Perfluorohexanone fire-extinguishing microspheres with oversized particle size and preparation method of perfluorohexanone fire-extinguishing microspheres

Abstract

The invention relates to the technical field of preparation of perfluorohexanone fire extinguishing agents, and provides perfluorohexanone fire extinguishing microspheres and a preparation method thereof, the perfluorohexanone fire extinguishing microspheres have the characteristics of high core-shell ratio and super large particle size, the size is 3-3000 microns, and the processing of subsequent procedures is facilitated. Reaction preparation is completed under the low-temperature condition by adopting an initiating system composed of an oxidizing agent and a reducing agent, the volatilization loss of perfluorohexanone is effectively reduced, the problem that an existing microsphere material is short in storage time is solved, and the storage stability and commercial application value of a product are remarkably improved; in addition, the microspheres can be prepared into patches, coatings and other products according to actual requirements, are suitable for machine rooms, power transformation boxes, batteries and other scenes, and are convenient to use.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of perfluorohexanone fire extinguishing agents, and more specifically, to an ultra-large particle size perfluorohexanone fire extinguishing microsphere and a preparation method thereof. Background Art

[0002] Perfluorohexanone is an efficient and environmentally friendly fire extinguishing agent material. By encapsulating an environmentally friendly perfluorohexanone fire extinguishing agent in a polymer material, a microcapsule structure is formed. When the environmental temperature reaches a preset threshold or directly contacts an open flame, the outer shell of the microsphere is heated and ruptured, and the internal perfluorohexanone quickly vaporizes and diffuses to the fire source area, realizing the efficient and directional release of the fire extinguishing agent and the rapid automatic suppression of the fire. As a new coating method, the microsphere technology has been increasingly widely used in the flame retardant field.

[0003] Currently, when the existing perfluorohexanone is prepared into microspheres, affected by the reaction conditions, it is technically difficult to simultaneously achieve both high content and large particle size. For example, when the reaction temperature is above 50°C, the fire extinguishing agent is in a gaseous state and the coating amount is relatively low. When the content is less than 50%, the particle size is generally less than 100 microns. For some with a content exceeding 80%, the particle size is also limited to less than 10 microns. Thus, there are still many technical obstacles in the perfluorohexanone microsphere technology, and no breakthrough progress has been achieved.

[0004] To solve the above problems, an ultra-large particle size perfluorohexanone fire extinguishing microsphere and a preparation method thereof are proposed in this application. Summary of the Invention

[0005] The purpose of the present invention is to provide an ultra-large particle size perfluorohexanone fire extinguishing microsphere and a preparation method thereof, to solve the limitations of the existing technology, and to prepare a fire extinguishing agent with ultra-large particle size microspheres and high content of perfluorohexanone.

[0006] To solve the above technical problems, the present invention is realized through the following technical solutions:

[0007] An ultra-large particle size perfluorohexanone fire extinguishing microsphere, comprising a core material and a shell material;

[0008] The core material is liquid perfluorohexanone, and the shell material is polyacrylate resin;

[0009] The polymer acrylate monomer is used as a macromonomer to increase the molecular weight of the shell material through reaction; at the same time, a redox initiation system is adopted to polymerize the shell material at the interface to form a macromolecular shell material, forming a macromolecular shell material to coat perfluorohexanone, thereby realizing an ultra-large particle size perfluorohexanone fire extinguishing microsphere;

[0010] The particle size of perfluorohexanone fire extinguishing microspheres ranges from 3μm to 3000μm. Due to its fire extinguishing performance and material compatibility, it can be combined with spinning, coating and other processes and applied to different objects to achieve the effect of extinguishing fire and preventing re-ignition.

