Nanowire array modified acrylate light-cured resin

Abstract

The invention relates to preparation of resin, in particular to nanowire array modified acrylate light-cured resin. A commercial photoinitiator 2-hydroxy-2-methyl propiophenone (PI-1173) is mainly introduced into a copper nanowire wrapped by rhenium, zirconium and iron, so that the contact area of the photoinitiator and resin is increased. Re, Zr and Fe on the prepared nanowire array have a synergistic effect, the dispersity of nanoparticles in the epoxy acrylate resin is remarkably improved, and the mechanical property of the acrylic light-cured resin is greatly improved through the combined effect of the two-dimensional layered graphene and the nanowires.

Description

Technical Field

[0001] This invention relates to the preparation of resins, specifically acrylate photocurable resins, and particularly to a nanowire array modified acrylate photocurable resin. Background Technology

[0002] Acrylic resins are obtained by polymerizing acrylic acid and methacrylic acid or their derivatives, including amides, acrylonitrile, vinyl-containing monomers, styrene, butadiene, and other olefin monomers. Depending on the type, properties, and applications, various structurally stable acrylic resins are synthesized by changing additives, selecting synthetic monomers with different structures, and modifying product formulations. These resins are used in various fields, including military and daily consumer goods. Acrylic resins modified with acrylates or methacrylates as the main monomers are widely used due to their high transparency, low toxicity, ease of processing, wide bonding range, good water resistance, and excellent durability. With the expanding applications of acrylic resins in industry, agriculture, aerospace, automotive, electronic materials, construction, pharmaceuticals, and daily life, the variety and quantity of acrylate monomers are increasing daily, driving the rapid development of various products such as epoxy acrylic resins, polyurethane acrylic resins, and hydroxypropyl acrylate resins.

[0003] Among various epoxy acrylates, bisphenol A epoxy acrylate resin has the fastest photocuring rate. In addition, bisphenol A epoxy acrylate also possesses advantages such as high hardness of the cured film, high gloss, excellent chemical resistance, good heat resistance, electrical properties, low price, and simple synthesis process. Ultraviolet (UV) photocuring technology has advantages such as high efficiency, energy saving, reliability, economy, and environmental friendliness, and is considered a new generation of green curing technology. Initiators play an indispensable role in photocurable resins, and the combination of organic and inorganic components has become an inevitable trend in producing new materials with properties superior to pure components. Therefore, this invention introduces the commercial photoinitiator 2-hydroxy-2-methylphenylacetone (PI-1173) into rhenium, zirconium, and iron-coated copper nanowires, increasing the contact area between the initiator and the resin. A synergistic effect exists between Re, Zr, and Fe on the prepared nanowire array, significantly improving the dispersibility of nanoparticles in the epoxy acrylate resin. The combined effect of graphene and nanowires greatly enhances the mechanical properties of the acrylic photocurable resin. Summary of the Invention

[0004] To address the above problems, this invention proposes a nanoneedle array modified acrylate photocurable resin, and the specific preparation steps are as follows: S1. Clean the copper foam with acetone, dilute hydrochloric acid, and anhydrous ethanol using ultrasonic cleaning for 10-15 min, and vacuum dry it in a vacuum drying oven for 1-3 h. Then, immerse the clean and dry copper foam in a 2-4 M KOH solution for 30-40 min at a temperature of 35-45℃ to grow Cu(OH)2 nanowire arrays on the surface of the copper foam. Then, calcine the Cu(OH)2 nanowire arrays in an Ar / H2 mixed gas at 150-180℃ and maintain the temperature for 1-2 h to obtain copper nanowire arrays.

[0005] S2. Weigh 0.8-1.3 g of ammonium perrhenate, 2-3 g of zirconium nitrate, 0.5-0.9 g of ferric chloride, 0.5-0.9 g of sodium thiosulfate, and 1-1.2 g of sodium citrate, and dissolve them in 80-100 ml of deionized water as an electrolyte. Then, using the copper foam CF with copper nanowire array prepared in step S1 as the cathode, a Pt sheet as the anode, and saturated calomel as the reference electrode, electroplating is performed at a potential of -1.8V for 10-15 min to obtain copper nanowires Re / Zr / Fe-O@Cu / CF grown on copper foam and encapsulated by rhenium, zirconium, and iron.

[0006] S3. Take 15-20 g of Re / Zr / Fe-O@Cu / CF prepared in step S2, and sonicate it in 30-50 ml of anhydrous ethanol solution for 30-45 min to separate the nanoarray from the copper foam. Take out the sonicated copper foam sheet, centrifuge and dry the liquid to obtain Re / Zr / Fe-O@Cu nanowires.

