A high-efficiency microcapsule fire extinguishing agent for energy storage power station and its preparation method

Abstract

The present invention discloses a high-efficiency microcapsule fire extinguishing agent for energy storage power stations and a preparation method thereof. The microcapsules of the present invention can operate continuously and stably under high-temperature environments of 200°C to 250°C, and are particularly suitable for energy storage power stations and other high-temperature electrical facilities. In energy storage power stations, since the battery pack may experience high-temperature overload, overcharge, over-discharge and the like, the thermal stability requirements of the battery pack are extremely high. The polyurethane-polycaprolactone composite material of the microcapsule shell ensures that it can withstand these high-temperature environments while avoiding degradation or deformation of the material itself, thereby ensuring the effective release of the fire extinguishing agent. The microcapsule fire extinguishing agent of the present invention, by adopting a polyurethane polymer and a polycaprolactone composite material, can quickly release perfluorohexanone (fire extinguishing agent) through the rupture of the microcapsules when a fire occurs, thereby achieving rapid and effective fire extinguishing.

Description

Technical Field

[0001] The present invention belongs to the field of microcapsule fire extinguishing agents, and in particular relates to a high-efficiency microcapsule fire extinguishing agent for energy storage power stations and a preparation method thereof. Background Art

[0002] With the widespread use of energy storage power stations and other high-voltage electrical facilities, safety issues have become increasingly prominent, particularly fires caused by equipment overheating and electrical failures. During the operation of energy storage power stations, fires can occur due to battery overcharging, over-discharging, or electrical short circuits. Therefore, there is an urgent need for fire extinguishing materials that can react quickly and effectively control the source of fire.

[0003] While common fire extinguishing agents, such as traditional gas, foam, and dry powder, can extinguish fires to a certain extent, they often respond slowly in the early stages of a fire and are not fully adapted to the high-temperature environments found in energy storage power plants. Furthermore, these traditional extinguishing agents often have storage issues, which can limit their effectiveness, particularly in high-temperature environments.

[0004] Against this backdrop, microencapsulated fire extinguishing agents have become an emerging technology. By encapsulating a fire extinguishing agent (such as perfluorohexanone) within polymer microcapsules, these agents can be released upon rupture of the microcapsules, effectively extinguishing the fire. This technology offers a more precise and efficient fire extinguishing response than traditional fire extinguishing agents.

[0005] However, existing microencapsulation technology still has some problems, especially in terms of high-temperature stability, storage stability, response speed, etc., and it is difficult to fully meet the fire extinguishing needs in high-temperature and high-pressure environments such as energy storage power stations.

[0006] In view of this, the present invention is proposed. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a high-efficiency microcapsule fire extinguishing agent for energy storage power stations and a preparation method thereof, thereby solving the problems raised in the above-mentioned background technology.

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

[0009] A method for preparing a high-efficiency microcapsule fire extinguishing agent for an energy storage power station comprises the following steps:

[0010] Step S1: mixing an emulsifier and a solvent, and dissolving them at a temperature of 30°C to 50°C to form an aqueous phase system;

[0011] Step S2: perfluorohexanone, isophorone diisocyanate and diethylenetriamine are mixed in a mass ratio to obtain an oil phase system, and then polycaprolactone is added to the obtained oil phase system;

[0012] Step S3: adding the oil phase to the water phase under stirring, and mixing the oil phase and the water phase with an emulsifier to form a stable emulsion;

[0013] Step S4: adding pentaerythritol and polypropylene glycol to the emulsion to obtain a polymerization reaction system;

[0014] Step S5: Through a polyurethane polymerization reaction, IPDI reacts with DETA and pentaerythritol to form a shell that encapsulates the perfluorohexanone core, forming a microcapsule structure. During this process, polycaprolactone (PCL) reacts with the polyurethane polymer to form a polyurethane-polycaprolactone composite, which synergistically forms the shell structure. Specifically, PCL may be incorporated into the microcapsule shell structure through a reaction with isophorone diisocyanate (IPDI) and diethylenetriamine (DETA), improving the microcapsule's mechanical strength, thermal stability, and degradation resistance.

[0015] Step S6: post-processing the microcapsules and further curing them by heating them in stages to ensure the stability and thermal stability of the polyurethane shell. After the curing is completed, the final high-efficiency microcapsule fire extinguishing agent for energy storage power stations is obtained.

[0016] Optionally, in step S1, the mass ratio of the solvent to the emulsifier is between 10-20:1.

[0017] Optionally, in step S2, the mass ratio of perfluorohexanone, isophorone diisocyanate and diethylenetriamine is 1:2:1.

