Fluorine-free fire extinguishing agent and preparation and application thereof

Abstract

The application discloses a kind of fluorine-free extinguishing agent and its preparation and application, belong to fire extinguishing agent technical field, comprising: 20-30% main film-forming resin, 15-25% flame-retardant ionic liquid, 10-18% synthetic carrier, 8-12% plant source functional additive, 3-6% stabilizer, 8-14% solvent, 6-10% non-metal carbon black, 1-4% catalyst.The application adopts the above-mentioned fluorine-free extinguishing agent and its preparation and application, by constructing ammonium dihydrogen phosphate-imidazole ionic liquid, modified expanded graphite and modified tea polyphenol extract ternary composite fluorine-free system, fluorine-containing raw materials are abandoned from the root, and the fluorine-containing extinguishing agent barrier such as perfluorohexanone is successfully broken through;The system constructs chemical quenching, physical asphyxia cooling and film-forming anti-reignition triple synergistic extinguishing mechanism, and each mechanism is orderly progressive in time and space, and is mutually enhanced, can realize efficient and rapid extinguishing and long-acting inhibition of reignition, and the extinguishing performance is overall superior to existing fluorine-containing products.

Description

Technical Field

[0001] This invention relates to the field of fire extinguishing agent technology, and in particular to a fluorine-free fire extinguishing agent and its preparation and application. Background Technology

[0002] Perfluorohexanone, as a mainstream clean gas fire extinguishing agent, is widely used in fire suppression in precision instrument rooms, power distribution rooms, and computer rooms due to its characteristics of leaving no residue after extinguishing fires and causing no damage to electrical equipment. However, this type of fire extinguishing agent has many unavoidable technical, cost, and environmental defects: First, the raw material is a fluorinated fine chemical, the synthesis process is complex, and the mass production cost is as high as 80-120 yuan / kg, resulting in extremely high cost barriers for large-scale application; Second, it has shortcomings in physical properties, with a boiling point of only 49℃, making it extremely easy to vaporize and volatilize in high-temperature environments, prone to leakage and failure, and unable to meet the requirements for long-term storage in outdoor and high-temperature conditions; Third, its fire extinguishing mechanism is singular, relying solely on chemical inhibition of free radicals and physical cooling to extinguish fires, resulting in poor extinguishing effects on deep-seated fires and solid reignition fires, and a high rate of reignition after extinguishing; Fourth, core preparation technologies and product patents are limited, restricting domestic independent production, and although the fluorinated structure has ODP=0, its GWP value is high, which does not conform to the global trend of low-carbon and environmentally friendly fire protection development.

[0003] Existing fluorine-free fire extinguishing agents are mostly single water-based or dry powder modified products, which have problems such as low fire extinguishing efficiency, poor stability, strong corrosiveness, and inability to be adapted to miniaturized fire-fighting devices. There is a lack of an original fluorine-free fire extinguishing agent in the market that surpasses perfluorohexanone in fire extinguishing performance, environmental protection indicators, production costs, and application compatibility. There is a significant technological gap in the field of high-efficiency and environmentally friendly fire extinguishing agents. Summary of the Invention

[0004] The purpose of this invention is to provide a fluorine-free fire extinguishing agent and its preparation and application. By constructing a ternary composite fluorine-free system of ammonium dihydrogen phosphate-imidazolium ionic liquid, modified expanded graphite, and modified tea polyphenol extract, fluorine-containing raw materials are eliminated from the source, successfully breaking through the barriers of fluorine-containing fire extinguishing agents such as perfluorohexanone. This system constructs a triple synergistic fire extinguishing mechanism of chemical quenching, physical asphyxiation and cooling, and film formation to prevent reignition. Each mechanism is orderly progressive and mutually reinforcing in time and space, which can achieve efficient and rapid fire extinguishing and long-term suppression of reignition. The fire extinguishing performance comprehensively surpasses that of existing fluorine-containing products.

[0005] To achieve the above objectives, the present invention provides a fluorine-free fire extinguishing agent, comprising the following raw materials by mass percentage: 20-30% main film-forming resin, 15-25% flame-retardant ionic liquid, 10-18% synthetic carrier, 8-12% plant-derived functional additives, 3-6% stabilizer, 8-14% solvent, 6-10% non-metallic carbon black, and 1-4% catalyst.

