Active fire extinguishing microcapsule, preparation method, use, ultraviolet-curable resin board and preparation method therefor

Abstract

The present invention relates to the technical field of fire extinguishing materials. Disclosed are an active fire extinguishing microcapsule, a preparation method, the use, an ultraviolet-curable resin board and a preparation method therefor. The microcapsule has a core-shell structure, in which a core material is perfluoro (2-methyl-3-pentanone) (PFMP) that, as an efficient fire extinguishing agent, is adapted to suppress the heat rise rate of ultraviolet-curable polymers in thermal runaway and fire environments, and a shell layer is a polymer wall material constituted by gelatin, has a certain thickness, and can rupture at a preset temperature. By means of simple agglomeration, PFMP is microencapsulated as the core material to prepare a microcapsule having a specific particle size distribution, which rapidly releases a fire extinguishing agent under high temperature conditions, effectively suppressing flames.

Description

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

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

[0002] UV-curable polymers are widely used in coatings, adhesives, 3D printing and medical fields due to their fast curing characteristics. However, such polymers are prone 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 some extent, most of them are passive protection and cannot effectively respond to direct ignition of fire sources. SUMMARY

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

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

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

[0006] Further, the active fire extinguishing microcapsule has a spherical shape and a particle size of 40-140 microns.

[0007] A preparation method of the active fire extinguishing microcapsule as described above, specifically comprising the following steps:

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

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

[0010] Step S3, microcapsule preparation, gradually add the pre-prepared wall material solution to the core material emulsion solution, and control the temperature within 30-50°C; adjust the pH of the reaction system to 4.0-5.0 by citric acid solution, and continuously stir at 200-600 rpm; after 90 minutes of reaction, a microcapsule suspension is obtained;

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

[0012] Further, the core material emulsifier in step S2 is one of potassium perfluorooctanesulfonate, sodium dodecylbenzenesulfonate (SDBS), perfluorooctanoic acid, and sodium dodecyl sulfate.

[0013] An application of the active fire extinguishing microcapsule as described above, the application of the active fire extinguishing microcapsule in fireproof materials, the microcapsule is 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, the application of the active fire extinguishing microcapsule in 3D printing technology, the microcapsule as an additive to improve the safety of 3D printing materials.

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

[0016] An application of the active fire extinguishing microcapsule as described above, the application of the active fire extinguishing microcapsule in lithium ion battery separators, the microcapsule as an additive to improve the thermal resistance and mechanical properties of lithium ion battery separators.

[0017] In the initial stage of lithium ion battery thermal runaway, the lithium ion battery thermal runaway is rapidly suppressed, and the disorderly temperature rise is avoided to cause thermal runaway. As a preferred, the temperature range for releasing the core material of the microcapsule fire extinguishing agent or flame retardant is set around 80°C. By attaching the microcapsule fire extinguishing agent to the lithium ion battery separator or the interlayer of the lithium ion battery separator and the aluminum plastic film, the release in the initial stage of lithium ion battery thermal runaway is ensured, and the heat accumulation is avoided, thereby improving the intrinsic safety of the lithium ion battery.

[0018] An ultraviolet light curing resin plate comprises the following components by weight: 1 part of the active fire extinguishing microcapsule as described above, 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 preparation method of the ultraviolet light curing resin plate as described above, specifically comprising the following steps:

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

[0021] Step b, ultraviolet light curing, using a 365 nm ultraviolet high-pressure mercury lamp to cure the mixture, and the curing time is 5 minutes.

[0022] The method for detecting the fireproof performance of the ultraviolet light curing resin plate as described above is as follows: placing the ultraviolet light curing resin plate in a simulated fire condition, and measuring the flame propagation and the amount of toxic gas released by the resin plate under the fire condition.

[0023] In the application of ultraviolet light curing resin, the active fire extinguishing microcapsule of the present application can rapidly release the fire extinguishing core material at the initial stage of the fire source, effectively inhibit the spread of the flame, and avoid the burning of the material caused by heat accumulation. As a preferred, the temperature range for releasing the core material of the microcapsule is set near 80-120℃, and by directly incorporating the microcapsule into the ultraviolet light curing resin or coating it on the surface of the resin, it is ensured that the fire extinguishing agent can be actively released at the initial stage of the fire, preventing the expansion of the fire, thereby improving the safety performance of the ultraviolet light curing material.

