Near-infrared-infrared deep curing resin precursor and preparation method thereof

Abstract

The invention discloses a preparation method of a near-infrared-infrared deep curing resin precursor. The preparation method specifically comprises the following steps: step 1, synthesizing a copper phthalocyanine (II) carbon quantum dot dispersion liquid; step 2, synthesizing urea-citric acid-acrylic acid based carbon quantum dots; step 3, preparing beryllium oxide dispersion liquid; and 4, synthesizing the near-infrared-infrared deep curing resin according to products obtained in the steps 1-3. The invention also discloses a near-infrared-infrared deep curing resin precursor, the resin precursor prepared by the invention realizes near-infrared and infrared dual curing, and solves the problem of difficulty in overall curing of resin in a current resin curing mode.

Description

Technical Field

[0001] The present invention belongs to the technical field of resin preparation, relates to a near-infrared-infrared deep-curing resin precursor, and also relates to a preparation method of the near-infrared-infrared deep-curing resin precursor. Background Art

[0002] Resin materials are widely used in many industrial fields such as electrics, machinery, aerospace, ship transportation, etc., and are also everywhere in people's lives. Before use, the resin needs to be cured. The resin curing methods include thermal curing and photocuring. For thin film materials with a small thickness, conventional thermal curing and photocuring can meet the requirements. However, for some resins with special requirements, such as OLED (organic light-emitting diode) encapsulation glue, potting glue for electronic devices and printed circuit boards, and structural glue for electronic appliances, the resin needs to have good curing depth under the action of light or heat. For thermal curing, due to the extremely low thermal conductivity of the resin itself, the curing depth is insufficient during thermal curing, usually the surface of the material is cured while the inside does not react; for photocuring, due to the presence of chromophores such as carbonyl groups and aromatic rings in the resin, and even the resin has a relatively dark color, the curing depth of ultraviolet light curing and visible light curing is insufficient. Therefore, when the resin is formed into a film and coated, the film thickness is usually only in the order of um. When the thickness increases, the outer layer is cured while the inner layer is not easily cured (while the resin needs to be cured as a whole when used as a filling material and potting material, rather than just the surface layer). Based on this, it is necessary to prepare a near-infrared-infrared deep-curing resin precursor. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation method of a near-infrared-infrared deep-curing resin precursor. The resin precursor prepared by this method realizes near-infrared and infrared dual curing, and solves the problem that it is difficult to cure the resin as a whole in the current resin curing methods.

[0004] Another purpose of the present invention is to provide a near-infrared-infrared deep-curing resin precursor.

[0005] The first technical solution adopted by the present invention is a preparation method of a near-infrared-infrared deep-curing resin precursor, which specifically includes the following steps: Step 1, synthesize a copper phthalocyanine (II) carbon quantum dot dispersion; Step 2, synthesize urea-citric acid-acrylic acid-based carbon quantum dots; Step 3, prepare a beryllium oxide dispersion; Step 4, synthesize a near-infrared-infrared deep-curing resin according to the products obtained in Steps 1 to 3.

[0006] The characteristics of the first technical solution of the present invention also lie in: The specific process of Step 1 is: Step 1.1: Take copper(II) phthalocyanine and put it into a 50 mL round-bottom flask. After adding deionized water and stirring evenly, place the round-bottom flask into a microwave reactor, and introduce O2 with a flow rate of 10 - 20 mL / min. Set the reaction temperature to 350 - 450 o °C, and the reaction time is 10 - 15 s. Wait for the temperature to cool to room temperature. The mass ratio of copper(II) phthalocyanine to deionized water is 2 - 4:1; Step 1.2: Add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1 is completed. Keep other reaction conditions unchanged and repeat the microwave reaction 3 times; Step 1.3: Add a 30 wt% HCl solution to the round-bottom flask after the reaction in Step 1.2 is completed, and stir for 30 - 60 min. Centrifuge the obtained solution to remove insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Collect the solution in the dialysis bag and freeze-dry it at -70 o °C for 7 days. Dissolve the obtained blue-black product with acrylic acid to obtain a copper(II) phthalocyanine carbon quantum dot dispersion.

[0007] In Step 1.3, the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:2 - 1.

[0008] In Step 1.3, the mass ratio of acrylic acid to copper(II) phthalocyanine is 10 - 5:1.

[0009] The specific process of Step 2 is as follows: Take urea, citric acid, acrylic acid and deionized water and mix them evenly according to the mass ratio of 5:5 - 10:1 - 2:20 - 40. Then put the mixed solution into a microwave reactor and directly heat it to 180 - 220 o °C for 2 - 4 min. After the reaction is completed, wait for the temperature to drop to room temperature. Centrifuge the obtained solution to remove insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Collect the solution in the dialysis bag, concentrate the solution volume by 1 / 2, and place it in the air for 10 days until the concentrated solution changes from yellow to black. Then, freeze-dry the black concentrated solution at -70 o °C for 7 days to obtain urea-citric acid-acrylic acid-based carbon quantum dots.

[0010] The specific process of Step 3 is as follows: Take beryllium oxide ceramic powder, phosphoric acid, zirconium oxide and deionized water and mix them evenly according to the mass ratio of 1:2-4:10-100:100-200. After mixing evenly, pour the mixed solution into a nano ball mill, with a rotation speed of 500-1000 r / min and a time of 6-12 h. After the ball milling is completed, collect the nano beryllium oxide mixed solution, put the nano beryllium oxide mixed solution into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times. Centrifuge the obtained solution to obtain wet nano beryllium oxide, and disperse the wet nano beryllium oxide into acrylic acid, where the mass ratio of nano beryllium oxide to acrylic acid is 1:1-2.

[0011] The specific process of Step 4 is as follows: Take a copper phthalocyanine (II) carbon quantum dot dispersion and a beryllium oxide dispersion, mix and stir them evenly, and then add urea-citric acid-acrylic acid-based carbon quantum dots and azobisisobutyronitrile; then continue to add isooctyl acrylate, butyl acrylate and glycerol triacrylate, and stir evenly to obtain a resin precursor.

[0012] In Step 4, the mass ratio of the copper phthalocyanine (II) carbon quantum dot dispersion, the beryllium oxide dispersion, the urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate and glycerol triacrylate is 1:1-3:1-3:0.05-0.15:1-5:1-5:0.05-0.15.

