Preparation process of methacrylate film-forming resin with high sensitivity and high sensitivity

Abstract

The invention relates to a preparation process of methacrylate film-forming resin with high sensitivity and high sensitivity. The preparation method comprises the following steps: preparation of high-purity indium, preparation of high-purity anhydrous indium trichloride, preparation of InP nanocrystals, preparation of cyclopentanone, preparation of a green-sensitive photosensitizer, preparation of methyl methacrylate, preparation of modified basalt fiber (BF), preparation of methacrylate film-forming resin and the like. The prepared high-sensitivity and high-sensitivity methacrylate film-forming resin has the advantages of high sensitivity, high sensitivity, relatively good resolution ratio and the like.

Description

Technical Field

[0001] The invention relates to a preparation process of a high-sensitivity methacrylate film-forming resin, belonging to the technical field of new materials. Background Art

[0002] Photoresist is composed of film-forming resin, photosensitizer, solvent and additives. Film-forming resin is the skeleton and basic material of photoresist, which has a decisive influence on the performance of photoresist. The main reasons for the restriction of photoresist's use are low resolution, high film hardness, brittleness, large film-fading particles, and the use of carcinogenic substance styrene.

[0003] In the application of resins, researchers are committed to finding new materials that are both environmentally friendly and efficient to overcome the limitations of existing technologies, such as good corrosion resistance but poor weather resistance, obvious discoloration over time, short shelf life, and must be stored at low temperatures. Ideal resin materials should have good corrosion resistance, excellent weather resistance, long shelf life, and excellent heat resistance and flame retardancy. These problems seriously limit their widespread promotion in practical applications. Therefore, it is particularly important to develop a film-forming resin with a simple preparation process, controllable costs, and excellent performance. Summary of the invention

[0004] In view of the above problems, the present invention provides a methacrylate film-forming resin with high sensitivity.

[0005] The invention relates to a preparation process of a methacrylate film-forming resin with high sensitivity, comprising the following steps: preparation of high-purity indium, preparation of high-purity anhydrous indium trichloride, preparation of InP nanocrystals, preparation of cyclopentanone, preparation of a green-sensitive photosensitizer, preparation of methyl methacrylate, preparation of modified basalt fiber (BF), and preparation of a methacrylate film-forming resin.

[0006] Preferably, step (1) preparation of high purity indium Put the surface oxidized In2O (indium oxide) into a quartz crucible, melt it at a high temperature under a certain pressure, heat it at a high temperature to make it sublime, and keep it at a high temperature for a period of time to obtain high-purity indium; Step (2) Preparation of high-purity anhydrous indium trichloride Weighing step (1) high-purity indium is placed in a beaker, hydrochloric acid solution is added, and the mixture is continuously stirred at a certain temperature until the metal indium is completely dissolved to obtain an indium chloride solution, and then the solution is heated to a certain temperature, and the solution is gradually evaporated to precipitate InCI3.4H2O crystals, and the secondary crystals are added to n-butanol for dissolution, and the solution is placed in a vacuum glove box, and the temperature is controlled to perform atmospheric distillation and dehydration to obtain an indium trichloride product InCI3.mBuOH (indium chloride tetrahydrate) that replaces the crystal water, and the complex is placed in a distillation device, and the temperature, vacuum degree, and distillation time are controlled to decompose the organic dehydrating agent under reduced pressure to obtain white anhydrous indium trichloride, and finally the obtained anhydrous indium trichloride product is taken out and placed in a vacuum sublimator, and the temperature is controlled to obtain high-purity anhydrous indium trichloride; Step (3) Preparation of InP nanocrystals Remove the crystal water of InCI3.4H2O, and seal and store the obtained high-purity anhydrous indium trichloride in step (2), and synthesize sodium phosphide using the sealed high-purity anhydrous indium trichloride in step (2), metallic sodium and analytical pure yellow phosphorus as raw materials, xylene as solvent, and nitrogen as protective gas, and then synthesize indium phosphide using Na3P (sodium phosphide) and an appropriate amount of InCI3 as raw materials, xylene as solvent, and nitrogen as protective gas, and then filter the indium phosphide with benzene and deionized water respectively, and then cool it by introducing nitrogen after vacuum drying at a certain temperature for a period of time, to obtain InP nanocrystals; Step (4) Preparation of cyclopentanone The reaction distillation device consists of a four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with a number of plates, a feed port connected to a feed metering pump, and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (3) are first added to the three-necked flask, the stirrer is turned on, and the reaction liquid is stirred in an oil bath to raise it to a certain temperature. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to balance the liquid discharge rate with the tower bottom feed rate to obtain cyclopentanone; Step (5) Preparation of green photosensitizer Add methanol, 5-dimethylaminothiophene-2-carboxaldehyde, cyclopentanone from step (4), and sodium hydroxide to a three-necked flask in sequence, stir at room temperature for a period of time, stop the reaction, remove the solvent, and separate and purify the obtained crude product by column chromatography using dichloromethane as an eluent, and then recrystallize using dichloromethane / petroleum ether in a certain proportion to obtain a green photosensitizer; Step (6) Preparation of methyl methacrylate The reaction is carried out at high temperature and high space velocity, and methacrolein (MAL) and methacrylic acid (MAA) reach the sum of the yields to obtain a phosphomolybdic acid catalyst, and an alkali metal and a green photosensitizer from step (5) are added to increase the thermal stability of the catalyst and increase the surface area to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at a certain temperature to obtain methyl methacrylate (MMA); Step (7) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at a high temperature to remove impurities on the surface of the original fiber. The fibers used in the subsequent patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed according to a mass ratio and stirred continuously to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Then, basalt fiber (BF) is placed in the above solution, and methyl methacrylate in step (6) is added and stirred for impregnation. After naturally drying, it is placed in a constant temperature drying oven and dried at a certain temperature to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane). Step (8) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) are added into a three-necked flask in proportion, and reacted in a sealed manner at a certain temperature. Then, an initiator (azobisisobutyronitrile) is added, and then the modified basalt fiber (BF) in step (7) is added. After reacting for a period of time, the temperature is lowered and the material is discharged to obtain a methacrylate film-forming resin.

[0007] The first technical purpose of the present invention is achieved through the following technical solutions: Preferably, step (1) preparation of high purity indium Place the surface oxidized In2O (indium oxide) in a quartz crucible at a pressure of 10 -4 -10 -5 Pa is melted at 200-250℃, heated at 600-700℃ to sublime, and kept at 800-900℃ for 5-6h to obtain high-purity indium.

[0008] The advantage of adopting the present invention is that the high-purity indium prepared in this step is effectively reduced in other impurities because it melts at high temperature. The high-temperature preparation helps to improve the chemical stability of indium, so that it can still maintain good corrosion resistance and oxidation resistance in a high temperature environment. In addition, indium itself has good light permeability and conductivity, so as to prepare a film-forming resin with excellent performance.