[0024] The present application has the following advantages:

[0025] (1) The active fire extinguishing microcapsule in the present application has the function of active fire extinguishing. When encountering high temperature, the microcapsule will break and rapidly release the contained core material, thereby directly inhibiting the spread of the flame at the initial stage of the fire. This active response greatly improves the fire extinguishing effect, while traditional flame-retardant resin relies on the fire resistance of the material and cannot provide similar immediate protection. Secondly, the thermal responsiveness of the active fire extinguishing microcapsule is precise, and it can start fire extinguishing at a specific temperature to prevent the spread of the fire, while traditional flame retardants only delay combustion or improve heat resistance to prevent fire.

[0026] (2) The active fire extinguishing microcapsule in the present application is also significantly superior to traditional flame-retardant materials in environmental friendliness. Perfluoro(2-methyl-3-pentanone) as a high-efficiency fire extinguishing agent is used in small amounts, has significant flame-retardant effect and reduces environmental pollution, avoiding the generation of harmful substances during the decomposition of traditional flame retardants at high temperatures.

[0027] (3), the active fire extinguishing microcapsule in the application has little influence on the mechanical properties of the resin, and by optimizing the addition proportion (such as 10wt%) of the microcapsule, the resin can not only maintain excellent mechanical properties, but also achieve high efficient fire-retardant effect, while the traditional fire retardant often causes the resin to become brittle or the strength to decrease, so that the mechanical properties of the material are damaged;

[0028] (4), the active fire extinguishing microcapsule in the application also ensures the long-term stability of the material, the shell material physically isolates the fire extinguishing agent, ensuring the long-term stability of the fire extinguishing agent, and the fire extinguishing agent will not fail due to time migration or volatilization, which is more advantageous than the traditional fire retardant;

[0029] (5), the active fire extinguishing microcapsule in the application also has outstanding flexibility in application, which is not only suitable for ultraviolet curing resin, but also can be applied to other resin systems, and is suitable for a wide range of industrial application scenarios, such as electronic equipment, automobile parts and building materials; in general, the active fire extinguishing microcapsule in the application has significant advantages in active fire extinguishing, environmental protection, mechanical property maintenance and long-term fire-retardant effect, and is an efficient and safe innovative fire-retardant material. BRIEF DESCRIPTION OF DRAWINGS

[0030] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings needed to be used in the specific embodiments or the prior art description. Obviously, the drawings described below are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0031] Fig. 1 is a picture of microcapsule core material emulsified core material droplets in Example 1;

[0032] Fig. 2 is a picture of microcapsules with stable coating in Example 1;

[0033] Fig. 3 is a picture of microcapsule surface texture uniform wall material in Example 1;

[0034] Fig. 4 is an SEM electron microscope picture of microcapsules before rupture in Example 1;

[0035] Fig. 5 is an SEM electron microscope picture of microcapsules after rupture in Example 1;

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

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

[0038] It should be noted that the following detailed description is illustrative only, and is intended to provide further description in order to provide a thorough understanding of the exemplary embodiments according to the present application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the application pertains. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0039] It is also important to note that the use of the terms "preferably", "preferably", "more preferably", "most preferably" and other terms of degree such as "comprising", "containing" or "including" or the like, used herein are used to describe a preference for, or useful or desirable, but not necessarily essential, features of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the application pertains. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0040] The technical solutions of the present application will be described below in detail with reference to the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

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

[0042] A preparation method of the active fire extinguishing microcapsule as described above, specifically comprising the following steps:

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

[0044] Step S2, core material emulsion solution preparation, mixing the core material and the core material emulsifier at a volume ratio of 1:1, shearing and emulsifying the mixture at a speed of 8000 rpm for 5 minutes by a high-speed shearing dispersion machine, so that the core material emulsion solution forms uniform small droplets with a diameter in the range of 10-100 microns, and a stable oil-in-water emulsion is formed;

[0045] Step S3, microcapsule preparation, the pre-prepared wall material solution is gradually added to the core material emulsified solution, and the temperature is controlled within 30-50℃; the pH of the reaction system is adjusted to 4.0-5.0 by citric acid solution, and the stirring speed is maintained at 200-600rpm, and the reaction is continued for 90 minutes to obtain a microcapsule suspension;

[0046] Step S4, microcapsule collection and drying, the obtained suspension is diluted and settled for 12 hours, and the microcapsules deposited at the bottom are collected using a filter; finally, drying at 40℃ for 6 hours to obtain the finished product of the active fire extinguishing microcapsule.