[0013] The second technical solution adopted by the present invention is a near-infrared-infrared deep curing resin precursor, which is prepared by using the above-mentioned preparation method of the near-infrared-infrared deep curing resin precursor.

[0014] The beneficial effects of the present invention are as follows: 1) In the preparation method of the present invention, copper phthalocyanine (II) carbon quantum dots with efficient near-infrared light-to-heat conversion and urea-citric acid-acrylic acid-based carbon quantum dots with infrared light-to-heat conversion are constructed, and beryllium oxide with high heat conduction efficiency is introduced, realizing near-infrared and infrared dual curing of the resin precursor, and the curing depth reaches more than 5 mm. 2) The present invention avoids traditional direct light curing and direct heat curing, and adopts light-to-heat curing induced by near-infrared and infrared. Although the obtained resin precursor contains copper phthalocyanine (II) carbon quantum dots and urea-citric acid-acrylic acid-based carbon quantum dots with relatively deep colors, the resin curing depth can reach 2-3 mm; especially under the introduction of beryllium oxide and the synergistic effect of copper phthalocyanine (II) carbon quantum dots and urea-citric acid-acrylic acid-based carbon quantum dots, the depth can reach 5-6 mm. Description of the Drawings

[0015] Figure 1It is the temperature rise change curve of the infrared-infrared deep curing resin prepared in Example 1 of the preparation method of the near-infrared-infrared deep curing resin precursor of the present invention under near-infrared and infrared light irradiation; Figure 2 It is the ultraviolet absorption spectrogram of urea-citric acid-acrylic acid-based carbon quantum dots before and after standing in Example 1 of the preparation method of the near-infrared-infrared deep curing resin precursor of the present invention. Detailed implementation manners

[0016] The present invention will be described in detail below with reference to the accompanying drawings and specific implementation manners.

[0017] The preparation method of the near-infrared-infrared deep curing resin precursor of the present invention specifically includes the following steps: Step 1, synthesis of copper phthalocyanine (II) carbon quantum dot dispersion, specifically: Step 1.1, take a certain mass of copper phthalocyanine (II) and put it into a 50 mL round-bottom flask. After adding a certain mass of deionized water and stirring evenly, place the round-bottom flask into a microwave reactor, and introduce O2 into it. The flow rate of O2 is 10 - 20 mL / min, set the reaction temperature to 350 - 450 o °C, the reaction time is 10 - 15 s, and wait for the temperature to cool to room temperature; the mass ratio of copper phthalocyanine (II) to deionized water is 2 - 4:1.

[0018] Step 1.2, add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1 is completed, keep other reaction conditions unchanged, and repeat the microwave reaction 3 times.

[0019] Step 1.3, add a 30 wt% HCl solution (the mass ratio of hydrochloric acid to copper phthalocyanine (II) is 10:2 - 1) to the round-bottom flask after the reaction in Step 1.2 is completed, and stir for 30 - 60 min. Centrifuge the obtained solution with a centrifuge (the rotation speed is 8000 - 10000 r / min) to remove insoluble solids, and put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da for dialysis 3 times. Collect the solution in the dialysis bag and freeze-dry it at -70 o °C for 7 days. Dissolve the obtained blue-black product with a certain amount of acrylic acid (the mass ratio of acrylic acid to copper phthalocyanine (II) is 10 - 5:1) to obtain the copper phthalocyanine (II) carbon quantum dot dispersion.

[0020] Step 2, synthesis of urea-citric acid-acrylic acid-based carbon quantum dots, specifically: Take urea, citric acid, acrylic acid and deionized water and mix them evenly according to the mass ratio of 5:5 - 10:1 - 2:20 - 40. Then put the mixed solution into a microwave reactor and directly heat it to 180 - 220 oReact for 2 - 4 min. After the reaction is completed, wait for the temperature to drop to room temperature. Centrifuge the resulting solution (rotation speed: 8000 - 10000 r / min) to remove insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Collect the solution in the dialysis bag, concentrate the solution volume by 1 / 2, and place it in air for 10 days until the concentrated solution changes from yellow to black. Then, freeze-dry the black concentrated solution at -70 o under the C condition for 7 days to obtain urea-citric acid-acrylic acid-based carbon quantum dots.

[0021] Step 3: Preparation of beryllium oxide dispersion, specifically: Take beryllium oxide ceramic powder, phosphoric acid, zirconia (ball milling medium, size 6 μm), and deionized water and mix them evenly according to a mass ratio of 1:2 - 4:10 - 100:100 - 200. Pour the mixed solution into a nano ball mill, with a rotation speed of 500 - 1000 r / min and a time of 6 - 12 h. After ball milling, collect the nano beryllium oxide mixed solution. Put the nano beryllium oxide mixed solution into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Centrifuge the resulting solution (rotation speed: 5000 - 10000 r / min) to obtain wet (undried) nano beryllium oxide. Disperse the wet nano beryllium oxide into acrylic acid, where the mass ratio of nano beryllium oxide to acrylic acid is 1:1 - 2.

[0022] Step 4: Synthesis of near-infrared-infrared deep-curing resin precursor, specifically: Take a certain mass of copper(II) phthalocyanine carbon quantum dot dispersion and beryllium oxide dispersion, mix and stir them evenly, and then add urea-citric acid-acrylic acid-based carbon quantum dots and azobisisobutyronitrile. Then continue to add a certain mass of isooctyl acrylate, butyl acrylate, and glycerol triacrylate, and stir evenly to obtain a resin precursor.

[0023] The mass ratio of copper(II) phthalocyanine carbon quantum dot dispersion, beryllium oxide dispersion, urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate, and glycerol triacrylate is 1:1 - 3:1 - 3:0.05 - 0.15:1 - 5:1 - 5:0.05 - 0.15.

[0024] Example 1 Step 1: Synthesis of copper(II) phthalocyanine carbon quantum dot dispersion, specifically: Step 1.1: Take 10 g of copper(II) phthalocyanine and put it into a 50 mL round-bottom flask. Add 5 g of deionized water and stir evenly. Then put the round-bottom flask into a microwave reactor and introduce O2 into it, with an O2 flow rate of 10 mL / min. Set the reaction temperature to 350 oC, the reaction time is 10 s, and wait for the temperature to cool to room temperature; in Step 1.1, the mass ratio of copper(II) phthalocyanine to deionized water is 2:1.

