Infrared LED light-emitting chip and preparation method thereof

Abstract

The invention relates to an infrared LED light-emitting chip and a preparation method thereof, and belongs to the technical field of infrared optics, the chemical formula of light-emitting powder of the light-emitting chip is RaQbOc: xCr < 3 + > and Yby, R is one or two of Y, La, Lu and Gd, Q is one or two of Ga and Al, 2.5 < = a < = 3.5, 4.5 < = b < = 5.5, 11.25 < = c < = 13.25, 0.02 < = x < = 0.30, 0.02 < = y < = 0.30; the preparation method of the infrared LED light-emitting chip comprises the following steps: step S1, mixing raw materials; step S2, high-temperature roasting; s3, packaging the fluorescent powder; the functional main material added in the invention contains phenolic hydroxyl groups, benzene rings,-Si-O-Si bonds and active phenolic hydroxyl groups, not only can form hydrogen-bond interaction among flame retardants, but also can react with the modified filler, so that the refractive index, thermal conductivity and mechanical properties of the chip are improved.

Description

Technical Field

[0001] This invention belongs to the field of infrared optical technology, specifically, it relates to an infrared LED light-emitting chip and its preparation method. Background Technology

[0002] In recent years, the application of near-infrared light in fields such as facial recognition, iris recognition, security monitoring, lidar, health detection, and 3D sensing has developed rapidly. Among them, near-infrared LEDs have become an international research focus due to their advantages such as good directivity, low power consumption, and small size.

[0003] Existing technologies utilize blue LED chips incorporating elements such as Ce, Eu, Tb, and Mn to excite the production of single-color or mixed-color luminescent materials (red, green, blue, etc.) and near-infrared luminescent materials. These materials offer advantages such as simple preparation processes, low cost, and high luminous efficiency. Furthermore, near-infrared luminescent materials emit a wide range of wavelengths, enabling the production of various specific wavelengths for near-infrared applications. Therefore, this approach has garnered significant attention in the industry. However, the main problem with this approach is that it requires a relatively high ratio of luminescent material to encapsulating adhesive. This not only increases light scattering and reduces light extraction efficiency but also leads to poor thermal conductivity in the encapsulating adhesive, thereby exacerbating the thermal quenching effect of the phosphor.

[0004] Therefore, providing an infrared LED light-emitting chip with high refractive index, good thermal conductivity, and excellent mechanical properties is a technical problem that needs to be solved. Summary of the Invention

[0005] To address the problems existing in current visible light chip composite near-infrared luminescent material technology, the purpose of this invention is to provide an infrared LED luminescent chip and its preparation method.

[0006] The objective of this invention can be achieved through the following technical solutions: An infrared LED light-emitting chip includes a light-emitting chip, a light-emitting powder, and a functionalized encapsulating adhesive, wherein the chemical formula of the light-emitting powder is R. a Q b O c xCr 3+ ,Yby, where R is one or two of the elements Y, La, Lu and Gd, Q is one or two of the elements Ga and Al, 2.5≤a≤3.5, 4.5≤b≤5.5, 11.25≤c≤13.25, 0.02≤x≤0.30, 0.02≤y≤0.30; Preferably, the luminescent powder has the chemical formula La. 3.0 Ga 5.0 O 11.25 0.025Cr 3+ Yb 0.02 Y3.0 Al 4.5 O 12.25 0.02Cr 3+ Yb 0.025 Or Lu 3.5 Ga 5.5 O 13.25 0.03Cr 3+ Yb 0.03 .

[0007] This invention also provides a method for preparing the infrared LED light-emitting chip described in the above technical solution, comprising the following steps: Step S1, Raw material mixing: Mix the substances containing R, Q, O and Cr to obtain a raw material mixture; Step S2, High-temperature calcination: The raw material mixture is calcined to obtain luminescent powder; Step S3, phosphor encapsulation: Mix component A and component B in the functionalized encapsulating adhesive evenly to obtain a mixed adhesive solution. Then encapsulate the phosphor from step S2 onto the surface of the blue LED chip and cure it at 130-140℃ for 35-45 minutes to obtain an infrared LED light-emitting chip. The mass ratio of the mixed adhesive solution to the phosphor is 1.6-2.0:1.

[0008] Preferably, the blue light chip is a blue light chip with an emission peak wavelength in the range of 420-470nm.

[0009] Preferably, the roasting includes a first roasting and a second roasting in sequence, wherein the temperature of the first roasting is 800-1000℃ and the holding time is 1.4-1.8h; and the temperature of the second roasting is 1200-1400℃ and the holding time is 2-4h.

[0010] The preferred infrared luminescent material of this invention is Cr. 3+ The activated infrared luminescent material has extremely strong absorption in the 400nm-480nm range, making it particularly suitable for blue light chip excitation. The main emission peak is located in the 850nm-1100nm range, and the infrared emission has strong anti-interference capabilities.

[0011] Preferred functionalized encapsulant comprises the following raw materials in parts by weight: 65-75 parts functionalized main material, 5-8 parts crosslinking agent, 22-28 parts modified filler, 10-14 parts flame retardant, 1-2 parts coupling agent and 25-35 parts organic solvent; The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Mix the functionalized main ingredient, modified filler and 3 / 4 part by weight of organic solvent evenly to prepare component A; Step A2: Mix the flame retardant, crosslinking agent, coupling agent and 1 / 4 part by weight of organic solvent evenly to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

[0012] Preferably, the flame retardant is magnesium hydroxide or aluminum hydroxide.

[0013] Preferably, the crosslinking agent is dibutyltin dilaurate or triethylamine.

[0014] Preferably, the coupling agent is KH-550 or KH-560.

[0015] Preferably, the organic solvent is N-methylpyrrolidone or N,N-dimethylformamide.

[0016] Preferably, the functionalized main ingredient is prepared by the following steps: Step B1: Under nitrogen protection, magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst are stirred evenly, heated to 70-80℃, and stirred for 3-5 hours to obtain modified silicone oil. The mass ratio of magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst is 40-60:260-300:1-1.4. The chloroplatinic acid catalyst is prepared by adding chloroplatinic acid hexahydrate to isopropanol, wherein the mass fraction of chloroplatinic acid is 2-6%. Step B2: Add the modified silicone oil to anhydrous toluene and stir until homogeneous. While stirring, add dropwise a mixture of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene, controlling the addition to be completed within 15 minutes. After the addition is complete, under nitrogen protection, heat to reflux and stir for 6-8 hours. After the reaction is complete, filter and rotary evaporate. Dissolve the rotary evaporated product in anhydrous acetone, filter, and then rotary evaporate the filtrate again to obtain phenylened silicone oil. The mixture contains modified silicone oil, anhydrous toluene, mixture a, and anhydrous toluene. The mass ratio of acetone is 10-15:60-80:32-36:22-26. In mixture a, the mass ratio of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene is 2-3:1.6-2.8:40-50:22-26. In the above reaction process, anhydrous toluene is used as solvent and triethylamine is used as catalyst. The phenolic hydroxyl groups on the modified silicone oil undergo a nucleophilic substitution reaction with the anhydride groups on the 4-hydroxyphthalic anhydride to obtain phenylened silicone oil. Step B3: The phenylenedilicate silicone oil is ultrasonically dispersed in methyl isobutyl ketone (MEK). While stirring, the temperature is raised to 78-84°C. Tetrabutylammonium bromide and anhydrous toluene are then added, followed by dropwise addition of epichlorohydrin, controlled to be completed within 10 minutes. After the addition is complete, the mixture is stirred and reacted for 3.6-4.2 hours. After the reaction is complete, the mixture is cooled to room temperature, and while stirring, an alkali solution is added dropwise, controlled to be completed within 30 minutes. Stirring continues for 1.2-1.6 hours. An alkali solution is added again, controlled to be completed within 15 minutes. Stirring continues for 2.2-2.6 hours. The mixture is then filtered under reduced pressure, washed, and dried to obtain the functionalized main material. The mass ratio of phenylenedilicate silicone oil, methyl isobutyl ketone (MEK), tetrabutylammonium bromide (MEK), anhydrous toluene, and epichlorohydrin is 3-5:45-55:0. 03-0.05:18-22:0.5-0.6, the first added alkali solution is a sodium hydroxide aqueous solution with a mass fraction of 42-46%, and the second added alkali solution is a sodium hydroxide aqueous solution with a mass fraction of 34-40%. The mass of the alkali solution added in the two drops is the same. In the above reaction process, methyl isobutyl ketone is used as solvent, tetrabutylammonium bromide is used as catalyst, and anhydrous toluene is used as dehydrating agent. The phenolic hydroxyl groups on the phenylenedilicate first undergo an addition reaction with epichlorohydrin, and then under the action of alkali, the ring is closed and hydrogen chloride is removed to obtain the functionalized epoxy resin component. The amount of phenylenedilicate is controlled to be slightly higher than that of epichlorohydrin so that after the reaction is completed, there are still residual phenolic hydroxyl groups that can participate in the subsequent reaction process.