[0007] S4. Photoinitiator composite onto the surface of Re / Zr / Fe-O@Cu: Disperse 5-8 g of 2-hydroxy-2-methylpropanone (PI-1173), 2-5 g of the Re / Zr / Fe-O@Cu nanoarray prepared in step S3, and 3-5 g of silica in 200-280 mL of toluene. Sonicate the mixture for 25-35 min, then react continuously at 60°C under light-shielding for 6 h. Filter the product, then wash the sample sequentially with toluene and acetone. After drying, the photoinitiator-coated Re / Zr / Fe-O@Cu nanowires are obtained. This step combines an organic initiator with inorganic nanowires, utilizing the advantages of nanowires to increase the contact area between the initiator and the resin.

[0008] S5. Add 0.1-0.5 g of p-methoxyphenol, 30-70 g of bisphenol A epoxy resin and 1-3 g of nano-silica to a three-necked flask, add 0.3-1.5 g of silane coupling agent, stir continuously and raise the temperature to 65 °C. Mix 0.2-0.4 g of tetraethylammonium bromide and 20-50 g of acrylic acid and add dropwise to the three-necked flask. Control the reaction temperature at 95-115 °C and stop the reaction after 3-4 h to prepare bisphenol A epoxy acrylate.

[0009] S6. Add 38-62 g of bisphenol A epoxy acrylate prepared in step S5 and 13-18 g of 1,6-hexanediol diacrylate, stir evenly, then add 3-5 g of initiator-coated Re / Zr / Fe-O@Cu nanowires prepared in step S4, along with 5-8 g of graphene and 6-9 g of hydroxyethyl methacrylate (HEMA). Disperse using a high-speed disperser, store in the dark, and set aside for later use. In this step, the graphene has a two-dimensional layered structure, which interweaves with the initiator-coated Re / Zr / Fe-O@Cu nanowires to form a network structure, greatly improving the mechanical properties of the cured resin.

[0010] S7. Pour the mixed solution prepared in step S6 into the resin tank, set the printing parameters, select the model and print. After completion, immerse the photocured resin sample in anhydrous ethanol for 20 minutes, then remove it and store it in the dark for later use.

[0011] Preferably, the foamed copper in step S1 is purchased from Kunshan City Yushan Town Yiwangxin New Material Technology Co., Ltd.

[0012] Preferably, in step S1, the foamed copper is ultrasonically cleaned with acetone, dilute hydrochloric acid, and anhydrous ethanol for 15 min, vacuum dried in a vacuum drying oven for 3 h, and then the clean and dried foamed copper is immersed in 3 M KOH solution for 30 min at a temperature of 35 ℃, so that the surface of the foamed copper is covered with needle-like Cu(OH)2 nanoarrays. Then, the Cu(OH)2 nanoarrays are calcined in an Ar / H2 mixed gas at 150-180 ℃ and the temperature is maintained for 2 h to obtain copper nanowire arrays.

[0013] Preferably: in step S2, 0.8 g of ammonium perrhenate, 3 g of zirconium nitrate, 0.5 g of ferric chloride, 0.5 g of sodium thiosulfate, and 1 g of sodium citrate are weighed and dissolved in 80 ml of deionized water as an electrolyte for later use. Preferably, in step S2, the copper foam CF with copper nanowire array prepared in step S1 is used as the cathode, Pt sheet is used as the anode, and saturated calomel is used as the reference electrode. Electroplating is performed at a potential of -1.8V for 15 min to obtain copper nanowires Re / Zr / Fe-O@Cu / CF grown on copper foam and wrapped with rhenium, zirconium and iron.

[0014] Preferably: In step S3, 15 g of the Re / Zr / Fe-O@Cu / CF prepared in step S2 is taken and placed in 30 ml of anhydrous ethanol solution for ultrasonic treatment for 30 min. The nanoarray is then ultrasonically separated from the copper foam. The ultrasonically treated copper foam sheet is removed, and the liquid is centrifuged and dried to obtain Re / Zr / Fe-O@Cu nanowires.

[0015] Preferably, in step S4, the photoinitiator is introduced onto the surface of Re / Zr / Fe-O@Cu: 5 g of 2-hydroxy-2-methylpropanone (PI-1173), 3 g of the Re / Zr / Fe-O@Cu nanoarray prepared in step S3, and 4 g of silica are dispersed in 250 mL of toluene, sonicated for 25 min, and then reacted continuously at 60°C under light-shielding for 6 h. The product is filtered, and then the sample is washed sequentially with toluene and acetone. After drying, the photoinitiator-coated Re / Zr / Fe-O@Cu nanowires are obtained.

[0016] Preferably, in step S5, 0.3 g of p-methoxyphenol, 55 g of bisphenol A epoxy resin and 2 g of nano-silica are added to a three-necked flask, along with 0.7 g of silane coupling agent. The mixture is stirred continuously and the temperature is raised to 65 °C. Then, 0.3 g of tetraethylammonium bromide and 33 g of acrylic acid are mixed and added dropwise to the three-necked flask. The reaction temperature is controlled at 105 °C, and the reaction is stopped after 3 h to prepare bisphenol A epoxy acrylate.