[0025] Step 1.2, add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1, keep other reaction conditions unchanged, and repeat the microwave reaction 3 times.

[0026] Step 1.3, add a 30 wt% HCl solution (the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:1) to the round-bottom flask after the reaction in Step 1.2, and stir for 30 min. Centrifuge the obtained solution (rotation speed is 8000 r / min) to remove insoluble solids, and put the supernatant into a 7000 Da dialysis bag for dialysis 3 times. Collect the solution in the dialysis bag and freeze-dry it for 7 days at -70 o °C. Dissolve the obtained blue-black product with a certain amount of acrylic acid (the mass ratio of acrylic acid to copper(II) phthalocyanine is 5:1) to obtain a copper(II) phthalocyanine carbon quantum dot dispersion.

[0027] Step 2, the synthesis of urea-citric acid-acrylic acid-based carbon quantum dots, the specific process is as follows: Take the raw materials urea (5 g), citric acid (5 g), acrylic acid (1 g) and deionized water (20 g), mix and stir evenly according to the mass ratio of 5:5:1:20, then put the mixed solution into a microwave reactor and directly heat it to 180 o °C for 2 min. After the reaction, wait for the temperature to drop to room temperature. Centrifuge the obtained solution (rotation speed is 8000 r / min) to remove insoluble solids, and put the supernatant into a 7000 Da dialysis bag for dialysis 3 times. Collect the solution in the dialysis bag, concentrate the solution volume by 1 / 2, and place it in the air for 10 days until the concentrated solution changes from yellow to black. Then, freeze-dry the black concentrated solution for 7 days at -70 o °C to obtain urea-citric acid-acrylic acid-based carbon quantum dots.

[0028] Step 3, the preparation of beryllium oxide dispersion, specifically: Take beryllium oxide ceramic powder (10 g), phosphoric acid (20 g), zirconia (100 g) and deionized water (1000 g), mix and stir them evenly according to the mass ratio of 1:2:10:100. Pour the mixed solution into a nano ball mill, with a rotation speed of 500 r / min and a time of 6 h. After the ball milling is completed, collect the nano beryllium oxide mixed solution. Put the mixed solution into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times. Centrifuge the obtained solution (rotation speed: 5000 r / min) to obtain wet (undried) nano beryllium oxide. Disperse the wet nano beryllium oxide into acrylic acid, where the mass ratio of nano beryllium oxide to acrylic acid is 1:1.

[0029] Step 4, synthesis of the near-infrared-infrared deep-curing resin precursor, specifically: Take 5 g of copper(II) phthalocyanine carbon quantum dot dispersion and 5 g of beryllium oxide dispersion, mix and stir them evenly, then add 5 g of urea-citric acid-acrylic acid-based carbon quantum dots and 0.25 g of azobisisobutyronitrile; then continue to add 5 g of isooctyl acrylate, 5 g of butyl acrylate and 0.25 g of glycerol triacrylate, and stir evenly to obtain the resin precursor.

[0030] The mass ratio of copper(II) phthalocyanine carbon quantum dot dispersion, beryllium oxide dispersion, urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate and glycerol triacrylate is 1:1:1:0.05:1:1:0.05.

[0031] Example 2 Step 1, synthesis of copper(II) phthalocyanine carbon quantum dot dispersion, specifically: Step 1.1, take a certain mass of copper(II) phthalocyanine and put it into a 50 mL round-bottom flask. After adding a certain mass of deionized water and stirring evenly, place the round-bottom flask in a microwave reactor and introduce O2 into it with an O2 flow rate of 20 mL / min. Set the reaction temperature to 450 o °C, and the reaction time is 15 s. Wait for the temperature to cool to room temperature; the mass ratio of copper(II) phthalocyanine to deionized water is 4:1.

[0032] Step 1.2, add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1 is completed, and keep other reaction conditions unchanged. Repeat the microwave reaction 3 times.

[0033] Step 1.3: Add a 30 wt% HCl solution (the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:2) to the round-bottom flask after the reaction in Step 1.2 is completed, and stir for 60 min. Centrifuge the resulting solution (at a rotational speed of 10,000 r / min) to remove insoluble solids, and dialyze the supernatant three times in a 7000 Da dialysis bag. Collect the solution in the dialysis bag and freeze-dry it at -70 o °C for 7 days. Dissolve the resulting blue-black product in a certain amount of acrylic acid (the mass ratio of acrylic acid to copper(II) phthalocyanine is 10:1) to obtain a copper(II) phthalocyanine carbon quantum dot dispersion.

[0034] Step 2: Synthesis of urea-citric acid-acrylic acid-based carbon quantum dots, specifically: Mix the raw materials urea, citric acid, acrylic acid, and deionized water in a mass ratio of 5:10:2:40 and stir evenly. Then, place the mixed solution in a microwave reactor and directly heat it to 220 o °C for 4 min. After the reaction is completed, wait for the temperature to drop to room temperature. Centrifuge the resulting solution (at a rotational speed of 10,000 r / min) to remove insoluble solids, and dialyze the supernatant three times in a 7000 Da dialysis bag. Collect the solution in the dialysis bag, concentrate the solution volume by 1 / 2, and place it in the air for 10 days until the concentrated solution changes from yellow to black. Then, freeze-dry the black concentrated solution at -70 o °C for 7 days to obtain urea-citric acid-acrylic acid-based carbon quantum dots.

[0035] Step 3: Preparation of beryllium oxide dispersion, specifically: Mix beryllium oxide ceramic powder, phosphoric acid, zirconia (ball milling medium, size 6 μm), and deionized water in a mass ratio of 1:4:100:200 and stir evenly. Pour the mixed solution into a nano ball mill, with a rotational speed of 1000 r / min and a time of 12 h. After ball milling is completed, collect the nano beryllium oxide mixed solution. Dialyze the mixed solution three times in a 7000 Da dialysis bag, and centrifuge the resulting solution (at a rotational speed of 10,000 r / min) to obtain wet (undried) nano beryllium oxide. Disperse the wet nano beryllium oxide in acrylic acid, where the mass ratio of nano beryllium oxide to acrylic acid is 1:2.

[0036] Step 4: Synthesis of near-infrared-infrared deep-curing resin precursor, specifically: Take a certain mass of copper(II) phthalocyanine carbon quantum dot dispersion and beryllium oxide dispersion, mix and stir evenly, and then add urea-citric acid-acrylic acid-based carbon quantum dots and azobisisobutyronitrile. Then, continue to add a certain mass of isooctyl acrylate, butyl acrylate, and glycerol triacrylate, and stir evenly to obtain a resin precursor.