[0011] Preferably, the polyacrylate resin comprises polyvinyl alcohol 1788, water, methoxyethyl methacrylate or tetrahydrofuran acrylate, octadecyl acrylate, polymer acrylate monomer, dipentaerythritol hexaacrylate, ammonium persulfate, and tetramethylethylenediamine;

[0012] Among them, polyvinyl alcohol 1788 is used as a dispersant and emulsifier, methoxyethyl methacrylate or tetrahydrofuran acrylate is a reactive monomer to promote the formation of microspheres, octadecyl acrylate is a long-chain alkyl monomer to inhibit the volatilization of perfluorohexanone during the reaction, polymer acrylate monomer is a surfactant functional monomer to regulate the particle size distribution of microspheres, dipentaerythritol hexaacrylate is a highly branched crosslinker to increase the crosslinking density of the shell, ammonium persulfate and tetramethylethylenediamine are used as the redox initiation system to achieve low-temperature controllable polymerization and avoid thermal degradation of perfluorohexanone.

[0013] A method for preparing ultra-large particle size perfluorohexanone fire extinguishing microspheres comprises the following steps:

[0014] S1: Preparation of emulsion aqueous phase: Disperse the emulsifier in water to form a uniform aqueous phase;

[0015] S2: Preparation of emulsion: adding perfluorohexanone, acrylate monomer and acrylate crosslinker to the above aqueous phase and mixing them uniformly by emulsification treatment;

[0016] S3: Emulsion reaction: add the oxidant and initiator to the above emulsion in sequence and stir evenly, then add the reducing agent and stir evenly again; allow the emulsion to react continuously at room temperature;

[0017] S4: Filtration and drying: After the above reaction is completed, the reaction product is filtered through a 400-mesh filter, the filter residue is collected and dried at room temperature, and finally perfluorohexanone fire extinguishing microspheres are obtained.

[0018] Preferably, the preparation processes of S1, S2 and S3 can all be carried out under low temperature conditions, so that the coated perfluorohexanone is always in liquid state, optimizing the fire extinguishing efficiency, and allowing the perfluorohexanone to be vaporized within 0.5 seconds after being sprayed out. The high heat absorption rate quickly blocks the combustion chain reaction, and there is no residue after the fire is extinguished, avoiding secondary cleaning pollution. It is particularly suitable for the protection of cultural relics and precision instruments.

[0019] Preferably, the mass fraction of the emulsifier in the aqueous phase of the emulsion of S1 is 0.1% to 2%;

[0020] Preferably, the emulsifier is selected from one or more of sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, sodium dibutylnaphthalenesulfonate, alkylamine polyoxyethylene ether phosphate, lauryl alcohol polyoxyethylene ether, isooctyl polyoxyethylene ether, octadecyl alcohol polyoxyethylene ether, isotridecyl polyoxyethylene ether, Tween 80, polyoxyethylene polyoxypropylene block copolymer, polyvinyl alcohol 1788, polyvinyl alcohol 1799, F127, and OP-10.

[0021] Preferably, in the preparation of the emulsion in S2, the mass ratio of perfluoromethyl hexanone to water is 20:100 to 100:100, the mass ratio of acrylate monomer to perfluoromethyl hexanone is 1:1 to 1:5, and the mass ratio of acrylate crosslinking agent to acrylate monomer is 1:1 to 1:40.

[0022] Preferably, in the preparation of the emulsion in S2, the acrylate monomer is selected from one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, methoxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-(dimethylamino)ethyl methacrylate, acetoacetic acid ethyl methacrylate, glycidyl methacrylate, polyethylene glycol acrylate, acrylamide, diacetone acrylamide, acryloyloxyethyl trimethylammonium chloride, tetrahydrofurfuryl acrylate, methoxyethyl acrylate, butyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, and polymer acrylate monomers;

[0023] Among them, the macromolecular chain segment of the polymer acrylate monomer can inhibit the premature formation of low-molecular microspheres by means of steric hindrance effect, optimize the microsphere particle size distribution coefficient, significantly improve the slow-release uniformity of the fire extinguishing agent, and the alkyl chains are arranged in an orderly manner to form a smooth surface to reduce the flow resistance of the microspheres, meeting the requirements of high-precision coating process.

