Active fire extinguishing microcapsule, preparation method and application thereof, ultraviolet curing resin plate and preparation method thereof

Abstract

The invention relates to the technical field of fire extinguishing materials, and discloses an active fire extinguishing microcapsule, a preparation method and application thereof, an ultraviolet curing resin plate and a preparation method thereof. The microcapsule has a core-shell structure, a core material is perfluoro (2-methyl-3-pentanone) (PFMP), and the microcapsule is used as an efficient fire extinguishing agent and is suitable for inhibiting the heat rise rate of an ultraviolet curing polymer in thermal runaway and fire scenes; and the shell layer is a polymer wall material formed by gelatin, has a certain thickness and can be broken at a preset temperature. Through simple condensation, PFMP is used as a core material for microencapsulation, and the microcapsule with specific particle size distribution is prepared, so that the microcapsule can quickly release a fire extinguishing agent under a high-temperature condition, and flames are effectively inhibited.

Description

Technical Field

[0001] The invention relates to the technical field of fire extinguishing materials, in particular to an active fire extinguishing microcapsule for improving the safety of ultraviolet light-cured polymers, a preparation method and application thereof, and an ultraviolet light-cured resin plate and a preparation method thereof. Background Art

[0002] UV-curable polymers are widely used in coatings, adhesives, 3D printing and medical fields due to their fast curing properties. However, these polymers tend to release flammable gases at high temperatures, increasing the risk of fire and limiting their further application. Therefore, improving the safety of UV-curable polymers is an urgent problem to be solved. Although existing flame retardant additives can reduce the flammability of materials to a certain extent, most of them are passive protection and cannot effectively deal with direct ignition of fire sources. Summary of the invention

[0003] The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide an active fire extinguishing microcapsule, a preparation method and application, an ultraviolet light curing resin plate and a preparation method thereof.

[0004] The technical solution adopted by the present invention to solve its technical problem is:

[0005] An active fire extinguishing microcapsule, the active fire extinguishing microcapsule is a core-shell structure, comprising a core material and a shell material wrapped around the outside of the core material; the core material is one or more of perfluoro(2-methyl-3-pentanone) (PFMP), dimethyl 1,4-cyclohexyldicarboxylate, trichloroethyl phosphate, ammonium polyphosphate or aluminum hydroxide, and the shell material is one or more of melamine-modified urea-formaldehyde resin, urea-formaldehyde resin, phenolic resin, melamine resin, polymethyl methacrylate, gelatin (GE), titanium dioxide and montmorillonite.

[0006] Furthermore, the active fire extinguishing microcapsules are spherical in shape and have a particle size of 40 to 140 microns.

[0007] A method for preparing the above-mentioned active fire extinguishing microcapsules specifically comprises the following steps:

[0008] Step S1, preparing a shell material solution, dissolving the shell material in deionized water, and preparing a primary shell material solution at a mass ratio of 1:4; using anhydrous sodium carbonate or sodium hydroxide as an alkaline regulator, adjusting the pH value of the primary shell material solution to about 8.0, placing the adjusted solution in a water bath and heating it, controlling the water bath temperature to 40° C. to 50° C., stirring for 30 minutes to ensure that the shell material is completely dissolved and a uniform shell material solution is formed;

[0009] Step S2, preparing a core material emulsified solution, mixing the core material and the core material emulsifier in a volume ratio of 1:1, and shearing and emulsifying the core material emulsified solution at a speed of 8000 rpm for 5 minutes in a high-speed shear disperser, so that the core material emulsified solution forms uniform small droplets with a diameter in the range of 10 μm to 100 μm, forming a stable water-in-oil emulsion;

[0010] Step S3, microcapsule preparation, gradually adding the pre-prepared wall material solution into the core material emulsified solution, and controlling the temperature within the range of 30°C to 50°C; adjusting the pH of the reaction system to 4.0 to 5.0 with a citric acid solution, and continuously stirring at 200rpm to 600rpm, and reacting for 90 minutes to obtain a microcapsule suspension;

[0011] Step S4, collecting and drying microcapsules, diluting the obtained suspension and letting it stand for 12 hours, using a filter to collect the microcapsules deposited on the bottom; finally, drying at 40° C. for 6 hours to obtain the active fire extinguishing microcapsule finished product.

