Environment-friendly perfluorocyclohexanone fire extinguishing composition and preparation method thereof
Patent Information
- Application Number
- CN202610906539.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-23
- Publication Date
- 2026-09-25
AI Technical Summary
[0003]然而，纯全氟己酮在实际应用中仍存在若干技术局限
[0016]本发明提供一种环保型全氟己酮灭火组合物及其制备方法，具备以下有益效果：通过特定配比的环保型全氟己酮与含氟共溶剂、协同灭火剂、热稳定剂、铺展助剂及抗静电剂的协同复配，结合低温预混合、氮气保护滴加、压力波动处理、多模式超声辅助分散、静置陈化及高真空充装等多步骤精细制备工艺，显著提升了组合物的组分相容性与长期储存稳定性，有效降低了表面张力与体积电阻率，实现了优异的铺展成膜能力和抗静电安全性；同时，通过引入二元含氟共溶剂、三元协同灭火剂及复合热稳定剂体系，在保持全氟己酮低全球增温潜势和环保特性的基础上，大幅提高了灭火效率、缩短了灭火时间、抑制了高温分解并增强了深位火灾的抗复燃能力，且所获得的组合物具有宽温域适应性、低黏度、高均质度和优异的高压喷射性能，能够充分满足复杂场景下对环保、高效、安全灭火介质的需求。
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Figure CN122806036A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of environmentally friendly fire extinguishing materials technology, specifically to an environmentally friendly perfluorohexanone fire extinguishing composition and its preparation method. Background Technology
[0002] Fire extinguishing compositions refer to mixtures with extinguishing agents as the main functional component, supplemented by co-solvents, stabilizers, surfactants, and other additives. They extinguish fires through mechanisms such as physical cooling, chemical inhibition, oxygen deprivation and asphyxiation, or film formation and coverage. Perfluorohexanone is a hydrofluoroketone compound with advantages such as zero ozone depletion potential, low global warming potential, no residue, non-conductivity, and non-corrosiveness. It is widely used in fighting Class B (liquid or fusible solid fires) and Class C (gas fires) fires, as well as fires involving electrical equipment, and is one of the important alternatives to halon extinguishing agents.
[0003] However, pure perfluorohexanone still has several technical limitations in practical applications. First, perfluorohexanone has a relatively low boiling point (approximately 49°C), making it prone to vaporization and decomposition in high-temperature storage or fire environments, leading to a decrease in effective extinguishing concentration. Second, perfluorohexanone has limited spreading ability for hydrocarbon fuels, making it difficult to quickly form a covering film when used alone, which can easily lead to reignition. Third, pure perfluorohexanone is prone to generating static electricity due to friction during high-speed injection, posing a risk of igniting flammable gases. Fourth, perfluorohexanone has poor compatibility with some commonly used co-solvents or additives, and may stratify or precipitate during storage, affecting the reliability of fire extinguishing and injection performance.
[0004] To overcome the aforementioned shortcomings, existing technologies have developed fire extinguishing compositions that combine perfluorohexanone with hydrofluoroethers, perfluoropolyethers, and fluorinated surfactants. However, these compositions often suffer from the following problems: limited selection of added components, lacking multi-scale synergistic design tailored to the properties of perfluorohexanone; insufficient thermal and long-term storage stability, with the active ingredient easily decomposing or volatilizing at high temperatures; difficulty in simultaneously achieving both spreading and antistatic properties, failing to meet the requirements of rapid fire extinguishing and safe operation with electricity; and simple preparation processes resulting in uneven component dispersion and poor batch-to-batch reproducibility. Therefore, developing an environmentally friendly perfluorohexanone fire extinguishing composition that combines high fire extinguishing efficiency, excellent thermal stability, good spreading and film-forming properties, antistatic safety, and long-term storage stability, along with a controllable and refined preparation method, has become an urgent technical problem to be solved in this field. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention provides an environmentally friendly perfluorohexanone fire extinguishing composition and its preparation method, thus solving the technical problems mentioned in the background section.
[0006] To achieve the above objectives, the present invention provides the following technical solution: an environmentally friendly perfluorohexanone fire extinguishing composition, comprising the following components by weight: 65-80 parts of perfluorohexanone; 8-18 parts of fluorinated cosolvent; 2-8 parts of synergistic fire extinguishing agent; Heat stabilizer 0.5–4 parts; Spreading agent 0.2–1.5 parts; The fluorinated cosolvent is a mixture of perfluoro-2-methyl-2-pentene and perfluorotriethylamine in a mass ratio of 1:2 to 3:1; The synergistic fire extinguishing agent is a mixture of hexafluoropropane and perfluorobutyl methyl ether in a mass ratio of 1:1 to 4:1. The heat stabilizer is a complex of 2,2,6,6-tetramethylpiperidine nitroxide radical and tris(2,2,2-trifluoroethyl) phosphite in a mass ratio of 1:1 to 2:1. The spreading aid is a perfluoroalkyl polyoxyethylene ether carboxylate, wherein the perfluoroalkyl chain has 6 to 8 carbon atoms and the polyoxyethylene chain has 4 to 10 segments.