[0037] The mass ratio of copper(II) phthalocyanine carbon quantum dot dispersion, beryllium oxide dispersion, urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate and glycerol triacrylate is 1:3:3:0.15:5:5:0.15.

[0038] Example 3 Step 1, synthesis of copper(II) phthalocyanine carbon quantum dot dispersion, specifically: Step 1.1, take a certain mass of copper(II) phthalocyanine and put it into a 50 mL round-bottom flask. After adding a certain mass of deionized water and stirring evenly, place the round-bottom flask into a microwave reactor, and introduce O2 into it. The flow rate of O2 is 15 mL / min, set the reaction temperature to 400 o °C, the reaction time is 12.5 s, and wait for the temperature to cool to room temperature; the mass ratio of copper(II) phthalocyanine to deionized water is 3:1.

[0039] Step 1.2, add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1 is completed, and keep other reaction conditions unchanged, and repeat the microwave reaction 3 times.

[0040] Step 1.3, add a 30 wt% HCl solution (the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:1.5) to the round-bottom flask after the reaction in Step 1.2 is completed, and stir for 45 min. Centrifuge the obtained solution with a centrifuge (rotation speed is 9000 r / min) to remove insoluble solids, and put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da for dialysis 3 times. Collect the solution in the dialysis bag and freeze-dry it at -70 o °C for 7 days. Dissolve the obtained blue-black product with a certain amount of acrylic acid (the mass ratio of acrylic acid to copper(II) phthalocyanine is 7.5:1), and set aside.

[0041] Step 2, synthesis of urea-citric acid-acrylic acid-based carbon quantum dots, specifically: Take urea, citric acid, acrylic acid and deionized water and mix them evenly according to the mass ratio of 5:7.5:1.5:30. Then put the mixed solution into a microwave reactor and directly heat it to 200 o °C for 3 min. After the reaction is completed, wait for the temperature to drop to room temperature. Centrifuge the obtained solution with a centrifuge (rotation speed is 9000 r / min) to remove insoluble solids, and put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da for dialysis 3 times. Collect the solution in the dialysis bag, concentrate the volume of the solution by 1 / 2, and place it in the air for 10 days until the concentrated solution changes from yellow to black. Then, freeze-dry the black concentrated solution at -70 oFreeze-dry for 7 days under the condition of C to obtain urea-citric acid-acrylic acid-based carbon quantum dots.

[0042] Step 3, preparation of beryllium oxide dispersion, specifically: Take beryllium oxide ceramic powder, phosphoric acid, zirconia (ball milling medium, size 6um) and deionized water and mix them evenly according to the mass ratio of 1:3:55:150. Pour the mixed solution into a nano ball mill, with a rotation speed of 750 r / min and a time of 9h. After ball milling, collect the nano beryllium oxide mixed solution. Dialyze the mixed solution 3 times in a dialysis bag with a molecular weight cut-off of 7000Da, and centrifuge the obtained solution (rotation speed: 7500 r / min) to obtain wet (undried) nano beryllium oxide. Disperse the wet nano beryllium oxide into acrylic acid, where the mass ratio of nano beryllium oxide to acrylic acid is 1:1.5.

[0043] Step 4, synthesis of near-infrared-infrared deep-curing resin precursor, specifically: Take a certain mass of copper(II) phthalocyanine carbon quantum dot dispersion and beryllium oxide dispersion, mix and stir evenly, then add urea-citric acid-acrylic acid-based carbon quantum dots and azobisisobutyronitrile. Then continue to add a certain mass of 2-ethylhexyl acrylate, butyl acrylate and glycerol triacrylate, and stir evenly to obtain a resin precursor.

[0044] The mass ratio of copper(II) phthalocyanine carbon quantum dot dispersion, beryllium oxide dispersion, urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, 2-ethylhexyl acrylate, butyl acrylate and glycerol triacrylate is 1:2:2:0.1:3:3:0.1.

[0045] Comparative Example 1 (When synthesizing copper(II) phthalocyanine carbon quantum dots, changing O2 to N2 cannot obtain copper(II) phthalocyanine carbon quantum dots) Step 1, synthesis of copper(II) phthalocyanine carbon quantum dot dispersion Step 1.1, take 10g of copper(II) phthalocyanine and put it into a 50 mL round-bottom flask, add 5g of deionized water and stir evenly, then place the round-bottom flask in a microwave reactor, and introduce N2 into it, with an N2 flow rate of 10mL / min, set the reaction temperature to 350 o C, the reaction time is 10s, and wait for the temperature to cool to room temperature; the mass ratio of copper(II) phthalocyanine to deionized water is 2:1.

[0046] Step 1.2, add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1 is completed, and keep other reaction conditions unchanged, and repeat the microwave reaction 3 times.

[0047] Step 1.3: Add a 30 wt% HCl solution (the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:1) to the round-bottom flask after the reaction in Step 1.2, and stir for 30 min. Centrifuge the resulting solution (at a rotation speed of 8000 r / min) to remove the insoluble solids, and dialyze the supernatant three times in a dialysis bag with a molecular weight cut-off of 7000 Da. Collect the solution in the dialysis bag and freeze-dry it for 7 days at -70 o °C. No blue-black product was collected.

[0048] Comparative Example 2 (When preparing the copper(II) phthalocyanine carbon quantum dot dispersion, replacing acrylic acid with methyl acrylate results in the inability to disperse the quantum dots) Step 1: Synthesis of the copper(II) phthalocyanine carbon quantum dot dispersion, specifically: Step 1.1: Take 10 g of copper(II) phthalocyanine and place it in a 50 mL round-bottom flask. After adding 5 g of deionized water and stirring evenly, place the round-bottom flask in a microwave reactor, and introduce O2 into it at a flow rate of 10 mL / min. Set the reaction temperature to 350 o °C, and the reaction time is 10 s. Wait for the temperature to cool to room temperature; the mass ratio of copper(II) phthalocyanine to deionized water is 2:1.

[0049] Step 1.2: Add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1, and keep other reaction conditions unchanged. Repeat the microwave reaction three times.