[0017] Preferably, in step S6, 38 g of the bisphenol A epoxy acrylate prepared in step S5 and 13 g of 1,6-hexanediol diacrylate are stirred evenly, then 4 g of the initiator-coated Re / Zr / Fe-O@Cu nanowires prepared in step S4 are added, along with 6 g of graphene. The mixture is dispersed using a high-speed disperser, stored in the dark, and set aside for later use. In this step, the graphene has a two-dimensional layered structure, which interweaves with the initiator-coated Re / Zr / Fe-O@Cu nanowires to form a network structure, significantly improving the mechanical properties of the cured resin.

[0018] The beneficial effects of this invention are: This invention introduces the commercial photoinitiator 2-hydroxy-2-methylphenylacetone (PI-1173) into rhenium, zirconium and iron-coated copper nanowires, thereby increasing the contact area between the initiator and the resin.

[0019] The nanowire array prepared by this invention exhibits a synergistic effect between Re, Zr, and Fe, which significantly improves the dispersibility of nanoparticles in epoxy acrylate resin. The combined effect of graphene and nanowires greatly enhances the mechanical properties of acrylic photocurable resin.

[0020] 3. In the preparation of bisphenol A epoxy acrylic acid, the present invention adds silane coupling agent and SiO2, which improves the dispersibility of nano-SiO2 particles and enhances the compatibility between nanoparticles and matrix resin, thereby effectively improving the performance of composite materials. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 SEM scan of Cu(OH)2 nanowires prepared in Example 1 of this invention.

[0023] Figure 2 SEM scan of Re / Zr / Fe-O@Cu prepared in Example 1 of this invention.

[0024] Figure 3 SEM image of Re / Zr / Fe-O@Cu nanowires coated with photoinitiator prepared in Example 1 of this invention.

[0025] Figure 4 SEM scan of Re / Zr / Fe-O coated with photoinitiator prepared in Comparative Example 1 of this invention.

[0026] Figure 5 Linear scanning energy dispersive spectroscopy (EDS) of copper nanowires Re / Zr / Fe-O@Cu coated with rhenium, zirconium and iron prepared in Example 2 of this invention. Detailed Implementation

[0027] To make the technical problem to be solved, the technical solution, and the beneficial effects of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the content of this invention and are not intended to limit this invention.

[0028] Example 1

[0029] S1. Clean the copper foam with acetone, dilute hydrochloric acid, and anhydrous ethanol using ultrasonic cleaning for 10 min, and then vacuum dry it in a vacuum drying oven for 1 h. Then, immerse the clean and dry copper foam in 2 M KOH solution for 30 min at a temperature of 35 ℃ to grow Cu(OH)2 nanowire arrays on the surface of the copper foam. Then, calcine the Cu(OH)2 nanowire arrays in an Ar / H2 mixed gas at 150 ℃ and maintain the temperature for 1 h to obtain copper nanowire arrays.

[0030] S2. Weigh 0.8 g of ammonium perrhenate, 2 g of zirconium nitrate, 0.5 g of ferric chloride, 0.5 g of sodium thiosulfate, and 1 g of sodium citrate and dissolve them in 80 ml of deionized water as an electrolyte. Then, using the copper foam CF with copper nanowire array prepared in step S1 as the cathode, a Pt sheet as the anode, and saturated calomel as the reference electrode, electroplating is performed at a potential of -1.8V for 10 min to obtain copper nanowires Re / Zr / Fe-O@Cu / CF grown on copper foam and encapsulated by rhenium, zirconium, and iron.

[0031] S3. Take 15 g of Re / Zr / Fe-O@Cu / CF prepared in step S2, place it in 30 ml of anhydrous ethanol solution and sonicate for 30 min to separate the nanoarray from the copper foam by sonication. Take out the copper foam sheet after sonication, centrifuge and dry the liquid to obtain Re / Zr / Fe-O@Cu nanowires.

[0032] S4. Photoinitiator composite onto the surface of Re / Zr / Fe-O@Cu: 5 g of 2-hydroxy-2-methylpropanone (PI-1173), 2 g of the Re / Zr / Fe-O@Cu nanoarray prepared in step S3, and 3 g of silica were dispersed in 200 mL of toluene. The mixture was sonicated for 25 min, and then reacted continuously at 60°C under light-shielding for 6 h. The product was filtered, and the sample was washed sequentially with toluene and acetone. After drying, the photoinitiator-coated Re / Zr / Fe-O@Cu nanowires were obtained. This step combines an organic initiator with inorganic nanowires, utilizing the advantages of nanowires to increase the contact area between the initiator and the resin.