[0017] Preferably, the modified filler is prepared by the following steps: Step C1: Dissolve aluminum nitrate nonahydrate and ammonium bicarbonate separately in equal masses of deionized water for later use, obtaining aluminum nitrate reaction solution and ammonium bicarbonate reaction solution 1 respectively; dissolve yttrium oxide in a mixture of nitric acid solution and deionized water (b), and adjust the pH to 4-5 to obtain yttrium oxide reaction solution; dissolve cerium oxide in a mixture of nitric acid solution and deionized water (c), and adjust the pH to 4-5 to obtain cerium oxide reaction solution; mix the aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution thoroughly. Add ammonium bicarbonate reaction solution 2 dropwise, completing the addition within 15 minutes. During the titration, add a mixture of ammonium bicarbonate and ammonia solution d dropwise, maintaining the pH at 7-8. After the addition is complete, continue stirring for 1-2 hours to obtain a pre-impregnation solution. Immerse the nano-alumina in the pre-impregnation solution and age at room temperature for 12-16 hours. Filter, wash the precipitate with water, dry, grind, and then calcine at 1100-1300℃ for 4-6 hours. After grinding, react at 950-1150℃ for 3-4 hours to obtain rare earth modified alumina. The mass ratio of aluminum nitrate, ammonium bicarbonate, and deionized water is 5-6:50-70:180-200; the mass ratio of yttrium oxide to mixture b is 1-2:50-60; in mixture b, the mass ratio of nitric acid solution to deionized water is 10-16:30; the mass ratio of cerium oxide to mixture c is 2-3:40-50; in mixture c, the mass ratio of nitric acid solution to deionized water is 18-22:35; and in mixture d, the mass ratio of ammonium bicarbonate to ammonia is... The mass ratio of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution is 1-3:1-2:0.3-0.5:0.6-0.8. The nano-alumina accounts for 20-30% of the total amount of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution. The mass fraction of nitric acid solution is 12-16%, and the mass fraction of ammonia water is 6-8%. In the above reaction process, rare earth modified alumina is obtained by sol-gel method. Step C2: Mix rare earth modified alumina, deionized water, anhydrous ethanol and KH-560 ultrasonically until homogeneous, stir at room temperature for 6-8 hours, centrifuge, wash and dry the precipitate to obtain epoxy alumina. Disperse epoxy alumina and anhydrous DMF ultrasonically, add a mixture of tetrabutylammonium bromide, 3,5-diaminobenzoic acid and anhydrous DMF dropwise. After the addition is complete, heat to 100-108℃ and stir for 3-5 hours. After the reaction is complete, centrifuge, wash and dry the precipitate to obtain the modified filler. The mass ratio of rare earth modified alumina, deionized water, anhydrous ethanol, and KH-560 is 3-5:15:25-30:0.4-0.6; the mass ratio of epoxy-modified alumina, anhydrous DMF, and mixture e is 5:50-60:10; and the mass ratio of tetrabutylammonium bromide, 3,5-diaminobenzoic acid, and anhydrous DMF in mixture e is 0.1:0.6-1.2:20. The rare earth modified alumina is first treated with KH-560, and then, under the action of tetrabutylammonium bromide, the carboxyl groups of 3,5-diaminobenzoic acid undergo a ring-opening reaction with the epoxy groups to obtain the modified filler.

[0018] In summary, this application has the following beneficial effects: To improve the refractive index, thermal conductivity, and mechanical properties of infrared LED light-emitting chips, this invention addresses the issue from two aspects. Firstly, it uses a functionalized main material as the base material for the functionalized encapsulant. This functionalized main material contains phenolic hydroxyl groups, benzene rings, and -Si-O-Si bonds. The active phenolic hydroxyl groups, on the one hand, can form hydrogen bonds with flame retardants, improving the dispersibility and compatibility between the functionalized main material and the flame retardant, thus improving the thermal conductivity and mechanical properties of the light-emitting chip. On the other hand, they act as anchoring points, undergoing ring-opening reactions with the epoxy groups of the modified filler, further increasing the degree of crosslinking and improving the thermal conductivity and mechanical properties of the light-emitting chip. The presence of benzene rings... The presence of surface energy and -Si-O-Si bonds together improves the refractive index and mechanical properties of the light-emitting chip. On the other hand, the π-π interaction between the benzene ring and the modified filler can enhance the bonding force between the functionalized encapsulant and the modified filler, further improving the thermal conductivity of the light-emitting chip. Secondly, the addition of modified filler can, on the one hand, leverage the excellent physical properties of nano-alumina to improve the thermal conductivity of the light-emitting chip. On the other hand, the rare earth oxides attached to the surface of nano-alumina have a complex and rich crystal structure, a large ionic radius, and a high refractive index. Introducing them into the functionalized encapsulant can work synergistically with the functionalized main material to jointly improve the refractive index, thermal conductivity, and mechanical properties of the light-emitting chip. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0021] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available products.

[0022] The hydrogen-containing phenyl silicone oil was produced by Hubei Yamaide Biomedical Co., Ltd., with CAS number YDE-8815. Preparation Examples 1-3 and Comparative Preparation Example 1-2 provide a functionalized main ingredient.

[0023] Preparation Example 1 This preparation example provides a functionalized main ingredient, which is prepared by the following steps: Step B1: Under nitrogen protection, magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst are stirred at 620 rpm for 12 min until homogeneous. The temperature is raised to 70℃, and the stirring speed is maintained at a constant speed for 3 h to obtain modified silicone oil. The mass ratio of magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst is 40:260:1. The chloroplatinic acid catalyst is prepared by adding chloroplatinic acid hexahydrate to isopropanol, wherein the mass fraction of chloroplatinic acid is 2%. Step B2: Add the modified silicone oil to anhydrous toluene and stir at 520 rpm for 16 minutes until homogeneous. While stirring, add dropwise a mixture of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene, completing the addition within 15 minutes. After the addition is complete, under nitrogen protection, heat to reflux and stir for 6 hours. After the reaction is complete, filter and control the rotary evaporation temperature at 62°C until anhydrous toluene is removed. Dissolve the rotary evaporation product in anhydrous acetone, filter, and then control the rotary evaporation temperature at 40°C until anhydrous acetone is removed to obtain phenylened silicone oil. The mass ratio of modified silicone oil, anhydrous toluene, mixture a, and anhydrous acetone is 10:60:32:22. In mixture a, the mass ratio of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene is 2:1.6:40:22. Step B3: Disperse the phenylenedilicate silicone oil ultrasonically in methyl isobutyl ketone (MBE) at a frequency of 35 kHz and a power of 550 W for 18 minutes, maintaining a rotation speed of 620 rpm. While stirring, raise the temperature to 78°C, then add tetrabutylammonium bromide and anhydrous toluene. Add epichlorohydrin dropwise over 10 minutes. After the addition is complete, stir the reaction for 3.6 hours. After the reaction is complete, cool to room temperature and add alkali solution dropwise while stirring over 30 minutes. Continue stirring for 1.2 hours, then add alkali solution again, maintaining the temperature at 78°C. The addition was completed within 15 minutes, and stirring continued for 2.2 hours. The mixture was then filtered under reduced pressure and washed three times with anhydrous ethanol and deionized water, respectively. After drying at 64°C to constant weight, the functionalized main material was obtained. The mass ratio of phenylenedilicate oil, methyl isobutyl ketone, tetrabutylammonium bromide, anhydrous toluene, and epichlorohydrin was 3:45:0.03:18:0.5. The first addition of alkali solution was a 42% sodium hydroxide aqueous solution, and the second addition of alkali solution was a 34% sodium hydroxide aqueous solution. The mass of the alkali solution added in both additions was the same.