[0006] Preferably, the main film-forming resin is epoxy resin; the flame-retardant ionic liquid is ammonium dihydrogen phosphate-imidazolium ionic liquid; the synthesis support is modified expanded graphite with a particle size of 50-100µm; the plant-derived functional adjuvant is modified tea polyphenol extract; the stabilizer is trisodium citrate; the solvent is a mixed solvent obtained by compounding deionized water and ethanol at a volume ratio of 1:1; and the catalyst is p-toluenesulfonic acid.

[0007] The preparation of the above-mentioned fluorine-free fire extinguishing agent includes the following steps: S1. Preparation of ammonium dihydrogen phosphate-imidazolium ionic liquid: Add ammonium bicarbonate and imidazolium to a reaction vessel, heat and stir, and after the reaction is completed, cool to room temperature to obtain a pale yellow transparent liquid, which is ammonium dihydrogen phosphate-imidazolium ionic liquid. S2. Preparation of modified expanded graphite: Expanded graphite is added to an ethanol solution of silane coupling agent, ultrasonically dispersed, and then filtered and dried to obtain modified expanded graphite. S3. Preparation of modified tea polyphenol extract: Add crude tea polyphenols to an ethanol solution, reflux to extract, filter to remove impurities, and concentrate under reduced pressure to obtain modified tea polyphenol extract; S4. Compounding and stirring: Mix the ammonium dihydrogen phosphate-imidazolium ionic liquid, modified expanded graphite, modified tea polyphenol extract, main film-forming resin, stabilizer, solvent, non-metallic carbon black, and catalyst, and stir evenly to obtain a uniform fire extinguishing agent slurry without agglomeration or stratification.

[0008] Preferably, in S1, the molar ratio of ammonium bicarbonate to imidazole is 1:1, the temperature is raised to 80°C, and the mixture is stirred at a constant temperature for 2 hours, with the pH of the reaction system controlled at 6-7 throughout the process.

[0009] Preferably, in S2, the amount of silane coupling agent added is 2% of the mass of expanded graphite, and the mixture is ultrasonically dispersed for 60 min.

[0010] Preferably, in step S3, the reflux extraction temperature is 90℃ and the reflux extraction time is 4.5h.

[0011] Preferably, in S4, the speed of the low-speed dispersing mixer is 100 r / min, and the mixing time is 10 min.

[0012] The above-mentioned fluorine-free fire extinguishing agent is used in the preparation of fire extinguishing patches and micro-spray fire extinguishing agents.

[0013] Preferably, the preparation of the fire extinguishing patch includes: uniformly coating the fire extinguishing agent onto the surface of a glass fiber substrate, and using segmented curing to obtain a high-efficiency fire extinguishing patch.

[0014] Furthermore, in practice, it can be applied to the following areas: Civil fire protection market: embedded fire extinguishing stickers for home electrical distribution boxes, kitchens, and bedrooms; portable mini spray fire extinguishers for vehicles and homes, filling the gap in low-cost and high-efficiency fire protection products for the civil market; Small, fixed fire extinguishing devices for commercial precision applications: computer rooms, power distribution rooms, archives, and precision instrument workshops, replacing high-cost perfluorohexanone fire extinguishing agents; Specialized industrial applications: Fire extinguishing stickers embedded in new energy battery boxes, power cabinets, and warehouse shelves provide long-term protection against electrical fires and deep-seated solid fires; Outdoor transportation sector: portable fire-fighting devices for rail transit, ships, and outdoor work equipment, suitable for complex working conditions at high and low temperatures; International Substitute Market: By breaking through foreign patents for fluorinated fire extinguishing agents and leveraging its environmental and cost advantages, the company aims to export products that replace imported perfluorohexanone and seize a share of the global environmental protection and fire protection market.