[0009] Preferably, step (2) preparation of high-purity anhydrous indium trichloride Weigh 11.5-14.5 g of high-purity indium from step (1) into a beaker, add 50-60 mL of a 30-34% hydrochloric acid solution, and continue stirring at 40-60 ° C for 10-12 h until the metal indium is completely dissolved to obtain an indium chloride solution, then heat the solution to 90-100 ° C, gradually evaporate the solution, and precipitate 29.3-33.3 g of InCI3.4H2O crystals, add 252-272 mL of n-butanol to dissolve the secondary crystals, and place the solution in a vacuum glove box, control The temperature is 120-150°C and atmospheric distillation is performed to dehydrate the product InCI3.mBuOH (indium chloride tetrahydrate) which replaces the crystal water. The complex is placed in a distillation device at a temperature of 180-210°C, a vacuum degree of 6-7kPa, and a distillation time of 0.5-1h. The organic dehydrating agent is decompressed and decomposed to obtain white anhydrous indium trichloride. Finally, the obtained anhydrous indium trichloride product is taken out and placed in a vacuum sublimator at a temperature of 300-350°C to obtain high-purity anhydrous indium trichloride.

[0010] The invention has the advantages that the high-purity anhydrous indium trichloride prepared in this step exhibits good thermal stability during the heating process and is not easily decomposed, so that it can maintain its high-purity performance during the high-temperature treatment process. In addition, in organic synthesis, the high-purity anhydrous indium trichloride can be used as a catalyst to promote the specific chemical reaction in the next step of preparation and improve the reaction efficiency.

[0011] Preferably, step (3) preparation of InP nanocrystals Remove the crystal water of InCI3.4H2O, and seal and store the obtained high-purity anhydrous indium trichloride in step (2) for 5-10 minutes, synthesize sodium phosphide using the sealed high-purity anhydrous indium trichloride in step (2), metallic sodium and analytical pure yellow phosphorus as raw materials, xylene as solvent, and nitrogen as protective gas, and then synthesize indium phosphide using Na3P (sodium phosphide) and InCI3 as raw materials, xylene as solvent, and nitrogen as protective gas, and then filter the indium phosphide with benzene and deionized water respectively, and dry it under vacuum at 60-70°C for 4-5 hours, and then cool it with nitrogen to obtain InP nanocrystals; The invention has the advantages that the InP nanocrystals prepared in this step are synthesized into indium phosphide through secondary synthesis of raw materials, diphenylmethane and nitrogen, thereby improving the quality of the product, and the InP nanocrystals have the characteristics of being environmentally friendly, low toxicity, and excellent optical and electrical properties.

[0012] Preferably, step (4) preparation of cyclopentanone The reaction distillation device consists of a 1000-1200mL four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with 30-35 plates, a feed port connected to a feed metering pump and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (3) are first added into the three-necked flask, the stirrer is started, the stirring speed is 50-60r / min, and the reaction liquid is heated to 124-134°C with an oil bath. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to 4-8:1-5 to balance the liquid discharge speed with the tower bottom feed speed to obtain cyclopentanone.

[0013] The advantage of the present invention is that the cyclopentanone prepared in this step has moderate volatility, moderate boiling point and moderate flash point, so that it can be uniformly volatilized in the drying and curing steps in the next preparation and resin manufacturing process, which is helpful to form a uniform film.

[0014] Preferably, step (5) preparation of green photosensitizer To a 20-30 mL three-necked flask, add 10-15 mL of methanol, 155-165 mg of 5-dimethylaminothiophene-2-carboxaldehyde, 43-48 mg of cyclopentanone from step (4), and 5-10 mg of sodium hydroxide in sequence, stir at room temperature for 2-3 h, then stop the reaction, remove the solvent, and separate and purify the obtained crude product by column chromatography using dichloromethane as eluent, and then recrystallize using dichloromethane / petroleum ether (1-5:1-5) to obtain a green photosensitizer.

[0015] The advantage of the present invention is that the green-sensitive photosensitizer prepared in this step can effectively absorb green light, thereby improving the efficiency of photo-initiated polymerization, which is crucial to the curing process of the resin because it can accelerate the reaction rate and shorten the production cycle. At the same time, the resin system containing the green-sensitive photosensitizer usually has a higher sensitivity, which means that they are more sensitive to light and can initiate polymerization reactions at lower light intensities, so that the prepared resin has the characteristics of high sensitivity.

[0016] Preferably, step (6) preparation of methyl methacrylate At a reaction temperature of 350-370° C. and an air velocity of 1000-1100 h / h, the sum of the yields of methacrolein (MAL) and methacrylic acid (MAA) is 90-95%, and a phosphomolybdic acid catalyst is obtained. An alkali metal and a green photosensitizer from step (5) are added to increase the thermal stability and surface area of ​​the catalyst to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at 70-100° C. to obtain methyl methacrylate (MMA).

[0017] The invention has the advantage that the methyl methacrylate prepared in this step can increase the movement speed of the molecules by high temperature, thereby increasing the chemical reaction rate, making the preparation process of methyl methacrylate faster and more efficient. Adding a green photosensitizer to methyl methacrylate can increase its photosensitivity under green light, making it easier for methyl methacrylate to undergo photopolymerization reaction under green light.

[0018] Preferably, step (7) preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at a high temperature of 500-700°C for 30-60 minutes to remove impurities on the surface of the original fiber. The fibers used in the subsequent patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed in a mass ratio of 9-14:1-6 and stirred continuously for 10-20 minutes to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Subsequently, 10-15g of basalt fiber (BF) is placed in the above solution, and 10-20g of methyl methacrylate in step (6) is added and stirred for 30-35 minutes and soaked for 20-25 minutes. After natural drying, the fiber is placed in a constant temperature drying oven and dried at a temperature of 100-150°C for 8-13 hours to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane).

[0019] The advantage of the present invention is that the modified basalt fiber (BF) prepared in this step is subjected to high temperature to remove impurities and to the mixed solution modification, and because the surface of the basalt fiber is relatively smooth and has a relatively low surface energy, after the surface modification, nano-SiO2 particles are added to the surface, which effectively improves the surface roughness of the fiber and increases the effective contact area between the resin and the carrier.

[0020] Preferably, in step (8), the preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) are added into a three-necked flask in a ratio of 25-50:50-100:25-50, and reacted in a sealed manner at 80-85°C for 30-40 minutes. Then, 10-20 g of the modified basalt fiber (BF) obtained in step (7) is added, and the reaction is continued for 2-5 hours. The material is cooled and discharged to obtain a methacrylate film-forming resin.

[0021] The advantage of the present invention is that the methacrylate film-forming resin prepared in this step has the characteristics of high sensitivity, high sensitivity, high diffraction efficiency, etc. after the closed reaction of methyl methacrylate, methacrylic acid and butyl acrylate. The addition of modified basalt fiber can significantly improve the mechanical properties, durability and high-temperature stability of the composite material.