[0024] Preparation Example 2 This preparation example provides a functionalized main ingredient, which is prepared by the following steps: Step B1: Under nitrogen protection, magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst were stirred at 640 rpm for 15 min until homogeneous. The temperature was raised to 75°C, and the stirring was continued for 4 h while maintaining the stirring speed to obtain modified silicone oil. The mass ratio of magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst was 50:280:1.2. The chloroplatinic acid catalyst was prepared by adding chloroplatinic acid hexahydrate to isopropanol, wherein the mass fraction of chloroplatinic acid was 4%. Step B2: Add the modified silicone oil to anhydrous toluene and stir at 560 rpm for 18 minutes until homogeneous. While stirring, add dropwise a mixture of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene, completing the addition within 15 minutes. After the addition is complete, under nitrogen protection, heat to reflux, maintain the stirring speed, and continue stirring for 7 hours. After the reaction is complete, filter and control the rotary evaporation temperature at 64°C until anhydrous toluene is removed. Dissolve the rotary evaporation product in anhydrous acetone, filter, and then control the rotary evaporation temperature at 44°C until anhydrous acetone is removed to obtain phenylened silicone oil. The mass ratio of modified silicone oil, anhydrous toluene, mixture a, and anhydrous acetone is 12.5:70:34:24. In mixture a, the mass ratio of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene is 2.5:2.2:45:24. Step B3: Disperse phenylenediamine oil ultrasonically in methyl isobutyl ketone (MBE) at a frequency of 40 kHz and a power of 600 W for 22 minutes, maintaining a rotation speed of 650 rpm. While stirring, raise the temperature to 81°C, then add tetrabutylammonium bromide and anhydrous toluene. Add epichlorohydrin dropwise over 10 minutes. After the addition is complete, stir the reaction for 3.9 hours. After the reaction is complete, cool to room temperature and add alkali solution dropwise while stirring over 30 minutes. Continue stirring for 1.4 hours, then add alkali solution again, maintaining a temperature of 1... The addition was completed within 5 minutes, and stirring continued for 2.4 hours. The mixture was then filtered under reduced pressure and washed four times with anhydrous ethanol and deionized water, and dried at 68°C to constant weight to obtain the functionalized main material. The mass ratio of phenylenedilicate oil, methyl isobutyl ketone, tetrabutylammonium bromide, anhydrous toluene, and epichlorohydrin was 4:50:0.04:20:0.55. The first addition of alkali solution was a 44% sodium hydroxide aqueous solution, and the second addition of alkali solution was a 37% sodium hydroxide aqueous solution. The mass of the alkali solution added in both additions was the same.

[0025] Preparation Example 3 This preparation example provides a functionalized main ingredient, which is prepared by the following steps: Step B1: Under nitrogen protection, magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst were stirred at 660 rpm for 18 min until homogeneous. The temperature was raised to 80℃, and the stirring was continued for 5 h while maintaining the stirring speed to obtain modified silicone oil. The mass ratio of magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst was 60:300:1.4. The chloroplatinic acid catalyst was prepared by adding chloroplatinic acid hexahydrate to isopropanol, and the mass fraction of chloroplatinic acid was 6%. Step B2: Add the modified silicone oil to anhydrous toluene and stir at 600 rpm for 20 minutes until homogeneous. While stirring, add dropwise a mixture of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene, completing the addition within 15 minutes. After the addition is complete, under nitrogen protection, heat to reflux and stir for 8 hours. After the reaction is complete, filter and control the rotary evaporation temperature at 66°C until anhydrous toluene is removed. Dissolve the rotary evaporation product in anhydrous acetone, filter, and then control the rotary evaporation temperature at 48°C until anhydrous acetone is removed to obtain phenylened silicone oil. The mass ratio of modified silicone oil, anhydrous toluene, mixture a, and anhydrous acetone is 15:80:36:26. In mixture a, the mass ratio of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene is 3:2.8:50:26. Step B3: Disperse the phenylenedilicate silicone oil ultrasonically in methyl isobutyl ketone (MBE) at a frequency of 46 kHz and a power of 650 W for 26 minutes, maintaining a rotation speed of 700 rpm. While stirring, raise the temperature to 84°C, then add tetrabutylammonium bromide and anhydrous toluene. Add epichlorohydrin dropwise over 10 minutes. After the addition is complete, stir the reaction for 4.2 hours. After the reaction is complete, cool to room temperature and add alkali solution dropwise while stirring over 30 minutes. Continue stirring for 1.6 hours, then add alkali solution again, maintaining the temperature at 84°C. The addition was completed within 15 minutes, and stirring continued for 2.6 hours. The mixture was then filtered under reduced pressure and washed five times with anhydrous ethanol and deionized water, respectively. After drying at 72°C to constant weight, the functionalized main material was obtained. The mass ratio of phenylenedilicate oil, methyl isobutyl ketone, tetrabutylammonium bromide, anhydrous toluene, and epichlorohydrin was 5:55:0.05:22:0.6. The first addition of alkali solution was a 46% sodium hydroxide aqueous solution, and the second addition of alkali solution was a 40% sodium hydroxide aqueous solution. The mass of the alkali solution added in both additions was the same.

[0026] Comparative Preparation Example 1 This comparative preparation example provides a functionalized main ingredient, which is prepared by the following steps: Step B1: Under nitrogen protection, magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst are stirred at 620 rpm for 12 min until homogeneous. The temperature is raised to 70℃, and the stirring speed is maintained at a constant speed for 3 h to obtain modified silicone oil. The mass ratio of magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst is 40:260:1. The chloroplatinic acid catalyst is prepared by adding chloroplatinic acid hexahydrate to isopropanol, wherein the mass fraction of chloroplatinic acid is 2%. Step B2: Add the modified silicone oil to anhydrous toluene and stir at 520 rpm for 16 minutes until homogeneous. While stirring, add a mixture of 2-methylsuccinic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene dropwise over 15 minutes. After the addition is complete, heat to reflux under nitrogen protection and stir for 6 hours. After the reaction is complete, filter and evaporate at 62°C until anhydrous toluene is removed. Dissolve the evaporated product in anhydrous acetone, filter, and then evaporate at 40°C until anhydrous acetone is removed to obtain phenylened silicone oil. The mass ratio of modified silicone oil, anhydrous toluene, mixture a, and anhydrous acetone is 10:60:32:22. In mixture a, the mass ratio of 2-methylsuccinic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene is 2:1.68:40:22. Step B3: Disperse the phenylenedilicate silicone oil ultrasonically in methyl isobutyl ketone (MBE) at a frequency of 35 kHz and a power of 550 W for 18 minutes, maintaining a rotation speed of 620 rpm. While stirring, raise the temperature to 78°C, then add tetrabutylammonium bromide and anhydrous toluene. Add epichlorohydrin dropwise over 10 minutes. After the addition is complete, stir the reaction for 3.6 hours. After the reaction is complete, cool to room temperature and add alkali solution dropwise while stirring over 30 minutes. Continue stirring for 1.2 hours, then add alkali solution again, maintaining the temperature at 78°C. The addition was completed within 15 minutes, and stirring continued for 2.2 hours. The mixture was then filtered under reduced pressure and washed three times with anhydrous ethanol and deionized water, respectively. After drying at 64°C to constant weight, the functionalized main material was obtained. The mass ratio of phenylenedilicate oil, methyl isobutyl ketone, tetrabutylammonium bromide, anhydrous toluene, and epichlorohydrin was 3:45:0.03:18:0.5. The first addition of alkali solution was a 42% sodium hydroxide aqueous solution, and the second addition of alkali solution was a 34% sodium hydroxide aqueous solution. The mass of the alkali solution added in both additions was the same.