[0047] The core material emulsifier in step S2 is one of potassium perfluorooctane sulfonate, sodium dodecyl benzene sulfonate, perfluorooctanoic acid and sodium dodecyl sulfate.

[0048] An application of the active fire extinguishing microcapsule as described above, the application of the active fire extinguishing microcapsule in fireproof materials, the microcapsule is incorporated into at least one fireproof material to improve the fireproof performance of the material.

[0049] An application of the active fire extinguishing microcapsule as described above, the application of the active fire extinguishing microcapsule in 3D printing technology, the microcapsule as an additive to improve the safety of 3D printing materials.

[0050] An application of the active fire extinguishing microcapsule as described above, the application of the active fire extinguishing microcapsule in coatings or adhesives, the microcapsule as an additive to improve the fireproof performance of coatings or adhesives.

[0051] An application of the active fire extinguishing microcapsule as described above, the application of the active fire extinguishing microcapsule in lithium ion battery separator, the microcapsule as an additive to improve the thermal resistance and mechanical properties of lithium ion battery separator.

[0052] An ultraviolet light curing resin plate, comprising the following components by weight: 1 part of active fire extinguishing microcapsule, 4 parts of resin prepolymer mixture; the resin prepolymer mixture is prepared by mixing epoxy acrylate, ethylene glycol diacrylate and photoinitiator.

[0053] A preparation method of an ultraviolet light curing resin plate, specifically comprising the following steps:

[0054] Step a, mixing, the microcapsule powder is uniformly mixed with the resin prepolymer mixture;

[0055] Step b, ultraviolet light curing, using a 365nm ultraviolet high pressure mercury lamp to cure the mixture, and the curing time is 5 minutes.

[0056] Example 1

[0057] A preparation method of the active fire extinguishing microcapsule as described above, specifically comprising the following steps:

[0058] Step S1, wall material solution preparation, 5 g of gelatin was dissolved in 100 ml of deionized water, stirred at 50°C water bath condition until completely dissolved, to obtain 5% w / v gelatin solution; by adjusting the pH to 8.0, to ensure the stability of the solution, ready for use;

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

[0060] Step S3, microcapsule preparation, the emulsified PFMP emulsion was gradually added to the gelatin solution, the stirring speed was maintained at 200 rpm to 800 rpm, and the reaction temperature was controlled between 30°C to 50°C; the pH value of the reaction system was adjusted to 4.0 to 5.0 by citric acid solution, and the reaction time was set to 90 minutes, during which the core-shell structure microcapsule suspension was formed;

[0061] Step S4, microcapsule collection and drying, after the reaction was completed, an appropriate amount of distilled water was added to the suspension for dilution, and it was allowed to stand and settle for 12 hours; the precipitated microcapsules were collected by filtration and dried at 40°C for 6 hours; the finished product of the active fire extinguishing microcapsule was obtained, which was the PFMP@GE microcapsule finished product.

[0062] Example 2

[0063] A method for preparing a ultraviolet light curing resin plate containing 10 wt% PFMP@GE microcapsules, comprising the following steps:

[0064] (1) Resin prepolymer synthesis, mix 98% epoxy acrylate (50 g) with ethylene glycol diacrylate (10 g), add an appropriate amount of photoinitiator ethyl (2,4,6-trimethylbenzoyl) phenyl phosphonate (0.5 g), and use a magnetic stirrer to stir uniformly at 25°C, to obtain a prepolymer solution;

[0065] (2) Incorporation of microcapsules, gradually add 10 wt% PFMP@GE microcapsules (based on the mass of the prepolymer) to the prepolymer solution, continue stirring until the microcapsules are uniformly dispersed in the resin, and ensure that the solution has no obvious bubbles or stratification;

[0066] (3) Resin plate preparation, pour the uniformly stirred resin prepolymer solution into a silicone mold, scrape the surface to ensure uniform thickness; then, expose to 365 nm ultraviolet light for 5 minutes for photopolymerization reaction, and form a solid resin plate after the resin is completely cured;

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

[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 the wall material solution, 5 g of gelatin is dissolved in 100 ml of deionized water, stirred in a 50°C water bath until completely dissolved, and prepared into a 5% w / v gelatin solution; adjust the pH to 8.0 to ensure the stability of the solution, and reserve for use;

[0071] (2) Emulsification of the core material, mix 50 ml of perfluoro(2-methyl-3-pentanone) with 50 ml of emulsifier sodium dodecylbenzenesulfonate (SDBS) solution (1% w / v); use a high-speed shear disperser to shear and disperse at a speed of 8000 rpm for 5 minutes to form a water-in-oil emulsion;