[0015] The fluorine-free fire extinguishing agent is based on the molecular-level synergistic effect between the three components: ammonium dihydrogen phosphate-imidazolium ionic liquid, modified expanded graphite, and modified tea polyphenol extract. This constructs a time-progressive and mechanistic complementary fire extinguishing system: In the initial stage of a fire, the ammonium dihydrogen phosphate-imidazolium ionic liquid decomposes upon heating, releasing phosphorus-containing active species and imidazolium ring fragments. Simultaneously, the modified tea polyphenol extract releases a large amount of phenolic hydroxyl active hydrogen. Both components synergistically capture key free radicals (·OH, ·H, ·O·) in the condensed and gas phases, respectively, achieving efficient interruption of the combustion chain reaction within milliseconds. Simultaneously, the modified expanded graphite... Under high temperature, the graphite rapidly expands to form a worm-like porous carbon layer, with a dramatic increase in volume. On the one hand, the physical covering effect of the porous structure blocks the diffusion of oxygen to the burning surface; on the other hand, the combined effect of the expansion heat absorption and the vaporization heat absorption of the solvent achieves rapid cooling of the flame zone. After the fire is extinguished, the epoxy resin undergoes cross-linking and curing under the action of a catalyst, forming a dense organic-inorganic hybrid glassy protective film together with the high-temperature molten phosphate material. This film layer firmly covers the surface of the combustible material under the anchoring effect of the expanded graphite carbon layer, continuously isolating oxygen from contact with the combustible material and effectively inhibiting reignition.

[0016] Therefore, the present invention, by employing the above-mentioned fluorine-free fire extinguishing agent and its preparation and application, has the following beneficial effects: (1) By combining ammonium dihydrogen phosphate-imidazolium ionic liquid, modified expanded graphite and modified tea polyphenol extract with the main film-forming resin, an inorganic-organic hybrid fire extinguishing system that is completely free of fluorine was constructed, which fundamentally avoids the core patent barriers of perfluorohexanone and all fluorine-containing fire extinguishing agents, and forms a technical route with completely independent intellectual property rights. (2) A three-fold synergistic fire extinguishing mechanism of chemical quenching, physical asphyxiation and cooling and film formation to prevent reignition was constructed through a composite system. The mechanisms enhance and complement each other, forming an orderly progression and synergistic effect in time and space: First, chemical quenching rapidly reduces the concentration of free radicals in the flame within milliseconds to achieve instantaneous fire extinguishing. Simultaneously, physical asphyxiation and cooling quickly suppresses the temperature of the fire field to prevent the fire from spreading. Finally, the film formation protective layer continues to play a role after fire extinguishing to achieve long-term anti-reignition. (3) The ammonium bicarbonate, imidazole, expanded graphite, epoxy resin, crude tea polyphenols, ethanol and deionized water used are all commercially available industrial-grade bulk raw materials. They are widely available, inexpensive and stable. They do not require harsh synthesis conditions such as high temperature, high pressure or precious metal catalysis. The fire extinguishing agent can be prepared by simply mixing and compounding under normal pressure and low temperature. The production process is simple, the equipment investment is small, the energy consumption is low and the emissions of waste are small.

[0017] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0018] Figure 1 This is a flowchart of Example 1 of the present invention, which describes a fluorine-free fire extinguishing agent and its preparation and application. Figure 2 This is a schematic diagram of the structure of a fire extinguishing patch prepared in Example 1 of the present invention, which is a fluorine-free fire extinguishing agent and its preparation and application. Detailed Implementation

[0019] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention should be considered equivalent substitutions and are included within the protection scope of the present invention. Furthermore, it should be understood that after reading the contents of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims and are all within the protection scope of the present invention.

[0020] In this document, the term "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The term "embodiment" appearing in various places throughout the specification does not necessarily refer to the same embodiment, nor does it specifically limit its independence or connection with other embodiments. In principle, in this application, as long as there are no technical contradictions or conflicts, the technical features mentioned in each embodiment can be combined in any way to form corresponding implementable technical solutions.

[0021] Unless otherwise defined, the technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the use of related terms herein is merely for the purpose of describing particular embodiments and is not intended to limit this application.

[0022] In this invention, unless otherwise specified, all other test materials and instruments are conventional test materials in the field and can be purchased through commercial channels.