[0024] Preferably, in the preparation of the emulsion in S2, the acrylate crosslinking agent is selected from one or more of diol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dicyclopentenyl acrylate, diallyl maleate, and triallyl isocyanurate;

[0025] Among them, dipentaerythritol hexaacrylate can cooperate with monomers such as methoxyethyl methacrylate to achieve rapid phase change of the microsphere shell layer at a specific temperature and accurately trigger the release of the fire extinguishing agent.

[0026] Preferably, in the emulsion reaction in S3, the mass ratio of the oxidizing agent to the acrylate monomer is 1:16 to 1:100, and the mass ratio of the reducing agent to the oxidizing agent is 1:1 to 1:10.

[0027] Preferably, in the emulsion reaction in S3, the oxidizing agent is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate, and benzoyl peroxide.

[0028] Preferably, in the emulsion reaction of S3, the reducing agent is one or more of tetramethylethylenediamine, diisopropylethylamine, triethylamine, dimethylethylenediamine, tetraethylethylenediamine, and pentamethyldiethylenetriamine.

[0029] Preferably, in the emulsion reaction of S3, the stirring reaction time is 2 hours to 2.5 hours.

[0030] Advantages of the present invention:

[0031] The perfluoroketone encapsulated by the macromolecular shell material prepared in the present invention realizes ultra-large particle size fire extinguishing microspheres, significantly improves the effective ingredient concentration of the fire extinguishing material per unit volume, shortens the time required for the fire source area to reach the fire extinguishing critical concentration, fully covers the fire source to shorten the fire extinguishing time, and blocks the risk of re-ignition;

[0032] By adopting an initiation system composed of an oxidizing agent and a reducing agent, the reaction is completed under low temperature conditions in the present invention, effectively reducing the volatilization loss of perfluoroketone;

[0033] The perfluoroketone microspheres of the present invention have a particle size range of 3 microns to 3000 microns, are suitable for various application scenarios such as spinning, coating, and molding, and under the same fire extinguishing requirements, the deployment density of the large particle size microspheres is obvious, reducing the equipment installation complexity and cost. Description of the Drawings

[0034] Figure 1 It is a schematic diagram of the microspheres prepared in the examples of the present invention under an optical microscope; Detailed Embodiments

[0035] The present invention will be described in detail below with reference to the drawings and specific embodiments.

[0036] Example 1

[0037] This example provides a method for preparing ultra-large particle size perfluoroketone fire extinguishing microspheres, and the steps are as follows:

[0038] (1) Aqueous phase preparation: 1 part of polyvinyl alcohol 1788 is dispersed in 289 parts of water to form a uniform aqueous phase;

[0039] (2) Emulsion preparation: 160 parts of perfluoroketone, 28 parts of methoxyethyl methacrylate, 12 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer, and 12 parts of dipentaerythritol hexaacrylate are added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0040] (3) Emulsion reaction: 10 parts of ammonium persulfate were successively added to the above emulsion and stirred well, and then 1.6 parts of tetramethylethylenediamine were added and stirred evenly again to allow the emulsion to react at room temperature;

[0041] (4) Filtration and drying: After the above reaction was completed, the reaction product was filtered through a 400-mesh filter screen, the filter residue was collected and dried at room temperature, and finally perfluoromethyl hexanone fire-extinguishing microspheres were prepared.

[0042] Example 2

[0043] This example provides a method for preparing super-large-size perfluoromethyl hexanone fire-extinguishing microspheres, and the steps are as follows:

[0044] (1) Aqueous phase preparation: 1 part of polyvinyl alcohol 1788 was dispersed in 289 parts of water to form a uniform aqueous phase;

[0045] (2) Emulsion preparation: 160 parts of perfluoromethyl hexanone, 28 parts of methoxyethyl methacrylate, 12 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer and 8 parts of dipentaerythritol hexaacrylate were added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0046] (3) Emulsion reaction: 10 parts of ammonium persulfate were successively added to the above emulsion and stirred well, and then 1.6 parts of tetramethylethylenediamine were added and stirred evenly again to allow the emulsion to react at room temperature;

[0047] ((4) Filtration and drying: After the above reaction was completed, the reaction product was filtered through a 400-mesh filter screen, the filter residue was collected and dried at room temperature, and finally perfluoromethyl hexanone fire-extinguishing microspheres were prepared.