[0022] In summary, the present invention has the following beneficial effects: 1. The advantage of the present invention is that the high-purity indium prepared in this step is effectively reduced because it melts at high temperature. High-temperature preparation helps to improve the chemical stability of indium, so that it can still maintain good corrosion resistance and oxidation resistance in a high temperature environment. In addition, indium itself has good light permeability and conductivity, so as to prepare a film-forming resin with excellent performance.

[0023] 2. The present invention has the advantage that the high-purity anhydrous indium chloride prepared in this step exhibits good thermal stability during the heating process and is not easily decomposed, which enables it to maintain its high-purity performance during the high-temperature treatment process. In addition, because the high-purity anhydrous indium chloride can be used as a catalyst in organic synthesis, it promotes the progress of a specific chemical reaction for the next step of preparation and improves the reaction efficiency.

[0024] 3. The advantage of the present invention is that the InP nanocrystals prepared in this step are synthesized into indium phosphide through secondary synthesis of raw materials, diphenylmethane and nitrogen, thereby improving the quality of the product. In addition, the InP nanocrystals are environmentally friendly, low in toxicity, and have excellent optical and electrical properties.

[0025] 4. The advantage of the present invention is that the cyclopentanone prepared in this step has moderate volatility, moderate boiling point and moderate flash point, so that it can be uniformly volatilized in the drying and curing steps in the next preparation and resin manufacturing process, which helps to form a uniform film.

[0026] 5. The advantage of the present invention is that the green-sensitive photosensitizer prepared in this step can effectively absorb green light, thereby improving the efficiency of photo-initiated polymerization, which is crucial to the curing process of the resin because it can accelerate the reaction rate and shorten the production cycle. At the same time, the resin system containing the green-sensitive photosensitizer usually has a higher sensitivity, which means that they are more sensitive to light and can initiate polymerization reactions at lower light intensities, so that the prepared resin has the characteristics of high sensitivity.

[0027] 6. The present invention has the advantage that the methyl methacrylate prepared in this step can increase the molecular movement speed by high temperature, thereby increasing the chemical reaction rate, making the preparation process of methyl methacrylate faster and more efficient. Adding a green photosensitizer to methyl methacrylate can increase its photosensitivity under green light, making methyl methacrylate more susceptible to photopolymerization under green light.

[0028] 7. The advantage of the present invention is that the modified basalt fiber (BF) prepared in this step is subjected to high temperature to remove impurities and to the mixed solution modification, and because the surface of the basalt fiber is relatively smooth and has a relatively low surface energy, after the surface modification, nano-SiO2 particles are added to the surface, which effectively improves the surface roughness of the fiber and increases the effective contact area between the resin and the carrier.

[0029] 8. The advantage of the present invention is that the methacrylate film-forming resin prepared in this step has the characteristics of high sensitivity, high sensitivity, and high diffraction efficiency after the closed reaction of methyl methacrylate, methacrylic acid, and butyl acrylate. The addition of modified basalt fiber can significantly improve the mechanical properties, durability and high-temperature stability of the composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 A process flow chart for preparing a highly sensitive methacrylate film-forming resin. DETAILED DESCRIPTION

[0031] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. Without departing from the spirit and substance of the present invention, modifications or substitutions made to the methods, steps or conditions of the present invention are within the scope of the present invention.

[0032] If not specifically stated, the technical means used in the examples are conventional means known to those skilled in the art. In addition, all the raw materials used in the examples are known commercial products.

[0033] Example 1

[0034] Step (1) Preparation of high purity indium Place the surface oxidized In2O (indium oxide) in a quartz crucible at a pressure of 10 -4 Pa is melted at 200°C, heated at 600°C to sublime, and kept at 800°C for 5 hours to obtain high-purity indium; Step (2) Preparation of high-purity anhydrous indium trichloride Weigh 11.5 g of high-purity indium from step (1) into a beaker, add 50 mL of a 30% hydrochloric acid solution by mass, and stir continuously at 40° C. for 10 h until the metal indium is completely dissolved to obtain an indium chloride solution, then heat the solution to 90° C., evaporate the solution gradually, and precipitate 29.3 g of InCI3.4H2O crystals, add 252 mL of n-butanol to dissolve the secondary crystals, place the solution in a vacuum glove box, control the temperature at 121° C. to perform atmospheric distillation and dehydration, and obtain an indium trichloride product InCI3.mBuOH (indium chloride tetrahydrate) that replaces the crystal water, place the complex in a distillation apparatus, control the temperature at 180° C., the vacuum degree at 6 kPa, and the distillation time at 0.5 h, and decompose the organic dehydrating agent under reduced pressure to obtain white anhydrous indium trichloride, and finally take out the obtained anhydrous indium trichloride product and place it in a vacuum sublimator, control the temperature at 300° C. to obtain high-purity anhydrous indium trichloride; Step (3) Preparation of InP nanocrystals Remove the crystal water of InCI3.4H2O, and seal and store the obtained high-purity anhydrous indium trichloride in step (2) for 5 minutes, and use the sealed high-purity anhydrous indium trichloride in step (2), sodium metal and analytical pure yellow phosphorus as raw materials, xylene as solvent, and nitrogen as protective gas to synthesize sodium phosphide, and then use Na3P (sodium phosphide) and InCI3 as raw materials, xylene as solvent, and nitrogen as protective gas to synthesize indium phosphide, and then use benzene and deionized water to filter the indium phosphide, vacuum dry at 60°C for 4 hours, and then cool it with nitrogen to obtain InP nanocrystals; Step (4) Preparation of cyclopentanone The reaction distillation device is composed of a 1000mL four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with 31 plates, a feed port connected to a feed metering pump, and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (3) are first added to the three-necked flask, and the stirrer is started at a stirring speed of 50r / min. The reaction liquid is heated to 124°C in an oil bath. At the initial stage of the reaction, the distillation column is fully refluxed. When the cyclopentanone in the kettle liquid reaches a certain concentration, the reflux ratio is adjusted to 4:1 to balance the liquid discharge rate with the tower kettle feed rate to obtain cyclopentanone. Step (5) Preparation of green photosensitizer To a 20 mL three-necked flask, 10 mL of methanol, 155 mg of 5-dimethylaminothiophene-2-carboxaldehyde, 43 mg of cyclopentanone from step (4), and 5 mg of sodium hydroxide were added in sequence. The reaction was stopped after stirring at room temperature for 2 h. The solvent was removed. The crude product was separated and purified by column chromatography using dichloromethane as an eluent, and then recrystallized using dichloromethane / petroleum ether (1:1) to obtain a green photosensitizer. Step (6) Preparation of methyl methacrylate At a reaction temperature of 350° C. and an air velocity of 1000 h / h, the sum of the yields of methacrolein (MAL) and methacrylic acid (MAA) is 90%, and a phosphomolybdic acid catalyst is obtained. An alkali metal and the green photosensitizer of step (5) are added to increase the thermal stability and surface area of ​​the catalyst to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at 70° C. to obtain methyl methacrylate (MMA); Step (7) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at 500°C for 30 minutes to remove impurities on the surface of the original fiber. The fibers used in the subsequent patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed in a mass ratio of 9:1 and stirred for 10 minutes to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Then, 10g of basalt fiber (BF) is put into the above solution, and 10-20g of methyl methacrylate in step (6) is added and stirred for 30 minutes and soaked for 20 minutes. After natural drying, the fiber is placed in a constant temperature drying oven and dried at 100°C for 8 hours to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane). Step (8) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) were added into a three-necked flask in a ratio of 25:50:25, and reacted in a sealed manner at 80°C for 30 minutes. Then, 10 g of an initiator (azobisisobutyronitrile) was added, and then 10 g of the modified basalt fiber (BF) obtained in step (7) was added. The reaction was continued for 2 hours, and the temperature was lowered and the material was discharged to obtain a methacrylate film-forming resin.