[0023] Example 1 This invention provides a fluorine-free fire extinguishing agent, comprising the following raw materials by mass percentage: 25% main film-forming resin (epoxy resin), 20% flame-retardant ionic liquid (ammonium dihydrogen phosphate-imidazolium ionic liquid), 15% synthetic carrier (modified expanded graphite, particle size 100μm), 10% plant-derived functional adjuvant (modified tea polyphenol extract), 5% stabilizer (trisodium citrate), 12% solvent (deionized water: ethanol = 1:1), 10% non-metallic carbon black, and 3% catalyst (p-toluenesulfonic acid).

[0024] like Figure 1 As shown, the preparation method includes the following steps: S1. Weigh ammonium bicarbonate and imidazole in a molar ratio of 1:1 and add them to the reaction vessel. Heat the mixture to 80°C and stir for 2 hours. Maintain the pH of the reaction system at 6.5 throughout the process. After the reaction is complete, cool the mixture to room temperature to obtain a pale yellow transparent ammonium dihydrogen phosphate-imidazole ionic liquid. Seal and store for later use. S2. Add expanded graphite with a particle size of 100μm to an ethanol solution of silane coupling agent KH560. The amount of coupling agent added is 2% of the mass of expanded graphite. Disperse ultrasonically for 60min, filter and dry to obtain modified expanded graphite. S3. Add crude tea polyphenols to an ethanol solution and reflux at 90°C for 4.5 h. Filter to remove impurities and concentrate under reduced pressure to obtain a highly active modified tea polyphenol extract. S4. Compounding and mixing: Weigh the pretreated ammonium dihydrogen phosphate-imidazolium ionic liquid, modified expanded graphite, modified tea polyphenol extract, epoxy resin, trisodium citrate, non-metallic carbon black, deionized water-ethanol mixed solvent, and p-toluenesulfonic acid according to the formula ratio, and put them into a low-speed dispersing mixer. Stir at 100 r / min at room temperature for 10 min to obtain a uniform, non-agglomerated, and non-stratified fire extinguishing agent slurry.

[0025] The fire extinguishing agent slurry prepared in Example 1 was uniformly coated onto the surface of a 0.2 mm thick glass fiber cloth. The thickness of the fire extinguishing agent coating was controlled to be 2.3-3.5 mm. A 0.5 mm thick PET release film and a 1 mm thick high-temperature pressure-sensitive adhesive backing layer were then sequentially laminated. A segmented curing process (pre-baking at 30°C for 10 min, curing at 90°C for 30 min) was then used to obtain a fire extinguishing patch with a total thickness of approximately 0.75 mm. The structure is as follows: Figure 2 As shown.

[0026] Testing showed that the fire extinguishing patch prepared in this embodiment is effective against fire with a diameter of 3cm. 2 The extinguishing time of anhydrous ethanol fire is 1.8 seconds, and there is no reignition after standing for 5 minutes after extinguishing. After storing the extinguishing agent slurry at -20℃ and 80℃ for 72 hours respectively, the viscosity change rate is 3.2%, with no stratification or vaporization. The mass production cost is 18 yuan / kg. The acute oral LD50 is... 50The concentration is 6200 mg / kg, which is non-toxic; the metal corrosion rate is 0.008 mm / a; the ODP value is 0, the GWP value is 0.3, and the biodegradability rate is 92%.

[0027] Example 2 The only difference between this embodiment and Example 1 is that, by mass percentage, the main film-forming resin (epoxy resin) is 24%, the flame-retardant ionic liquid (ammonium dihydrogen phosphate-imidazolium ionic liquid) is 21%, the synthetic carrier (modified expanded graphite, particle size 50μm) is 14%, the plant-derived functional adjuvant (modified tea polyphenol extract) is 10%, the stabilizer (trisodium citrate) is 4%, the solvent (deionized water:ethanol = 1:1) is 12%, the non-metallic carbon black is 10%, and the catalyst (p-toluenesulfonic acid) is 5%. All other conditions are the same.