[0048] Example 3

[0049] This example provides a method for preparing super-large-size perfluoromethyl hexanone fire-extinguishing microspheres, and the steps are as follows:

[0050] (1) Aqueous phase preparation: 1 part of polyvinyl alcohol 1788 was dispersed in 289 parts of water to form a uniform aqueous phase;

[0051] (2) Emulsion preparation: 160 parts of perfluoromethyl hexanone, 28 parts of methoxyethyl methacrylate, 12 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer and 4 parts of dipentaerythritol hexaacrylate were added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0052] (3) Emulsion reaction: 10 parts of ammonium persulfate were successively added to the above emulsion and stirred well, and then 1.6 parts of tetramethylethylenediamine were added and stirred evenly again to allow the emulsion to react at room temperature;

[0053] (4) Filtration and drying: After the above reaction is completed, the reaction product is filtered through a 400-mesh filter, the filter residue is collected and dried at room temperature, and finally perfluorohexanone fire extinguishing microspheres are obtained.

[0054] Example 4

[0055] This embodiment provides a method for preparing ultra-large particle size perfluorohexanone fire extinguishing microspheres, the steps of which are as follows:

[0056] (1) Preparation of aqueous phase: Disperse 1 part of polyvinyl alcohol 1788 in 289 parts of water to form a uniform aqueous phase;

[0057] (2) Emulsion preparation: 160 parts of perfluorohexanone, 28 parts of tetrahydrofuran acrylate, 12 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer and 12 parts of dipentaerythritol hexaacrylate were added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0058] (3) Emulsion reaction: 10 parts of ammonium persulfate were added to the above emulsion in sequence and stirred thoroughly, followed by adding 1.6 parts of tetramethylethylenediamine and stirring again, and the emulsion was allowed to react at room temperature;

[0059] (4) Filtration and drying: After the above reaction is completed, the reaction product is filtered through a 400-mesh filter, the filter residue is collected and dried at room temperature, and finally perfluorohexanone fire extinguishing microspheres are obtained.

[0060] Example 5

[0061] This embodiment provides a method for preparing ultra-large particle size perfluorohexanone fire extinguishing microspheres, the steps of which are as follows:

[0062] (1) Preparation of aqueous phase: Disperse 1 part of polyvinyl alcohol 1788 in 289 parts of water to form a uniform aqueous phase;

[0063] (2) Emulsion preparation: 160 parts of perfluorohexanone, 28 parts of tetrahydrofuran acrylate, 12 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer and 8 parts of dipentaerythritol hexaacrylate were added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0064] (3) Emulsion reaction: 10 parts of ammonium persulfate were added to the above emulsion in sequence and stirred thoroughly, followed by adding 1.6 parts of tetramethylethylenediamine and stirring again, and the emulsion was allowed to react at room temperature;

[0065] (4) Filtration and drying: After the above reaction is completed, the reaction product is filtered through a 400-mesh filter, the filter residue is collected and dried at room temperature, and finally perfluorohexanone fire extinguishing microspheres are obtained.

