, the amount of perfluorobutyl ethyl acrylate used in Examples 4 and 5 exceeds the preferred range, which may change the internal structure and performance of the fluorine-containing resin, affect the flame retardancy, and prolong the flame extinguishing time; the content of the high-efficiency fluorocarbon microcapsule fire extinguishing agent in Example 6 changes, and the fire extinguishing effect becomes worse; the carbonization and thermal stability of the methyl silicone resin used in Example 7 are worse than those of the methylphenyl silicone resin, which reduces the flame retardancy of the fluorine-containing coating and worsens the fire extinguishing effect; in Comparative Example 1, methylphenyl silicone resin is used instead of fluorine-containing resin, and the flame retardancy of the fire extinguishing coating is reduced, and the fire extinguishing effect is worse; in Comparative Example 2, no fire extinguishing agent microcapsules are added, and it does not have the function of active fire extinguishing, and the fire extinguishing time is the longest.

[0099] The above is only a preferred embodiment of the present invention and does not constitute any form of limitation to the present application. Although the present application is disclosed as above in the preferred embodiment, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution.

Claims

1. A method for preparing a fluorocarbon-modified phenolic melt-blown nonwoven composite material for fire extinguishing, characterized in that: The following steps are involved: 1) dissolving the organosilicon resin in an anhydrous solvent, adding an initiator, controlling the temperature at 60-90° C. under an inert atmosphere and continuously stirring, adding a fluorinated acrylate dropwise to the mixed solution, maintaining the reaction temperature and continuing stirring for 3-8 hours after the addition is complete, cooling, purifying, and drying to obtain a fluorinated resin; 2) dissolving the fluorine-containing resin in an organic solvent, controlling the temperature at 60-80° C., adding a microcapsule fire extinguishing agent, continuously stirring for 1-3 hours, and cooling to obtain a fire extinguishing agent coating; 3) coating the fire extinguishing agent coating on the surface of the phenolic melt-blown nonwoven material and curing the coating to obtain a fluorocarbon-modified phenolic melt-blown nonwoven composite material.

2. The method for preparing a fluorocarbon-modified phenolic melt-blown nonwoven composite material for fire extinguishing according to claim 1, characterized in that In step (1), the silicone resin is methylphenyl silicone resin; the fluorine-containing acrylate is perfluorobutylethyl acrylate; and the initiator is benzoyl peroxide.

3. The method for preparing a fluorocarbon modified phenolic melt-blown nonwoven composite material for fire extinguishing according to claim 2, characterized in that The mass ratio of the perfluorobutyl ethyl acrylate to the methylphenyl silicone resin is (1-3):

1.

4. The method for preparing a fluorocarbon-modified phenolic melt-blown nonwoven composite material for fire extinguishing according to claim 1, characterized in that In step (2), the mass ratio of the microcapsule fire extinguishing agent to the fluorine-containing resin is 1:(3-5).

5. The method for preparing a fluorocarbon modified phenolic melt-blown nonwoven composite material for fire extinguishing according to claim 1, characterized in that The preparation of the microcapsule fire extinguishing agent in step (2) comprises the following steps: S1: completely dissolving the foam stabilizer in water, stirring continuously, adding hydrocarbon surfactant, preservative, flame retardant, antifreeze agent and fluorocarbon surfactant in sequence, adjusting the temperature to 50°C until the fluorocarbon surfactant is completely dissolved; cooling, diluting and stirring evenly to obtain a fluorocarbon fire extinguishing agent; S2: Dissolve gelatin and gum arabic in water at 50-55°C, mix the two solutions evenly, add the fluorocarbon fire extinguishing agent dropwise thereto, stir, emulsify, and form a primary emulsion; S3: Continue stirring, add acetic acid solution to the primary emulsion, adjust the pH value to 4.0-4.5, then add formaldehyde solution, continue stirring and reacting for 1-2 hours after the addition is complete, adjust the pH value to 7-8, dialyze, and dry to obtain a microcapsule fire extinguishing agent.

6. The method for preparing a fluorocarbon modified phenolic melt-blown nonwoven composite material for fire extinguishing according to claim 5, characterized in that In the step S1, the fluorocarbon fire extinguishing agent, calculated on a mass basis as 100%, comprises the following components: 2.5-3.5% fluorocarbon surfactant; 1.5-2.5% hydrocarbon surfactant; 1-2% foam stabilizer; 7-9% flame retardant; 12.5-17.5% antifreeze agent; and 0.1-1% preservative. In the dilution step, water is added to 100%.

7. The method for preparing a fluorocarbon modified phenolic melt-blown nonwoven composite material for fire extinguishing according to claim 6, characterized in that The fluorocarbon surfactant is a perfluorobutyl surfactant; the perfluorobutyl surfactant is potassium perfluorobutyl sulfonate; The hydrocarbon surfactant is sodium dodecylbenzene sulfonate; The foam stabilizer is sodium carboxymethyl cellulose; The flame retardant is diammonium phosphate; The antifreeze agent is propylene glycol; The preservative is sodium benzoate.

8. The method for preparing a fluorocarbon modified phenolic melt-blown nonwoven composite material for fire extinguishing according to claim 5, characterized in that The mass ratio of the gelatin to the gum arabic is 1:1; the total mass of the gelatin and the gum arabic is 5-10% of the fluorocarbon fire extinguishing agent.

9. The method for preparing a fluorocarbon modified phenolic melt-blown nonwoven composite material for fire extinguishing according to claim 1, characterized in that In step (3), the amount of the fire extinguishing agent coating relative to the phenolic melt-blown nonwoven material is 150-250 g / m 2 .

10. A fluorocarbon modified phenolic melt-blown nonwoven composite material for fire extinguishing, characterized in that: The method is prepared according to any one of claims 1 to 9.

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