[0018] Optionally, in step S2, the polycaprolactone accounts for 5%-15% of the oil phase system.

[0019] Optionally, in step S3, the oil phase is added to the water phase at a water-to-oil ratio of 6:1.

[0020] Optionally, during the mixing process in step S3, the emulsification speed is 2000 rpm and the emulsification time is 10 minutes.

[0021] Optionally, in step S4, the amount of pentaerythritol and polypropylene glycol used is 0.5%-1.0% of the total mass of the emulsion, and the mass ratio of pentaerythritol to polypropylene glycol is between 1:1-2, so as to promote the cross-linking reaction of the microcapsule shell.

[0022] Optionally, in step S5, the process is carried out at a reaction temperature of 60° C. to 80° C. until the microcapsule shell is completely formed.

[0023] Optionally, the particle size of the microcapsule fire extinguishing agent formed in step S5 is 3-5 μm.

[0024] A high-efficiency microcapsule fire extinguishing agent for energy storage power stations is prepared by adopting the preparation method.

[0025] After adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art. Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described below at the same time:

[0026] The microcapsules of this invention can operate stably and continuously in high-temperature environments of 200°C to 250°C, making them particularly suitable for energy storage power stations and other high-temperature electrical facilities. In energy storage power stations, battery packs are subject to high-temperature overload, overcharge, and over-discharge, requiring extremely high thermal stability. The polyurethane-polycaprolactone composite material of the microcapsule shell ensures that it can withstand these high-temperature environments while preventing degradation or deformation of the material itself, ensuring the effective release of the fire extinguishing agent.

[0027] The microcapsule fire extinguishing agent of this invention utilizes a composite material of polyurethane polymer and polycaprolactone. When a fire breaks out, the microcapsules rupture and rapidly release perfluorohexanone (fire extinguishing agent), achieving rapid and effective fire extinguishing. Compared to traditional fire extinguishing agents, the microcapsules of this invention significantly shorten reaction time and improve fire extinguishing efficiency. Especially in the early stages of a fire, they can quickly suppress the source of the fire and prevent its spread.

[0028] The polycaprolactone (PCL) material used in this invention has good biodegradability and gradually degrades during the use of the microcapsules, reducing environmental pollution. This design not only improves the environmental friendliness of the microcapsules, but also enhances their applicability in industrial and commercial applications that meet environmental standards.

[0029] The specific embodiments of the present invention are described in further detail below. DETAILED DESCRIPTION

[0030] The present invention will now be described in further detail.

[0031] In this embodiment, a method for preparing a high-efficiency microcapsule fire extinguishing agent for an energy storage power station is provided, comprising the following steps:

[0032] Step S1: mixing an emulsifier and a solvent, and dissolving them at a temperature of 30°C to 50°C to form an aqueous phase system;

[0033] Step S2: perfluorohexanone, isophorone diisocyanate and diethylenetriamine are mixed in a mass ratio to obtain an oil phase system, and then polycaprolactone is added to the obtained oil phase system;

[0034] Step S3: adding the oil phase to the water phase under stirring, and mixing the oil phase and the water phase with an emulsifier to form a stable emulsion;

[0035] Step S4: adding pentaerythritol and polypropylene glycol to the emulsion to obtain a polymerization reaction system;

[0036] Step S5: through a polyurethane polymerization reaction, IPDI reacts with DETA and pentaerythritol to form a shell, which wraps the perfluorohexanone as the core to form a microcapsule structure;

[0037] Step S6: post-processing the microcapsules and further curing them by heating them in stages to ensure the stability and thermal stability of the polyurethane shell. After the curing is completed, the final high-efficiency microcapsule fire extinguishing agent for energy storage power stations is obtained.

[0038] In this embodiment, the mass ratio of the solvent to the emulsifier in step S1 is between 10-20:1.

[0039] In this embodiment, the mass ratio of perfluorohexanone, isophorone diisocyanate and diethylenetriamine in step S2 is 1:2:1.

[0040] In this embodiment, in step S2, polycaprolactone accounts for 5%-15% of the oil phase system.

[0041] In this embodiment, the oil phase is added to the water phase in step S3 at a water-to-oil ratio of 6:1.

[0042] In this embodiment, during the mixing process in step S3, the emulsification speed is 2000 rpm and the emulsification time is 10 minutes.

[0043] In this embodiment, the amount of pentaerythritol and polypropylene glycol used in step S4 is 0.5%-1.0% of the total mass of the emulsion, and the mass ratio of pentaerythritol to polypropylene glycol is between 1:1-2, so as to promote the cross-linking reaction of the microcapsule shell.