[0012] Furthermore, in step S2, the core material emulsifier is one of potassium perfluorooctane sulfonate, sodium dodecylbenzene sulfonate (SDBS), perfluorooctanoic acid, and sodium dodecyl sulfate.

[0013] An application of the active fire extinguishing microcapsules as described above, application of the active fire extinguishing microcapsules in fireproof materials, wherein the microcapsules are incorporated into at least one fireproof material to improve the fireproof performance of the material.

[0014] An application of the active fire extinguishing microcapsule as described above, application of the active fire extinguishing microcapsule in 3D printing technology, and the microcapsule is used as an additive to improve the safety of 3D printing materials.

[0015] An application of the active fire extinguishing microcapsule as described above, application of the active fire extinguishing microcapsule in coatings or adhesives, wherein the microcapsule is used as an additive to improve the fireproof performance of the coatings or adhesives.

[0016] An application of the active fire extinguishing microcapsule as described above, application of the active fire extinguishing microcapsule in a lithium ion battery separator, and the microcapsule being an additive for improving the thermal resistance and mechanical properties of the lithium ion battery separator.

[0017] Rapidly suppress the thermal runaway of lithium-ion batteries in the early stage of thermal runaway to avoid thermal runaway caused by disordered temperature rise. Preferably, the temperature range for releasing the microcapsule fire extinguishing agent or flame retardant core material is set at around 80°C. By attaching the microcapsule fire extinguishing agent to the lithium-ion battery separator or in the interlayer between the lithium-ion battery separator and the aluminum-plastic film, the thermal runaway of the lithium-ion battery can be released in the early stage to avoid heat accumulation, thereby improving the intrinsic safety of the lithium-ion battery.

[0018] A UV-curable resin plate comprises the following components in parts by weight: 1 part of the above-mentioned active fire-extinguishing microcapsules and 4 parts of a resin prepolymer mixture; the resin prepolymer mixture is prepared by mixing epoxy acrylate (EA), ethylene glycol diacrylate (EDA) and a photoinitiator.

[0019] A method for preparing the above-mentioned UV-curable resin plate specifically comprises the following steps:

[0020] Step a, mixing, mixing the microcapsule powder and the resin prepolymer mixture uniformly;

[0021] Step b: UV curing: using a 365nm UV high pressure mercury lamp to cure the mixture for 5 minutes.

[0022] The method for testing the fireproof performance of the above-mentioned UV-curable resin plate is: placing the above-mentioned UV-curable resin plate under simulated fire conditions, and measuring the flame propagation and toxic gas release of the resin plate under the fire conditions.

[0023] In the application of UV-curable resin, the active fire-extinguishing microcapsules of the present invention can quickly release the fire-extinguishing core material at the early stage of the fire source, effectively inhibit the spread of flames, and avoid the combustion of materials caused by heat accumulation. Preferably, the temperature range for the microcapsule to release the core material is set at about 80°C to 120°C. By directly incorporating the microcapsules into the UV-curable resin or coating them on the resin surface, it is ensured that the fire extinguishing agent can be actively released at the early stage of the fire to prevent the fire from spreading, thereby improving the safety performance of the UV-curable material.

[0024] The beneficial effects of the present invention are as follows: the present invention has a reasonable design, a simple preparation method, and has the following advantages:

[0025] (1) The active fire extinguishing microcapsules of the present invention have an active fire extinguishing function. When encountering high temperature, the microcapsules will rupture and quickly release the core material contained therein, thereby directly suppressing the spread of flames in the early stages of a fire. This active response characteristic greatly improves the fire extinguishing effect, while traditional flame retardant resins rely more on the fire resistance of the material and cannot provide similar immediate protection. Secondly, the thermal responsiveness of the active fire extinguishing microcapsules is precise, and fire extinguishing can be initiated at a specific temperature to prevent the spread of fire, while traditional flame retardants only prevent fire by delaying combustion or improving heat resistance.

[0026] (2) The active fire extinguishing microcapsules of the present invention are also significantly more environmentally friendly than traditional flame retardant materials. Perfluoro(2-methyl-3-pentanone) is a highly efficient fire extinguishing agent, which is used in a small amount, has a significant flame retardant effect and reduces pollution to the environment, avoiding the harmful substances that may be produced when traditional flame retardants decompose at high temperatures;

[0027] (3) The active fire extinguishing microcapsules in the present invention have little effect on the mechanical properties of the resin in terms of material properties. By optimizing the addition ratio of the microcapsules (e.g., 10 wt%), the resin can maintain excellent mechanical properties and achieve efficient flame retardant effects. Traditional flame retardants often cause the resin to become brittle or reduce strength, thereby impairing the mechanical properties of the material.