[0035] Example 2 Step (1) Preparation of high purity indium Place the surface oxidized In2O (indium oxide) in a quartz crucible at a pressure of 10 -4 Pa was melted at 210°C, heated at 620°C to sublime, and kept at 820°C for 5.1h to obtain high-purity indium; Step (2) Preparation of high-purity anhydrous indium trichloride Weigh 12 g of high-purity indium from step (1) into a beaker, add 52 mL of a 31% hydrochloric acid solution, and continue stirring at 42° C. for 10.5 h until the metal indium is completely dissolved to obtain an indium chloride solution, then heat the solution to 92° C., evaporate the solution gradually, and precipitate 30 g of InCI3.4H2O crystals, add 254 mL of n-butanol to dissolve the secondary crystals, place the solution in a vacuum glove box, control the temperature at 125° C. to perform atmospheric distillation and dehydration, and obtain an indium trichloride product InCI3.mBuOH (indium chloride tetrahydrate) that replaces the crystal water, place the complex in a distillation apparatus, control the temperature at 190° C., the vacuum degree at 6.5 kPa, and the distillation time at 0.6 h, and decompose the organic dehydrating agent under reduced pressure to obtain white anhydrous indium trichloride, and finally take out the obtained anhydrous indium trichloride product and place it in a vacuum sublimator, control the temperature at 310° C. to obtain high-purity anhydrous indium trichloride; Step (3) Preparation of InP nanocrystals Remove the crystal water of InCI3.4H2O, and seal and store the obtained high-purity anhydrous indium trichloride in step (2) for 6 minutes, and synthesize sodium phosphide using the sealed high-purity anhydrous indium trichloride in step (2), metallic sodium and analytical pure yellow phosphorus as raw materials, xylene as solvent, and nitrogen as protective gas, and then synthesize indium phosphide using Na3P (sodium phosphide) and InCI3 as raw materials, xylene as solvent, and nitrogen as protective gas, and then filter the indium phosphide with benzene and deionized water respectively, and then cool it by introducing nitrogen after vacuum drying at 62°C for 4.1 hours to obtain InP nanocrystals; Step (4) Preparation of cyclopentanone The reaction distillation device consists of a 1050mL four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with 31 plates, a feed port connected to a feed metering pump, and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (3) are first added to the three-necked flask, and the stirrer is started at a stirring speed of 52r / min. The reaction liquid is heated to 126°C using an oil bath. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to 5:2 to balance the liquid discharge rate with the tower bottom feed rate to obtain cyclopentanone. Step (5) Preparation of green photosensitizer To a 22 mL three-necked flask, 11 mL of methanol, 157 mg of 5-dimethylaminothiophene-2-carboxaldehyde, 44 mg of cyclopentanone from step (4), and 6 mg of sodium hydroxide were added in sequence. The reaction was stopped after stirring at room temperature for 2.2 h. The solvent was removed. The crude product was separated and purified by column chromatography using dichloromethane as an eluent, and then recrystallized using dichloromethane / petroleum ether (2:2) to obtain a green photosensitizer. Step (6) Preparation of methyl methacrylate At a reaction temperature of 355°C and a space velocity of 1050h, the sum of the yields of methacrolein (MAL) and methacrylic acid (MAA) is 91%, and a phosphomolybdic acid catalyst is obtained. An alkali metal and a green photosensitizer from step (5) are added to increase the thermal stability and surface area of ​​the catalyst to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at 80°C to obtain methyl methacrylate (MMA); Step (7) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at 550°C for 40 minutes to remove impurities on the surface of the original fiber. The fibers used in this patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed in a mass ratio of 10:2 and stirred for 12 minutes to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Then, 11g of basalt fiber (BF) is put into the above solution, and 12g of methyl methacrylate in step (6) is added and stirred for 31 minutes and soaked for 21 minutes. After natural drying, the fiber is placed in a constant temperature drying oven and dried at 110°C for 9 hours to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane). Step (8) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) were added into a three-necked flask in a ratio of 30:55:30. After the reaction was carried out at 81°C in a sealed manner for 31 minutes, 11 g of an initiator (azobisisobutyronitrile) was added, and then 11 g of the modified basalt fiber (BF) obtained in step (7) was added. The reaction was continued for 3 hours, and the temperature was lowered and the material was discharged to obtain a methacrylate film-forming resin.