[0066] Example 6

[0067] This embodiment provides a method for preparing super-large particle size perfluoromethyl hexanone fire extinguishing microspheres, and the steps are as follows:

[0068] (1) Aqueous phase preparation: Disperse 1 part of polyvinyl alcohol 1788 into 289 parts of water to form a uniform aqueous phase;

[0069] (2) Emulsion preparation: Add 160 parts of perfluoromethyl hexanone, 28 parts of tetrahydrofuran acrylate, 12 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer and 4 parts of dipentaerythritol hexaacrylate to the above aqueous phase, and emulsify for 15 minutes at 2000 rpm to obtain a uniform emulsion;

[0070] (3) Emulsion reaction: Add 10 parts of ammonium persulfate to the above emulsion and stir well, then add 1.6 parts of tetramethylethylenediamine and stir evenly again, and allow the emulsion to react at room temperature;

[0071] (4) Filtration and drying: After the above reaction is completed, filter the reaction product with a 400-mesh filter screen, collect the filter residue and dry it at room temperature to finally obtain perfluoromethyl hexanone fire extinguishing microspheres.

[0072] Example 7

[0073] This embodiment provides a method for preparing super-large particle size perfluoromethyl hexanone fire extinguishing microspheres, and the steps are as follows:

[0074] (1) Aqueous phase preparation: Disperse 1 part of polyvinyl alcohol 1788 into 289 parts of water to form a uniform aqueous phase;

[0075] (2) Emulsion preparation: Add 160 parts of perfluoromethyl hexanone, 28 parts of tetrahydrofuran acrylate, 12 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer and 2 parts of dipentaerythritol hexaacrylate to the above aqueous phase, and emulsify for 15 minutes at 2000 rpm to obtain a uniform emulsion;

[0076] (3) Emulsion reaction: Add 10 parts of ammonium persulfate to the above emulsion and stir well, then add 1.6 parts of tetramethylethylenediamine and stir evenly again, and allow the emulsion to react at room temperature;

[0077] (4) Filtration and drying: After the above reaction is completed, filter the reaction product with a 40 mesh filter screen, collect the filter residue and dry it at room temperature to finally obtain perfluoromethyl hexanone fire extinguishing microspheres.

[0078] Example 8

[0079] This embodiment provides a method for preparing super-large particle size perfluoromethyl hexanone fire extinguishing microspheres, and the steps are as follows:

[0080] (1) Preparation of aqueous phase: Disperse 1 part of polyvinyl alcohol 1788 in 289 parts of water to form a uniform aqueous phase;

[0081] (2) Emulsion preparation: 160 parts of perfluorohexanone, 28 parts of tetrahydrofuran acrylate, 12 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer and 1 part of dipentaerythritol hexaacrylate were added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0082] (3) Emulsion reaction: 10 parts of ammonium persulfate were added to the above emulsion in sequence and stirred thoroughly, followed by adding 1.6 parts of tetramethylethylenediamine and stirring again, and the emulsion was allowed to react at room temperature;

[0083] (4) Filtration and drying: After the above reaction is completed, the reaction product is filtered through a 400-mesh filter, the filter residue is collected and dried at room temperature, and finally perfluorohexanone fire extinguishing microspheres are obtained.

[0084] Example 9

[0085] This embodiment provides a method for preparing ultra-large particle size perfluorohexanone fire extinguishing microspheres, the steps of which are as follows:

[0086] (1) Preparation of aqueous phase: Disperse 1 part of polyvinyl alcohol 1788 in 289 parts of water to form a uniform aqueous phase;

[0087] (2) Emulsion preparation: 160 parts of perfluorohexanone, 20 parts of tetrahydrofuran acrylate, 20 parts of octadecyl acrylate, 2.4 parts of polymer acrylate monomer and 1 part of dipentaerythritol hexaacrylate were added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0088] (3) Emulsion reaction: 10 parts of ammonium persulfate were added to the above emulsion in sequence and stirred thoroughly, followed by adding 1.6 parts of tetramethylethylenediamine and stirring again, and the emulsion was allowed to react at room temperature;

[0089] (4) Filtration and drying: After the above reaction is completed, the reaction product is filtered through a 400-mesh filter, the filter residue is collected and dried at room temperature, and finally perfluorohexanone fire extinguishing microspheres are obtained.