[0027] Comparative Preparation Example 2 This comparative preparation example provides a functionalized main ingredient, which is prepared by the following steps: Step B1: Under nitrogen protection, magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst are stirred at 620 rpm for 12 min until homogeneous. The temperature is raised to 70℃, and the stirring speed is maintained at a constant speed for 3 h to obtain modified silicone oil. The mass ratio of magnolol, hydrogen-containing phenyl silicone oil, and chloroplatinic acid catalyst is 40:260:1. The chloroplatinic acid catalyst is prepared by adding chloroplatinic acid hexahydrate to isopropanol, wherein the mass fraction of chloroplatinic acid is 2%. Step B2: Add the modified silicone oil to anhydrous toluene and stir at 520 rpm for 16 minutes until homogeneous. While stirring, add a mixture of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene dropwise over 15 minutes. After the addition is complete, heat to reflux under nitrogen protection and stir for 6 hours. After the reaction is complete, filter and evaporate at 62°C until anhydrous toluene is removed. Dissolve the evaporated product in anhydrous acetone, filter, and then evaporate at 40°C until anhydrous acetone is removed to obtain phenylened silicone oil. The mass ratio of modified silicone oil, anhydrous toluene, mixture a, and anhydrous acetone is 10:60:32:22. In mixture a, the mass ratio of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene is 2:1.68:40:22. Step B3: Disperse the phenylenedilicate silicone oil ultrasonically in methyl isobutyl ketone (MBE) at a frequency of 35 kHz and a power of 550 W for 18 minutes, maintaining a rotation speed of 620 rpm. While stirring, raise the temperature to 78°C, then add tetrabutylammonium bromide and anhydrous toluene. Add 2-chloropropane dropwise over 10 minutes. After the addition is complete, stir the reaction for 3.6 hours. After the reaction is complete, cool to room temperature and add alkali solution dropwise while stirring over 30 minutes. Continue stirring for 1.2 hours, then add alkali solution again, maintaining the temperature at 78°C. The addition was completed within 15 minutes, and stirring continued for 2.2 hours. The mixture was then filtered under reduced pressure and washed three times with anhydrous ethanol and deionized water, respectively. After drying at 64°C to constant weight, the functionalized main material was obtained. The mass ratio of phenylenedilicate oil, methyl isobutyl ketone, tetrabutylammonium bromide, anhydrous toluene, and 2-chloropropane was 3:45:0.03:18:0.5. The first addition of alkali solution was a 42% sodium hydroxide aqueous solution, and the second addition of alkali solution was a 34% sodium hydroxide aqueous solution. The mass of the alkali solution added in both additions was the same.

[0028] Preparation Examples 4-6 and Comparative Preparation Examples 3-4 provide a modified filler.

[0029] Preparation Example 4 This preparation example provides a modified filler, which is prepared by the following steps: Step C1: Dissolve aluminum nitrate nonahydrate and ammonium bicarbonate separately in equal masses of deionized water for later use, obtaining aluminum nitrate reaction solution and ammonium bicarbonate reaction solution 1 respectively; dissolve yttrium oxide in a mixture of 12% nitric acid solution and deionized water (b), and adjust the pH to 4 with 6.0% ammonia solution to obtain yttrium oxide reaction solution; dissolve cerium oxide in a mixture of 12% nitric acid solution and deionized water (c), and adjust the pH to 6.0% ammonia solution to... 4. Obtain the cerium oxide reaction solution; stir the aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution at 500 rpm for 12 minutes until homogeneous, then add them dropwise to 16% ammonium bicarbonate reaction solution 2, controlling the addition to be completed within 15 minutes. During the titration, add a mixture of ammonium bicarbonate and 6.0% ammonia solution d, controlling the pH to 7. After the addition is complete, maintain the stirring speed and continue stirring for 1 hour to obtain the pre-impregnation solution. Impregnate the nano-alumina. The alumina was soaked in a pre-impregnation solution and aged at room temperature for 12 hours. After filtration, the precipitate was washed three times with deionized water, dried at 60°C to constant weight, ground, passed through a 100-mesh sieve, and then calcined at 1100°C for 4 hours. After further grinding and passing through a 140-mesh sieve, it was reacted at 950°C for 3 hours to obtain rare earth-modified alumina. The mass ratio of aluminum nitrate, ammonium bicarbonate, and deionized water was 5:50:180, and the mass ratio of yttrium oxide to mixture b was 1:50. In mixture b, the nitric acid solution and deionized water... The mass ratio is 10:30, the mass ratio of cerium oxide to mixture c is 2:40, the mass ratio of nitric acid solution to deionized water in mixture c is 18:35, the mass ratio of ammonium bicarbonate to ammonia in mixture d is 1:4, the mass ratio of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution is 1:1:0.3:0.6, and the nano-alumina accounts for 20% of the total amount of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution. Step C2: Rare earth modified alumina, deionized water, anhydrous ethanol, and KH-560 were ultrasonically mixed at a frequency of 25 kHz, a power of 400 W, and a time of 12 min until homogeneous. The mixture was stirred at 500 rpm for 6 h at room temperature. After centrifugation, the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 55 °C to constant weight to obtain epoxy-based alumina. The epoxy-based alumina and anhydrous DMF were ultrasonically mixed for 35 min until homogeneous, with the ultrasonic frequency controlled at 25 kHz and the power at 400 W. Tetrabutylammonium bromide and 3,5-diaminobenzene were added dropwise. After the benzoic acid and anhydrous DMF mixture e was added dropwise, the mixture was heated to 100℃ and stirred for 3 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 65℃ to constant weight to obtain the modified filler. The mass ratio of rare earth modified alumina, deionized water, anhydrous ethanol and KH-560 was 3:15:25:0.4, the mass ratio of epoxy alumina, anhydrous DMF and mixture e was 5:50:10, and the mass ratio of tetrabutylammonium bromide, 3,5-diaminobenzoic acid and anhydrous DMF in mixture e was 0.1:0.6:20.

[0030] Preparation Example 5 This preparation example provides a modified filler, which is prepared by the following steps: Step C1: Dissolve aluminum nitrate nonahydrate and ammonium bicarbonate separately in equal masses of deionized water for later use, obtaining aluminum nitrate reaction solution and ammonium bicarbonate reaction solution 1 respectively; dissolve yttrium oxide in a mixture of 14% nitric acid solution and deionized water (b), and adjust the pH to 4.5 to obtain yttrium oxide reaction solution; dissolve cerium oxide in a mixture of 14% nitric acid solution and deionized water (c), and adjust the pH to 4.5 to obtain cerium oxide reaction solution; combine the aluminum nitrate reaction solution and ammonium bicarbonate... Reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution were stirred at 550 rpm for 16 minutes until homogeneous. Then, they were added dropwise to 17% ammonium bicarbonate reaction solution 2, with the addition completed within 15 minutes. During titration, a mixture of ammonium bicarbonate and 7.0% ammonia solution (d) was added dropwise, maintaining the pH at 7.5. After the addition was complete, stirring was continued for 1.5 hours to obtain a pre-impregnation solution. Nano-alumina was then impregnated in the pre-impregnation solution and aged at room temperature for 14 hours. The mixture was then filtered, and the precipitate was collected. After washing four times with deionized water, drying at 65℃ to constant weight, grinding, passing through a 120-mesh sieve, and then calcining at 1200℃ for 5 hours, grinding again, passing through a 160-mesh sieve, and then reacting at 1050℃ for 3.5 hours, rare earth modified alumina was obtained. The mass ratio of aluminum nitrate, ammonium bicarbonate, and deionized water was 5.5:60:190, the mass ratio of yttrium oxide to mixture b was 1.5:55, and the mass ratio of nitric acid solution to deionized water in mixture b was 13:3. 0. The mass ratio of cerium oxide to mixture c is 2.5:45. In mixture c, the mass ratio of nitric acid solution to deionized water is 20:35. In mixture d, the mass ratio of ammonium bicarbonate to ammonia is 2:4. The mass ratio of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution is 2:1.5:0.4:0.7. Nano-alumina accounts for 25% of the total amount of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution. Step C2: Rare earth modified alumina, deionized water, anhydrous ethanol, and KH-560 were ultrasonically mixed at a frequency of 30 kHz, a power of 450 W, and a time of 16 min until homogeneous. The mixture was stirred at 550 rpm for 7 h at room temperature. After centrifugation, the precipitate was washed four times with anhydrous ethanol and deionized water, and dried at 60 °C to constant weight to obtain epoxy-based alumina. The epoxy-based alumina and anhydrous DMF were ultrasonically mixed for 40 min until homogeneous, with an ultrasonic frequency of 35 kHz and a power of 500 W. Tetrabutylammonium bromide and 3,5-diaminobenzene were added dropwise. After the formic acid and anhydrous DMF mixture e was added dropwise, the mixture was heated to 104℃ and stirred for 4 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed four times with anhydrous ethanol and deionized water, and dried at 70℃ to constant weight to obtain the modified filler. The mass ratio of rare earth modified alumina, deionized water, anhydrous ethanol and KH-560 was 4:15:27.5:0.5, the mass ratio of epoxy alumina, anhydrous DMF and mixture e was 5:55:10, and the mass ratio of tetrabutylammonium bromide, 3,5-diaminobenzoic acid and anhydrous DMF in mixture a was 0.1:0.9:20.