[0036] Example 3 Step (1) Preparation of high purity indium Place the surface oxidized In2O (indium oxide) in a quartz crucible at a pressure of 10 -4 Pa was melted at 220°C, heated at 640°C to sublime, and kept at 840°C for 5.3h to obtain high-purity indium; Step (2) Preparation of high-purity anhydrous indium trichloride Weigh 12.5 g of high-purity indium from step (1) into a beaker, add 54 mL of a 32% hydrochloric acid solution, and continue stirring at 44° C. for 10.8 h until the metal indium is completely dissolved to obtain an indium chloride solution, then heat the solution to 94° C., evaporate the solution gradually, and precipitate 31 g of InCI3.4H2O crystals, add 260 mL of n-butanol to dissolve the secondary crystals, place the solution in a vacuum glove box, control the temperature at 130° C. to perform atmospheric distillation and dehydration, and obtain an indium trichloride product InCI3.mBuOH (indium chloride tetrahydrate) that replaces the crystal water, place the complex in a distillation apparatus, control the temperature at 195° C., the vacuum degree at 6.6 kPa, and the distillation time at 0.7 h, and decompose the organic dehydrating agent under reduced pressure to obtain white anhydrous indium trichloride, and finally take out the obtained anhydrous indium trichloride product and place it in a vacuum sublimator, control the temperature at 320° C. to obtain high-purity anhydrous indium trichloride; Step (3) Preparation of InP nanocrystals Remove the crystal water of InCI3.4H2O, and seal and store the obtained high-purity anhydrous indium trichloride in step (2) for 7 minutes, and use the sealed high-purity anhydrous indium trichloride in step (2), sodium metal and analytical pure yellow phosphorus as raw materials, xylene as solvent, and nitrogen as protective gas to synthesize sodium phosphide, and then use Na3P (sodium phosphide) and InCI3 as raw materials, xylene as solvent, and nitrogen as protective gas to synthesize indium phosphide, and then use benzene and deionized water to filter the indium phosphide, vacuum dry at 64°C for 4.2 hours, and then cool it with nitrogen to obtain InP nanocrystals; Step (4) Preparation of cyclopentanone The reaction distillation device consists of a 1100 mL four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with 32 plates, a feed port connected to a feed metering pump, and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (3) are first added to the three-necked flask, and the stirrer is started at a stirring speed of 54 r / min. The reaction liquid is heated to 128° C. in an oil bath. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to 6:3 to balance the liquid discharge rate with the tower bottom feed rate to obtain cyclopentanone. Step (5) Preparation of green photosensitizer To a 24 mL three-necked flask, 12 mL of methanol, 159 mg of 5-dimethylaminothiophene-2-carboxaldehyde, 45 mg of cyclopentanone from step (4), and 7 mg of sodium hydroxide were added in sequence. The reaction was stopped after stirring at room temperature for 2.4 h. The solvent was removed. The crude product was separated and purified by column chromatography using dichloromethane as an eluent, and then recrystallized using dichloromethane / petroleum ether (3:3) to obtain a green photosensitizer. Step (6) Preparation of methyl methacrylate At a reaction temperature of 360°C and an air velocity of 1060h, the sum of the yields of methacrolein (MAL) and methacrylic acid (MAA) is 92%, and a phosphomolybdic acid catalyst is obtained. An alkali metal and a green photosensitizer from step (5) are added to increase the thermal stability and surface area of ​​the catalyst to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at 85°C to obtain methyl methacrylate (MMA); Step (7) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at 600°C for 40 minutes to remove impurities on the surface of the original fiber. The fibers used in this patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed in a mass ratio of 11:3 and stirred for 14 minutes to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Then, 12g of basalt fiber (BF) is put into the above solution, and 14g of methyl methacrylate in step (6) is added and stirred for 32 minutes and soaked for 22 minutes. After natural drying, the fiber is placed in a constant temperature drying oven and dried at 120°C for 10 hours to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane). Step (8) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) were added into a three-necked flask in a ratio of 35:60:35, and reacted in a sealed manner at 82°C for 34 minutes. Then, 14 g of an initiator (azobisisobutyronitrile) was added, and then 14 g of the modified basalt fiber (BF) obtained in step (7) was added. The reaction was continued for 4 hours, and the temperature was lowered and the material was discharged to obtain a methacrylate film-forming resin.

[0037] Example 4 Step (1) Preparation of high purity indium Place the surface oxidized In2O (indium oxide) in a quartz crucible at a pressure of 10 -4 Pa was melted at 240°C, heated at 660°C to sublime, and kept at 860°C for 5.5h to obtain high-purity indium; Step (2) Preparation of high-purity anhydrous indium trichloride Weigh 13 g of high-purity indium from step (1) into a beaker, add 56 mL of a 34% hydrochloric acid solution, and continue stirring at 46° C. for 11 h until the metal indium is completely dissolved to obtain an indium chloride solution, then heat the solution to 96° C., evaporate the solution gradually, and precipitate 32 g of InCI3.4H2O crystals, add 265 mL of n-butanol to dissolve the secondary crystals, place the solution in a vacuum glove box, control the temperature to 140° C., and perform atmospheric distillation to dehydrate, to obtain an indium trichloride product InCI3.mBuOH (indium chloride tetrahydrate) that replaces the crystal water, place the complex in a distillation apparatus, control the temperature to 200° C., the vacuum degree to 6.8 kPa, and the distillation time to 0.8 h, and decompose the organic dehydrating agent under reduced pressure to obtain white anhydrous indium trichloride, and finally take out the obtained anhydrous indium trichloride product and place it in a vacuum sublimator, control the temperature to 340° C., and obtain high-purity anhydrous indium trichloride; Step (3) Preparation of InP nanocrystals Remove the crystal water of InCI3.4H2O, and seal and store the obtained high-purity anhydrous indium trichloride in step (2) for 8 minutes, and synthesize sodium phosphide using the sealed high-purity anhydrous indium trichloride in step (2), metallic sodium and analytical pure yellow phosphorus as raw materials, xylene as solvent, and nitrogen as protective gas, and then synthesize indium phosphide using Na3P (sodium phosphide) and InCI3 as raw materials, xylene as solvent, and nitrogen as protective gas, and then filter the indium phosphide with benzene and deionized water respectively, and then cool it by introducing nitrogen after vacuum drying at 66°C for 4.5 hours to obtain InP nanocrystals; Step (4) Preparation of cyclopentanone The reaction distillation device consists of a 1150mL four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with 34 plates, a feed port connected to a feed metering pump, and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (3) are first added to the three-necked flask, and the stirrer is started at a stirring speed of 55r / min. The reaction liquid is heated to 130°C using an oil bath. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to 7:4 to balance the liquid discharge rate with the tower bottom feed rate to obtain cyclopentanone. Step (5) Preparation of green photosensitizer To a 26 mL three-necked flask, 13 mL of methanol, 160 mg of 5-dimethylaminothiophene-2-carboxaldehyde, 47 mg of cyclopentanone from step (4), and 8 mg of sodium hydroxide were added in sequence. The reaction was stopped after stirring at room temperature for 2.8 h. The solvent was removed. The crude product was separated and purified by column chromatography using dichloromethane as an eluent, and then recrystallized using dichloromethane / petroleum ether (4:4) to obtain a green photosensitizer. Step (6) Preparation of methyl methacrylate At a reaction temperature of 365°C and an air velocity of 1080h, the sum of the yields of methacrolein (MAL) and methacrylic acid (MAA) is 94%, and a phosphomolybdic acid catalyst is obtained. An alkali metal and a green photosensitizer from step (5) are added to increase the thermal stability and surface area of ​​the catalyst to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at 90°C to obtain methyl methacrylate (MMA); Step (7) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at 650°C for 45 minutes to remove impurities on the surface of the original fiber. The fibers used in this patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed in a mass ratio of 12:4 and stirred for 16 minutes to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Then, 14g of basalt fiber (BF) is placed in the above solution, and 16g of methyl methacrylate in step (6) is added and stirred for 33 minutes and soaked for 23 minutes. After natural drying, the fiber is placed in a constant temperature drying oven and dried at 130°C for 13 hours to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane). Step (8) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) were added into a three-necked flask in a ratio of 40:65:40, and reacted in a sealed manner at 85°C for 40 minutes. Then, 20 g of an initiator (azobisisobutyronitrile) was added, and then 20 g of the modified basalt fiber (BF) obtained in step (7) was added. The reaction was continued for 5 hours, and the temperature was lowered and the material was discharged to obtain a methacrylate film-forming resin.