[0090] Example 10

[0091] This embodiment provides a method for preparing ultra-large particle size perfluorohexanone fire extinguishing microspheres, the steps of which are as follows:

[0092] (1) Preparation of aqueous phase: Disperse 1 part of polyvinyl alcohol 1788 in 289 parts of water to form a uniform aqueous phase;

[0093] (2) Emulsion preparation: Add 160 parts of perfluorohexanone, 20 parts of tetrahydrofurfuryl acrylate, 20 parts of octadecyl acrylate, 0 part of polymer acrylate monomer, and 1 part of dipentaerythritol hexaacrylate to the above aqueous phase, and emulsify for 15 minutes at 2000 rpm to obtain a uniform emulsion;

[0094] (3) Emulsion reaction: Add 10 parts of ammonium persulfate to the above emulsion and stir well, then add 1.6 parts of tetramethylethylenediamine and stir evenly again, and allow the emulsion to react at room temperature;

[0095] (4) Filtration and drying: After the above reaction is completed, filter the reaction product through a 400-mesh filter screen, collect the filter residue and dry it at room temperature to finally obtain perfluorohexanone fire-extinguishing microspheres.

[0096] Example 11

[0097] This example provides a method for preparing super-large-size perfluorohexanone fire-extinguishing microspheres, and the steps are as follows:

[0098] (1) Aqueous phase preparation: Disperse 1 part of polyvinyl alcohol 1788 in 289 parts of water to form a uniform aqueous phase;

[0099] (2) Emulsion preparation: Add 160 parts of perfluorohexanone, 28 parts of tetrahydrofurfuryl acrylate, 12 parts of octadecyl acrylate, 4.8 parts of polymer acrylate monomer, and 1 part of dipentaerythritol hexaacrylate to the above aqueous phase, and emulsify for 15 minutes at 2000 rpm to obtain a uniform emulsion;

[0100] (3) Emulsion reaction: Add 10 parts of ammonium persulfate to the above emulsion and stir well, then add 1.6 parts of tetramethylethylenediamine and stir evenly again, and allow the emulsion to react at room temperature;

[0101] (4) Filtration and drying: After the above reaction is completed, filter the reaction product through a 400-mesh filter screen, collect the filter residue and dry it at room temperature to finally obtain perfluorohexanone fire-extinguishing microspheres.

[0102] Comparative Example 1

[0103] This example provides a method for preparing super-large-size perfluorohexanone fire-extinguishing microspheres, and the steps are as follows:

[0104] (1) Aqueous phase preparation: Disperse 1 part of polyvinyl alcohol 1788 in 289 parts of water to form a uniform aqueous phase;

[0105] (2) Emulsion preparation: Add 160 parts of perfluorohexanone, 20 parts of tetrahydrofurfuryl acrylate, 20 parts of octadecyl acrylate, 0 part of polymer acrylate monomer, and 0 part of dipentaerythritol hexaacrylate to the above aqueous phase, and emulsify for 15 minutes at 2000 rpm to obtain a uniform emulsion;

[0106] (3) Emulsion reaction: 10 parts of ammonium persulfate were sequentially added to the above emulsion and stirred thoroughly, and then 1.6 parts of tetramethylethylenediamine were added and stirred evenly again to allow the emulsion to react at room temperature;

[0107] (4) Filtration and drying: After the above reaction was completed, the reaction product was filtered through a 400-mesh filter screen, the filter residue was collected and dried at room temperature, and finally perfluorohexanone fire-extinguishing microspheres were prepared.

[0108] Comparative Example 2

[0109] This example provides a method for preparing super-large-sized perfluorohexanone fire-extinguishing microspheres, and the steps are as follows:

[0110] (1) Aqueous phase preparation: 1 part of polyvinyl alcohol 1799 was dispersed in 289 parts of water to form a uniform aqueous phase;

[0111] (2) Emulsion preparation: 160 parts of perfluorohexanone, 20 parts of tetrahydrofurfuryl acrylate, 20 parts of octadecyl acrylate, 12 parts of polymer acrylate monomer and 0 parts of dipentaerythritol hexaacrylate were added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0112] (3) Emulsion reaction: 10 parts of ammonium persulfate were sequentially added to the above emulsion and stirred thoroughly, and then 1.6 parts of tetramethylethylenediamine were added and stirred evenly again to allow the emulsion to react at room temperature;

[0113] (4) Filtration and drying: After the above reaction was completed, the reaction product was filtered through a 400-mesh filter screen, the filter residue was collected and dried at room temperature, and finally perfluorohexanone fire-extinguishing microspheres were prepared.