[0050] Step 1.3: Add a 30 wt% HCl solution (the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:1) to the round-bottom flask after the reaction in Step 1.2, and stir for 30 min. Centrifuge the resulting solution (at a rotation speed of 8000 r / min) to remove the insoluble solids, and dialyze the supernatant three times in a dialysis bag with a molecular weight cut-off of 7000 Da. Collect the solution in the dialysis bag and freeze-dry it for 7 days at -70 o °C. Dissolve the resulting blue-black product with a certain amount of methyl acrylate (the mass ratio of methyl acrylate to copper(II) phthalocyanine is 5:1), and it is found that the dissolution fails.

[0051] Comparative Example 3 (When synthesizing copper(II) phthalocyanine carbon quantum dots, replacing hydrochloric acid with deionized water results in the inability to collect copper(II) phthalocyanine carbon quantum dots) Step 1: Synthesis of the copper(II) phthalocyanine carbon quantum dot dispersion, specifically: Step 1.1: Take 10 g of copper(II) phthalocyanine and place it in a 50 mL round-bottom flask. After adding 5 g of deionized water and stirring evenly, put the round-bottom flask into a microwave reactor, and introduce O2 into it. The flow rate of O2 is 10 mL / min. Set the reaction temperature to 350 o °C, and the reaction time is 10 s. Wait for the temperature to cool to room temperature. In Step 1.1, the mass ratio of copper(II) phthalocyanine to deionized water is 2:1.

[0052] Step 1.2: Add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1. Keep other reaction conditions unchanged and repeat the microwave reaction 3 times.

[0053] Step 1.3: Add deionized water (the mass ratio of deionized water to copper(II) phthalocyanine is 10:1) to the round-bottom flask after the reaction in Step 1.2 and stir for 30 - 60 min. Centrifuge the obtained solution with a centrifuge (rotation speed: 8000 r / min) to remove insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Collect the solution in the dialysis bag and freeze-dry it at -70 o °C for 7 days. A blue-black product was not obtained.

[0054] Comparative Example 4 (When synthesizing urea-citric acid-acrylic acid-based carbon quantum dots, the dialysis solution is directly freeze-dried without being concentrated and allowed to stand, and the obtained product is yellow) Step 1: Synthesis of copper(II) phthalocyanine carbon quantum dot dispersion, specifically: Step 1.1: Take 10 g of copper(II) phthalocyanine and place it in a 50 mL round-bottom flask. After adding 5 g of deionized water and stirring evenly, put the round-bottom flask into a microwave reactor, and introduce O2 into it. The flow rate of O2 is 10 mL / min. Set the reaction temperature to 350 o °C, and the reaction time is 10 s. Wait for the temperature to cool to room temperature. In Step 1.1, the mass ratio of copper(II) phthalocyanine to deionized water is 2:1.

[0055] Step 1.2: Add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1. Keep other reaction conditions unchanged and repeat the microwave reaction 3 times.

[0056] Step 1.3: Add a 30 wt% HCl solution (the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:1) to the round-bottom flask after the reaction in Step 1.2 and stir for 30 min. Centrifuge the obtained solution with a centrifuge (rotation speed: 8000 r / min) to remove insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Collect the solution in the dialysis bag and freeze-dry it at -70 oFreeze-dry for 7 days under the condition of C. Dissolve the obtained blue-black product with a certain amount of acrylic acid (the mass ratio of acrylic acid to copper(II) phthalocyanine is 5:1), and set aside.

[0057] Step 2, Synthesis of urea-citric acid-acrylic acid-based carbon quantum dots. The specific process is as follows: Take the raw materials urea (5 g), citric acid (5 g), acrylic acid (1 g) and deionized water (20 g), mix and stir evenly according to the mass ratio of 5:5:1:20. Then put the mixed solution into a microwave reactor and directly heat it to 180 o C and react for 2 min. After the reaction, wait for the temperature to drop to room temperature. Centrifuge the obtained solution with a centrifuge (rotation speed: 8000 r / min) to remove insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times. Collect the solution in the dialysis bag and freeze-dry the solution for 7 days under the condition of -70 o C to obtain urea-citric acid-acrylic acid-based carbon quantum dots.

[0058] Step 3, Preparation of beryllium oxide dispersion. Specifically: Take beryllium oxide ceramic powder (10 g), phosphoric acid (20 g), zirconia ball milling medium (100 g) and deionized water (1000 g), mix and stir evenly according to the mass ratio of 1:2:10:100. Pour the mixed solution into a nano ball mill with a rotation speed of 500 r / min for 6 h. After ball milling, collect the nano beryllium oxide mixed solution. Put the mixed solution into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times. Centrifuge the obtained solution with a centrifuge (rotation speed: 5000 r / min) to obtain wet (undried) nano beryllium oxide. Disperse the wet nano beryllium oxide into acrylic acid, and the mass ratio of nano beryllium oxide to acrylic acid is 1:1.

[0059] Step 4, Synthesis of near-infrared-infrared deep-curing resin precursor. Specifically: Take 5 g of copper(II) phthalocyanine carbon quantum dot dispersion and 5 g of beryllium oxide dispersion, mix and stir evenly, then add 5 g of urea-citric acid-acrylic acid-based carbon quantum dots and 0.25 g of azobisisobutyronitrile. Then continue to add 5 g of isooctyl acrylate, 5 g of butyl acrylate and 0.25 g of glycerol triacrylate, and stir evenly to obtain a resin precursor.

[0060] The mass ratio of copper(II) phthalocyanine carbon quantum dot dispersion, beryllium oxide dispersion, urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate and glycerol triacrylate is 1:1:1:0.05:1:1:0.05.

[0061] Comparative Example 5 (When preparing the beryllium oxide dispersion, replace acrylic acid with methyl acrylate, and nano beryllium oxide cannot be dispersed) Step 1, preparation of beryllium oxide dispersion, specifically: Take beryllium oxide ceramic powder (10 g), phosphoric acid (20 g), zirconia ball milling medium (100 g) and deionized water (1000 g), mix and stir evenly according to the mass ratio of 1:2:10:100. Pour the mixed solution into a nano ball mill, with a rotation speed of 500 r / min and a time of 6 h. After ball milling, collect the nano beryllium oxide mixed solution. Put the mixed solution into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Centrifuge the obtained solution (rotation speed: 5000 r / min) to obtain wet (undried) nano beryllium oxide. Add the wet nano beryllium oxide to methyl acrylate, with the mass ratio of nano beryllium oxide to methyl acrylate being 1:1, and it is found that the nano beryllium oxide cannot be dispersed.