[0038] Comparative Example 1 Step (1) Preparation of InP nanocrystals Remove the crystal water of InCI3.4H2O, and seal the obtained high-purity anhydrous indium trichloride for 11 minutes, use the sealed high-purity anhydrous indium trichloride, sodium metal and analytical pure yellow phosphorus as raw materials, xylene as solvent, and nitrogen as protective gas to synthesize sodium phosphide, then use Na3P (sodium phosphide) and InCI3 as raw materials, xylene as solvent, and nitrogen as protective gas to synthesize indium phosphide, and then use benzene and deionized water to filter the indium phosphide, vacuum dry at 71°C for 6 hours, and then cool it with nitrogen to obtain InP nanocrystals; Step (2) Preparation of cyclopentanone The reaction distillation device consists of a 1250 mL four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with 37 plates, a feed port connected to a feed metering pump, and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (1) are first added into the three-necked flask, and the stirrer is started at a stirring speed of 65 r / min. The reaction liquid is heated to 136° C. in an oil bath. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to 10:6 to balance the liquid discharge rate with the tower bottom feed rate to obtain cyclopentanone. Step (3) Preparation of green photosensitizer To a 35 mL three-necked flask, add 20 mL of methanol, 170 mg of 5-dimethylaminothiophene-2-carboxaldehyde, 50 mg of cyclopentanone from step (2), and 12 mg of sodium hydroxide in sequence, stir at room temperature for 4 h, stop the reaction, remove the solvent, and separate and purify the obtained crude product by column chromatography using dichloromethane as eluent, and then recrystallize using dichloromethane / petroleum ether (6:6) to obtain a green photosensitizer; Step (4) Preparation of methyl methacrylate At a reaction temperature of 375°C and an air velocity of 1150h, the sum of the yields of methacrolein (MAL) and methacrylic acid (MAA) is 96%, and a phosphomolybdic acid catalyst is obtained. An alkali metal and the green photosensitizer of step (3) are added to increase the thermal stability and surface area of ​​the catalyst to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at 105°C to obtain methyl methacrylate (MMA); Step (5) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at 710°C for 61 minutes to remove impurities on the surface of the original fiber. The fibers used in this patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed in a mass ratio of 15:7 and stirred for 11 minutes to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Then, 16g of basalt fiber (BF) is placed in the above solution, and 21g of methyl methacrylate in step (4) is added and stirred for 36 minutes and soaked for 26 minutes. After natural drying, the fiber is placed in a constant temperature drying oven and dried at 151°C for 14 hours to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane). Step (6) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) were added into a three-necked flask in a ratio of 55:110:55, and reacted in a sealed manner at 86°C for 30-40 minutes. Then, 21 g of an initiator (azobisisobutyronitrile) was added, and then 21 g of the modified basalt fiber (BF) obtained in step (7) was added. The reaction was continued for 6 hours, and the temperature was lowered and the material was discharged to obtain a methacrylate film-forming resin.

[0039] Comparative Example 2 Step (1) Preparation of high purity indium Place the surface oxidized In2O (indium oxide) in a quartz crucible at a pressure of 10 -4 Pa is melted at 260°C, heated at 710°C to sublime, and kept at 910°C for 7h to obtain high-purity indium; Step (2) Preparation of cyclopentanone The reaction distillation device consists of a 1300 mL four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with 38 plates, a feed port connected to a feed metering pump, and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, high-purity indium, cyclopentanol and nickel catalyst in step (1) are first added to the three-necked flask, and the stirrer is started at a stirring speed of 70 r / min. The reaction liquid is heated to 137° C. in an oil bath. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to 11:7 to balance the liquid discharge rate with the tower bottom feed rate to obtain cyclopentanone. Step (3) Preparation of green photosensitizer To a 36 mL three-necked flask, 22 mL of methanol, 171 mg of 5-dimethylaminothiophene-2-carboxaldehyde, 52 mg of cyclopentanone from step (2), and 13 mg of sodium hydroxide were added in sequence. The reaction was stopped after stirring at room temperature for 5 h. The solvent was removed. The crude product was separated and purified by column chromatography using dichloromethane as an eluent, and then recrystallized using dichloromethane / petroleum ether (7:7) to obtain a green photosensitizer. Step (4) Preparation of methyl methacrylate At a reaction temperature of 380°C and an air velocity of 1200 h, the sum of the yields of methacrolein (MAL) and methacrylic acid (MAA) is 97%, and a phosphomolybdic acid catalyst is obtained. An alkali metal and the green photosensitizer of step (3) are added to increase the thermal stability and surface area of ​​the catalyst to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at 1100°C to obtain methyl methacrylate (MMA); Step (5) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at 720°C for 62 minutes to remove impurities on the surface of the original fiber. The fibers used in this patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed in a mass ratio of 16:8 and stirred for 12 minutes to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Then, 17g of basalt fiber (BF) is placed in the above solution, and 22g of methyl methacrylate in step (4) is added and stirred for 37 minutes and soaked for 27 minutes. After natural drying, the fiber is placed in a constant temperature drying oven and dried at 152°C for 15 hours to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane). Step (6) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) were added into a three-necked flask in a ratio of 60:65:60, and reacted in a sealed manner at 87°C for 42 minutes. Then, 12 g of an initiator (azobisisobutyronitrile) was added, and then 22 g of the modified basalt fiber (BF) obtained in step (7) was added. The reaction was continued for 7 hours, and the temperature was lowered and the material was discharged to obtain a methacrylate film-forming resin.

[0040] Comparison of detection experiments: The methacrylate film-forming resins obtained in Examples 1 to 4 and Comparative Example Products 1 and 2 were tested. The specific testing method is as follows: Infrared spectroscopy Infrared spectroscopy analysis can be used to study the structure and chemical bonds of molecules, and can also be used as a method to characterize and identify chemical species. Infrared spectra are highly characteristic, and the infrared spectra of methacrylate film-forming resins are compared with those of standard compounds for analysis and identification. The higher the transmittance, the better the resolution of the preparation, and the lower the transmittance, the worse the resolution of the preparation.

[0041] UV-Vis absorption spectroscopy Ultraviolet-visible absorption spectroscopy utilizes the principle of interference to record the light wave information of an object and utilizes the principle of diffraction to reproduce the light wave information of an object. The maximum diffraction efficiency that the green photosensitizer can achieve after exposure is a major indicator for measuring the holographic performance of the material. The higher the diffraction efficiency, the better the holographic performance of the green photosensitizer, and the higher the sensitivity of the prepared resin. The lower the diffraction efficiency, the worse the holographic performance of the green photosensitizer, and the lower the sensitivity of the prepared resin.