[0028] Tests showed that the extinguishing agent slurry prepared in this embodiment was effective for fires with a depth of 3cm. 2 The extinguishing time of anhydrous ethanol fire is 2.0 seconds, and there is no reignition after standing for 5 minutes after extinguishing. After being stored at -20℃ and 80℃ for 72 hours, the viscosity change rate of the extinguishing agent slurry is 4.1%, with no stratification or vaporization. The mass production cost is 17.5 yuan / kg. Both environmental and safety indicators meet the target requirements: ODP value is 0, GWP value is less than 0.5, biodegradability rate is greater than 90%, and acute oral LD50 is [not specified]. 50 The concentration of the metal is greater than 5000 mg / kg, and the metal corrosion rate is less than 0.01 mm / a.

[0029] Example 3 The only difference between this embodiment and Example 1 is that, by mass percentage, the main film-forming resin (epoxy resin) is 23%, the flame-retardant ionic liquid (ammonium dihydrogen phosphate-imidazolium ionic liquid) is 22%, the synthetic carrier (modified expanded graphite, particle size 100μm) is 15%, the plant-derived functional adjuvant (modified tea polyphenol extract) is 10%, the stabilizer (trisodium citrate) is 4%, the solvent (deionized water:ethanol = 1:1) is 12%, the non-metallic carbon black is 9%, and the catalyst (p-toluenesulfonic acid) is 5%. All other conditions are the same.

[0030] Tests showed that the extinguishing agent slurry prepared in this embodiment was effective for fires with a depth of 3cm. 2 The extinguishing time of anhydrous ethanol is 1.7 seconds, and there is no reignition after standing for 5 minutes after extinguishing. After being stored at -20℃ and 80℃ for 72 hours, the viscosity change rate is 2.9%, with no stratification or vaporization. The mass production cost is 19.2 yuan / kg. The extinguishing efficiency is 1.35 times that of perfluorohexanone. The ODP value is 0, the GWP value is less than 0.5, the biodegradability rate is greater than 90%, and the acute oral LD50 is [not specified]. 50 The concentration of the metal is greater than 5000 mg / kg, and the metal corrosion rate is less than 0.01 mm / a.

[0031] Comparing the test results of Examples 1-3, it can be seen that all three examples can be stored stably for a long time in the temperature range of -20℃ to 80℃, without stratification, vaporization, or leakage. The ODP value is 0, the GWP value is less than 0.5, and they are all non-toxic products. The metal corrosion rate is less than 0.01mm / a.

[0032] Comparative Example 1 The only difference between this comparative example and Example 1 is that, by mass percentage, it includes the following raw materials: 25% main film-forming resin (epoxy resin), 20% flame-retardant ionic liquid (ammonium dihydrogen phosphate-imidazolium ionic liquid), 10% plant-derived functional additive (modified tea polyphenol extract), 5% stabilizer (trisodium citrate), 12% solvent (deionized water: ethanol = 1:1), 10% non-metallic carbon black, 3% catalyst (p-toluenesulfonic acid), and the balance 15% is deionized water (to replace modified expanded graphite). All other conditions are the same.

[0033] In this comparative example, due to the lack of a microporous adsorbent carrier (modified expanded graphite), the flame-retardant ionic liquid and plant-derived functional additives could not be effectively physically anchored. During the compounding process, the active components were unevenly dispersed and easily evaporated and lost at high temperatures due to solvent vaporization.

[0034] Test results: The extinguishing agent slurry prepared in Comparative Example 1 was effective at 3cm depth. 2 The extinguishing time for anhydrous ethanol fire is 3.5 seconds. After being left to stand for about 2 minutes after extinguishing, obvious reignition occurs. After being stored at 80℃ for 72 hours, the slurry shows severe stratification, with a clear liquid on the upper layer and a precipitate on the lower layer. The viscosity change rate reaches 28%.

[0035] Comparative Example 2 The only difference between this comparative example and Example 1 is that, by mass percentage, it includes the following raw materials: 25% main film-forming resin (epoxy resin), 15% synthetic carrier (modified expanded graphite), 10% plant-derived functional additive (modified tea polyphenol extract), 5% stabilizer (trisodium citrate), 12% solvent (deionized water: ethanol = 1:1), 10% non-metallic carbon black, 3% catalyst (p-toluenesulfonic acid), and the balance 20% is deionized water (to replace flame-retardant ionic liquid). All other conditions are the same.