[0028] (4) The active fire extinguishing microcapsules of the present invention also ensure the long-term stability of the material. The physical isolation of the shell material from the fire extinguishing agent ensures the long-term stability of the fire extinguishing agent and prevents it from becoming ineffective due to time migration or volatilization. This is more advantageous than traditional flame retardants.

[0029] (5) The active fire extinguishing microcapsules of the present invention have outstanding application flexibility. They are not only suitable for UV-curable resins, but also can be applied to other resin systems. They are suitable for a wide range of industrial application scenarios, such as electronic equipment, automotive parts and building materials. In general, the active fire extinguishing microcapsules of the present invention show significant advantages in active fire extinguishing, environmental protection, mechanical property maintenance and long-term flame retardant effect, and are an efficient and safe innovative flame retardant material. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1 This is a picture of the emulsified core material droplets of the microcapsule core material in Example 1;

[0032] Figure 2 is a picture of the stably coated microcapsules in Example 1;

[0033] Figure 3 This is a picture of the wall material of the microcapsule with uniform surface texture in Example 1;

[0034] Figure 4 This is a SEM electron microscope image of the microcapsule before rupture in Example 1;

[0035] Figure 5 This is a SEM electron microscope image of the microcapsules after rupture in Example 1;

[0036] Figure 6 1 is the resin stress-strain curve of the resin plates with different microcapsule contents in Example 2, Comparative Example 5, Comparative Example 6 and Comparative Example 7;

[0037] Figure 7It is the DSC curve of the resin containing 10 wt% microcapsules in Example 2 and the blank group. DETAILED DESCRIPTION

[0038] It should be noted that the following detailed descriptions are illustrative and are intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present application belongs.

[0039] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form also includes the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this description, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0040] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] An active fire extinguishing microcapsule, which is a core-shell structure, including a core material and a shell material wrapped around the outside of the core material; the core material is one or more of perfluoro(2-methyl-3-pentanone), dimethyl 1,4-cyclohexyldicarboxylate, trichloroethyl phosphate, ammonium polyphosphate or aluminum hydroxide, and the shell material is one or more of melamine-modified urea-formaldehyde resin, urea-formaldehyde resin, phenolic resin, melamine resin, polymethyl methacrylate, gelatin, titanium dioxide and montmorillonite. The active fire extinguishing microcapsule is spherical in shape, with a particle size of 40 to 140 microns.

[0042] A method for preparing the above-mentioned active fire extinguishing microcapsules specifically comprises the following steps:

[0043] Step S1, preparing a shell material solution, dissolving the shell material in deionized water, and preparing a primary shell material solution at a mass ratio of 1:4; using anhydrous sodium carbonate or sodium hydroxide as an alkaline regulator, adjusting the pH value of the primary shell material solution to about 8.0, placing the adjusted solution in a water bath and heating it, controlling the water bath temperature to 40° C. to 50° C., stirring for 30 minutes to ensure that the shell material is completely dissolved and a uniform shell material solution is formed;

[0044] Step S2, preparing a core material emulsified solution, mixing the core material and the core material emulsifier in a volume ratio of 1:1, and shearing and emulsifying the core material emulsified solution at a speed of 8000 rpm for 5 minutes in a high-speed shear disperser, so that the core material emulsified solution forms uniform small droplets with a diameter in the range of 10 μm to 100 μm, forming a stable water-in-oil emulsion;

[0045] Step S3, microcapsule preparation, gradually adding the pre-prepared wall material solution into the core material emulsified solution, and controlling the temperature within the range of 30°C to 50°C; adjusting the pH of the reaction system to 4.0 to 5.0 with a citric acid solution, and continuously stirring at 200rpm to 600rpm, and reacting for 90 minutes to obtain a microcapsule suspension;

[0046] Step S4, collecting and drying microcapsules, diluting the obtained suspension and letting it stand for 12 hours, using a filter to collect the microcapsules deposited on the bottom; finally, drying at 40° C. for 6 hours to obtain the active fire extinguishing microcapsule finished product.

[0047] In step S2, the core material emulsifier is one of potassium perfluorooctane sulfonate, sodium dodecylbenzene sulfonate, perfluorooctanoic acid, and sodium dodecyl sulfate.