[0007] In some embodiments, the mass ratio of perfluoro-2-methyl-2-pentene to perfluorotriethylamine is 2:1; the mass ratio of hexafluoropropane to perfluorobutyl methyl ether is 2:1; and the mass ratio of 2,2,6,6-tetramethylpiperidine nitroxide radical to tris(2,2,2-trifluoroethyl) phosphite is 1.5:1.
[0008] In some embodiments, the synergistic extinguishing agent further comprises 5% to 15% of perfluoro-2-methyl-3-pentanone by mass of the total synergistic extinguishing agent.
[0009] In some embodiments, the spreading aid has 6 carbon atoms in its perfluoroalkyl chain, 6 polyoxyethylene chain segments, and its carboxylate salt is a sodium or potassium salt.
[0010] In some embodiments, the composition further includes 0.1 to 1 part by weight of an antistatic agent, wherein the antistatic agent is lithium fluorinated alkyl sulfonyl imide.
[0011] A method for preparing the environmentally friendly perfluorohexanone fire extinguishing composition according to the above description, characterized in that the method for preparing the environmentally friendly perfluorohexanone fire extinguishing composition includes the following steps: Step 1: Heat perfluorohexanone to 15-25°C, stir at 300-500 rpm in a sealed stirred tank, add fluorinated co-solvent according to the ratio, and continue stirring for 10-20 minutes to obtain the first mixture; Step 2: Premix the synergistic extinguishing agent and the heat stabilizer at 5-10°C and stir at 200-300 rpm for 5-10 minutes to obtain the premixed solution; Step 3: Add the premixed solution to the first mixture dropwise under nitrogen protection at a rate of 2-5 mL / min, while increasing the stirring speed to 600-800 rpm and controlling the system temperature to not exceed 30°C. After the dropwise addition is completed, continue stirring for 15-25 min to obtain the second mixture. Step 4: Add a spreading agent to the second mixture and apply ultrasound at a frequency of 20-40 kHz and a power density of 0.5-2 W / mL. Sonicate at 25-35°C for 10-30 min to obtain the third mixture. Step 5: Let the third mixture stand at 5-15°C for 2-4 hours, then stir slowly at 100-200 rpm for 20-40 minutes to defoam, thus obtaining the environmentally friendly perfluorohexanone fire extinguishing composition.
[0012] In some embodiments, the premixing in step two is performed with ultrasonic assistance, at a frequency of 40 kHz, a power of 50–100 W, and a time of 3–5 min.
[0013] In some embodiments, after the dripping is completed in step three, a pressure fluctuation treatment is performed: the pressure inside the stirred tank is increased from atmospheric pressure to 0.2-0.4 MPa within 30-60 seconds, and then quickly depressurized back to atmospheric pressure, and this process is repeated 2-4 times.
[0014] In some embodiments, the ultrasonic treatment in step four is performed at a frequency of 28 kHz, a power density of 1.2 W / mL, and a treatment time of 20 min, while simultaneously stirring at 400–600 rpm during the ultrasonic treatment.
[0015] In some embodiments, step five is followed by a filling process: the obtained composition is filled into a pressure-resistant container under a vacuum of -0.09 to -0.1 MPa, and an inert propellant gas is introduced to a pressure of 1.2 to 1.5 MPa, wherein the inert propellant gas is a mixture of nitrogen and carbon dioxide in a volume ratio of 3:1 to 1:1.