[0031] Preparation Example 6 This preparation example provides a modified filler, which is prepared by the following steps: Step C1: Dissolve aluminum nitrate nonahydrate and ammonium bicarbonate separately in equal masses of deionized water for later use, obtaining aluminum nitrate reaction solution and ammonium bicarbonate reaction solution 1 respectively; dissolve yttrium oxide in a mixture of 16% nitric acid solution and deionized water (b), and adjust the pH to 5 with 8.0% ammonia solution to obtain yttrium oxide reaction solution; dissolve cerium oxide in a mixture of 16% nitric acid solution and deionized water (c), and adjust the pH to 5 with 8.0% ammonia solution. A cerium oxide reaction solution was obtained. The aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution were stirred at 600 rpm for 20 minutes until homogeneous. This mixture was then added dropwise to an 18% (w / w) ammonium bicarbonate reaction solution 2, with the addition completed within 15 minutes. During the titration, a mixture of ammonium bicarbonate and 8.0% (w / w) ammonia solution d was added dropwise, maintaining the pH at 8. After the addition was complete, the stirring speed was kept constant, and stirring continued for 2 hours to obtain a pre-impregnation solution. Nano-alumina was then impregnated with this solution. The precipitate was aged in the pre-impregnation solution at room temperature for 16 hours, filtered, washed five times with deionized water, dried at 70°C to constant weight, ground, passed through a 140-mesh sieve, and then calcined at 1300°C for 6 hours. After grinding and passing through a 180-mesh sieve, it was reacted at 1150°C for 4 hours to obtain rare earth modified alumina. The mass ratio of aluminum nitrate, ammonium bicarbonate, and deionized water was 6:70:200, and the mass ratio of yttrium oxide to mixture b was 2:60. In mixture b, the nitric acid solution and deionized water... The mass ratio is 16:30, the mass ratio of cerium oxide to mixed solution c is 3:50, the mass ratio of nitric acid solution to deionized water in mixed solution c is 22:35, the mass ratio of ammonium bicarbonate to ammonia in mixed solution d is 3:4, the mass ratio of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution is 3:2:0.5:0.8, and the nano-alumina accounts for 30% of the total amount of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution; Step C2: Rare earth modified alumina, deionized water, anhydrous ethanol, and KH-560 were ultrasonically mixed at a frequency of 35 kHz, a power of 500 W, and a time of 20 min until homogeneous. The mixture was stirred at room temperature for 8 h, centrifuged, and the precipitate was washed five times with anhydrous ethanol and deionized water, and dried at 65 °C to constant weight to obtain epoxy-modified alumina. The epoxy-modified alumina and anhydrous DMF were ultrasonically mixed for 45 min until homogeneous at a frequency of 30 kHz and a power of 450 W. Tetrabutylammonium bromide, 3,5-diaminobenzoic acid, and anhydrous DMF were added dropwise while stirring at 700 rpm. DMF mixture e was added dropwise over 15 minutes. After the addition was complete, the mixture was heated to 108°C and stirred for 5 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed five times with anhydrous ethanol and deionized water, and dried at 75°C to constant weight to obtain the modified filler. The mass ratio of rare earth modified alumina, deionized water, anhydrous ethanol and KH-560 was 5:15:30:0.6. The mass ratio of epoxy alumina, anhydrous DMF and mixture a was 5:60:10. In mixture e, the mass ratio of tetrabutylammonium bromide, 3,5-diaminobenzoic acid and anhydrous DMF was 0.1:1.2:20.

[0032] Comparative preparation example 3 This comparative preparation example provides a modified filler, which is prepared by the following steps: Step C1: Dissolve aluminum nitrate nonahydrate and ammonium bicarbonate separately in equal masses of deionized water for later use, obtaining aluminum nitrate reaction solution and ammonium bicarbonate reaction solution 1 respectively; dissolve yttrium oxide in a mixture of 12% nitric acid solution and deionized water (b), and adjust the pH to 4 with 6.0% ammonia solution to obtain yttrium oxide reaction solution; dissolve cerium oxide in a mixture of 12% nitric acid solution and deionized water (c), and adjust the pH to 6.0% ammonia solution to... 4. Obtain the cerium oxide reaction solution; stir the aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution at 500 rpm for 12 minutes until homogeneous, then add them dropwise to 16% ammonium bicarbonate reaction solution 2, controlling the addition to be completed within 15 minutes. During the titration, add a mixture of ammonium bicarbonate and 6.0% ammonia solution d, controlling the pH to 7. After the addition is complete, maintain the stirring speed and continue stirring for 1 hour to obtain the pre-impregnation solution. Impregnate the nano-alumina. The alumina was soaked in a pre-impregnation solution and aged at room temperature for 12 hours. After filtration, the precipitate was washed three times with deionized water, dried at 60°C to constant weight, ground, passed through a 100-mesh sieve, and then calcined at 1100°C for 4 hours. After further grinding and passing through a 140-mesh sieve, it was reacted at 950°C for 3 hours to obtain rare earth-modified alumina. The mass ratio of aluminum nitrate, ammonium bicarbonate, and deionized water was 5:50:180, and the mass ratio of yttrium oxide to mixture b was 1:50. In mixture b, the nitric acid solution and deionized water... The mass ratio is 10:30, the mass ratio of cerium oxide to mixture c is 2:40, the mass ratio of nitric acid solution to deionized water in mixture c is 18:35, the mass ratio of ammonium bicarbonate to ammonia in mixture d is 1:4, the mass ratio of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution is 1:1:0.3:0.6, and the nano-alumina accounts for 20% of the total amount of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution. Step C2: Rare earth modified alumina, deionized water, anhydrous ethanol, and KH-560 were ultrasonically mixed at a frequency of 25 kHz, a power of 400 W, and a time of 12 min until homogeneous. The mixture was stirred at 500 rpm for 6 h at room temperature. After centrifugation, the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 55 °C to constant weight to obtain epoxy-based alumina. The epoxy-based alumina and anhydrous DMF were ultrasonically mixed for 35 min until homogeneous, with the ultrasonic frequency controlled at 25 kHz and the power at 400 W. Tetrabutylammonium bromide was then added dropwise. After the mixture of glycine and anhydrous DMF (e) was added dropwise, the mixture was heated to 100℃ and stirred for 3 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 65℃ to constant weight to obtain the modified filler. The mass ratio of rare earth modified alumina, deionized water, anhydrous ethanol and KH-560 was 3:15:25:0.4, the mass ratio of epoxy alumina, anhydrous DMF and mixture e was 5:50:10, and the mass ratio of tetrabutylammonium bromide, glycine and anhydrous DMF in mixture e was 0.1:0.6:20.