[0033] S5. Add 0.1 g of p-methoxyphenol, 30 g of bisphenol A epoxy resin and 1 g of nano silica to a three-necked flask, add 0.3 g of silane coupling agent, stir continuously and raise the temperature to 65 °C. Mix 0.2 g of tetraethylammonium bromide and 20 g of acrylic acid and add dropwise to the three-necked flask. Control the reaction temperature at 95 °C and stop the reaction after 3 h to prepare bisphenol A epoxy acrylate.

[0034] S6. 38 g of the bisphenol A epoxy acrylate prepared in step S5 and 13 g of 1,6-hexanediol diacrylate were stirred until homogeneous. Then, 3 g of the initiator-coated Re / Zr / Fe-O@Cu nanowires prepared in step S4 were added, along with 5 g of graphene and 7 g of hydroxyethyl methacrylate (HEMA). The mixture was dispersed using a high-speed disperser, stored in the dark, and set aside for later use. In this step, the graphene, with its two-dimensional layered structure, intertwines with the initiator-coated Re / Zr / Fe-O@Cu nanowires to form a network structure, significantly improving the mechanical properties of the cured resin.

[0035] S7. Pour the mixed solution prepared in step S6 into the resin tank, set the printing parameters, select the model and print. After completion, immerse the photocured resin sample in anhydrous ethanol for 20 minutes, then remove it and store it in the dark for later use.

[0036] Comparative Example 1: Except for step S2, in which empty copper foam is used instead of copper nanowire array-grown copper foam, all other steps are the same as in Example 1.

[0037] Figure 1 The image shown is a SEM scan of Cu(OH)2 nanowires prepared in Example 1 of this invention, which shows that the morphology is that of nanowires. Figure 2 The image shows a SEM scan of Re / Zr / Fe-O@Cu prepared in Example 1 of this invention. It can be seen that the nanowires become soft and curved after metal deposition, but still maintain the nanowire structure. Figure 3 The image shows a SEM image of the initiator-coated Re / Zr / Fe-O@Cu nanowires prepared in Example 1 of this invention. It can be seen from the image that the nanowire substrate effectively supports the initiator. Figure 4 This is a SEM image of the Re / Zr / Fe-O initiator-coated resin prepared in Comparative Example 1 of this invention. Without the support of a nanowire substrate, the prepared initiator is in an amorphous state, and the photoinitiation effect is greatly reduced after mixing. This invention combines an organic initiator with inorganic nanowires, utilizing the advantages of nanowires to increase the contact area between the initiator and the resin.

[0038] Example 2

[0039] S1. The foamed copper was ultrasonically cleaned with acetone, dilute hydrochloric acid and anhydrous ethanol for 15 min, and then vacuum dried in a vacuum drying oven for 3 h. The cleaned and dried foamed copper was then immersed in 4 M KOH solution for 40 min at a temperature of 45 ℃, so that Cu(OH)2 nanowire arrays were grown on the surface of the foamed copper. The Cu(OH)2 nanowire arrays were then calcined in Ar / H2 mixed gas at 180 ℃ and held at the temperature for 2 h to obtain copper nanowire arrays.

[0040] S2. Weigh 1.3 g of ammonium perrhenate, 3 g of zirconium nitrate, 0.9 g of ferric chloride, 0.9 g of sodium thiosulfate, and 1.2 g of sodium citrate and dissolve them in 100 ml of deionized water as an electrolyte. Then, using the copper foam CF with copper nanowire array prepared in step S1 as the cathode, a Pt sheet as the anode, and saturated calomel as the reference electrode, electroplating is performed at a potential of -1.8V for 15 min to obtain copper nanowires Re / Zr / Fe-O@Cu / CF grown on copper foam and encapsulated by rhenium, zirconium, and iron.

[0041] S3. Take 20 g of Re / Zr / Fe-O@Cu / CF prepared in step S2, place it in 50 ml of anhydrous ethanol solution and sonicate for 45 min to separate the nanoarray from the copper foam by sonication. Take out the copper foam sheet after sonication, centrifuge and dry the liquid to obtain Re / Zr / Fe-O@Cu nanowires.

[0042] S4. Photoinitiator composite onto the surface of Re / Zr / Fe-O@Cu: 8 g of 2-hydroxy-2-methylpropanone (PI-1173), 5 g of the Re / Zr / Fe-O@Cu nanoarray prepared in step S3, and 5 g of silica were dispersed in 280 mL of toluene. The mixture was sonicated for 35 min, and then reacted continuously at 60°C under light-shielding for 6 h. The product was filtered, and the sample was washed sequentially with toluene and acetone. After drying, initiator-coated Re / Zr / Fe-O@Cu nanowires were obtained. This step combines an organic initiator with inorganic nanowires, utilizing the advantages of nanowires to increase the contact area between the initiator and the resin.