[0048] An application of the active fire extinguishing microcapsules as described above, and an application of the active fire extinguishing microcapsules in fireproof materials, wherein the microcapsules are incorporated into at least one fireproof material to improve the fireproof performance of the material.

[0049] An application of the active fire extinguishing microcapsules as described above, application of the active fire extinguishing microcapsules in 3D printing technology, and the microcapsules as additives for improving the safety of 3D printing materials.

[0050] An application of the active fire extinguishing microcapsules as described above, application of the active fire extinguishing microcapsules in coatings or adhesives, and the microcapsules are used as additives to improve the fireproof performance of coatings or adhesives.

[0051] An application of the active fire extinguishing microcapsules as described above, the application of the active fire extinguishing microcapsules in lithium ion battery separators, and the microcapsules are used as additives to improve the thermal resistance and mechanical properties of lithium ion battery separators.

[0052] A UV-curable resin plate comprises the following components in parts by weight: 1 part of active fire-extinguishing microcapsules and 4 parts of a resin prepolymer mixture; the resin prepolymer mixture is prepared by mixing epoxy acrylate, ethylene glycol diacrylate and a photoinitiator.

[0053] A method for preparing a UV-curable resin plate comprises the following steps:

[0054] Step a, mixing, mixing the microcapsule powder and the resin prepolymer mixture uniformly;

[0055] Step b: UV curing: using a 365nm UV high pressure mercury lamp to cure the mixture for 5 minutes.

[0056] Example 1

[0057] A method for preparing the above-mentioned active fire extinguishing microcapsules specifically comprises the following steps:

[0058] Step S1, preparation of wall material solution, dissolving 5g of gelatin in 100ml of deionized water, stirring in a 50°C water bath until completely dissolved, to obtain a 5% w / v gelatin solution; adjusting the pH to 8.0 to ensure the stability of the solution, and setting aside;

[0059] Step S2, emulsifying the core material, taking 50 ml of perfluoro(2-methyl-3-pentanone) (PFMP) as the core material, and mixing it with 50 ml of sodium dodecylbenzene sulfonate (SDBS) emulsifier solution (2% w / v); using a high-speed shear disperser to perform shear dispersion at a speed of 8000 rpm for 5 minutes to form a uniform and stable oil-in-water emulsion; the droplet diameter is controlled within the range of 10 μm to 100 μm;

[0060] Step S3, microcapsule preparation, gradually adding the emulsified PFMP emulsion into the gelatin solution, maintaining the stirring speed at 200 rpm to 800 rpm, and controlling the reaction temperature between 30° C. and 50° C.; adjusting the pH value of the reaction system to 4.0 to 5.0 with a citric acid solution, and setting the reaction time to 90 minutes, during which a microcapsule suspension with a core-shell structure is formed;

[0061] Step S4, collecting and drying microcapsules. After the reaction is completed, add an appropriate amount of distilled water to the suspension for dilution, and let it stand for 12 hours; collect the precipitated microcapsules by filtration, and dry them at 40° C. for 6 hours; obtain the finished active fire extinguishing microcapsules, i.e., the finished PFMP@GE microcapsules.

[0062] Example 2

[0063] A method for preparing a UV-curable resin plate containing 10 wt% PFMP@GE microcapsules comprises the following steps:

[0064] (1) Synthesis of resin prepolymer: 98% epoxy acrylate (50 g) and ethylene glycol diacrylate (10 g) were mixed, an appropriate amount of photoinitiator ethyl (2,4,6-trimethylbenzoyl) phenylphosphonate (0.5 g) was added, and stirred evenly at 25° C. using a magnetic stirrer to obtain a prepolymer solution;

[0065] (2) Incorporation of microcapsules: 10 wt% PFMP@GE microcapsules (based on the mass of prepolymer) were gradually added to the prepolymer solution, and stirring was continued until the microcapsules were evenly dispersed in the resin, ensuring that there were no obvious bubbles or stratification in the solution;

[0066] (3) Preparation of resin plate: pour the stirred resin prepolymer solution into a silicone mold, scrape the surface to ensure uniform thickness; then, expose it to a 365nm ultraviolet lamp for 5 minutes to perform a photocuring reaction, and the resin is completely cured to form a solid resin plate;

[0067] (4) Post-treatment of the resin plate: The cured resin plate is taken out from the mold and left to stand at room temperature for 12 hours to ensure complete curing and volatilization of residual gas.