[0062] Comparative Example 6 (copper(II) phthalocyanine carbon quantum dot dispersion is not added to the deep-curing resin, and the near-infrared light curing effect is poor) Step 1, synthesis of urea-citric acid-acrylic acid-based carbon quantum dots, specifically: Take raw materials urea (5 g), citric acid (5 g), acrylic acid (1 g) and deionized water (20 g), mix and stir evenly according to the mass ratio of 5:5:1:20. Put the mixed solution into a microwave reactor and directly heat it to 180 o °C and react for 2 min. After the reaction, wait for the temperature to drop to room temperature. Centrifuge the obtained solution (rotation speed: 8000 r / min) to remove insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Collect the solution in the dialysis bag, concentrate the solution volume by 1 / 2, and place it in the air for 10 days until the concentrated solution changes from yellow to black. Then, freeze-dry the black concentrated solution at -70 o °C for 7 days to obtain urea-citric acid-acrylic acid-based carbon quantum dots for standby.

[0063] Step 2, preparation of beryllium oxide dispersion, specifically: Take beryllium oxide ceramic powder (10 g), phosphoric acid (20 g), zirconia ball milling medium (100 g) and deionized water (1000 g), mix and stir evenly according to the mass ratio of 1:2:10:100. Pour the mixed solution into a nano ball mill, with a rotation speed of 500 r / min and a time of 6 h. After ball milling, collect the nano beryllium oxide mixed solution. Put the mixed solution into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times. Centrifuge the obtained solution (rotation speed: 5000 r / min) to obtain wet (undried) nano beryllium oxide. Disperse the wet nano beryllium oxide into acrylic acid, with the mass ratio of nano beryllium oxide to acrylic acid being 1:1.

[0064] Step 4, Synthesis of near-infrared-infrared deep-curing resin precursor, specifically: Take 5 g of beryllium oxide dispersion and add 5 g of urea-citric acid-acrylic acid-based carbon quantum dots and 0.25 azobisisobutyronitrile, then continue to add 5 g of isooctyl acrylate, 5 g of butyl acrylate, and 0.25 g of glycerol triacrylate, and stir evenly to obtain the resin precursor.

[0065] The mass ratio of beryllium oxide dispersion, urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate, and glycerol triacrylate is 1:1:0.05:1:1:0.05.

[0066] Comparative Example 7 (Urea-citric acid-acrylic acid-based carbon quantum dots were not added to the deep-curing resin, and the infrared curing effect was poor) Step 1, Synthesis of copper(II) phthalocyanine carbon quantum dot dispersion, specifically: Step 1.1, Take 10 g of copper(II) phthalocyanine and put it into a 50 mL round-bottom flask, add 5 g of deionized water and stir evenly, then place the round-bottom flask in a microwave reactor, and introduce O2 into it, the O2 flow rate is 10 mL / min, set the reaction temperature to 350 o °C, the reaction time is 10 s, and wait for the temperature to cool to room temperature; the mass ratio of copper(II) phthalocyanine to deionized water is 2:1.

[0067] Step 1.2, Add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1 is completed, and keep other reaction conditions unchanged, and repeat the microwave reaction 3 times.

[0068] Step 1.3, Add a 30 wt% HCl solution by mass (the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:1) to the round-bottom flask after the reaction in Step 1.2 is completed, and stir for 30 - 60 min. Centrifuge the obtained solution (the rotation speed is 8000 r / min) to remove insoluble solids, and put the supernatant into a 7000 Da dialysis bag and dialyze 3 times. Collect the solution in the dialysis bag and freeze-dry it at -70 o °C for 7 days. Dissolve the obtained blue-black product with a certain amount of acrylic acid (the mass ratio of acrylic acid to copper(II) phthalocyanine is 5:1) to obtain the copper(II) phthalocyanine carbon quantum dot dispersion.

[0069] Step 2, Preparation of beryllium oxide dispersion, specifically: Take 10 g of beryllium oxide ceramic powder, 20 g of phosphoric acid, 100 g of zirconia ball milling medium, and 1000 g of deionized water, mix and stir them evenly according to the mass ratio of 1:2:10:100. Pour the mixed solution into a nano ball mill, with a rotation speed of 500 r / min and a time of 6 h. After the ball milling is completed, collect the nano beryllium oxide mixed solution. Put the mixed solution into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times. Centrifuge the obtained solution (rotation speed: 5000 r / min) to obtain wet (undried) nano beryllium oxide. Disperse the wet nano beryllium oxide into acrylic acid, where the mass ratio of nano beryllium oxide to acrylic acid is 1:1.

[0070] Step 4, synthesis of the near-infrared and infrared deep-curing resin precursor, specifically: Take 5 g of copper(II) phthalocyanine carbon quantum dot dispersion and 5 g of beryllium oxide dispersion, mix and stir them evenly, and then add 0.25 g of azobisisobutyronitrile. Then continue to add 5 g of isooctyl acrylate, 5 g of butyl acrylate, and 0.25 g of glycerol triacrylate, and stir evenly to obtain the resin precursor. The mass ratio of copper(II) phthalocyanine carbon quantum dot dispersion, beryllium oxide dispersion, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate, and glycerol triacrylate is 1:1:0.05:1:1:0.05.

[0071] Comparative Example 8 (No beryllium oxide dispersion is added to the deep-curing resin, and the near-infrared and infrared curing depths are insufficient) Step 1, synthesis of copper(II) phthalocyanine carbon quantum dot dispersion, specifically: Step 1.1, take 10 g of copper(II) phthalocyanine and put it into a 50 mL round-bottom flask, add 5 g of deionized water and stir evenly. Then place the round-bottom flask in a microwave reactor, and introduce O2 into it, with an O2 flow rate of 10 mL / min. Set the reaction temperature to 350 o °C, and the reaction time is 10 s. Wait for the temperature to cool to room temperature; in Step 1.1, the mass ratio of copper(II) phthalocyanine to deionized water is 2:1.

[0072] Step 1.2, add the same mass of deionized water as in Step 1.1 to the round-bottom flask after the reaction in Step 1.1 is completed, and keep other reaction conditions unchanged. Repeat the microwave reaction 3 times.