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

[0073] (4) Microcapsule collection and drying, dilute the microcapsule suspension with distilled water and let it stand for 12 hours; then, collect the precipitated microcapsules through a filter and dry them 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 speed is higher. This comparative example uses a higher shear speed to prepare PFMP@GE microcapsules. The preparation method of this comparative example includes the following steps:

[0076] (1) Preparation of the wall material solution, 5 g of gelatin is dissolved in 100 ml of deionized water, stirred in a 50°C water bath until completely dissolved, and prepared into a 5% w / v gelatin solution; adjust the pH to 8.0 to ensure the stability of the solution, and reserve for use;

[0077] (2) Emulsification of the core material, mix 50 ml of perfluoro(2-methyl-3-pentanone) with 50 ml of emulsifier SDBS solution (2% w / v); use a high-speed shear disperser to shear and disperse at a speed of 9000 rpm for 5 minutes to form a water-in-oil emulsion;

[0078] (3) Microcapsule preparation, the emulsified PFMP emulsion was gradually added to the gelatin solution, the stirring speed was maintained between 200 rpm and 800 rpm, and the reaction temperature was controlled between 30 °C and 50 °C; the pH was adjusted to 4.0-5.0 by citric acid solution, and the reaction was carried out for 90 minutes to form a microcapsule suspension;

[0079] (4) Microcapsule collection and drying, the microcapsule suspension was diluted with distilled water and then left to stand for 12 hours; the precipitated microcapsules were collected by 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 speed is lower, and this comparative example uses a lower shear speed to prepare the PFMP@GE microcapsule. The preparation method of this comparative example includes the following steps:

[0082] (1) Wall material solution preparation, 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 stability of the solution was ensured by adjusting the pH to 8.0, and it was ready for use;

[0083] (2) Core material emulsification, 50 ml of perfluoro(2-methyl-3-pentanone) was mixed with 50 ml of emulsifier SDBS solution (2% w / v); a high-speed shear disperser was used to shear and disperse at a speed of 7000 rpm for 5 minutes to form a water-in-oil emulsion;

[0084] (3) Microcapsule preparation, the emulsified PFMP emulsion was gradually added to the gelatin solution, the stirring speed was maintained between 200 rpm and 800 rpm, and the reaction temperature was controlled between 30 °C and 50 °C; the pH was adjusted to 4.0-5.0 by citric acid solution, and the reaction was carried out for 90 minutes to form a microcapsule suspension;

[0085] (4) Microcapsule collection and drying, the microcapsule suspension was diluted with distilled water and then left to stand for 12 hours; the precipitated microcapsules were collected by 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, and this comparative example uses a higher emulsifier concentration to prepare the PFMP@GE microcapsule. The preparation method of this comparative example includes the following steps:

[0088] (1) Wall material solution preparation, 5 g of gelatin was dissolved in 100 ml of deionized water, stirred in a 50 °C water bath until completely dissolved, prepared into a 5% w / v gelatin solution; by adjusting the pH to 8.0, ensure the stability of the solution, ready for use;

[0089] (2) Core material emulsification, 50 ml of perfluoro(2-methyl-3-pentanone) was mixed with 50 ml of emulsifier SDBS solution (3% w / v); using a high-speed shearing disperser, shearing dispersion at a speed of 8000 rpm for 5 minutes, forming a water-in-oil emulsion;

[0090] (3) Microcapsule preparation, the emulsified PFMP emulsion was gradually added to the gelatin solution, the stirring speed was maintained between 200 rpm and 800 rpm, and the reaction temperature was controlled between 30 °C and 50 °C; by adjusting the pH to 4.0-5.0 with citric acid solution, reaction for 90 minutes, forming a microcapsule suspension;

[0091] (4) Microcapsule collection and drying, the microcapsule suspension was diluted with distilled water and left to stand for 12 hours; the precipitated microcapsules were collected by filter and dried at 40 °C for 6 hours, to get the final PFMP@GE microcapsule product.