[0068] Comparative Example 1

[0069] The difference from Example 1 is that the concentration of the emulsifier is lower. This comparative example uses a lower emulsifier concentration to prepare PFMP@GE microcapsules. The preparation method of this comparative example includes the following steps:

[0070] (1) Preparation of wall material solution: 5 g of gelatin was dissolved in 100 ml of deionized water, and stirred in a 50° C. water bath until completely dissolved to prepare a 5% w / v gelatin solution; the pH was adjusted to 8.0 to ensure the stability of the solution, and the solution was set aside;

[0071] (2) emulsifying the core material: 50 ml of perfluoro(2-methyl-3-pentanone) was mixed with 50 ml of an emulsifier sodium dodecylbenzene sulfonate (SDBS) solution (1% w / v); shearing and dispersing was performed using a high-speed shear disperser at a speed of 8000 rpm for 5 minutes to form an oil-in-water emulsion;

[0072] (3) Preparation of microcapsules: gradually add the emulsified PFMP emulsion to the gelatin solution, keep the stirring speed between 200 rpm and 800 rpm, and control the reaction temperature between 30° C. and 50° C.; adjust the pH to 4.0 to 5.0 with a citric acid solution, react for 90 minutes, and form a microcapsule suspension;

[0073] (4) Microcapsule collection and drying: the microcapsule suspension was diluted with distilled water and allowed to stand for 12 hours; thereafter, the precipitated microcapsules were collected through a filter and dried at 40° C. for 6 hours to obtain the final PFMP@GE microcapsule product.

[0074] Comparative Example 2

[0075] The difference from Example 1 is that the shear rate is higher. This comparative example uses a higher shear rate to prepare PFMP@GE microcapsules. The preparation method of this comparative example includes the following steps:

[0076] (1) Preparation of wall material solution: 5 g of gelatin was dissolved in 100 ml of deionized water, and stirred in a 50° C. water bath until completely dissolved to prepare a 5% w / v gelatin solution; the pH was adjusted to 8.0 to ensure the stability of the solution, and the solution was set aside;

[0077] (2) Emulsifying the core material: 50 ml of perfluoro(2-methyl-3-pentanone) was mixed with 50 ml of an emulsifier SDBS solution (2% w / v); shearing and dispersing was performed using a high-speed shear disperser at a speed of 9000 rpm for 5 minutes to form an oil-in-water emulsion;

[0078] (3) Preparation of microcapsules: gradually add the emulsified PFMP emulsion to the gelatin solution, keep the stirring speed between 200 rpm and 800 rpm, and control the reaction temperature between 30° C. and 50° C.; adjust the pH to 4.0 to 5.0 with a citric acid solution, react for 90 minutes, and form a microcapsule suspension;

[0079] (4) Collection and drying of microcapsules: the microcapsule suspension was diluted with distilled water and allowed to stand for 12 hours; the precipitated microcapsules were collected through a filter and dried at 40° C. for 6 hours to obtain the final PFMP@GE microcapsule product.

[0080] Comparative Example 3

[0081] The difference from Example 1 is that the shear rate is lower. This comparative example uses a lower shear rate to prepare PFMP@GE microcapsules. The preparation method of this comparative example includes the following steps:

[0082] (1) Preparation of wall material solution: 5 g of gelatin was dissolved in 100 ml of deionized water, and stirred in a 50° C. water bath until completely dissolved to prepare a 5% w / v gelatin solution; the pH was adjusted to 8.0 to ensure the stability of the solution, and the solution was set aside;

[0083] (2) Emulsifying the core material: 50 ml of perfluoro(2-methyl-3-pentanone) was mixed with 50 ml of emulsifier SDBS solution (2% w / v); shearing and dispersing was performed using a high-speed shear disperser at a speed of 7000 rpm for 5 minutes to form an oil-in-water emulsion;

[0084] (3) Preparation of microcapsules: gradually add the emulsified PFMP emulsion to the gelatin solution, keep the stirring speed between 200 rpm and 800 rpm, and control the reaction temperature between 30° C. and 50° C.; adjust the pH to 4.0 to 5.0 with a citric acid solution, react for 90 minutes, and form a microcapsule suspension;

[0085] (4) Microcapsule collection and drying: the microcapsule suspension was diluted with distilled water and allowed to stand for 12 hours; thereafter, the precipitated microcapsules were collected through a filter and dried at 40° C. for 6 hours to obtain the final PFMP@GE microcapsule product.