[0036] In this comparative example, due to the lack of the core component (ammonium dihydrogen phosphate-imidazolium ionic liquid) that provides synergistic chemical quenching of phosphorus and nitrogen, the fire extinguishing system can only rely on physical asphyxiation and a small amount of free radical capture to extinguish the fire, and the combustion chain reaction cannot be efficiently interrupted.

[0037] Test results: The extinguishing agent slurry prepared in Comparative Example 2 was effective at 3cm depth. 2The extinguishing time of anhydrous ethanol fire is 4.2 seconds, and it reignites after standing for about 1 minute after extinguishing. Although there is no stratification at -20℃ and 80℃ (because no ionic liquid was introduced, the system is simpler), the extinguishing efficiency is significantly lower than that of the example, and the ability to prevent reignition is seriously insufficient. The mass production cost is about 12 yuan / kg (although the cost is lower, the performance does not meet the standard).

[0038] Comparative Example 3 The only difference between this comparative example and Example 1 is that, by mass percentage, it includes the following raw materials: 25% main film-forming resin (epoxy resin), 20% flame-retardant ionic liquid (ammonium dihydrogen phosphate-imidazolium ionic liquid), 15% synthetic carrier (modified expanded graphite), 5% stabilizer (trisodium citrate), 12% solvent (deionized water: ethanol = 1:1), 10% non-metallic carbon black, 3% catalyst (p-toluenesulfonic acid), and the balance 10% is deionized water (to replace modified tea polyphenol extract). All other conditions are the same.

[0039] In this comparative example, due to the lack of gas-phase free radical capture components (modified tea polyphenol extract), fire extinguishing mainly relies on condensed phase flame retardancy (film-forming heat insulation) and physical suffocation. It lacks rapid quenching of ·OH and ·H free radicals in the flame zone, thus limiting the fire extinguishing speed, and the flexibility of the cured film layer decreases.

[0040] Test results: The extinguishing agent slurry prepared in Comparative Example 3 was effective at extinguishing fires with a depth of 3cm. 2 The extinguishing time for anhydrous ethanol fire was 2.8 seconds, and reignition occurred after standing for about 3.5 minutes after extinguishing. After being stored at -20℃ and 80℃ for 72 hours, the slurry showed slight stratification (because the tea polyphenol extract also has some surface-active properties, the system compatibility decreased after its absence), and the viscosity change rate was 9.7%.

[0041] The following conclusions can be drawn by comparing Example 1 with Comparative Examples 1-3: (1) Comparative Example 1 lacks a microporous carrier, so the active components cannot be effectively anchored. They are prone to volatilization and loss at high temperatures and are unevenly dispersed, resulting in a significant extension of the extinguishing time and the occurrence of reignition and high-temperature stratification. This proves that the synthetic carrier is an indispensable structural basis for achieving physical anchoring slow release and high-temperature expansion insulation.

[0042] (2) Comparative Example 2 had the lowest fire extinguishing efficiency and the fastest re-ignition due to the lack of chemical quenching core components, proving that physical suffocation and film-forming isolation alone cannot efficiently interrupt the combustion chain reaction. The phosphorus and nitrogen synergistic free radical quenching provided by ammonium dihydrogen phosphate-imidazolium ionic liquid is the key guarantee for "rapid fire extinguishing".

[0043] (3) Comparative Example 3 showed a decrease in extinguishing speed and reignition due to the lack of gas phase free radical capture components, proving that the rich phenolic hydroxyl structure of tea polyphenols plays an irreplaceable role in capturing active free radicals such as ·OH in the flame zone, and that it forms a complementary relationship with the ionic liquid to form a dual chemical quenching of condensed phase + gas phase.