[0073] Step 1.3, add a 30 wt% HCl solution (the mass ratio of hydrochloric acid to copper(II) phthalocyanine is 10:1) to the round-bottom flask after the reaction in Step 1.2 is completed, and stir for 30 min. Centrifuge the obtained solution (rotation speed: 8000 r / min) to remove the insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times. Collect the solution in the dialysis bag and store it at -70 oFreeze-dry for 7 days under the condition of C. Dissolve the obtained blue-black product with a certain amount of acrylic acid (the mass ratio of acrylic acid to copper(II) phthalocyanine is 5:1) and set aside.

[0074] Step 2, Synthesis of urea-citric acid-acrylic acid-based carbon quantum dots. The specific process is as follows: Take the raw materials urea (5 g), citric acid (5 g), acrylic acid (1 g) and deionized water (20 g), mix and stir evenly according to the mass ratio of 5:5:1:20. Then put the mixed solution into a microwave reactor and directly heat it to 180 o C and react for 2 min. After the reaction is completed, wait for the temperature to drop to room temperature. Centrifuge the obtained solution with a centrifuge (rotation speed of 8000 r / min) to remove insoluble solids. Put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times. Collect the solution in the dialysis bag, concentrate the solution volume by 1 / 2, and place it in the air for 10 days until the concentrated solution changes from yellow to black. Then, freeze-dry the black concentrated solution for 7 days under the condition of -70 o C to obtain urea-citric acid-acrylic acid-based carbon quantum dots.

[0075] Step 3, Synthesis of near-infrared-infrared deep-curing resin precursor, specifically: Take 5 g of copper(II) phthalocyanine carbon quantum dot dispersion, 5 g of urea-citric acid-acrylic acid-based carbon quantum dots and 0.25 azobisisobutyronitrile. Then continue to add 5 g of isooctyl acrylate, 5 g of butyl acrylate and 0.25 g of glycerol triacrylate, and stir evenly to obtain the resin precursor.

[0076] The mass ratio of copper(II) phthalocyanine carbon quantum dot dispersion, urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate and glycerol triacrylate is 1:1:0.05:1:1:0.05.

[0077] Table 1 Performance characterization of Examples 1-3 and Comparative Examples 1-8

[0078] Use a thermal conductivity measuring instrument to measure the thermal conductivity of the near-infrared-infrared deep-curing resin precursor before curing. The determination of the curing time is to put the near-infrared-infrared deep-curing resin into a polytetrafluoroethylene mold with a length, width and height of 1 x 1 x 1 cm (filled), and irradiate it with a 5 W near-infrared light source and a 5 W infrared light source respectively to determine the time required for complete curing. The determination of the curing depth is to put the near-infrared-infrared deep-curing resin into a polytetrafluoroethylene mold with a length, width and height of 1 x 1 x 1 cm (filled), and irradiate it with a 5 W near-infrared light source and a 5 W infrared light source for 1 min respectively, and then measure the cured thickness.

[0079] Results and Discussion In Examples 1-3, beryllium oxide is contained, and they all have good thermal conductivity. Due to the presence of copper(II) phthalocyanine carbon quantum dots and urea-citric acid-acrylic acid-based carbon quantum dots, when irradiated with near-infrared and infrared light, the near-infrared light and infrared light can be converted into heat to achieve the thermal curing of the resin precursor. The presence of beryllium oxide can accelerate the deep curing of the resin. In a 10-mm-thick resin precursor, it only takes 600-610 s and 302-321 s to complete curing under near-infrared and infrared light irradiation, and the curing depth can reach 5 mm and 6 mm. Compared with near-infrared light, infrared light has a stronger thermal effect and a faster heating rate, resulting in a shorter curing time and a deeper curing depth. Figure 1 It is the heating change curve of the near-infrared-infrared deep-curing resin precursor prepared in Example 1 under near-infrared and infrared light irradiation.

[0080] In Comparative Example 1, when synthesizing copper(II) phthalocyanine carbon quantum dots, O2 was changed to N2. Without the participation of O2, H2O could not be generated, resulting in the failure of the graphitization of copper(II) phthalocyanine and the inability to obtain copper(II) phthalocyanine carbon quantum dots.

[0081] In Comparative Example 2, copper(II) phthalocyanine was graphitized to form carbon quantum dots. Due to its large conjugation, the molecules are prone to stacking. A large number of N atoms are contained in this type of quantum dots. After associating with H+ on acrylic acid, the dispersibility of copper(II) phthalocyanine carbon quantum dots can be improved. However, when acrylic acid is replaced with methyl acrylate, the quantum dots cannot be dispersed.

[0082] In Comparative Example 3, hydrochloric acid was replaced with deionized water. When synthesizing copper(II) phthalocyanine carbon quantum dots, the quantum dots are densely stacked, and acid etching is required to disperse the copper(II) phthalocyanine carbon quantum dots. Importantly, copper(II) phthalocyanine carbon quantum dots are almost insoluble in water.

[0083] In Comparative Example 4, when synthesizing urea-citric acid-acrylic acid-based carbon quantum dots, the dialysis solution was directly freeze-dried without being concentrated and allowed to stand, and the self-assembly process could not be completed, and the obtained product was yellow. This led to poor infrared light curing effect, incomplete curing, and the curing depth was only 1 mm. On the contrary, the initial urea-citric acid-acrylic acid-based carbon quantum dots in Example 1 were light yellow, and further self-assembly in a high-concentration solution was required to improve the conjugation of the molecules, causing the absorption wavelength to undergo a red shift to observe the blue-black end product. The maximum absorption peak wavelength shifted from 430 nm to 881 nm, as Figure 2 shown.

[0084] In Comparative Example 5, when preparing the beryllium oxide dispersion, phosphoric acid was used as the dispersant. After long-term ball milling, a phosphoric acid modification layer was formed on the surface of beryllium oxide. Since phosphoric acid is acidic, it can be dispersed in acidic acrylic acid but cannot be dispersed in neutral methyl acrylate.

[0085] Comparative Example 6: Copper(II) phthalocyanine carbon quantum dot dispersion was not added to the deep-curing resin precursor, resulting in poor absorption and conversion of near-infrared light by the resin precursor, leading to slow near-infrared curing and limited curing thickness. However, compared with Example 1, the infrared light curing depth effect was reduced, the curing time was delayed, and the synergistic effect of copper(II) phthalocyanine carbon quantum dots and urea-citric acid-acrylic acid-based carbon quantum dots was lacking.