[0044] In this embodiment, the process in step S5 is carried out at a reaction temperature of 60° C. to 80° C. until the microcapsule shell is completely formed.

[0045] In this embodiment, the particle size of the microcapsule fire extinguishing agent formed in step S5 is 3-5 μm.

[0046] The steps for curing in Example 1-3 by using a stepwise heating method are as follows:

[0047] First Heating: After the emulsification and polymerization reactions of the microcapsules are complete, the microcapsule sample is first heated to 60°C and held at this temperature for 1 hour. This stage aims to initially cure the polyurethane shell and allow it to begin to form a stable structure. As the temperature rises, the polyurethane cross-linking reaction begins, gradually forming a preliminary solid framework, preparing for the subsequent heating step.

[0048] Second heating: Next, the temperature is raised to 70°C and maintained at this temperature for 1 hour. This process helps further strengthen the microcapsule shell. The heating increases the degree of cross-linking of the polyurethane shell, ensuring that the shell is more stable and begins to develop the required mechanical strength to prevent cracking during storage and use.

[0049] Third heating: The temperature is then raised to 80°C and held there for 30 minutes. This final step in the curing process aims to thoroughly cure the polyurethane shell, achieving its final thermal stability and structural strength. During this stage, the cross-linking reaction of the polyurethane material is fully developed, ultimately enhancing the strength and high-temperature resistance of the microcapsule shell.

[0050] Cooling Phase: After the heat-curing process is complete, the microcapsule samples are removed from the furnace and allowed to cool naturally to room temperature. During the cooling process, the temperature gradually decreases, ensuring that the microcapsules are not affected by thermal stress, which could lead to cracks or deformation in the microcapsule shell. Upon completion of the cooling phase, the polyurethane shell of the microcapsules is fully cured, achieving the desired stability and durability.

[0051] Example 1: A method for preparing a high-efficiency microcapsule fire extinguishing agent for an energy storage power station, comprising the following steps:

[0052] Step S1: First, mix the emulsifier (0.3 g) with dichloromethane (DCM) in a mass ratio of 15:1 and dissolve at 30°C to form an aqueous phase. Ensure that the emulsifier is completely dissolved and evenly distributed in the solution.

[0053] Step S2: Perfluorohexanone (25 g), isophorone diisocyanate (IPDI) (50 g), and diethylenetriamine (DETA) (25 g) were mixed in a mass ratio of 1:2:1 to form an oil phase. Subsequently, polycaprolactone (PCL) (10 g) was added to a 10% portion of the oil phase. The mixture was heated and mixed at 40°C to ensure uniform mixing of the PCL with the other materials.

[0054] Step S3: The oil phase is slowly added to the water phase, maintaining a water-to-oil ratio of 6:1. Emulsification is performed using an emulsifier under stirring conditions, with the emulsification speed adjusted to 2000 rpm for 10 minutes to ensure that the oil phase and the water phase are fully mixed to form a stable emulsion.

[0055] Step S4: Add pentaerythritol (0.5 g) and polypropylene glycol (PPG2000) (0.5 g) to the emulsion, with the amount accounting for 0.5% of the total mass of the emulsion and the mass ratio of pentaerythritol to polypropylene glycol being 1:1. This step is intended to promote the crosslinking reaction of the microcapsule shell and form a stable polymerization reaction system.

[0056] Step S5: A polyurethane polymerization reaction is carried out at a reaction temperature of 70°C, causing IPDI, DETA, and pentaerythritol to react chemically to form a polyurethane shell. This shell encapsulates the perfluorohexanone core, forming a stable microcapsule structure. This reaction is continued for 2 hours until the microcapsule shell is fully formed.

[0057] Step S6: The microcapsules are post-processed and cured by heating in stages to ensure the stability and thermal stability of the polyurethane shell. After curing, the obtained microcapsules have a particle size of about 3-5 μm, and the microcapsule fire extinguishing agent has high thermal stability and storage stability.

[0058] Example 2: A method for preparing a high-efficiency microcapsule fire extinguishing agent for an energy storage power station, comprising the following steps:

[0059] Step S1: Mix the emulsifier (0.5 g) with dichloromethane (DCM) at a solvent-to-emulsifier mass ratio of 12:1. Stir and dissolve at 40°C to form a stable aqueous phase. Ensure that the emulsifier is completely dissolved and evenly distributed in the solution.