[0092] Comparative Example 5

[0093] The difference from Example 2 is that no PFMP@GE microcapsules are added, and the ultraviolet curing resin plate prepared in this comparative example does not contain microcapsules, and the preparation steps of this comparative example are as follows:

[0094] (1) Resin prepolymer synthesis, the same as Example 2, 98% epoxy acrylate (50 g) was mixed with ethylene glycol diacrylate (10 g), and an appropriate amount of photoinitiator ethyl (2,4,6-trimethylbenzoyl) phenyl phosphonate (0.5 g) was added, stirred uniformly at 25 °C, to get a prepolymer solution;

[0095] (2) Resin plate preparation, without adding microcapsules, the prepolymer solution was directly poured into a silicone mold and the surface was scraped flat;

[0096] (3) Ultraviolet curing, exposed to 365 nm 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 of the mold and left 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, and the preparation steps of this comparative example are as follows:

[0100] (1) Resin prepolymer synthesis, 98% epoxy acrylate (50 g) was mixed with ethylene glycol diacrylate (10 g), and an appropriate amount of photoinitiator ethyl (2, 4, 6-trimethylbenzoyl) phenyl phosphonate (0.5 g) was added, stirred uniformly to obtain a prepolymer solution;

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

[0102] (3) Resin plate preparation, the uniformly stirred resin prepolymer solution was poured into a silica gel mold, and the surface was scraped flat;

[0103] (4) UV curing and post-processing, exposure under 365 nm UV light for 5 minutes to complete curing, and the finished product was taken out after 12 hours of standing.

[0104] Comparative Example 7

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

[0106] (1) Resin prepolymer synthesis, 98% epoxy acrylate (50 g) was mixed with ethylene glycol diacrylate (10 g), and an appropriate amount of photoinitiator ethyl (2, 4, 6-trimethylbenzoyl) phenyl phosphonate (0.5 g) was added, stirred uniformly to obtain a prepolymer solution;

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

[0108] (3) Resin plate preparation, the uniformly stirred resin prepolymer solution was poured into a silica gel mold, and the surface was scraped flat;

[0109] (4) UV curing and post-processing, exposure under 365 nm UV light for 5 minutes to complete curing, and the finished product was taken out after 12 hours of standing.

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

[0111] The morphology of the microcapsule extinguishing agent prepared in Example 1 before and after release was characterized, and the results are shown in Figures 4 and 5. The core material inside the microcapsule is released after the microcapsule is broken.

[0112] The emulsion prepared in Example 1 and Comparative Examples 1-3 was allowed to stand for 10 minutes, and the observation results are shown in Table 1.

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

[0114] From the above examples and comparative examples, it can be seen that, by observing the emulsion after standing for 10 minutes under different emulsification conditions, the following conclusions are drawn: in Example 1 (the mass ratio of emulsifier to core material is 2.0%, and the shear speed is 8000 rpm), the emulsion shows good dispersion uniformity, the oil phase droplets are uniformly distributed, and no obvious stratification occurs after standing, 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 the preparation of microcapsules. In Comparative Example 1 (the mass ratio of emulsifier to core material is 1.0%, and the shear speed is 8000 rpm), although the shear speed is the same, the low concentration of emulsifier leads to uneven dispersion of oil phase droplets, and the emulsion stratifies after standing, with poor stability. Although Comparative Example 2 (the mass ratio of emulsifier to core material is 2.0%, and the shear speed is 9000 rpm) has uniform droplets and no stratification, the high shear speed generates a large amount of foam in the emulsion, which may affect the final quality of the microcapsules. In Comparative Example 3 (the mass ratio of emulsifier to core material is 2.0%, and the shear speed is 7000 rpm), the insufficient shear speed leads to poor dispersion of oil phase droplets, poor stability of the emulsion, and stratification. Comparative Example 4 (the mass ratio of emulsifier to core material is 3.0%, and the shear speed is 8000 rpm) also shows good dispersion uniformity and no stratification, but a large amount of foam is generated, indicating that a high emulsifier concentration, although improving the uniformity of the emulsion, may lead to the generation of excessive foam, which in turn affects the quality of the microcapsules. Therefore, the emulsification conditions of Example 1 achieve a good balance between uniformity and stability, and are the preferred process conditions.

[0115] In the mechanical test of the present application, as shown in FIGS. 6 and 7, by stress-strain test on resin plates with different microcapsule contents, the following conclusions are drawn: in Example 2 (microcapsule content of 10 wt%), the resin plate shows good mechanical properties, and the stress-strain curve shows that the material has high tensile strength and ductility. This indicates that at this microcapsule content, a good balance between the mechanical properties and fire extinguishing effect of the resin plate is achieved, 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 the active fire extinguishing function. Comparative Example 6 (microcapsule content of 15 wt%) 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 of 20 wt%) shows a significant decrease in mechanical properties, and the tensile strength of the resin plate is significantly reduced, the material becomes more brittle, and the ductility also decreases significantly. This indicates that too high microcapsule content significantly improves the fire extinguishing effect, but 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 (10 wt% microcapsules) show good overall performance, and can have fire extinguishing function while maintaining certain mechanical strength.