[0086] Comparative Example 4

[0087] The difference from Example 1 is that the concentration of the emulsifier is higher. This comparative example uses a higher emulsifier concentration to prepare PFMP@GE microcapsules. The preparation method of this comparative example includes the following steps:

[0088] (1) Preparation of wall material solution: 5 g of gelatin was dissolved in 100 ml of deionized water, and stirred in a 50° C. water bath until completely dissolved to prepare a 5% w / v gelatin solution; the pH was adjusted to 8.0 to ensure the stability of the solution, and the solution was set aside;

[0089] (2) Emulsifying the core material: 50 ml of perfluoro(2-methyl-3-pentanone) was mixed with 50 ml of emulsifier SDBS solution (3% w / v); shearing and dispersing was performed using a high-speed shear disperser at a speed of 8000 rpm for 5 minutes to form an oil-in-water emulsion;

[0090] (3) Preparation of microcapsules: gradually add the emulsified PFMP emulsion to the gelatin solution, keep the stirring speed between 200 rpm and 800 rpm, and control the reaction temperature between 30° C. and 50° C.; adjust the pH to 4.0 to 5.0 with a citric acid solution, react for 90 minutes, and form a microcapsule suspension;

[0091] (4) Collection and drying of microcapsules: the microcapsule suspension was diluted with distilled water and allowed to stand for 12 hours; the precipitated microcapsules were collected through a filter and dried at 40° C. for 6 hours to obtain the final PFMP@GE microcapsule product.

[0092] Comparative Example 5

[0093] The difference from Example 2 is that no PFMP@GE microcapsules are added. This comparative example prepares a UV-curable resin plate without microcapsules. The preparation steps of this comparative example are as follows:

[0094] (1) Synthesis of resin prepolymer: The same as in Example 2, 98% epoxy acrylate (50 g) and ethylene glycol diacrylate (10 g) were mixed, and an appropriate amount of photoinitiator ethyl (2,4,6-trimethylbenzoyl) phenylphosphonate (0.5 g) was added, and the mixture was stirred at 25° C. to obtain a prepolymer solution;

[0095] (2) Preparation of resin plate: without adding microcapsules, the prepolymer solution is directly poured into the silicone mold and the surface is scraped flat;

[0096] (3) UV curing, exposure to 365nm ultraviolet light for 5 minutes to complete the curing process;

[0097] (4) Post-treatment of the resin plate: The cured resin plate was taken out from the mold and allowed to stand at room temperature for 12 hours.

[0098] Comparative Example 6

[0099] The difference from Example 2 is that 15 wt% of PFMP@GE microcapsules are added. The preparation steps of this comparative example are as follows:

[0100] (1) Synthesis of resin prepolymer: The same as in Example 2, 98% epoxy acrylate (50 g) and ethylene glycol diacrylate (10 g) were mixed, and an appropriate amount of photoinitiator ethyl (2,4,6-trimethylbenzoyl) phenylphosphonate (0.5 g) was added, and stirred evenly to obtain a prepolymer solution;

[0101] (2) Incorporation of microcapsules: 15 wt % of PFMP@GE microcapsules were gradually added to the prepolymer solution and stirred until the microcapsules were uniformly dispersed;

[0102] (3) Preparation of resin plate: pour the stirred resin prepolymer solution into the silicone mold and scrape the surface flat;

[0103] (4) UV curing and post-treatment: Expose to a 365nm UV lamp for 5 minutes to complete the curing, and take out the finished product after standing for 12 hours.

[0104] Comparative Example 7

[0105] The difference from Example 2 is that 20 wt% of PFMP@GE microcapsules are added. The preparation steps of this comparative example are as follows:

[0106] (1) Synthesis of resin prepolymer: The same as in Example 2, 98% epoxy acrylate (50 g) and ethylene glycol diacrylate (10 g) were mixed, and an appropriate amount of photoinitiator ethyl (2,4,6-trimethylbenzoyl) phenylphosphonate (0.5 g) was added, and stirred evenly to obtain a prepolymer solution;

[0107] (2) Incorporation of microcapsules: 20 wt% PFMP@GE microcapsules were gradually added to the prepolymer solution and stirred until the microcapsules were uniformly dispersed;

[0108] (3) Preparation of resin plate: pour the stirred resin prepolymer solution into the silicone mold and scrape the surface flat;

[0109] (4) UV curing and post-treatment: Expose to a 365nm UV lamp for 5 minutes to complete the curing, and take out the finished product after standing for 12 hours.