[0033] Comparative preparation example 4 This comparative preparation example provides a modified filler, which is prepared by the following steps: Step C1: Dissolve aluminum nitrate nonahydrate and ammonium bicarbonate separately in equal masses of deionized water for later use, obtaining aluminum nitrate reaction solution and ammonium bicarbonate reaction solution 1 respectively; dissolve yttrium oxide in a mixture of nitric acid solution and deionized water (b), and adjust the pH to 4 with a 6.0% ammonia solution to obtain yttrium oxide reaction solution; dissolve cerium oxide in a mixture of 12% nitric acid solution and deionized water (c), and adjust the pH to 4 with a 6.0% ammonia solution to obtain cerium oxide reaction solution. The aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution were stirred at 500 rpm for 12 minutes until homogeneous. Then, ammonium bicarbonate reaction solution 2 (16% by mass) was added dropwise over 15 minutes. During titration, a mixture of ammonium bicarbonate and ammonia solution d (6.0% by mass) was added dropwise, maintaining the pH at 7. After titration, the stirring speed was kept constant, and stirring continued for 1 hour to obtain a pre-impregnation solution. Nano-alumina was then impregnated in the pre-impregnation solution. After aging at a warm temperature for 12 hours, the mixture was filtered, washed three times with deionized water, dried at 60°C to constant weight, ground, passed through a 100-mesh sieve, and then calcined at 1100°C for 4 hours. After further grinding and passing through a 140-mesh sieve, the mixture was reacted at 950°C for 3 hours and held at that temperature for 1 hour to obtain rare earth modified alumina. The mass ratio of aluminum nitrate, ammonium bicarbonate, and deionized water was 5:50:180, and the mass ratio of yttrium oxide to mixture b was 1:50. In mixture b, the mass ratio of nitric acid solution to deionized water was... The mass ratio is 10:30, the mass ratio of cerium oxide to mixed solution c is 2:40, the mass ratio of nitric acid solution to deionized water in mixed solution c is 18:35, the mass ratio of ammonium bicarbonate to ammonia in mixed solution d is 1:4, the mass ratio of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution is 1:1:0.3:0.6, and the nano-alumina accounts for 20% of the total amount of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution; Step C2: Rare earth modified alumina, deionized water, anhydrous ethanol, and KH-560 were ultrasonically mixed at a frequency of 25 kHz, a power of 400 W, and a time of 12 min until homogeneous. The mixture was stirred at 500 rpm for 6 h at room temperature. After centrifugation, the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 55 °C to constant weight to obtain epoxy-based alumina. The epoxy-based alumina and anhydrous DMF were ultrasonically mixed for 35 min until homogeneous, with the ultrasonic frequency controlled at 25 kHz and the power at 400 W. Tetrabutylammonium bromide was then added dropwise. Mixture e of benzoic acid and anhydrous DMF was added dropwise, and the mixture was heated to 100℃ and stirred for 3 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times with anhydrous ethanol and deionized water, and dried at 65℃ to constant weight to obtain the modified filler. The mass ratio of rare earth modified alumina, deionized water, anhydrous ethanol and KH-560 was 3:15:25:0.4, the mass ratio of epoxy-modified alumina, anhydrous DMF and mixture e was 5:50:10, and the mass ratio of tetrabutylammonium bromide, benzoic acid and anhydrous DMF in mixture e was 0.1:0.6:20. Preparation Examples 7-9 and Comparative Preparation Examples 5-8 provide a functionalized encapsulating adhesive.

[0034] Preparation Example 7 This preparation example provides a functionalized encapsulating adhesive, which is prepared by the following steps: The functionalized encapsulating adhesive comprises the following raw materials in parts by weight: 65 parts of the functionalized main material prepared in Preparation Example 1, 5 parts of dibutyltin dilaurate, 22 parts of the modified filler prepared in Preparation Example 4, 10 parts of magnesium hydroxide, 1 part of KH-550 and 25 parts of N-methylpyrrolidone. The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Stir the functionalized main ingredient, modified filler and 3 / 4 parts by weight of N-methylpyrrolidone at 560 rpm for 12 minutes until homogeneous to prepare component A; Step A2: Stir magnesium hydroxide, dibutyltin dilaurate, KH-550 and 1 / 4 part by weight of N-methylpyrrolidone at 600 rpm for 14 minutes until homogeneous to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

[0035] Preparation Example 8 This preparation example provides a functionalized encapsulating adhesive, which is prepared by the following steps: The functionalized encapsulating adhesive comprises the following raw materials in parts by weight: 70 parts of the functionalized main material prepared in Preparation Example 2, 6.5 parts of triethylamine, 25 parts of the modified filler prepared in Preparation Example 5, 12 parts of aluminum hydroxide, 1.5 parts of KH-560 and 30 parts of N,N-dimethylformamide; The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Mix the functionalized main material, modified filler and 3 / 4 parts by weight of N,N-dimethylformamide at 600 rpm for 14 minutes until homogeneous to prepare component A; Step A2: Mix aluminum hydroxide, triethylamine, KH-560 and 1 / 4 part by weight of N,N-dimethylformamide at 640 rpm for 18 minutes until homogeneous to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

[0036] Preparation Example 9 This preparation example provides a functionalized encapsulating adhesive comprising the following parts by weight of raw materials: 75 parts of the functionalized main material prepared in Preparation Example 3, 8 parts of dibutyltin dilaurate, 28 parts of the modified filler prepared in Preparation Example 6, 14 parts of aluminum hydroxide, 1.5 parts of KH-560 and 30 parts of N,N-dimethylformamide; The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Mix the functionalized main material, modified filler and 3 / 4 parts by weight of N,N-dimethylformamide at 640 rpm for 16 minutes until homogeneous to prepare component A; Step A2: Stir the flame retardant, dibutyltin dilaurate, KH-560 and 1 / 4 part by weight of N,N-dimethylformamide at 680 rpm for 22 minutes until homogeneous to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

[0037] Comparative preparation example 5 This comparative preparation example provides a functionalized encapsulating adhesive, which is prepared by the following steps: The functionalized encapsulating adhesive comprises the following raw materials in parts by weight: 65 parts of the functionalized main material prepared in Comparative Preparation Example 1, 5 parts of dibutyltin dilaurate, 22 parts of the modified filler prepared in Preparation Example 4, 10 parts of magnesium hydroxide, 1 part of KH-550 and 25 parts of N-methylpyrrolidone. The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Stir the functionalized main ingredient, modified filler and 3 / 4 parts by weight of N-methylpyrrolidone at 560 rpm for 12 minutes until homogeneous to prepare component A; Step A2: Stir magnesium hydroxide, dibutyltin dilaurate, KH-550 and 1 / 4 part by weight of N-methylpyrrolidone at 600 rpm for 14 minutes until homogeneous to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

[0038] Comparative preparation example 6 This comparative preparation example provides a functionalized encapsulating adhesive, which is prepared by the following steps: The functionalized encapsulating adhesive comprises the following raw materials in parts by weight: 65 parts of the functionalized main material prepared in Comparative Preparation Example 2, 5 parts of dibutyltin dilaurate, 22 parts of the modified filler prepared in Preparation Example 4, 10 parts of magnesium hydroxide, 1 part of KH-550 and 25 parts of N-methylpyrrolidone. The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Stir the functionalized main ingredient, modified filler and 3 / 4 parts by weight of N-methylpyrrolidone at 560 rpm for 12 minutes until homogeneous to prepare component A; Step A2: Stir magnesium hydroxide, dibutyltin dilaurate, KH-550 and 1 / 4 part by weight of N-methylpyrrolidone at 600 rpm for 14 minutes until homogeneous to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