[0016] This invention provides an environmentally friendly perfluorohexanone fire extinguishing composition and its preparation method, which has the following beneficial effects: Through the synergistic compounding of environmentally friendly perfluorohexanone with a fluorinated co-solvent, synergistic fire extinguishing agent, heat stabilizer, spreading aid, and antistatic agent in a specific ratio, combined with a multi-step refined preparation process including low-temperature premixing, nitrogen-protected dripping, pressure fluctuation treatment, multi-mode ultrasonic-assisted dispersion, static aging, and high-vacuum filling, the composition's component compatibility and long-term storage stability are significantly improved, surface tension and volume resistivity are effectively reduced, and excellent spreading and film-forming ability and antistatic safety are achieved. Simultaneously, by introducing a binary fluorinated co-solvent, a ternary synergistic fire extinguishing agent, and a composite heat stabilizer system, while maintaining the low global warming potential and environmentally friendly characteristics of perfluorohexanone, the fire extinguishing efficiency is greatly improved, the fire extinguishing time is shortened, high-temperature decomposition is inhibited, and the anti-reignition ability of deep-seated fires is enhanced. Furthermore, the obtained composition has wide temperature range adaptability, low viscosity, high homogeneity, and excellent high-pressure injection performance, which can fully meet the needs of environmentally friendly, efficient, and safe fire extinguishing media in complex scenarios. Attached Figure Description
[0017] Figure 1 This is a schematic flowchart of the preparation method of the present invention. Detailed Implementation
[0018] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0019] This invention provides an environmentally friendly perfluorohexanone fire extinguishing composition: by weight, it comprises the following components: 65-80 parts perfluorohexanone; 8-18 parts fluorinated co-solvent; 2-8 parts synergistic extinguishing agent; 0.5-4 parts heat stabilizer; 0.2-1.5 parts spreading aid; the fluorinated co-solvent is a mixture of perfluoro-2-methyl-2-pentene and perfluorotriethylamine in a mass ratio of 1:2-3:1; the synergistic extinguishing agent is a mixture of hexafluoropropane and perfluorobutyl methyl ether in a mass ratio of 1:1-4:1; the heat stabilizer is a complex of 2,2,6,6-tetramethylpiperidine nitroxide radical and tris(2,2,2-trifluoroethyl) phosphite in a mass ratio of 1:1-2:1; the spreading aid is perfluoroalkyl polyoxyethylene ether carboxylate, wherein the perfluoroalkyl chain has 6-8 carbon atoms and the polyoxyethylene chain has 4-10 segments.
[0020] Through the synergistic combination of the above-mentioned specific components and proportions, this composition significantly improves the extinguishing efficiency for Class B fires while maintaining the excellent environmental performance of perfluorohexanone. The binary mixing design of the fluorinated co-solvent effectively improves the compatibility of perfluorohexanone with other additives and avoids phase separation. The compounding effect of the synergistic extinguishing agent enhances the gas-phase chemical inhibition ability, the complex of the heat stabilizer significantly inhibits the decomposition of perfluorohexanone at high temperatures, and the spreading aid greatly improves the spreading speed and film uniformity of the composition on oil surfaces, thereby achieving comprehensive performance of stable storage, rapid fire extinguishing, and environmental protection without toxicity.
[0021] In some embodiments, the mass ratio of perfluoro-2-methyl-2-pentene to perfluorotriethylamine is 2:1; the mass ratio of hexafluoropropane to perfluorobutyl methyl ether is 2:1; and the mass ratio of 2,2,6,6-tetramethylpiperidine nitroxide radical to tris(2,2,2-trifluoroethyl) phosphite is 1.5:1.
[0022] Perfluorohexanone fire extinguishing composition is a homogeneous mixture system formed by compounding perfluorohexanone, a hydrofluoroketone compound, as the main extinguishing base material, with functional components such as a fluorinated co-solvent, synergistic extinguishing agent, heat stabilizer, spreading agent, and antistatic agent. The fluorinated co-solvent improves the miscibility of perfluorohexanone with other components and regulates its volatility; the synergistic extinguishing agent enhances extinguishing efficiency through gas-phase chemical inhibition; the heat stabilizer inhibits the decomposition of perfluorohexanone at high temperatures; the spreading agent significantly reduces the surface tension of the composition to promote rapid film formation and coverage on the fuel surface; and the antistatic agent prevents secondary ignition caused by static electricity accumulation during high-speed spraying. This composition maintains the inherent environmentally friendly properties of perfluorohexanone while comprehensively improving extinguishing speed, resistance to reignition, thermal stability, storage homogeneity, and safety for use with electrical equipment. It is a highly efficient and environmentally friendly fire extinguishing material suitable for Class B and Class C fires and fires involving electrical equipment. When the above-mentioned optimal mass ratio is used, the miscibility and dielectric constant matching degree of the fluorinated cosolvent reach the best balance, the gas phase extinguishing concentration of the synergistic extinguishing agent reaches the lowest value, and the self-oxidation-reduction cycle efficiency of the heat stabilizer is the highest. As a result, the overall extinguishing performance, thermal stability and storage stability of the composition all reach the optimal range, while further reducing the global warming potential and atmospheric residence time of the composition.
[0023] In some embodiments, the synergistic extinguishing agent further comprises 5% to 15% of perfluoro-2-methyl-3-pentanone by mass of the total synergistic extinguishing agent.
[0024] The introduction of this additional component can further optimize the vapor pressure curve of the synergistic extinguishing agent, rapidly release the gas-phase suppression component in the early stage of a fire, and form a ternary azeotropic effect with hexafluoropropane and perfluorobutyl methyl ether, significantly improving the atomization fineness of the extinguishing agent after it is sprayed from the nozzle, shortening the extinguishing time. Furthermore, the decomposition products of perfluoro-2-methyl-3-pentanone in high-temperature flames have additional free radical scavenging capabilities, thereby enhancing the suppression effect on deep-seated fires.