[0110] The morphology of the microcapsule fire extinguishing agent prepared in Example 1 was characterized. The results are as follows Figure 1 , Figure 2 and Figure 3 As shown, the microcapsule fire extinguishing agent has a typical core-shell structure.

[0111] The morphology of the microcapsule fire extinguishing agent prepared in Example 1 before and after release was characterized. The results are as follows: Figure 4 , Figure 5 As shown, the core material inside the microcapsule is released after it is ruptured.

[0112] The emulsions prepared in Example 1 and Comparative Examples 1 to 3 were left to stand for 10 minutes and their properties were observed. The results are shown in Table 1 below.

[0113] Table 1 Experimental data of Example 1 and Comparative Examples 1 to 3

[0114]

[0115] Based on the above embodiments and comparative examples, it can be seen that the following conclusions are drawn by observing the emulsion after standing for 10 minutes under different emulsification conditions: In Example 1 (the mass ratio of emulsifier to core material is 2.0%, and the shear rate is 8000rpm), the emulsion exhibits good dispersion uniformity, the oil phase droplets are evenly distributed, and there is no obvious stratification after standing, and only a small amount of foam is generated, indicating that the emulsion under this condition has high stability and is suitable as an ideal process for preparing microcapsules. In Comparative Example 1 (the mass ratio of emulsifier to core material is 1.0%, and the shear rate is 8000 rpm), although the shear rate is the same, due to the low emulsifier concentration, the oil phase droplets are unevenly dispersed, and the emulsion is stratified after standing, and the stability is poor. In Comparative Example 2 (the mass ratio of emulsifier to core material is 2.0%, and the shear rate is 9000rpm), although the droplets are uniform and there is no stratification, due to the high shear rate, a large amount of foam is generated in the emulsion, which may affect the final quality of the microcapsules. Comparative Example 3 (emulsifier to core material mass ratio of 2.0%, shear rate 7000rpm) has poor dispersion of oil phase droplets, poor emulsion stability, and stratification due to insufficient shear rate. Comparative Example 4 (emulsifier to core material mass ratio of 3.0%, shear rate 8000rpm) also shows good dispersion uniformity and no stratification, but produces a large amount of foam, indicating that although too high emulsifier concentration improves the uniformity of the emulsion, it may lead to the generation of too much foam, thereby affecting the quality of the microcapsules. Therefore, the emulsification conditions of Example 1 have achieved a good balance between uniformity and stability, and are preferred process conditions.

[0116] In the mechanical test of the present invention, Figure 6 and Figure 7As shown, by conducting stress-strain tests on resin plates with different microcapsule contents, the following conclusions were drawn: In Example 2 (microcapsule content is 10wt%), the resin plate exhibits good mechanical properties, and the stress-strain curve shows that the material has high tensile strength and ductility. This shows that at this microcapsule content, a good balance is achieved between the mechanical properties and fire extinguishing effect of the resin plate, and the toughness and rigidity of the material remain relatively ideal. In Comparative Example 5 (without microcapsules), due to the absence of microcapsules, the mechanical properties of the resin plate are the most excellent, showing the highest tensile strength and ductility. However, due to the lack of microcapsules, the material does not have an active fire extinguishing function. Comparative Example 6 (microcapsule content is 15wt%) shows that with the increase of microcapsule content, the mechanical properties of the resin plate decrease, and the tensile strength and ductility are slightly lower than those of Example 2. Although the fire extinguishing effect is enhanced, excessive microcapsule filling may affect the mechanical strength of the material. Comparative Example 7 (microcapsule content is 20wt%) shows a significant decrease in mechanical properties, the tensile strength of the resin plate is significantly reduced, the material becomes more brittle, and the ductility is greatly reduced. This shows that although the excessively high microcapsule content significantly improves the fire extinguishing effect, it significantly weakens the mechanical properties of the material, making it unsuitable for use in scenarios requiring high mechanical strength. In summary, the mechanical properties of Example 2 (10wt% microcapsules) show good comprehensiveness, and can have a fire extinguishing function while maintaining a certain mechanical strength.