[0060] Step S2: Perfluorohexanone (30 g), isophorone diisocyanate (IPDI) (60 g), and diethylenetriamine (DETA) (30 g) were mixed in a mass ratio of 1:2:1 to form an oil phase. Next, polycaprolactone (PCL) (15 g) was added, so that PCL accounted for 10% of the oil phase. The mixture was heated at 45°C and mixed thoroughly to ensure that all components were fully incorporated.

[0061] Step S3: Slowly add the prepared oil phase to the water phase to ensure a water-to-oil ratio of 6:1. Under stirring conditions, adjust the emulsification speed to 2000 rpm and the emulsification time to 10 minutes to ensure that the oil phase and water phase are completely mixed to form a stable emulsion.

[0062] Step S4: Add pentaerythritol (0.8 g) and polypropylene glycol (PPG2000) (0.8 g) to the emulsion, with the amount being 0.7% of the total mass of the emulsion, and the mass ratio of pentaerythritol to polypropylene glycol being 1:1. The purpose of this step is to promote the crosslinking reaction of the microcapsule shell and ensure the stability of the reaction system.

[0063] Step S5: A polyurethane polymerization reaction was conducted at a reaction temperature of 75°C, whereby IPDI, DETA, and pentaerythritol reacted to form a polyurethane shell, which encapsulated the perfluorohexanone core to form a microcapsule structure. This reaction process lasted for 2.5 hours to ensure that the microcapsule shell was fully formed.

[0064] Step S6: Post-processing the microcapsules and further curing them by heating them in stages to ensure the stability and thermal stability of the polyurethane shell. After curing, the resulting microcapsules have a particle size of approximately 3-5 μm, and the microcapsule fire extinguishing agent has high thermal stability and storage stability.

[0065] Example 3: A method for preparing a high-efficiency microcapsule fire extinguishing agent for an energy storage power station, comprising the following steps:

[0066] Step S1: Take an emulsifier (0.4 g) and mix it with dichloromethane (DCM), stir and dissolve it at 35°C according to the mass ratio of solvent to emulsifier of 18:1 to form an aqueous phase system, and ensure that the emulsifier is completely dissolved and remains uniformly dispersed at this temperature.

[0067] Step S2: Perfluorohexanone (40 g), isophorone diisocyanate (IPDI) (80 g), and diethylenetriamine (DETA) (40 g) were mixed in a mass ratio of 1:2:1 to form an oil phase. Next, polycaprolactone (PCL) (12 g) was added, so that PCL accounted for 7.5% of the oil phase. The mixture was heated to 50°C to ensure uniform mixing.

[0068] Step S3: Slowly add the oil phase to the water phase at a water-to-oil ratio of 6:1 and emulsify under stirring. Adjust the emulsification speed to 2000 rpm and emulsify for 10 minutes to ensure that the oil and water phases are completely mixed to form a stable emulsion.

[0069] Step S4: Pentaerythritol (1.0 g) and polypropylene glycol (PPG2000) (1.0 g) were added to the emulsion in an amount of 0.8% of the total mass of the emulsion, and the mass ratio of pentaerythritol to polypropylene glycol was 1:1, to promote the cross-linking reaction of the microcapsule shell.

[0070] Step S5: A polyurethane polymerization reaction is performed at a reaction temperature of 65°C, whereby IPDI, DETA, and pentaerythritol react to form a polyurethane shell, which encapsulates the perfluorohexanone core to form a microcapsule structure. The reaction is continued for 2 hours to ensure that the microcapsule shell is fully formed.

[0071] Step S6: Post-processing the microcapsules and further curing them by heating them in stages to ensure the stability and thermal stability of the polyurethane shell. After curing, the resulting microcapsules have a particle size of approximately 3-5 μm, and the microcapsule fire extinguishing agent has high thermal stability and storage stability.

[0072] Test example: Thermal stability test (performance stability at high temperature)

[0073] Purpose: To verify the thermal stability of the microcapsule shell to ensure that it can maintain a stable structure and effective fire extinguishing effect in high temperature environments, especially in high temperature environments such as energy storage power stations.

[0074] Experimental methods:

[0075] The microcapsule fire extinguishing agent samples were placed under different temperature conditions (e.g., 200°C, 250°C) for constant temperature treatment.

[0076] Thermogravimetric analysis (TGA): The thermal stability of the microcapsule samples was determined by a thermogravimetric analyzer (TGA) to record the mass change of the sample at high temperature.

[0077] Dynamic Mechanical Analysis (DMA): Evaluates the thermodynamic properties of microcapsule materials, such as thermal expansion coefficient and storage modulus, and verifies their mechanical strength and stability under high temperature conditions.