[0043] S5. Add 0.5 g of p-methoxyphenol, 70 g of bisphenol A epoxy resin and 3 g of nano silica to a three-necked flask, add 1.5 g of silane coupling agent, stir continuously and raise the temperature to 65 °C. Mix 0.4 g of tetraethylammonium bromide and 50 g of acrylic acid and add dropwise to the three-necked flask. Control the reaction temperature at 115 °C and stop the reaction after 4 h to prepare bisphenol A epoxy acrylate.

[0044] S6. Mix 62 g of bisphenol A epoxy acrylate prepared in step S5 and 18 g of 1,6-hexanediol diacrylate evenly, then add 5 g of initiator-coated Re / Zr / Fe-O@Cu nanowires prepared in step S4, and add 8 g of graphene. Disperse using a high-speed disperser, store in the dark, and set aside for later use. In this step, the graphene has a two-dimensional layered structure, which interweaves with the initiator-coated Re / Zr / Fe-O@Cu nanowires to form a network structure, greatly improving the mechanical properties of the cured resin.

[0045] S7. Pour the mixed solution prepared in step S6 into the resin tank, set the printing parameters, select the model and print. After completion, immerse the photocured resin sample in anhydrous ethanol for 20 minutes, then remove it and store it in the dark for later use.

[0046] Figure 5 The linear scanning energy dispersive spectroscopy (EDS) spectrum of the copper nanowires Re / Zr / Fe-O@Cu coated with rhenium, zirconium, and iron prepared in Example 2 of this invention is shown. The figure shows that Re, Zr, and Fe elements are uniformly distributed on the outside of the copper nanowires. During the preparation process, these metals are easily oxidized, allowing for better bonding with the photoinitiator.

[0047] Example 3

[0048] S1. The foamed copper was ultrasonically cleaned with acetone, dilute hydrochloric acid and anhydrous ethanol for 13 min, and then vacuum dried in a vacuum drying oven for 2 h. The cleaned and dried foamed copper was then immersed in 3 M KOH solution for 35 min at a temperature of 40 ℃, so that Cu(OH)2 nanowire arrays were grown on the surface of the foamed copper. The Cu(OH)2 nanowire arrays were then calcined in Ar / H2 mixed gas at 160 ℃ and maintained at the temperature for 1.5 h to obtain copper nanowire arrays.

[0049] S2. Weigh 0.9 g of ammonium perrhenate, 2.5 g of zirconium nitrate, 0.7 g of ferric chloride, 0.7 g of sodium thiosulfate, and 1.1 g of sodium citrate and dissolve them in 90 ml of deionized water as an electrolyte. Then, using the copper foam CF with copper nanowire array prepared in step S1 as the cathode, a Pt sheet as the anode, and saturated calomel as the reference electrode, electroplating is performed at a potential of -1.8V for 14 min to obtain copper nanowires Re / Zr / Fe-O@Cu / CF grown on copper foam and encapsulated by rhenium, zirconium, and iron.

[0050] S3. Take 17 g of Re / Zr / Fe-O@Cu / CF prepared in step S2, place it in 40 ml of anhydrous ethanol solution and sonicate for 37 min to separate the nanoarray from the copper foam by sonication. Take out the copper foam sheet after sonication, centrifuge and dry the liquid to obtain Re / Zr / Fe-O@Cu nanowires.

[0051] S4. Photoinitiator composite onto the surface of Re / Zr / Fe-O@Cu: 7 g of 2-hydroxy-2-methylpropanone (PI-1173), 3 g of the Re / Zr / Fe-O@Cu nanoarray prepared in step S3, and 4 g of silica were dispersed in 260 mL of toluene. The mixture was sonicated for 29 min, and then reacted continuously at 60°C under light-shielding for 6 h. The product was filtered, and the sample was washed sequentially with toluene and acetone. After drying, initiator-coated Re / Zr / Fe-O@Cu nanowires were obtained. This step combines an organic initiator with inorganic nanowires, utilizing the advantages of nanowires to increase the contact area between the initiator and the resin.

[0052] S5. Add 0.3 g of p-methoxyphenol, 65 g of bisphenol A epoxy resin and 2 g of nano silica to a three-necked flask, add 0.9 g of silane coupling agent, stir continuously and raise the temperature to 65 °C. Mix 0.3 g of tetraethylammonium bromide and 44 g of acrylic acid and add dropwise to the three-necked flask. Control the reaction temperature at 105 °C and stop the reaction after 3 h to prepare bisphenol A epoxy acrylate.