[0117] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An active fire extinguishing microcapsule, characterized in that: The active fire extinguishing microcapsule is a core-shell structure, including a core material and a shell material wrapped around the outside of the core material; the core material is one or more of perfluoro(2-methyl-3-pentanone), dimethyl 1,4-cyclohexyldicarboxylate, trichloroethyl phosphate, ammonium polyphosphate or aluminum hydroxide, and the shell material is one or more of melamine-modified urea-formaldehyde resin, urea-formaldehyde resin, phenolic resin, melamine resin, polymethyl methacrylate, gelatin, titanium dioxide and montmorillonite.

2. The active fire extinguishing microcapsule according to claim 1, characterized in that: The active fire extinguishing microcapsule is spherical in shape and has a particle size of 40 to 140 microns.

3. A method for preparing the active fire extinguishing microcapsule according to any one of claims 1 to 2, characterized in that: The specific steps include: Step S1, preparing a shell material solution, dissolving the shell material in deionized water, and preparing a primary shell material solution at a mass ratio of 1:4; using anhydrous sodium carbonate or sodium hydroxide as an alkaline regulator, adjusting the pH value of the primary shell material solution to about 8.0, placing the adjusted solution in a water bath and heating it, controlling the water bath temperature to 40° C. to 50° C., stirring for 30 minutes to ensure that the shell material is completely dissolved and a uniform shell material solution is formed; Step S2, preparing a core material emulsified solution, mixing the core material and the core material emulsifier in a volume ratio of 1:1, and shearing and emulsifying the core material emulsified solution at a speed of 8000 rpm for 5 minutes in a high-speed shear disperser, so that the core material emulsified solution forms uniform small droplets with a diameter in the range of 10 μm to 100 μm, forming a stable water-in-oil emulsion; Step S3, microcapsule preparation, gradually adding the pre-prepared wall material solution into the core material emulsified solution, and controlling the temperature within the range of 30°C to 50°C; adjusting the pH of the reaction system to 4.0 to 5.0 with a citric acid solution, and continuously stirring at 200rpm to 600rpm, and reacting for 90 minutes to obtain a microcapsule suspension; Step S4, collecting and drying microcapsules, diluting the obtained suspension and letting it stand for 12 hours, using a filter to collect the microcapsules deposited on the bottom; finally, drying at 40° C. for 6 hours to obtain the active fire extinguishing microcapsule finished product.

4. The method for preparing active fire extinguishing microcapsules according to claim 3, characterized in that: In step S2, the core material emulsifier is one of potassium perfluorooctane sulfonate, sodium dodecylbenzene sulfonate, perfluorooctanoic acid, and sodium dodecyl sulfate.

5. An application of the active fire extinguishing microcapsule according to any one of claims 1 to 2, characterized in that: The active fire extinguishing microcapsules are used in fireproof materials. The microcapsules are added into at least one fireproof material to improve the fireproof performance of the material.

6. An application of the active fire extinguishing microcapsule according to any one of claims 1 to 2, characterized in that: The active fire extinguishing microcapsules are used in 3D printing technology, and the microcapsules are used as additives to improve the safety of 3D printing materials.

7. An application of the active fire extinguishing microcapsule according to any one of claims 1 to 2, characterized in that: The active fire extinguishing microcapsules are used in coatings or adhesives, and the microcapsules are used as additives to improve the fireproof performance of coatings or adhesives.

8. An application of the active fire extinguishing microcapsule according to any one of claims 1 to 2, characterized in that: The active fire extinguishing microcapsules are used in lithium ion battery separators. The microcapsules are used as additives to improve the thermal resistance and mechanical properties of lithium ion battery separators.

9. A UV-curable resin plate, characterized in that: The invention comprises the following components in parts by weight: 1 part of the active fire extinguishing microcapsule as claimed in any one of claims 1 to 2, and 4 parts of a resin prepolymer mixture; the resin prepolymer mixture is prepared by mixing epoxy acrylate, ethylene glycol diacrylate and a photoinitiator.

10. A method for preparing a UV-curable resin plate as claimed in claim 9, characterized in that: The specific steps include: Step a, mixing, mixing the microcapsule powder and the resin prepolymer mixture uniformly; Step b: UV curing: using a 365nm UV high pressure mercury lamp to cure the mixture for 5 minutes.

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