[0039] Comparative preparation example 7 This comparative preparation example provides a functionalized encapsulating adhesive, which is prepared by the following steps: The functionalized encapsulant comprises the following raw materials in parts by weight: 65 parts of the functionalized main material prepared in Preparation Example 1, 5 parts of dibutyltin dilaurate, 22 parts of the modified filler prepared in Comparative Preparation Example 3, 10 parts of magnesium hydroxide, 1 part of KH-550 and 25 parts of N-methylpyrrolidone. The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Stir the functionalized main ingredient, modified filler and 3 / 4 parts by weight of N-methylpyrrolidone at 560 rpm for 12 minutes until homogeneous to prepare component A; Step A2: Stir magnesium hydroxide, dibutyltin dilaurate, KH-550 and 1 / 4 part by weight of N-methylpyrrolidone at 600 rpm for 14 minutes until homogeneous to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

[0040] Comparative Preparation Example 8 This comparative preparation example provides a functionalized encapsulating adhesive, which is prepared by the following steps: The functionalized encapsulating adhesive comprises the following raw materials in parts by weight: 65 parts of the functionalized main material prepared in Preparation Example 1, 5 parts of dibutyltin dilaurate, 22 parts of the modified filler prepared in Comparative Preparation Example 4, 10 parts of magnesium hydroxide, 1 part of KH-550 and 25 parts of N-methylpyrrolidone. The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Stir the functionalized main ingredient, modified filler and 3 / 4 parts by weight of N-methylpyrrolidone at 560 rpm for 12 minutes until homogeneous to prepare component A; Step A2: Stir magnesium hydroxide, dibutyltin dilaurate, KH-550 and 1 / 4 part by weight of N-methylpyrrolidone at 600 rpm for 14 minutes until homogeneous to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

[0041] Examples 1-3 and Comparative Examples 1-4 provide an infrared LED light-emitting chip.

[0042] Example 1 This embodiment provides an infrared LED light-emitting chip, the light-emitting chip having the chemical formula La. 3.0 Ga 5.0 O 11.25 0.025Cr 3+ Yb 0.02 The preparation method includes the following steps: Step S1, Raw material mixing: According to La 3.0 Ga 5.0 O 11.25 0.025Cr 3+ Yb 0.02 Weigh out analytical grade La2O3, analytical grade Ga2O3, analytical grade Cr2O3 and analytical grade Yb2O3 according to the stoichiometric ratio, and grind and mix the above raw materials evenly; Step S2, High-temperature calcination: The uniformly mixed raw materials are loaded into an alumina crucible, and the alumina crucible is placed in air for sintering; the sintering includes: heating from room temperature to 800℃ at 10℃ / min, holding at 800℃ for 1.4h; heating from 800℃ to 1200℃ at 6℃ / min, holding at 1200℃ for 2h; furnace cooling to room temperature, pulverizing, washing three times with deionized water, passing through a 360-mesh sieve, and drying at 75℃ to constant weight to obtain luminescent powder; Step S3, phosphor encapsulation: Component A and component B obtained in preparation 7 are stirred at 500 rpm for 30 min until homogeneous to obtain a mixed adhesive solution. Then, the phosphor from step S2 is encapsulated on the surface of the NBT-LED50 blue light chip. The coating thickness of the mixed adhesive solution is controlled to be 50 μm. The chip is cured at 130℃ for 45 min to obtain an infrared LED light-emitting chip. The mass ratio of the mixed adhesive solution to the phosphor is 1.6:1.

[0043] Example 2 This embodiment provides an infrared LED light-emitting chip, wherein the chemical formula of the light-emitting powder in the chip is Y. 3.0 Al 4.5 O 12.25 0.02Cr 3+ Yb 0.025 The preparation method includes the following steps: Step S1, Raw material mixing: According to Y 3.0 Al 4.5 O 12.25 0.02Cr 3+ Yb 0.025 Weigh out analytical grade Y2O3, analytical grade Al2O3, analytical grade Cr2O3 and analytical grade Yb2O3 raw materials according to the stoichiometric ratio, and grind and mix the above raw materials evenly; Step S2, High-temperature calcination: The uniformly mixed raw materials are loaded into an alumina crucible, and the alumina crucible is placed in air for sintering; the sintering includes: heating from room temperature to 900℃ at 12℃ / min, holding at 900℃ for 1.6h; heating from 900℃ to 1300℃ at 8℃ / min, holding at 1300℃ for 3h; furnace cooling to room temperature, pulverizing, washing with deionized water 4 times, passing through a 400-mesh sieve, and drying at 80℃ to constant weight to obtain luminescent powder; Step S3, phosphor encapsulation: Component A and component B obtained in preparation 8 are stirred at 520 rpm for 32 min until homogeneous to obtain a mixed adhesive solution. Then, the phosphor from step S2 is encapsulated on the surface of the LR-TBL-445 / 1~50mW blue light chip, and the coating thickness of the mixed adhesive solution is controlled to be 60 μm. The chip is cured at 135℃ for 40 min to obtain an infrared LED light-emitting chip. The mass ratio of the mixed adhesive solution to the phosphor is 1.8:1.

[0044] Example 3 This embodiment provides an infrared LED light-emitting chip, wherein the chemical formula of the light-emitting powder in the chip is Lu. 3.5 Ga 5.5 O 13.25 0.03Cr 3+ Yb 0.03 The preparation method includes the following steps: Step S1, Raw material mixing: According to Lu3.5 Ga 5.5 O 13.25 0.03Cr 3+ Yb 0.03 Weigh out analytical grade Lu2O3, analytical grade Ga2O3, analytical grade Cr2O3 and analytical grade Yb2O3 raw materials according to the chemical stoichiometric ratio, and grind and mix the above raw materials evenly; Step S2, High-temperature calcination: The uniformly mixed raw materials are loaded into an alumina crucible, and the alumina crucible is placed in air for sintering; the sintering includes: heating from room temperature to 1000℃ at 14℃ / min, holding at 1000℃ for 1.8h; heating from 1000℃ to 1400℃ at 10℃ / min, holding at 1400℃ for 4h; furnace cooling to room temperature, pulverizing, washing with deionized water 5 times, passing through a 440-mesh sieve, and drying at 85℃ to constant weight to obtain luminescent powder; Step S3, phosphor encapsulation: Component A and component B obtained in preparation 9 are stirred at 540 rpm for 34 min until homogeneous to obtain a mixed adhesive solution. The phosphor from step S2 is then encapsulated on the surface of the OD-470 blue LED chip. The coating thickness of the mixed adhesive solution is controlled to be 70 μm. The chip is cured at 140℃ for 35 min to obtain an infrared LED chip. The mass ratio of the mixed adhesive solution to the phosphor is 2.0:1.

[0045] Comparative Example 1 Comparative Example 1 is the same as Example 1, except that components A and B in Example 1 are replaced with components A and B prepared in Comparative Preparation Example 5.

[0046] Comparative Example 2 Comparative Example 2 is the same as Example 1, except that components A and B in Example 1 are replaced with components A and B prepared in Comparative Preparation Example 6.

[0047] Comparative Example 3 Comparative Example 3 is the same as Example 1, except that components A and B in Example 1 are replaced with components A and B prepared in Comparative Preparation Example 7.

[0048] Comparative Example 4 Comparative Example 4 is the same as Example 1, except that components A and B in Example 1 are replaced with components A and B prepared in Comparative Preparation Example 8.

[0049] Performance testing The A and B components from Preparation Examples 7-9 and Comparative Preparation Examples 5-8 were mixed and cured to prepare test samples for testing. The specific curing conditions were: curing reaction at 135℃ for 40 min. The following performance tests were performed: tensile strength and elongation at break were determined according to GB / T 528-2009, tear strength was determined according to GB / T529-2008, hardness was tested according to GB / T531.2-2009, transmittance was determined according to GB / T2410-2008, refractive index was determined according to GB / T6488-2008, and thermal conductivity was determined according to the American test standard test method ASTM E1530.

[0050] Table 1 Performance tests of the functionalized encapsulants in Examples 1-3 and Comparative Examples 1-4

[0051] As shown in Table 1, compared with Comparative Examples 1-4, the functionalized encapsulant in the infrared LED light-emitting chips prepared in Examples 1-3 has a higher refractive index, better thermal conductivity and mechanical properties, which can avoid poor thermal conductivity of the encapsulant and thus aggravate the thermal quenching effect of the phosphor.