[0053] S6. 42 g of the bisphenol A epoxy acrylate prepared in step S5 and 16 g of 1,6-hexanediol diacrylate were stirred until homogeneous. Then, 4 g of the initiator-coated Re / Zr / Fe-O@Cu nanowires prepared in step S4 were added, along with 6 g of graphene and 7 g of hydroxyethyl methacrylate (HEMA). The mixture was dispersed using a high-speed disperser, stored in the dark, and set aside for later use. In this step, the graphene, with its two-dimensional layered structure, intertwines with the initiator-coated Re / Zr / Fe-O@Cu nanowires to form a network structure, significantly improving the mechanical properties of the cured resin.

[0054] S7. Pour the mixed solution prepared in step S6 into the resin tank, set the printing parameters, select the model and print. After completion, immerse the photocured resin sample in anhydrous ethanol for 20 minutes, then remove it and store it in the dark for later use.

[0055] Comparative Example 2 is identical to Example 3 except that graphene is not added in step S6.

[0056] Comparative Example 3 is identical to Example 3 except that in step S2, empty copper foam is used instead of copper foam with a copper nanowire array.

[0057] This invention refers to the method of national standard GB / T2567-2008, and uses a SANS7CMT-4304 universal testing machine (Shenzhen Xin Sansi Metrology Instrument Co., Ltd., China) to characterize the mechanical properties of the samples prepared in Example 3 and Comparative Examples 2 and 3. The samples were prepared with dimensions of (60×10×3) mm. 3Dumbbell-shaped specimens were prepared, and at least five specimens were prepared for each sample. The test was repeated at least five times, and the average value was used as the final result. All tests were conducted at room temperature, and the tensile speed of the specimens was controlled at 5 mm / min during the test.

[0058] Table 1. Comparison of tensile and flexural properties of UV-cured resins

[0059] Table 1 is a comparison chart of the tensile strength properties of the photocurable resins prepared in Example 3 and Comparative Examples 2-3 of the present invention. The addition of graphene and the design of nanowire structures greatly improve the mechanical properties of the cured resin. The two complement each other and form an internal network structure, which is conducive to the rapid and stable molding of the resin.

[0060] Example 4

[0061] S1. The foamed copper was ultrasonically cleaned with acetone, dilute hydrochloric acid, and anhydrous ethanol for 13 min, and then vacuum dried in a vacuum drying oven for 2 h. The cleaned and dried foamed copper was then immersed in 3 M KOH solution for 37 min at a temperature of 42 ℃, so that Cu(OH)2 nanowire arrays grew on the surface of the foamed copper. The Cu(OH)2 nanowire arrays were then calcined in an Ar / H2 mixed gas at 175 ℃ and maintained at the temperature for 1.8 h to obtain copper nanowire arrays.

[0062] S2. Weigh 1.1 g of ammonium perrhenate, 2.5 g of zirconium nitrate, 0.8 g of ferric chloride, 0.7 g of sodium thiosulfate, and 1.08 g of sodium citrate and dissolve them in 95 ml of deionized water as an electrolyte. Then, using the copper foam CF with copper nanowire array prepared in step S1 as the cathode, a Pt sheet as the anode, and saturated calomel as the reference electrode, electroplating is performed at a potential of -1.8V for 14 min to obtain copper nanowires Re / Zr / Fe-O@Cu / CF grown on copper foam and encapsulated by rhenium, zirconium, and iron.

[0063] S3. Take 18 g of Re / Zr / Fe-O@Cu / CF prepared in step S2, place it in 45 ml of anhydrous ethanol solution and sonicate for 32 min to separate the nanoarray from the copper foam by sonication. Take out the copper foam sheet after sonication, centrifuge and dry the liquid to obtain Re / Zr / Fe-O@Cu nanowires.

[0064] S4. Applying the photoinitiator to the surface of Re / Zr / Fe-O@Cu: Disperse 6 g of 2-hydroxy-2-methylpropanone (PI-1173), 4 g of the Re / Zr / Fe-O@Cu nanoarray prepared in step S3, and 2 g of silica in 270 mL of toluene. Sonicate the mixture for 28 min, then react it under continuous light protection at 60°C for 6 h. Filter the product, then wash the sample sequentially with toluene and acetone. After drying, the photoinitiator-coated Re / Zr / Fe-O@Cu nanowires are obtained. This step combines an organic initiator with inorganic nanowires, utilizing the advantages of nanowires to increase the contact area between the initiator and the resin.

[0065] S5. Add 0.35 g of p-methoxyphenol, 49 g of bisphenol A epoxy resin and 2 g of nano-silica to a three-necked flask, add 0.9 g of silane coupling agent, stir continuously and raise the temperature to 65 °C. Mix 0.3 g of tetraethylammonium bromide and 44 g of acrylic acid and add dropwise to the three-necked flask. Control the reaction temperature at 99 °C and stop the reaction after 3.5 h to prepare bisphenol A epoxy acrylate.