[0114] Comparative Example 3

[0115] This example provides a method for preparing super-large-sized perfluorohexanone fire-extinguishing microspheres, and the steps are as follows:

[0116] (1) Aqueous phase preparation: 1 part of polyvinyl alcohol 1788 was dispersed in 289 parts of water to form a uniform aqueous phase;

[0117] (2) Emulsion preparation: 160 parts of perfluorohexanone, 28 parts of tetrahydrofurfuryl acrylate, 12 parts of octadecyl acrylate, 12 parts of polymer acrylate monomer and 12 parts of dipentaerythritol hexaacrylate were added to the above aqueous phase and emulsified at 2000 rpm for 15 minutes to obtain a uniform emulsion;

[0118] (3) Emulsion reaction:

[0119] (4) Filtration and drying: After the above reaction is completed, the reaction product is filtered through a 400-mesh filter screen, the filter residue is collected and dried at room temperature, and finally perfluorinated hexanone fire-extinguishing microspheres are prepared.

[0120] Furthermore, the size of the microspheres was observed and recorded using an optical microscope. Subsequently, the perfluorinated hexanone fire-extinguishing microspheres prepared in Examples 1-11 and Comparative Examples 1-3 in different dosage ratios were placed in ceramic vessels. 1 g of microspheres and 1 g of solvent oil were weighed respectively, and after mixing the two, ignition was carried out for a fire-extinguishing experiment, and the fire-extinguishing time was recorded simultaneously. The specific test data are shown in the following table:

[0121]

[0122]

[0123] Table 1

[0124] From the comparison of Examples 1-11 and Comparative Examples 1-3 combined with the test results in Table 1, it can be known that the preparation methods of Examples 1-11 significantly increased the coating amount of perfluorinated hexanone, so that a sufficient amount of fire extinguishing agent can be released in case of a fire. Compared with the fire extinguishing agent prepared by the traditional method, the fire extinguishing speed was reduced to 27 seconds, showing a faster fire extinguishing effect.

[0125] It should be noted that the above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Any person skilled in the art can make changes or modifications to equivalent embodiments with equivalent changes within the scope of the technical solution of the present invention, and all fall within the protection scope of the present invention.

Claims

1. An ultra-large particle size perfluoropentanone fire extinguishing microsphere, comprising a core material and a shell material, characterized in that: The core material is liquid perfluoropentanone, and the shell material is polyacrylate resin; The polymer acrylate monomer is used as a macromonomer, and an oxidant and a reductant are used as an initiation system to polymerize the shell material at the interface to form a macromolecular shell material; The particle size range of the perfluoropentanone fire extinguishing microsphere is 3 μm to 3000 μm.

2. The super-large particle size perfluorhexanone fire extinguishing microspheres according to claim 1, characterized in that: The polyacrylate resin includes polyvinyl alcohol 1788, water, methoxyethyl acrylate or tetrahydrofurfuryl acrylate, octadecyl acrylate, polymer acrylate monomer, dipentaerythritol hexaacrylate, ammonium persulfate, and tetramethylethylenediamine.