[0116] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, and are not limited thereto; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions described in the foregoing examples, or make equivalent substitutions for part or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solution to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A proactive fire extinguishing microcapsule, characterized by: The active fire extinguishing microcapsule has a core-shell structure, comprising a core material and a shell material surrounding 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, wherein: The active fire extinguishing microcapsules are spherical in shape with a particle size of 40–140 micrometers.

3. A process for the preparation of the microcapsules for active fire extinguishing according to any one of claims 1-2, characterized by the fact that: Specifically, the steps include the following: Step S1: Preparation of shell material solution. Dissolve the shell material in deionized water and prepare the initial shell material solution at a mass ratio of 1:

4. Use anhydrous sodium carbonate or sodium hydroxide as an alkaline regulator to adjust the pH value of the initial shell material solution to about 8.

0. Place the adjusted solution in a water bath and heat it. Control the water bath temperature at 40℃~50℃ and stir for 30 minutes to ensure that the shell material is completely dissolved and forms a uniform shell material solution. Step S2: Preparation of core material emulsion solution. The core material and core material emulsifier are mixed at a volume ratio of 1:1 and sheared and emulsified at a speed of 8000 rpm for 5 minutes using a high-speed shear disperser, so that the core material emulsion solution forms uniform small droplets with a diameter in the range of 10μm to 100μm, forming a stable oil-in-water emulsion. Step S3: Microcapsule preparation. The pre-prepared wall material solution is gradually added to the core material emulsion solution, and the temperature is controlled within 30℃~50℃. The pH of the reaction system is adjusted to 4.0~5.0 by citric acid solution, and the mixture is continuously stirred at 200rpm~600rpm. After the reaction lasts for 90 minutes, a microcapsule suspension is obtained. Step S4: Microcapsule collection and drying. After diluting the obtained suspension, let it stand for 12 hours to settle. Use a filter to collect the microcapsules deposited at the bottom. Finally, dry at 40°C for 6 hours to obtain the finished active fire extinguishing microcapsule product.

4. The method of claim 3, wherein the method is characterized by: In step S2, the core material emulsifier is one of potassium perfluorooctane sulfonate, sodium dodecylbenzene sulfonate, perfluorooctanoic acid, and sodium dodecyl sulfate.

5. Use of the microcapsules according to any one of claims 1 to 2 for active fire extinguishing. The active fire extinguishing microcapsules are used in fire-resistant materials, wherein the microcapsules are incorporated into at least one fire-resistant material to improve the fire-resistant performance of the material.

6. Use of the microcapsules according to any one of claims 1 to 2 for active fire extinguishing. The active fire extinguishing microcapsules are used in 3D printing technology, whereby the microcapsules serve as additives to improve the safety of 3D printing materials.

7. Use of the microcapsules according to any one of claims 1 to 2 for active fire extinguishing. The active fire extinguishing microcapsules are used in coatings or adhesives, whereby the microcapsules serve as additives to improve the fire resistance of the coatings or adhesives.

8. Use of the microcapsules according to any one of claims 1 to 2 for active fire extinguishing. The active fire extinguishing microcapsules are used in lithium-ion battery separators as additives to improve the thermal resistance and mechanical properties of lithium-ion battery separators.

9. An ultraviolet light-cured resin plate, characterized by: The product comprises the following components in parts by weight: 1 part of the active fire extinguishing microcapsule as described in any one of claims 1 to 2, and 4 parts of the resin prepolymer mixture; wherein the resin prepolymer mixture is prepared by mixing epoxy acrylate, ethylene glycol diacrylate and a photoinitiator.

10. A method of producing an ultraviolet light-cured resin plate according to claim 9, characterized by: Specifically, the steps include the following: Step a, Mixing: Mix the microcapsule powder and resin prepolymer mixture evenly; Step b, UV curing, the mixture was cured using a 365 nm UV high pressure mercury lamp for 5 minutes. Step b, UV curing, the mixture was cured using a 365 nm UV high pressure mercury lamp for 5 minutes. Step b, UV curing, the mixture was cured using a 365 nm UV high pressure mercury lamp for

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