[0052] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0053] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. An infrared LED light-emitting chip, characterized in that, It includes a light-emitting chip, a light-emitting powder, and a functionalized encapsulating adhesive, wherein the chemical formula of the light-emitting powder is R. a Q b O c xCr 3+ The formula is: Yby, where R is one or two of the elements Y, La, Lu and Gd, Q is one or two of the elements Ga and Al, 2.5≤a≤3.5, 4.5≤b≤5.5, 11.25≤c≤13.25, 0.02≤x≤0.30, 0.02≤y≤0.30; the light-emitting chip is a blue light chip with an excitation wavelength of 420-470nm, which excites the light-emitting powder to emit visible light and red light. The functionalized encapsulating adhesive comprises the following raw materials in parts by weight: 65-75 parts of functionalized main material, 5-8 parts of crosslinking agent, 22-28 parts of modified filler, 10-14 parts of flame retardant, 1-2 parts of coupling agent and 25-35 parts of organic solvent. The preparation method of this functionalized encapsulating adhesive includes the following steps: Step A1: Mix the functionalized main ingredient, modified filler and 3 / 4 part by weight of organic solvent evenly to prepare component A; Step A2: Mix the flame retardant, crosslinking agent, coupling agent and 1 / 4 part by weight of organic solvent evenly to prepare component B; Step A3: Encapsulate component A and component B separately to obtain functionalized encapsulant.

2. The infrared LED light-emitting chip according to claim 1, characterized in that, The functionalized main ingredient is prepared by the following steps: Step B1: Under nitrogen protection, magnolol, hydrogen-containing phenyl silicone oil and chloroplatinic acid catalyst are stirred evenly, heated to 70-80℃, and stirred for 3-5 hours to obtain modified silicone oil. Step B2: Add the modified silicone oil to anhydrous toluene and stir until homogeneous. While stirring, add dropwise a mixture of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene, controlling the addition to be completed within 15 minutes. After the addition is complete, under nitrogen protection, heat to reflux and stir for 6-8 hours. After the reaction is complete, filter and rotary evaporate. Dissolve the rotary evaporated product in anhydrous acetone, filter, and rotary evaporate the filtrate again to obtain phenylened silicone oil. Step B3: Disperse phenylenedilicate silicone oil ultrasonically in methyl isobutyl ketone, and heat to 78-84℃ while stirring. Then add tetrabutylammonium bromide and anhydrous toluene, and add epichlorohydrin dropwise, controlling the addition to be completed within 10 minutes. After the addition is completed, stir and react for 3.6-4.2 hours. After the reaction is completed, cool to room temperature, and add alkali solution dropwise while stirring, controlling the addition to be completed within 30 minutes. Continue stirring for 1.2-1.6 hours, add alkali solution dropwise again, controlling the addition to be completed within 15 minutes, and continue stirring for 2.2-2.6 hours. Filter under reduced pressure, wash, and dry to obtain the functionalized main material.

3. An infrared LED light-emitting chip according to claim 2, characterized in that, In step B1, the mass ratio of magnolol, hydrogen-containing phenyl silicone oil and chloroplatinic acid catalyst is 40-60:260-300:1-1.

4. The chloroplatinic acid catalyst is prepared by adding chloroplatinic acid hexahydrate to isopropanol, wherein the mass fraction of chloroplatinic acid is 2-6%.

4. An infrared LED light-emitting chip according to claim 2, characterized in that, In step B2, the mass ratio of modified silicone oil, anhydrous toluene, mixture a, and anhydrous acetone is 10-15:60-80:32-36:22-26. In mixture a, the mass ratio of 4-hydroxyphthalic anhydride, triethylamine, anhydrous DMF, and anhydrous toluene is 2-3:1.6-2.8:40-50:22-26.

5. An infrared LED light-emitting chip according to claim 2, characterized in that, In step B3, the mass ratio of phenylenedilicate oil, methyl isobutyl ketone, tetrabutylammonium bromide, anhydrous toluene, and epichlorohydrin is 3-5:45-55:0.03-0.05:18-22:0.5-0.

6. The first added alkali solution is a sodium hydroxide aqueous solution with a mass fraction of 42-46%, and the second added alkali solution is a sodium hydroxide aqueous solution with a mass fraction of 34-40%. The mass of the alkali solution added in both drops is the same.

6. An infrared LED light-emitting chip according to claim 1, characterized in that, The modified filler is prepared by the following steps: Step C1: Dissolve aluminum nitrate nonahydrate and ammonium bicarbonate separately in equal masses of deionized water for later use, obtaining aluminum nitrate reaction solution and ammonium bicarbonate reaction solution 1 respectively; dissolve yttrium oxide in a mixture of nitric acid solution and deionized water (b), adjust the pH to 4-5, obtaining yttrium oxide reaction solution; dissolve cerium oxide in a mixture of nitric acid solution and deionized water (c), adjust the pH to 4-5, obtaining cerium oxide reaction solution; mix the aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution thoroughly, then... Add ammonium bicarbonate reaction solution 2 dropwise, controlling the addition to be completed within 15 minutes. During the titration, add a mixture of ammonium bicarbonate and ammonia solution d dropwise, controlling the pH to 7-8. After the addition is completed, continue stirring for 1-2 hours to obtain a pre-impregnation solution. Impregnate the nano-alumina in the pre-impregnation solution and age at room temperature for 12-16 hours. Filter, wash the precipitate with water, dry, grind, and then calcine at 1100-1300℃ for 4-6 hours. After grinding, react at 950-1150℃ for 3-4 hours to obtain rare earth modified alumina. Step C2: Mix rare earth modified alumina, deionized water, anhydrous ethanol and KH-560 ultrasonically until homogeneous, stir at room temperature for 6-8 hours, centrifuge, wash and dry the precipitate to obtain epoxy alumina. Disperse epoxy alumina and anhydrous DMF ultrasonically, add a mixture of tetrabutylammonium bromide, 3,5-diaminobenzoic acid and anhydrous DMF dropwise. After the addition is complete, heat to 100-108℃ and stir for 3-5 hours. After the reaction is complete, centrifuge, wash and dry the precipitate to obtain the modified filler.

7. An infrared LED light-emitting chip according to claim 6, characterized in that, In step C1, the mass ratio of aluminum nitrate, ammonium bicarbonate, and deionized water is 5-6:50-70:180-200; the mass ratio of yttrium oxide to mixture b is 1-2:50-60; in mixture b, the mass ratio of nitric acid solution to deionized water is 10-16:30; the mass ratio of cerium oxide to mixture c is 2-3:40-50; in mixture c, the mass ratio of nitric acid solution to deionized water is 18-22:35; in mixture d, the mass ratio of ammonium bicarbonate to ammonia is 1-3:4; the mass ratio of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution is 1-3:1-2:0.3-0.5:0.6-0.8; and the mass of nano-alumina is 20-30% of the total mass of aluminum nitrate reaction solution, ammonium bicarbonate reaction solution 1, yttrium oxide reaction solution, and cerium oxide reaction solution.

8. An infrared LED light-emitting chip according to claim 6, characterized in that, In step C2, the mass ratio of rare earth modified alumina, deionized water, anhydrous ethanol, and KH-560 is 3-5:15:25-30:0.4-0.6, the mass ratio of epoxy-modified alumina, anhydrous DMF, and mixture e is 5:50-60:10, and the mass ratio of tetrabutylammonium bromide, 3,5-diaminobenzoic acid, and anhydrous DMF in mixture e is 0.1:0.6-1.2:

20.

9. A method for preparing an infrared LED light-emitting chip as described in any one of claims 1-8, comprising the following steps: Step S1, Raw material mixing: Mix the substances containing R, Q, O and Cr to obtain a raw material mixture; Step S2, High-temperature calcination: The raw material mixture is calcined to obtain luminescent powder; Step S3, phosphor encapsulation: Mix component A and component B in the functionalized encapsulating adhesive evenly to obtain a mixed adhesive solution, then encapsulate the phosphor from step S2 onto the surface of the blue light chip, and cure at 130-140℃ for 35-45 minutes to obtain an infrared LED light-emitting chip.

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