[0066] S6. Mix 55 g of bisphenol A epoxy acrylate and 15 g of 1,6-hexanediol diacrylate prepared in step S5, then add 4 g of initiator-coated Re / Zr / Fe-O@Cu nanowires prepared in step S4, along with 6 g of graphene and 7 g of hydroxyethyl methacrylate (HEMA). Disperse the mixture using a high-speed disperser, then store it in the dark for later use. In this step, the graphene has a two-dimensional layered structure, which interweaves with the initiator-coated Re / Zr / Fe-O@Cu nanowires to form a network structure, greatly improving the mechanical properties of the cured resin.

[0067] S7. Pour the mixed solution prepared in step S6 into the resin tank, set the printing parameters, select the model and print. After completion, immerse the photocured resin sample in anhydrous ethanol for 20 minutes, then remove it and store it in the dark for later use.

[0068] Comparative Example 4 was identical to Example 4 except that hydroxyethyl methacrylate (HEMA) was not added in step S6.

[0069] Comparative Example 5 was identical to Example 4 except that zirconium nitrate was not added in step S2.

[0070] Comparative Example 6 was identical to Example 4 except that ammonium perrhenate was not added in step S2.

[0071] Comparative Example 7 was identical to Example 4 except that ferric chloride was not added in step S2.

[0072] Gel content is a key indicator of crosslinking systems because it is directly related to the final properties of the resulting thermosetting resin. The gel content of the sample prepared in this invention was determined by Soxhlet extraction. Approximately 0.5 g of the sample was accurately weighed and recorded as m0. The sample was then heated under reflux in acetone for 36 h. After this, the extracted sample was placed in a vacuum oven and dried at 80°C for 24 h. The mass of the sample at this point was recorded as m1. The final gel content C of the sample was then obtained. gel The value is calculated using the formula m1 / m0.

[0073] Table 2. Comparison of Gel Content in Photocurable Resins

[0074] Table 2 compares the gel content of the photocurable resins prepared in Example 4 and Comparative Examples 4-7 of this invention. Analysis shows that the addition of hydroxyethyl methacrylate (HEMA) reduces the viscosity of the system, which is beneficial for the photocuring crosslinking reaction and increases the gel content of the final resin material. Comparative Examples 5-7 indicate that the addition of Fe, Zr, and Re is beneficial for the combination of photoinitiators and nanowires. There is a synergistic effect among the three metal elements; after oxidation, they can effectively combine inorganic materials and organic photoinitiators, thereby improving the photopolymerization effect of the material.

Claims

1. A nanowire array modified acrylate photocurable resin, characterized in that: The specific preparation method is as follows: S1. Clean the foamed copper with acetone, dilute hydrochloric acid, and anhydrous ethanol using ultrasonic cleaning for 10-15 min, and vacuum dry it in a vacuum drying oven for 1-3 h. Then, immerse the clean and dry foamed copper in a 2-4 M KOH solution for 30-40 min at a temperature of 35-45℃ to grow Cu(OH)2 nanowire arrays on the surface of the foamed copper. Then, calcine the Cu(OH)2 nanowire arrays in an Ar / H2 mixed gas at 150-180℃ and maintain the temperature for 1-2 h to obtain copper nanowire arrays. S2. Weigh 0.8-1.3 g of ammonium perrhenate, 2-3 g of zirconium nitrate, 0.5-0.9 g of ferric chloride, 0.5-0.9 g of sodium thiosulfate, and 1-1.2 g of sodium citrate, and dissolve them in 80-100 ml of deionized water as an electrolyte. Then, using the copper foam CF with copper nanowire array prepared in step S1 as the cathode, a Pt sheet as the anode, and saturated calomel as the reference electrode, electroplating is performed at a potential of -1.8V for 10-15 min to obtain copper nanowires Re / Zr / Fe-O@Cu / CF grown on copper foam and encapsulated by rhenium, zirconium, and iron. S3. Take 15-20 g of Re / Zr / Fe-O@Cu / CF prepared in step S2, place it in 30-50 ml of anhydrous ethanol solution and sonicate for 30-45 min to separate the nanoarray from the copper foam. Take out the sonicated copper foam sheet, centrifuge and dry the liquid to obtain Re / Zr / Fe-O@Cu nanowires. S4. Photoinitiator is composited onto the surface of Re / Zr / Fe-O@Cu: 5-8 g of 2-hydroxy-2-methylpropanone (PI-1173), 2-5 g of the Re / Zr / Fe-O@Cu nanowire array prepared in step S3, and 3-5 g of silica are dispersed in 200-280 mL of toluene. The mixture is ultrasonically treated for 25-35 min, and then reacted continuously at 60°C under light-shielding for 6 h. The product is filtered, and the sample is washed sequentially with toluene and acetone. After drying, the initiator-coated Re / Zr / Fe-O@Cu nanowires are obtained. S5. Add 0.1-0.5 g of p-methoxyphenol, 30-70 g of bisphenol A epoxy resin and 1-3 g of nano silica to a three-necked flask, add 0.3-1.5 g of silane coupling agent, stir continuously and raise the temperature to 65 °C. Mix 0.2-0.4 g of tetraethylammonium bromide and 20-50 g of acrylic acid and add dropwise to the three-necked flask. Control the reaction temperature at 95-115 °C and stop the reaction after 3-4 h to prepare bisphenol A epoxy acrylate. S6. Add 38-62 g of bisphenol A epoxy acrylate prepared in step S5 and 13-18 g of 1,6-hexanediol diacrylate, stir evenly, then add 3-5 g of Re / Zr / Fe-O@Cu nanowires coated with initiator prepared in step S4, 5-8 g of graphene, and 6-9 g of hydroxyethyl methacrylate (HEMA). Disperse using a high-speed disperser, store in the dark, and set aside for later use. S7. Pour the mixed solution prepared in step S6 into the resin tank, set the printing parameters, select the model and print. After completion, immerse the photocured resin sample in anhydrous ethanol for 20 minutes, then remove it and store it in the dark for later use.