[0025] In some embodiments, the spreading aid has 6 carbon atoms in its perfluoroalkyl chain, 6 polyoxyethylene chain segments, and its carboxylate salt is a sodium or potassium salt.
[0026] The specific carbon chain length and number of hydrophilic chain segments ensure that the hydrophilic-lipophilic balance of the spreading agent is within the range most suitable for extinguishing hydrocarbon fires. The carboxylate form further improves its solubility and ionic stability in perfluorohexanone-based liquids, ensuring that the spreading performance of the composition does not decrease during long-term storage. At the same time, it can quickly form a dense aqueous film layer on the fuel surface after spraying, effectively preventing reignition.
[0027] In some embodiments, the composition further includes 0.1 to 1 part by weight of an antistatic agent, wherein the antistatic agent is lithium fluorinated alkyl sulfonyl imide.
[0028] The addition of this antistatic agent can reduce the volume resistivity of the composition to [value missing]. The following features effectively prevent the risk of secondary ignition caused by static electricity accumulation during high-speed spraying or pipeline transportation of the composition. At the same time, lithium fluorinated alkyl sulfonyl imide has excellent compatibility with perfluorohexanone-based liquid, and will not precipitate or affect the fire extinguishing performance, thus ensuring the safety of the composition in fire scenarios involving energized equipment.
[0029] This invention provides an environmentally friendly perfluorohexanone fire extinguishing composition and its preparation method: The preparation method of the environmentally friendly perfluorohexanone fire extinguishing composition includes the following steps: Step 1: Heat perfluorohexanone to 15-25°C, stir at 300-500 rpm in a sealed stirred tank, add fluorinated co-solvent according to the ratio, and continue stirring for 10-20 minutes to obtain the first mixture; Step 2: Premix the synergistic extinguishing agent and the heat stabilizer at 5-10°C and stir at 200-300 rpm for 5-10 minutes to obtain the premixed solution; Step 3: Add the premixed solution to the first mixture dropwise under nitrogen protection at a rate of 2-5 mL / min, while increasing the stirring speed to 600-800 rpm and controlling the system temperature to not exceed 30℃. After the dropwise addition is complete, continue stirring for 15-25 min to obtain the second mixture. Step 4: Add a spreading agent to the second mixture and apply ultrasound at a frequency of 20-40 kHz and a power density of 0.5-2 W / mL. Sonicate at 25-35℃ for 10-30 min to obtain the third mixture. Step 5: Let the third mixture stand at 5-15℃ for 2-4 hours, then stir slowly at 100-200 rpm for 20-40 minutes to degas, and the environmentally friendly perfluorohexanone fire extinguishing composition is obtained.
[0030] like Figure 1 The core process shown above, through the multi-step, segmented temperature control, dropwise mixing, and ultrasonic-assisted preparation technology, achieves uniform dispersion of each component at the molecular level, avoiding side reactions or precipitation caused by excessively high local concentrations. The low-temperature premixing step protects the heat-sensitive components, nitrogen protection and temperature control prevent the oxidative decomposition of perfluorohexanone, ultrasonic treatment promotes the nanoscale dispersion of spreading agents in the system, and aging and slow degassing steps completely eliminate microbubbles. The final composition has excellent homogeneity, transparency, and long-term storage stability, and high batch-to-batch reproducibility, making it suitable for industrial production.
[0031] In some embodiments, the premixing in step two is performed with ultrasonic assistance, at a frequency of 40 kHz, a power of 50–100 W, and a time of 3–5 min.
[0032] This ultrasonic-assisted premixing process can uniformly disperse the synergistic fire extinguishing agent and heat stabilizer to a near molecular level mixture under low temperature conditions, significantly shortening the time required for subsequent dripping and mixing. At the same time, it avoids local overheating caused by mechanical stirring, effectively protecting the free radical active components in the heat stabilizer, thereby enabling it to exert a longer-lasting antioxidant and anti-decomposition effect in the final composition.
[0033] In some embodiments, after the dripping is completed in step three, a pressure fluctuation process is performed: the pressure inside the stirred tank is increased from atmospheric pressure to 0.2-0.4 MPa within 30-60 seconds, and then quickly depressurized back to atmospheric pressure, and this process is repeated 2-4 times.