[0086] Comparative Example 7: Urea-citric acid-acrylic acid-based carbon quantum dots were not added to the deep-curing resin precursor, resulting in poor absorption and conversion of infrared light by the deep-curing resin precursor, leading to slow infrared curing and limited curing thickness. Compared with Example 1, the near-infrared light curing depth effect was reduced, the curing time was prolonged, and the synergistic effect of urea-citric acid-acrylic acid-based carbon quantum dots and copper(II) phthalocyanine carbon quantum dots was lacking.

[0087] Comparative Example 8: Beryllium oxide dispersion was not added to the deep-curing resin precursor, resulting in low heat conduction efficiency, leading to slow near-infrared and infrared curing speeds and insufficient depth. Nevertheless, in the absence of beryllium oxide, the curing depth could still reach 2 mm and 3 mm, benefiting from the good penetration of near-infrared and infrared light.

[0088] Example 4 Compared with Example 1, in Step 1.1, the O2 flow rate was 18 mL / min, the reaction temperature was 430 o °C, and the reaction time was 11 s, with the remaining steps unchanged.

[0089] Example 5 Compared with Example 1, in Step 1.3, the centrifuge rotation speed was 8500 r / min, with the remaining steps unchanged.

[0090] Example 6 Compared with Example 1, in Step 3, the rotation speed of the mixed solution in the ball mill was 700 r / min, with the remaining steps unchanged.

Claims

1. A method for preparing a near-infrared-infrared deep-curing resin precursor, characterized in that: Specifically, it includes the following steps: Step 1: Synthesize a copper phthalocyanine (II) carbon quantum dot dispersion; Step 2: Synthesize urea-citric acid-acrylic acid-based carbon quantum dots; Step 3: Prepare a beryllium oxide dispersion; Step 4: Synthesize a near-infrared-infrared deep-curing resin precursor from the products obtained in Steps 1 to 3.

2. The preparation method of the near-infrared to infrared deep curing resin precursor according to claim 1, wherein: The specific process of Step 1 is as follows: Step 1.1, put copper(II) phthalocyanine into a 50 mL round-bottom flask. After adding deionized water and stirring evenly, place the round-bottom flask into a microwave reactor and introduce O2 with a flow rate of 10 - 20 mL / min. Set the reaction temperature to 350 - 450 o °C, and the reaction time is 10 - 15 s. Wait for the temperature to cool to room temperature; the mass ratio of copper(II) phthalocyanine to deionized water is 2 - 4:1; Step 1.2: Add deionized water with the same mass as that in Step 1.1 to the round-bottom flask after the reaction in Step 1.1 is completed, keep other reaction conditions unchanged, and repeat the microwave reaction 3 times; Step 1.3, add 30 wt% HCl solution into the round-bottom flask after the reaction in Step 1.2 is completed, stir for 30 - 60 min, centrifuge the resulting solution to remove insoluble solids, put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze 3 times, collect the solution in the dialysis bag, and freeze-dry it for 7 days at -70 o °C. Dissolve the resulting blue-black product in acrylic acid to obtain a copper phthalocyanine (II) carbon quantum dot dispersion.

3. The preparation method of the near-infrared-infrared deep curing resin precursor according to claim 2, characterized in that: In Step 1.3, the mass ratio of hydrochloric acid to copper phthalocyanine (II) is 10:2 - 1.

4. The preparation method of the near-infrared to infrared deep curing resin precursor according to claim 2, wherein: In Step 1.3, the mass ratio of acrylic acid to copper phthalocyanine (II) is 10 - 5:

1.

5. The preparation method of the near-infrared-infrared deep curing resin precursor according to claim 2, characterized in that: The specific process of the said Step 2 is as follows: Take urea, citric acid, acrylic acid and deionized water and mix them evenly according to the mass ratio of 5:5-10:1-2:20-40. After that, put the mixed solution into a microwave reactor and directly heat it to 180-220 o °C for 2-4 min. After the reaction ends, wait for the temperature to drop to room temperature; centrifuge the obtained solution to remove insoluble solids, and put the supernatant into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times; collect the solution in the dialysis bag, concentrate the solution volume by 1 / 2, and place it in the air for 10 days until the concentrated solution changes from yellow to black; then, freeze-dry the black concentrated solution at -70 o °C for 7 days to obtain urea-citric acid-acrylic acid-based carbon quantum dots.

6. The preparation method of the near-infrared-infrared deep curing resin precursor according to claim 5, characterized in that: The specific process of Step 3 is as follows: Take beryllium oxide ceramic powder, phosphoric acid, zirconia, and deionized water and mix them evenly according to the mass ratio of 1:2 - 4:10 - 100:100 - 200, then pour the mixed solution into a nano ball mill, with a rotation speed of 500 - 1000 r / min and a time of 6 - 12 h. After the ball milling is completed, collect the nano beryllium oxide mixed solution, put the nano beryllium oxide mixed solution into a dialysis bag with a molecular weight cut-off of 7000 Da and dialyze it 3 times. Centrifuge the obtained solution to get wet nano beryllium oxide, and disperse the wet nano beryllium oxide into acrylic acid, where the mass ratio of nano beryllium oxide to acrylic acid is 1:1 - 2.

7. The preparation method of the near-infrared-infrared deep curing resin precursor according to claim 6, wherein: The specific process of Step 4 is as follows: Take the copper phthalocyanine (II) carbon quantum dot dispersion and the beryllium oxide dispersion, mix and stir them evenly, then add urea-citric acid-acrylic acid-based carbon quantum dots and azobisisobutyronitrile; then continue to add isooctyl acrylate, butyl acrylate, and glycerol triacrylate, and stir evenly to obtain a resin precursor.

8. The preparation method of the near-infrared to infrared deep curing resin precursor according to claim 7, characterized in that: In Step 4, the mass ratio of the copper phthalocyanine (II) carbon quantum dot dispersion, the beryllium oxide dispersion, the urea-citric acid-acrylic acid-based carbon quantum dots, azobisisobutyronitrile, isooctyl acrylate, butyl acrylate, and glycerol triacrylate is 1:1 - 3:1 - 3:0.05 - 0.15:1 - 5:1 - 5:0.05 - 0.

15.

9. A near-infrared-infrared deep-curing resin precursor prepared by using the preparation method of the near-infrared-infrared deep-curing resin precursor according to any one of claims 1 to 8.

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