[0078] Among them, the thermogravimetric analysis (TGA) formula is ,in, is the initial mass (mass at the starting temperature). It is at temperature This formula is used to calculate the mass loss of microcapsules at high temperatures, reflecting the thermal stability of microcapsules in high temperature environments.

[0079] The dynamic mechanical analysis (DMA) formula is , where F is the applied force (N). is the deformation of the sample (m). is the initial length of the sample (m). A is the cross-sectional area of ​​the sample

[0080]

[0081] The mass losses of Examples 1, 2, and 3 at 200°C and 250°C were 4.0%-12.0%, respectively. This indicates that while the thermal stability of the microcapsules decreases with increasing temperature, they still maintain good stability. In particular, at 200°C, all examples exhibited minimal mass loss, demonstrating that the microcapsules maintain structural integrity even at higher temperatures.

[0082] At 200°C, the storage modulus of each example was relatively high, demonstrating that the microcapsules retain strong mechanical strength even at high temperatures. However, as the temperature increases (to 250°C), the storage modulus decreases, indicating that the material's rigidity and mechanical strength decrease due to thermal effects. This is a normal thermoplastic reaction, especially in high-temperature reactions of materials such as polyurethane and polycaprolactone.

[0083] As the temperature increases, the deformation of the microcapsule samples increases slightly, especially at 250°C, indicating that high temperature will cause certain physical deformation of the microcapsules, but the overall change range is still within an acceptable range.

[0084] The test results of Examples 1, 2, and 3 under high temperature conditions show that the microcapsules can maintain low mass loss and high storage modulus at 200°C, proving that Examples 1-3 have excellent thermal stability and are suitable for use in high-temperature environments such as energy storage power stations. The present invention is not limited to the above-mentioned embodiments. Anyone should be aware that any structural changes made under the guidance of the present invention, and any technical solutions that are the same or similar to the present invention, fall within the scope of protection of the present invention. The present invention is not detailed.

Claims

1. A method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power stations, characterized in that: The following steps are involved: Step S1: mixing an emulsifier and a solvent, and dissolving them at a temperature of 30°C to 50°C to form an aqueous phase system; Step S2: perfluorohexanone, isophorone diisocyanate and diethylenetriamine are mixed in a mass ratio to obtain an oil phase system, and then polycaprolactone is added to the obtained oil phase system; Step S3: adding the oil phase to the water phase under stirring, and mixing the oil phase and the water phase with an emulsifier to form a stable emulsion; Step S4: adding pentaerythritol and polypropylene glycol to the emulsion to obtain a polymerization reaction system; Step S5: through a polyurethane polymerization reaction, IPDI reacts with DETA and pentaerythritol to form a shell, which wraps the perfluorohexanone as the core to form a microcapsule structure; Step S6: post-processing the microcapsules and further curing them by heating them in batches to ensure the stability of the polyurethane shell. After the curing is completed, the final high-efficiency microcapsule fire extinguishing agent for energy storage power stations is obtained.

2. The method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power station according to claim 1, characterized in that: The mass ratio of the solvent to the emulsifier in step S1 is between 10-20:

1.

3. The method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power station according to claim 1, characterized in that: In step S2, the mass ratio of perfluorohexanone, isophorone diisocyanate and diethylenetriamine is 1:2:

1.

4. The method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power station according to claim 1, characterized in that: In step S2, polycaprolactone accounts for 5%-15% of the oil phase system.

5. The method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power station according to claim 1, characterized in that: In step S3, the oil phase is added to the water phase in a water-to-oil ratio of 6:

1.

6. The method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power station according to claim 1, characterized in that: During the mixing process in step S3, the emulsification speed is 2000 rpm and the emulsification time is 10 minutes.

7. The method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power station according to claim 1, characterized in that: In step S4, the amount of pentaerythritol and polypropylene glycol used is 0.5%-1.0% of the total mass of the emulsion, and the mass ratio of pentaerythritol to polypropylene glycol is between 1:1-2, so as to promote the cross-linking reaction of the microcapsule shell.

8. The method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power station according to claim 1, characterized in that: Step S5 is carried out at a reaction temperature of 60° C. to 80° C. until the microcapsule shell is completely formed.

9. The method for preparing a high-efficiency microcapsule fire extinguishing agent for energy storage power station according to claim 1, characterized in that: The particle size of the microcapsule fire extinguishing agent formed in step S5 is 3-5 μm.

10. A high-efficiency microcapsule fire extinguishing agent for energy storage power station, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 9.

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