[0034] This pressure fluctuation treatment generates a transient cavitation effect in the mixture through rapid pressure changes, which can disrupt metastable micelle aggregates that may form during the dropping process, promote the re-uniform distribution of components at the microscale, and further remove trace amounts of gas dissolved in the liquid. This significantly improves the clarity and homogenization of the composition, effectively preventing stratification or precipitation during long-term storage. In some embodiments, the ultrasonic treatment in step four is performed at a frequency of 28 kHz, a power density of 1.2 W / mL, and a treatment time of 20 min, while simultaneously stirring at 400–600 rpm during the ultrasonic treatment.
[0035] This specific ultrasonic frequency and power density can generate the strongest cavitation effect without causing the decomposition of perfluorohexanone. Combined with the synergistic effect of mechanical stirring, the micelle size formed by the spreading aid is controlled within the range of 50-100 nm, thereby significantly improving the spreading and film-forming speed of the composition after spraying. At the same time, the composition treated under these conditions has the lowest dynamic viscosity and the optimal spray atomization angle.
[0036] In some embodiments, step five is followed by a filling process: the obtained composition is filled into a pressure-resistant container under a vacuum of -0.09 to -0.1 MPa, and an inert propellant gas is introduced to a pressure of 1.2 to 1.5 MPa. The inert propellant gas is a mixture of nitrogen and carbon dioxide in a volume ratio of 3:1 to 1:1.
[0037] The filling process completely removes air and moisture from the container through high-vacuum filling, preventing the composition from deteriorating due to oxygen or water vapor intrusion during storage. The use of a mixed propellant gas of nitrogen and carbon dioxide ensures sufficient injection pressure stability and utilizes the slight solubility of carbon dioxide to improve the interfacial tension between the gas and liquid phases, resulting in more uniform droplet size and longer spray distance of the sprayed fire extinguishing composition. At the same time, it avoids the static electricity accumulation problem that may be caused by pure nitrogen propellant.
[0038] It is worth noting that all standard parts used in this invention can be purchased from the market, and irregularly shaped parts can be customized according to the description and drawings. The specific connection methods of each part all adopt conventional methods such as bolts, rivets, and welding that are mature in the prior art. The models of electrical structure equipment involved can be selected according to the user's needs, as long as they meet the requirements of this application. In addition, the circuit connection adopts conventional connection methods in the prior art. The supporting electrical structures such as the control, current detection, position feedback, predicted voltage synchronization and parameter adjustment of the electrical equipment are all existing technologies, such as PLC controllers and module structures, so they will not be described in detail here.
[0039] A specific embodiment of this application is described below with reference to the accompanying drawings: Example 1
[0040] Formula composition (by weight): Perfluorohexanone: 72 parts Fluorinated cosolvent: 12 parts (where the mass ratio of perfluoro-2-methyl-2-pentene to perfluorotriethylamine is 2:1) Synergistic extinguishing agent: 5 parts (of which the mass ratio of hexafluoropropane to perfluorobutyl methyl ether is 2:1, and an additional 10% of perfluoro-2-methyl-3-pentanone is added to the total mass of the synergistic extinguishing agent). Heat stabilizer: 2 parts (of which the mass ratio of 2,2,6,6-tetramethylpiperidine nitroxide radical to tris(2,2,2-trifluoroethyl) phosphite is 1.5:1) Spreading aid: 0.8 parts (sodium perfluoroalkyl polyoxyethylene ether carboxylate with 6 carbon atoms in the perfluoroalkyl chain and 6 polyoxyethylene chain segments) Antistatic agent: 0.5 parts (lithium fluorinated alkyl sulfonyl imide) Preparation method: Step 1: Heat perfluorohexanone to 20°C, stir at 400 rpm in a sealed stirred tank, add fluorinated co-solvent according to the ratio, and continue stirring for 15 min to obtain the first mixture.
[0041] Step 2: Premix the synergistic extinguishing agent and heat stabilizer at 8°C, and apply ultrasonic assistance at a frequency of 40kHz and a power of 80W, stirring at 250rpm for 8min to obtain the premixed solution.
[0042] Step 3: Add the premixed solution to the first mixture dropwise under nitrogen protection at a rate of 3 mL / min, while simultaneously increasing the stirring speed to 700 rpm and controlling the system temperature to not exceed 30°C. After the dropwise addition is complete, continue stirring for 20 min, and then perform pressure fluctuation treatment: increase the pressure in the stirred tank from atmospheric pressure to 0.3 MPa within 45 s, and then quickly depressurize to atmospheric pressure. Repeat this process 3 times to obtain the second mixture.
[0043] Step 4: Add spreading agent and antistatic agent to the second mixture, and apply ultrasound at a frequency of 28kHz and a power density of 1.2W / mL. Stir at 500rpm during the ultrasonic treatment and ultrasonic treatment at 30℃ for 20min to obtain the third mixture.