[0042] Dehydrogenation Test The dehydrogenation temperature has a great influence on the conversion rate of cyclopentanol. The dehydrogenation test method can analyze the high sensitivity of the prepared methacrylate film-forming resin. The higher the temperature, the greater the impact on the conversion rate of cyclopentanol, the better the high sensitivity of the prepared resin, and the resin has good solubility, which is conducive to its application in the electronics industry. The lower the temperature, the smaller the impact on the conversion rate of cyclopentanol, and the worse the high sensitivity of the prepared resin.

[0043] Table 1 Infrared spectroscopy analysis

[0044] As can be seen from Table 1, Example 1 is the best, while Comparative Example 2 is relatively poor. In Example 1, its transmittance is 95%, which means that the prepared methacrylate film-forming resin has regular and orderly internal molecular arrangement, so that the prepared methacrylate film-forming resin has better physical properties, reflecting the high resolution of the methacrylate film-forming resin. The transmittance of Comparative Example 2 is 45%, indicating that the prepared methacrylate film-forming resin has insufficient crystallinity and structural orderliness, and the resolution of the methacrylate film-forming resin is low.

[0045] Table 2 Holographic technology test method

[0046] As can be seen from Table 2, Example 1 is the best, while Comparative Example 2 is the worst. In Example 1, the diffraction efficiency of Example 1 is 85%, and the sample of the photosensitizer has better holographic performance, indicating that the prepared methacrylate film-forming resin has the best sensitivity. In Comparative Example 2, its diffraction efficiency is 35%, and the sample of the photosensitizer has poor holographic performance, and the prepared methacrylate film-forming resin has poor sensitivity and is not suitable for use in the optoelectronic information industry and the semiconductor industry.

[0047] Table 3 Dehydrogenation test method

[0048] As can be seen from Table 3, Example 1 is the best and Comparative Example 2 is relatively poor. In Example 1, its conversion rate is 20%, indicating that the better the high sensitivity of the methacrylate film-forming resin, the better the performance. In Comparative Example 2, its conversion rate is 5%, indicating that the worse the high sensitivity of the methacrylate film-forming resin, the poorer the performance.

[0049] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art can make non-creative modifications to the present embodiment as needed, but they are protected by patent law as long as they are within the scope of the claims of the present invention.

Claims

1. A process for preparing a highly sensitive methacrylate film-forming resin, characterized in that: include: Preparation of high-purity indium, preparation of high-purity anhydrous indium trichloride, preparation of InP nanocrystals, preparation of cyclopentanone, preparation of green photosensitizer, preparation of methyl methacrylate, preparation of modified basalt fiber (BF), preparation of methacrylate film-forming resin; The preparation of high-purity anhydrous indium trichloride comprises: weighing a small amount of high-purity indium obtained in step (1) into a beaker, adding hydrochloric acid solution and continuously stirring at a certain temperature until the metal indium is completely dissolved to obtain an indium chloride solution, then heating the solution to a certain temperature, gradually evaporating the solution, precipitating InCI3.4H2O crystals, adding n-butanol to dissolve the secondary crystals, placing the solution in a vacuum glove box, controlling the temperature to perform atmospheric distillation and dehydration, obtaining an indium trichloride product InCI3.mBuOH (indium chloride tetrahydrate) that replaces the crystal water, then placing the solution in a distillation device, controlling the temperature, vacuum degree, and distillation time, and decompressing and decomposing an organic dehydrating agent to obtain white anhydrous indium trichloride, and finally taking out the obtained anhydrous indium trichloride product and placing it in a vacuum sublimator, controlling the temperature, and obtaining high-purity anhydrous indium trichloride.

2. The process for preparing a highly sensitive methacrylate film-forming resin according to claim 1, characterized in that include: Step (1) Preparation of high purity indium Put the surface oxidized In2O (indium oxide) into a quartz crucible, heat and melt it at a high temperature under a certain pressure to make it sublime, and keep it at a high temperature for a period of time to obtain high-purity indium; Step (2) Preparation of high-purity anhydrous indium trichloride Weigh a small amount of high-purity indium obtained in step (1) into a beaker, add hydrochloric acid solution and continue stirring at a certain temperature until the metal indium is completely dissolved to obtain an indium chloride solution, then heat the solution to a certain temperature, gradually evaporate the solution, precipitate InCI3.4H2O crystals, add n-butanol to dissolve the secondary crystals, place the solution in a vacuum glove box, control the temperature and perform atmospheric distillation to dehydrate, obtain an indium trichloride product InCI3.mBuOH (indium chloride tetrahydrate) that replaces the crystal water, then place it in a distillation device, control the temperature, vacuum degree, and distillation time, and decompose the organic dehydrating agent under reduced pressure to obtain white anhydrous indium trichloride, finally take out the obtained anhydrous indium trichloride product and place it in a vacuum sublimator, control the temperature, and obtain high-purity anhydrous indium trichloride; Step (3) Preparation of InP nanocrystals Remove the crystal water of InCI3.4H2O, and seal and store the obtained high-purity anhydrous indium trichloride in step (2), and synthesize sodium phosphide using the sealed high-purity anhydrous indium trichloride in step (2), metallic sodium and analytical pure yellow phosphorus as raw materials, xylene as solvent, and nitrogen as protective gas, and then synthesize indium phosphide using Na3P (sodium phosphide) and InCI3 as raw materials, xylene as solvent, and nitrogen as protective gas, and then filter the indium phosphide with benzene and deionized water respectively, and then cool it by introducing nitrogen after vacuum drying at a certain temperature for a period of time, to obtain InP nanocrystals; Step (4) Preparation of cyclopentanone The reaction distillation device consists of a four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with a number of plates, a feed port connected to a feed metering pump, and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (3) are first added to the three-necked flask, the stirrer is turned on, and the reaction liquid is stirred in an oil bath to raise it to a certain temperature. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to balance the liquid discharge rate with the tower bottom feed rate to obtain cyclopentanone; Step (5) Preparation of green photosensitizer Add methanol, 5-dimethylaminothiophene-2-carboxaldehyde, cyclopentanone from step (4), and sodium hydroxide to a three-necked flask in sequence, stir at room temperature for a period of time, stop the reaction, remove the solvent, and separate and purify the obtained crude product by column chromatography using dichloromethane as an eluent, and then recrystallize using dichloromethane / petroleum ether in a certain proportion to obtain a green photosensitizer; Step (6) Preparation of methyl methacrylate The reaction is carried out at high temperature and high space velocity, and methacrolein (MAL) and methacrylic acid (MAA) reach the sum of the yields to obtain a phosphomolybdic acid catalyst, and an alkali metal and a green photosensitizer from step (5) are added to increase the thermal stability of the catalyst and increase the surface area to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at a certain temperature to obtain methyl methacrylate (MMA); Step (7) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at a high temperature to remove impurities on the surface of the original fiber. The fibers used in the subsequent patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed according to a mass ratio and stirred continuously to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Then, basalt fiber (BF) is placed in the above solution, and methyl methacrylate in step (6) is added and stirred for impregnation. After naturally drying, it is placed in a constant temperature drying oven and dried at a certain temperature to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane). Step (8) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) are added into a three-necked flask in proportion, and reacted in a sealed manner at a certain temperature. Then, an initiator (azobisisobutyronitrile) is added, and then the modified basalt fiber (BF) in step (7) is added. After reacting for a period of time, the temperature is lowered and the material is discharged to obtain a methacrylate film-forming resin.