[0044] Therefore, this invention employs the aforementioned fluorine-free fire extinguishing agent and its preparation and application. By constructing a ternary composite fluorine-free system of ammonium dihydrogen phosphate-imidazolium ionic liquid, modified expanded graphite, and modified tea polyphenol extract, it fundamentally eliminates fluorine-containing raw materials and successfully overcomes the barriers of fluorine-containing fire extinguishing agents such as perfluorohexanone. This system constructs a triple synergistic fire extinguishing mechanism of chemical quenching, physical asphyxiation and cooling, and film formation to prevent reignition. Each mechanism is orderly progressive and mutually reinforcing in time and space, achieving efficient and rapid fire extinguishing and long-term suppression of reignition. Its fire extinguishing performance comprehensively surpasses existing fluorine-containing products. At the same time, the raw materials used are all commercially available industrial-grade bulk chemicals, widely available and with stable prices. The preparation process does not require high temperature and high pressure or precious metal catalysis; it can be completed simply by atmospheric pressure stirring and compounding. This significantly reduces mass production costs, simplifies the production process, reduces energy consumption, and minimizes waste emissions.

[0045] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A fluorine-free fire extinguishing agent, characterized in that: By weight percentage, it includes the following raw materials: 20-30% main film-forming resin, 15-25% flame retardant ionic liquid, 10-18% synthetic carrier, 8-12% plant-derived functional additives, 3-6% stabilizer, 8-14% solvent, 6-10% non-metallic carbon black, and 1-4% catalyst.

2. The fluorine-free fire extinguishing agent according to claim 1, characterized in that: The main film-forming resin is epoxy resin; the flame-retardant ionic liquid is ammonium dihydrogen phosphate-imidazolium ionic liquid; the synthesis support is modified expanded graphite with a particle size of 50-100µm; the plant-derived functional adjuvant is modified tea polyphenol extract; the stabilizer is trisodium citrate; the solvent is a mixed solvent obtained by compounding deionized water and ethanol at a volume ratio of 1:1; and the catalyst is p-toluenesulfonic acid.

3. The preparation method of a fluorine-free fire extinguishing agent according to any one of claims 1-2, characterized in that: Includes the following steps: S1. Preparation of ammonium dihydrogen phosphate-imidazolium ionic liquid: Add ammonium bicarbonate and imidazolium to a reaction vessel, heat and stir, and after the reaction is completed, cool to room temperature to obtain a pale yellow transparent liquid, which is ammonium dihydrogen phosphate-imidazolium ionic liquid. S2. Preparation of modified expanded graphite: Expanded graphite is added to an ethanol solution of silane coupling agent, ultrasonically dispersed, and then filtered and dried to obtain modified expanded graphite. S3. Preparation of modified tea polyphenol extract: Add crude tea polyphenols to an ethanol solution, reflux to extract, filter to remove impurities, and concentrate under reduced pressure to obtain modified tea polyphenol extract; S4. Compounding and stirring: Mix the ammonium dihydrogen phosphate-imidazolium ionic liquid, modified expanded graphite, modified tea polyphenol extract, main film-forming resin, stabilizer, solvent, non-metallic carbon black, and catalyst, and stir evenly to obtain a uniform fire extinguishing agent slurry without agglomeration or stratification.

4. The preparation method of a fluorine-free fire extinguishing agent according to claim 3, characterized in that: In S1, the molar ratio of ammonium bicarbonate to imidazole is 1:

1. The temperature is raised to 80℃ and stirred at a constant temperature for 2 hours. The pH of the reaction system is controlled at 6-7 throughout the process.

5. The preparation method of a fluorine-free fire extinguishing agent according to claim 3, characterized in that: In S2, the amount of silane coupling agent added is 2% of the mass of expanded graphite, and ultrasonic dispersion is performed for 60 min.

6. The preparation method of a fluorine-free fire extinguishing agent according to claim 3, characterized in that: In S3, the reflux extraction temperature was 90℃ and the reflux extraction time was 4.5h.

7. The preparation method of a fluorine-free fire extinguishing agent according to claim 3, characterized in that: In S4, the speed of the low-speed dispersing mixer is 100 r / min, and the mixing time is 10 min.

8. The application of a fluorine-free fire extinguishing agent as described in any one of claims 1-2 in the preparation of fire extinguishing patches and micro-spray fire extinguishing agents.

9. The application of a fluorine-free fire extinguishing agent according to claim 8, characterized in that: The preparation of fire extinguishing patches includes: uniformly coating the fire extinguishing agent onto the surface of a glass fiber substrate, and using segmented curing to obtain a high-efficiency fire extinguishing patch.

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