[0044] Step 5: Let the third mixture stand at 10°C for 3 hours to age, then stir slowly at 150 rpm for 30 minutes to degas, thus obtaining the environmentally friendly perfluorohexanone fire extinguishing composition.
[0045] Step 6 (Filling Process): The obtained composition is filled into a pressure-resistant container under a vacuum of -0.095 MPa, and an inert propellant gas is added to a pressure of 1.35 MPa. The inert propellant gas is a mixture of nitrogen and carbon dioxide in a volume ratio of 2:1.
[0046] Effect description: This embodiment achieved excellent component compatibility by using a moderate proportion of perfluorohexanone and an optimized binary fluorinated co-solvent system. The composition showed no stratification or precipitation after being stored at room temperature for 12 months. After introducing perfluoro-2-methyl-3-pentanone into the synergistic extinguishing agent, it passed a standard Class B fire extinguishing test (1m). 2(For oil-filled fires), the extinguishing time was shortened by approximately 18% compared to the control sample without this component. The synergistic effect of pressure fluctuation treatment and ultrasonic-assisted premixing resulted in uniform distribution of the active ingredients of the heat stabilizer. After heat aging at 150°C for 24 hours, the perfluorohexanone decomposition rate was less than 0.5%. The combined use of spreading aids and antistatic agents reduced the surface tension of the composition to 14.2 mN / m (25°C), and no increase in electrostatic potential was detected during spraying. The overall performance meets the practical requirements of environmentally friendly fire extinguishing agents.
[0047] Example 2
[0048] Formula composition (by weight): Perfluorohexanone: 80 parts Fluorinated co-solvent: 8 parts (where the mass ratio of perfluoro-2-methyl-2-pentene to perfluorotriethylamine is 1:1.5) Synergistic extinguishing agent: 8 parts (of which the mass ratio of hexafluoropropane to perfluorobutyl methyl ether is 3:1, without the addition of perfluoro-2-methyl-3-pentanone) Heat stabilizer: 4 parts (of which the mass ratio of 2,2,6,6-tetramethylpiperidine nitroxide radical to tris(2,2,2-trifluoroethyl) phosphite is 1.2:1) Spreading aid: 1.5 parts (potassium perfluoroalkyl polyoxyethylene ether carboxylate with 8 carbon atoms in the perfluoroalkyl chain and 4 polyoxyethylene chain segments) Antistatic agent: 0.1 parts (lithium fluorinated alkyl sulfonyl imide) Preparation method: Step 1: Heat perfluorohexanone to 15°C, stir at 500 rpm in a sealed stirred tank, add fluorinated co-solvent according to the ratio, and continue stirring for 20 min to obtain the first mixture.
[0049] Step 2: Premix the synergistic extinguishing agent and heat stabilizer at 5°C and stir at 300 rpm for 10 min (without ultrasonic assistance) to obtain the premixed solution.
[0050] Step 3: Add the premixed solution to the first mixture dropwise under nitrogen protection at a rate of 2 mL / min, while increasing the stirring speed to 600 rpm and controlling the system temperature to not exceed 28°C. Continue stirring for 25 min after the addition is complete, without performing pressure fluctuation treatment, to obtain the second mixture.
[0051] Step 4: Add spreading agent and antistatic agent to the second mixture, and apply ultrasound at a frequency of 40kHz and a power density of 0.5W / mL. Sonicate at 25℃ for 30min (without mechanical stirring during the sonication process) to obtain the third mixture.
[0052] Step 5: Let the third mixture stand at 15°C for 2 hours to age, then stir slowly at 200 rpm for 40 minutes to degas, thus obtaining the environmentally friendly perfluorohexanone fire extinguishing composition.
[0053] Step 6: Fill the obtained composition into a pressure-resistant container under a vacuum of -0.09 MPa, and fill it with inert propellant gas to a pressure of 1.2 MPa. The inert propellant gas is a mixture of nitrogen and carbon dioxide in a volume ratio of 3:1.
[0054] Effect description: This embodiment uses a high perfluorohexanone content (80 parts), which reduces the proportion of auxiliary components while ensuring fire extinguishing activity, making it suitable for use in northern winter scenarios where high purity of the composition is required and the ambient temperature is low. The fluorinated co-solvent uses a low proportion of perfluoro-2-methyl-2-pentene, increasing the dielectric strength of the co-solvent and preventing flashover in the composition during a 35kV charged spray test. Due to the absence of perfluoro-2-methyl-3-pentanone, the atmospheric residence time of the composition is further shortened, and the estimated global warming potential (GWP) is below 230. Although ultrasonic-assisted premixing and pressure fluctuation treatment were not used, a composition with good phase stability was still obtained by extending the processing time of each step, and no stratification was observed in centrifugation tests (3000 rpm, 30 min). The spreading aid has a structure with 8 carbon chains and 4 polyoxyethylene chain segments, achieving a spreading diameter of 125 mm / 0.5 mL on the diesel surface. Fire extinguishing tests show outstanding suppression ability against deep-seated oil fires, with a reignition time exceeding 10 min.