2. The nanowire array modified acrylate photocurable resin according to claim 1, characterized in that: In step S1, the foamed copper is ultrasonically cleaned with acetone, dilute hydrochloric acid, and anhydrous ethanol for 15 min, and then vacuum dried in a vacuum drying oven for 3 h. The clean and dried foamed copper is then immersed in a 3 M KOH solution for 30 min at a temperature of 35°C, so that the surface of the foamed copper is covered with Cu(OH)2 nanowire arrays. The Cu(OH)2 nanowire arrays are then calcined in an Ar / H2 mixed gas at 150-180°C for 2 h to obtain copper nanowire arrays.

3. The nanowire array modified acrylate photocurable resin according to claim 1 or 2, characterized in that: In step S2, 0.8 g of ammonium perrhenate, 3 g of zirconium nitrate, 0.5 g of ferric chloride, 0.5 g of sodium thiosulfate, and 1 g of sodium citrate are weighed and dissolved in 80 ml of deionized water as an electrolyte for later use.

4. The nanowire array modified acrylate photocurable resin according to claim 3, characterized in that: In step S2, the copper foam CF with copper nanowire array prepared in step S1 is used as the cathode, Pt sheet is used as the anode, and saturated calomel is used as the reference electrode. Electroplating is performed at a potential of -1.8V for 15 min to obtain copper nanowires Re / Zr / Fe-O@Cu / CF grown on copper foam and wrapped with rhenium, zirconium and iron.

5. The nanowire array modified acrylate photocurable resin according to claim 4, characterized in that: In step S3, 15 g of the Re / Zr / Fe-O@Cu / CF prepared in step S2 is taken and placed in 30 ml of anhydrous ethanol solution for ultrasonic treatment for 30 min. The nanowire array is then ultrasonically separated from the copper foam. The ultrasonically treated copper foam sheet is removed, and the liquid is centrifuged and dried to obtain Re / Zr / Fe-O@Cu nanowires.

6. The nanowire array modified acrylate photocurable resin according to claim 4, characterized in that: In step S4, 5 g of 2-hydroxy-2-methylpropanone (PI-1173), 3 g of the Re / Zr / Fe-O@Cu nanowire array prepared in step S3, and 4 g of silica were dispersed in 250 mL of toluene, sonicated for 25 min, and then reacted continuously at 60°C under light for 6 h. The product was filtered, and the sample was washed with toluene and acetone in sequence. After drying, the initiator-coated Re / Zr / Fe-O@Cu nanowires were obtained.

7. The nanowire array modified acrylate photocurable resin according to claim 6, characterized in that: In step S5, 0.3 g of p-methoxyphenol, 55 g of bisphenol A epoxy resin, and 2 g of nano-silica are added to a three-necked flask. 0.7 g of silane coupling agent is added, and the mixture is stirred continuously and heated to 65 °C. 0.3 g of tetraethylammonium bromide and 33 g of acrylic acid are mixed and added dropwise to the three-necked flask. The reaction temperature is controlled at 105 °C, and the reaction is stopped after 3 h to prepare bisphenol A epoxy acrylate.

8. The nanowire array modified acrylate photocurable resin according to claim 7, characterized in that: In step S6, 38 g of bisphenol A epoxy acrylate and 13 g of 1,6-hexanediol diacrylate prepared in step S5 are stirred evenly, and then 4 g of Re / Zr / Fe-O@Cu nanowires coated with initiator prepared in step S4 are added, along with 6 g of graphene and 8 g of hydroxyethyl methacrylate (HEMA). The mixture is dispersed using a high-speed disperser, protected from light, and stored for later use.

9. The nanowire array modified acrylate photocurable resin prepared according to any one of claims 1-8.

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