3. The process for preparing a highly sensitive methacrylate film-forming resin according to claim 2, characterized in that: Step (1) Preparation of high purity indium Place the surface oxidized In2O (indium oxide) in a quartz crucible at a pressure of 10 -4 -10 -5 Pa is melted at 200-250℃, heated at 600-700℃ to sublime, and kept at 800-900℃ for 5-6h to obtain high-purity indium.

4. A process for preparing a highly sensitive methacrylate film-forming resin according to claim 3, characterized in that: Step (2) Preparation of high-purity anhydrous indium trichloride Weigh 11.5-14.5 g of high-purity indium from step (1) into a beaker, add 50-60 mL of a 30-34% hydrochloric acid solution, and continue stirring at 40-60 ° C for 10-12 h until the metal indium is completely dissolved to obtain an indium chloride solution, then heat the solution to 90-100 ° C, gradually evaporate the solution, and precipitate 29.3-33.3 g of InCI3.4H2O crystals, add 252-272 mL of n-butanol to dissolve the secondary crystals, and place the solution in a vacuum glove box, control The temperature is 120-150°C and atmospheric distillation is performed to dehydrate the product InCI3.mBuOH (indium chloride tetrahydrate) which replaces the crystal water. The complex is placed in a distillation device at a temperature of 180-210°C, a vacuum degree of 6-7kPa, and a distillation time of 0.5-1h. The organic dehydrating agent is decompressed and decomposed to obtain white anhydrous indium trichloride. Finally, the obtained anhydrous indium trichloride product is taken out and placed in a vacuum sublimator at a temperature of 300-350°C to obtain high-purity anhydrous indium trichloride.

5. The process for preparing a highly sensitive methacrylate film-forming resin according to claim 4, characterized in that: Step (3) Preparation of InP nanocrystals The crystal water of InCI3.4H2O is removed, and the obtained high-purity anhydrous indium trichloride of step (2) is sealed and stored for 5-10 minutes. Sodium phosphide is synthesized using the sealed high-purity anhydrous indium trichloride of step (2), metallic sodium and analytical pure yellow phosphorus as raw materials, xylene as solvent and nitrogen as protective gas. Indium phosphide is then synthesized using Na3P (sodium phosphide) and InCI3 as raw materials, xylene as solvent and nitrogen as protective gas. Indium phosphide is then filtered with benzene and deionized water respectively, and dried in vacuum at 60-70°C for 4-5 hours, and then cooled with nitrogen to obtain InP nanocrystals.

6. The process for preparing a highly sensitive methacrylate film-forming resin according to claim 5, characterized in that: Step (4) Preparation of cyclopentanone The reaction distillation device consists of a 1000-1200mL four-necked flask and a distillation column. The four-necked flask is respectively equipped with a thermometer, a vacuum insulation packing distillation column with 30-35 plates, a feed port connected to a feed metering pump and a stirring device. A reflux ratio control valve and a hydrogen discharge port are installed on the upper part of the distillation column. During operation, the InP nanocrystals, cyclopentanol and nickel catalyst in step (3) are first added into the three-necked flask, the stirrer is started, the stirring speed is 50-60r / min, and the reaction liquid is heated to 124-134°C with an oil bath. At the initial stage of the reaction, the distillation column is fully refluxed, and the reflux ratio is adjusted to 4-8:1-5 to balance the liquid discharge speed with the tower bottom feed speed to obtain cyclopentanone.

7. The process for preparing a highly sensitive methacrylate film-forming resin according to claim 6, characterized in that: Step (5) Preparation of green photosensitizer To a 20-30 mL three-necked flask, add 10-15 mL of methanol, 155-165 mg of 5-dimethylaminothiophene-2-carboxaldehyde, 43-48 mg of cyclopentanone from step (4), and 5-10 mg of sodium hydroxide in sequence, stir at room temperature for 2-3 h, then stop the reaction, remove the solvent, and separate and purify the obtained crude product by column chromatography using dichloromethane as eluent, and then recrystallize using dichloromethane / petroleum ether (1-5:1-5) to obtain a green photosensitizer.

8. The process for preparing a high-sensitivity methacrylate film-forming resin according to claim 7, characterized in that: Step (6) Preparation of methyl methacrylate At a reaction temperature of 350-370° C. and an air velocity of 1000-1100 h / h, the sum of the yields of methacrolein (MAL) and methacrylic acid (MAA) is 90-95%, and a phosphomolybdic acid catalyst is obtained. An alkali metal and a green photosensitizer from step (5) are added to increase the thermal stability and surface area of ​​the catalyst to obtain crystals, which are placed in a mixed solution of sulfuric acid and methanol and subjected to an esterification reaction at 70-100° C. to obtain methyl methacrylate (MMA).

9. The process for preparing a highly sensitive methacrylate film-forming resin according to claim 8, characterized in that: Step (7) Preparation of modified basalt fiber (BF) First, the fiber is pretreated and sintered at a high temperature of 500-700°C for 30-60 minutes to remove impurities on the surface of the original fiber. The fibers used in the subsequent patent are all sintered fibers. Anhydrous ethanol and deionized water are mixed in a mass ratio of 9-14:1-6 and stirred continuously for 10-20 minutes to allow KH550 (γ-aminopropyltriethoxysilane) to hydrolyze. Subsequently, 10-15g of basalt fiber (BF) is placed in the above solution, and 10-20g of methyl methacrylate in step (6) is added and stirred for 30-35 minutes and soaked for 20-25 minutes. After natural drying, the fiber is placed in a constant temperature drying oven and dried at a temperature of 100-150°C for 8-13 hours to obtain modified basalt fiber (BF) modified with KH550 (γ-aminopropyltriethoxysilane).

10. The process for preparing a high-sensitivity methacrylate film-forming resin according to claim 8, characterized in that: Step (8) Preparation of methacrylate film-forming resin Methacrylic acid (MAA), methyl methacrylate (MMA) and butyl acrylate (BA) are added into a three-necked flask in a ratio of 25-50:50-100:25-50, and reacted in a sealed container at 80-85°C for 30-40 minutes. Then, 10-20 g of an initiator (azobisisobutyronitrile) is added, and then 10-20 g of the modified basalt fiber (BF) obtained in step (7) is added. The reaction is continued for 2-5 hours, and the temperature is lowered and the material is discharged to obtain a methacrylate film-forming resin.

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