[0055] Example 3
[0056] Formula composition (by weight): Perfluorohexanone: 65 parts Fluorinated cosolvent: 18 parts (where the mass ratio of perfluoro-2-methyl-2-pentene to perfluorotriethylamine is 3:1) Synergistic extinguishing agent: 2 parts (of which the mass ratio of hexafluoropropane to perfluorobutyl methyl ether is 1:1, and an additional 15% of perfluoro-2-methyl-3-pentanone is added to the total mass of the synergistic extinguishing agent). Heat stabilizer: 0.5 parts (of which the mass ratio of 2,2,6,6-tetramethylpiperidine nitroxide radical to tris(2,2,2-trifluoroethyl) phosphite is 2:1) Spreading aid: 0.2 parts (sodium perfluoroalkyl polyoxyethylene ether carboxylate with 6 carbon atoms in the perfluoroalkyl chain and 10 polyoxyethylene chain segments) Antistatic agent: 1.0 part (lithium fluorinated alkyl sulfonyl imide) Preparation method: Step 1: Heat perfluorohexanone to 25°C, stir at 300 rpm in a sealed stirred tank, add fluorinated co-solvent according to the ratio, and continue stirring for 10 min to obtain the first mixture.
[0057] Step 2: Premix the synergistic extinguishing agent and heat stabilizer at 10°C, and apply ultrasonic assistance at a frequency of 40kHz and a power of 100W, stirring at 200rpm for 5min to obtain the premixed solution.
[0058] Step 3: Add the premixed solution to the first mixture dropwise under nitrogen protection at a rate of 5 mL / min, while simultaneously increasing the stirring speed to 800 rpm and controlling the system temperature to not exceed 30°C. After the dropwise addition is complete, continue stirring for 15 min, and then perform pressure fluctuation treatment: within 30 s, increase the pressure in the stirred tank from atmospheric pressure to 0.4 MPa, and then quickly depressurize it back to atmospheric pressure. Repeat this process 4 times to obtain the second mixture.
[0059] Step 4: Add spreading agent and antistatic agent to the second mixture, and apply ultrasound at a frequency of 20kHz and a power density of 2W / mL. Stir at 400rpm during the ultrasound treatment and sonicate at 35℃ for 10min to obtain the third mixture.
[0060] Step 5: Let the third mixture stand at 5°C for 4 hours to age, then stir slowly at 100 rpm for 20 minutes to degas, thus obtaining the environmentally friendly perfluorohexanone fire extinguishing composition.
[0061] Step 6: Fill the obtained composition into a pressure-resistant container under a vacuum of -0.10 MPa, and fill it with inert propellant gas to a pressure of 1.5 MPa. The inert propellant gas is a mixture of nitrogen and carbon dioxide in a volume ratio of 1:1.
[0062] Effect description: This embodiment uses a lower perfluorohexanone content (65 parts) and a higher fluorinated co-solvent content (18 parts), which significantly reduces the viscosity of the composition (kinematic viscosity of 0.78 mm at 20°C). 2 / s), particularly suitable for rapid spraying in low-temperature environments (-30℃). The synergistic extinguishing agent contains up to 15% perfluoro-2-methyl-3-pentanone, forming a strong synergistic extinguishing effect with hexafluoropropane. In the UL 711 standard fire extinguishing test, the minimum extinguishing concentration was reduced by 32% compared to pure perfluorohexanone. A high proportion of antistatic agent (1.0 part) reduces the volume resistivity of the composition to... This completely eliminates the risk of electrostatic ignition, making it suitable for use in explosive environments such as petroleum and chemical plants. Short-duration, high-intensity ultrasonic treatment (20kHz, 2W / mL, 10min) combined with pressure fluctuation treatment causes the spreading aid to form nanomicelles with an average particle size of 45nm, achieving an initial spreading speed of 312mm on the gasoline surface. 2 / s. Low-temperature compliance tests show that the composition of this embodiment remains transparent and homogeneous without crystallization after being frozen at -40°C for 24 hours, fully demonstrating its wide temperature range adaptability.
[0063] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, the phrase "comprising an element defined as..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.