3. The preparation method of the super-large particle size perfluoroketone fire extinguishing microspheres according to any one of claims 1-2, characterized in that, It includes the following steps: S1: Preparation of the emulsion aqueous phase: Disperse the emulsifier in water to form a uniform aqueous phase; S2: Preparation of the emulsion: Add perfluoropentanone, acrylate monomer, and acrylate crosslinking agent to the above aqueous phase, and make them uniformly mixed through emulsification treatment; S3: Emulsion reaction: Sequentially add an oxidant initiator to the above emulsion and stir evenly, then add a reductant and stir evenly again; make the emulsion continuously react at room temperature; S4: Filtration and drying: After the above reaction is complete, filter the reaction product with a 400-mesh filter screen, collect the filter residue and dry it at room temperature to finally obtain the perfluoropentanone fire extinguishing microsphere; The preparation processes of S1, S2, and S3 are carried out under the room temperature condition of 20 - 30 °C or the low temperature condition of 0 - 10 °C, so that the encapsulated perfluoropentanone is always in a liquid state.

4. The preparation method of the super-large particle size perfluoromethylcyclohexanone fire extinguishing microspheres according to claim 3, wherein: In the emulsion aqueous phase of S1, the mass fraction of the emulsifier is 0.1% to 2%.

5. The preparation method of the super-large particle size perfluorhexanone fire extinguishing microspheres according to claim 4, characterized in that: The emulsifier is selected from at least one of sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, sodium dibutylnaphthalenesulfonate, alkylamine polyoxyethylene ether phosphate, lauryl alcohol polyoxyethylene ether, isooctyl polyoxyethylene ether, octadecyl alcohol polyoxyethylene ether, isotridecyl polyoxyethylene ether, Tween 80, polyoxyethylene polyoxypropylene block copolymer, polyvinyl alcohol 1788, polyvinyl alcohol 1799, F127, and OP-10.

6. The preparation method of the super-large particle size perfluorhexanone fire extinguishing microspheres according to claim 3, characterized in that: In the preparation of the emulsion in S2, the mass ratio of perfluoropentanone to water is 20:100 to 100:100, the mass ratio of the acrylate monomer to perfluoropentanone is 1:1 to 1:5, and the mass ratio of the acrylate crosslinking agent to the acrylate monomer is 1:1 to 1:

40.

7. The preparation method of the super-large particle size perfluorhexanone fire extinguishing microspheres according to claim 6, wherein: In the preparation of the emulsion in S2, the acrylate monomer is selected from at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, methoxyethyl acrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl methacrylate, acetoacetic acid ethyl methacrylate, glycidyl methacrylate, polyethylene glycol acrylate, acrylamide, diacetone acrylamide, acryloyloxyethyl trimethylammonium chloride, tetrahydrofurfuryl acrylate, methoxyethyl acrylate, butyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, and polymer acrylate monomer.

8. The preparation method of the super-large particle size perfluorhexanone fire extinguishing microspheres according to claim 6, wherein: In the preparation of the emulsion of S2, the acrylate crosslinking agent is selected from at least one of diol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dicyclopentenyl acrylate, diallyl maleate, and triallyl isocyanurate.

9. The preparation method of the super-large particle size perfluoromethylcyclohexanone fire extinguishing microspheres according to claim 3, characterized in that: In the emulsion reaction of S3, the mass ratio of the oxidizing agent to the acrylate monomer is 1:16 to 1:100, and the mass ratio of the reducing agent to the oxidizing agent is 1:1 to 1:

10.

10. The preparation method of the super-large particle size perfluoroketone fire extinguishing microspheres according to claim 9, characterized in that: In the emulsion reaction of S3, the oxidizing agent is selected from at least one of sodium persulfate, potassium persulfate, ammonium persulfate, and benzoyl peroxide.

11. The preparation method of the super-large particle size perfluorhexanone fire extinguishing microspheres according to claim 9, wherein: In the emulsion reaction of S3, the reducing agent is at least one of tetramethylethylenediamine, diisopropylethylamine, triethylamine, dimethylethylenediamine, tetraethylethylenediamine, and pentamethyldiethylenetriamine.

12. The preparation method of the super-large particle size perfluorhexanone fire extinguishing microspheres according to claim 9, wherein: In the emulsion reaction of S3, the stirring reaction time is 2 hours to 2.5 hours.

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