[0064] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. An environmentally friendly perfluorohexanone fire extinguishing composition, characterized in that, By weight, it consists of the following components: 65-80 parts of perfluorohexanone; 8-18 parts of fluorinated co-solvent; 2-8 parts of synergistic fire extinguishing agent; Heat stabilizer 0.5–4 parts; Spreading agent 0.2–1.5 parts; The fluorinated cosolvent is a mixture of perfluoro-2-methyl-2-pentene and perfluorotriethylamine in a mass ratio of 1:2 to 3:1; The synergistic fire extinguishing agent is a mixture of hexafluoropropane and perfluorobutyl methyl ether in a mass ratio of 1:1 to 4:
1. The heat stabilizer is a complex of 2,2,6,6-tetramethylpiperidine nitroxide radical and tris(2,2,2-trifluoroethyl) phosphite in a mass ratio of 1:1 to 2:
1. The spreading aid is a perfluoroalkyl polyoxyethylene ether carboxylate, wherein the perfluoroalkyl chain has 6 to 8 carbon atoms and the polyoxyethylene chain has 4 to 10 segments.
2. The environmentally friendly perfluorohexanone fire extinguishing composition according to claim 1, characterized in that, The mass ratio of perfluoro-2-methyl-2-pentene to perfluorotriethylamine is 2:1; the mass ratio of hexafluoropropane to perfluorobutyl methyl ether is 2:1; and the mass ratio of 2,2,6,6-tetramethylpiperidine nitroxide radical to tris(2,2,2-trifluoroethyl) phosphite is 1.5:
1.
3. The environmentally friendly perfluorohexanone fire extinguishing composition according to claim 1, characterized in that, The synergistic fire extinguishing agent also contains 5% to 15% of perfluoro-2-methyl-3-pentanone by mass of the total synergistic fire extinguishing agent.
4. The environmentally friendly perfluorohexanone fire extinguishing composition according to claim 1, characterized in that, The spreading aid has a perfluoroalkyl chain with 6 carbon atoms, a polyoxyethylene chain with 6 segments, and its carboxylate salt is a sodium or potassium salt.
5. The environmentally friendly perfluorohexanone fire extinguishing composition according to claim 1, characterized in that, The composition further includes 0.1 to 1 part by weight of an antistatic agent, wherein the antistatic agent is lithium fluorinated alkyl sulfonyl imide.
6. A method for preparing an environmentally friendly perfluorohexanone fire extinguishing composition according to any one of claims 1 to 5, characterized in that, The preparation method of the environmentally friendly perfluorohexanone fire extinguishing composition includes the following steps: Step 1: Heat perfluorohexanone to 15-25°C, stir at 300-500 rpm in a sealed stirred tank, add fluorinated co-solvent according to the ratio, and continue stirring for 10-20 minutes to obtain the first mixture; Step 2: Premix the synergistic extinguishing agent and the heat stabilizer at 5-10°C and stir at 200-300 rpm for 5-10 minutes to obtain the premixed solution; Step 3: Add the premixed solution to the first mixture dropwise under nitrogen protection at a rate of 2-5 mL / min, while increasing the stirring speed to 600-800 rpm and controlling the system temperature to not exceed 30°C. After the dropwise addition is completed, continue stirring for 15-25 min to obtain the second mixture. Step 4: Add a spreading agent to the second mixture and apply ultrasound at a frequency of 20-40 kHz and a power density of 0.5-2 W / mL. Sonicate at 25-35°C for 10-30 min to obtain the third mixture. Step 5: Let the third mixture stand at 5-15°C for 2-4 hours, then stir slowly at 100-200 rpm for 20-40 minutes to defoam, thus obtaining the environmentally friendly perfluorohexanone fire extinguishing composition.
7. The method for preparing an environmentally friendly perfluorohexanone fire extinguishing composition according to claim 6, characterized in that, The premixing in step two is performed with ultrasonic assistance at a frequency of 40 kHz, a power of 50–100 W, and a duration of 3–5 min.
8. The method for preparing an environmentally friendly perfluorohexanone fire extinguishing composition according to claim 6, characterized in that, After the addition is completed in step three, a pressure fluctuation treatment is performed: the pressure in the stirred tank is increased from atmospheric pressure to 0.2-0.4 MPa within 30-60 seconds, and then quickly depressurized back to atmospheric pressure. This process is repeated 2-4 times.
9. The method for preparing an environmentally friendly perfluorohexanone fire extinguishing composition according to claim 6, characterized in that, In step four, the ultrasonic treatment frequency is 28kHz, the power density is 1.2W / mL, the treatment time is 20min, and the ultrasonic treatment is simultaneously stirred at 400-600rpm.
10. The method for preparing an environmentally friendly perfluorohexanone fire extinguishing composition according to claim 6, characterized in that, Step five is followed by a filling process: the obtained composition is filled into a pressure-resistant container under a vacuum of -0.09 to -0.1 MPa, and an inert propellant gas is added to a pressure of 1.2 to 1.5 MPa. The inert propellant gas is a mixture of nitrogen and carbon dioxide in a volume ratio of 3:1 to 1:1.