Impact-resistant tempered glass and preparation method thereof

Abstract

The invention discloses impact-resistant tempered glass and a preparation method thereof, and relates to the field of tempered glass. The preparation method comprises the following steps: treating raw moso bamboos, sequentially performing biological enzyme degumming and bleaching, sulfhydrylation, spinning and spiral superposition to obtain modified spiral bamboo fibers; manufacturing a honeycomb silica gel template by using a photoetching template method, injecting raw materials such as self-made transparent resin and modified spiral bamboo fibers into the template, and performing UV curing to obtain a buffer layer; after plasma gas cleaning and double silane compound coating are carried out on the surface of the tempered glass, hot-pressing compounding is carried out according to a glass-honeycomb buffer layer-glass structure, and the impact-resistant tempered glass is obtained. The impact-resistant toughened glass prepared by the invention has an impact-resistant effect.

Description

Technical Field

[0001] The present invention relates to the technical field of tempered glass, and specifically to an impact-resistant tempered glass and a preparation method thereof. Background Art

[0002] In the fields of architecture, transportation, and electronic devices, tempered glass is widely used. However, existing tempered glass has certain limitations in terms of performance. Traditional tempered glass often relies on increasing thickness to improve impact resistance, which is difficult to meet the current demand for lightweight, and also increases costs and installation difficulties. At the same time, the interfacial bonding strength between the buffer layer and the glass is insufficient, and the buffer layer is prone to peeling failure when subjected to impact, resulting in a significant reduction in the protective performance of the glass. In addition, some petrochemical-based materials used in current buffer layers, such as polyurethane, have poor environmental friendliness and do not meet the requirements of sustainable development. Although electrospinning technology can be used to prepare nanofiber mats and silane coupling agents are also used for glass surface treatment, the existing technology still needs to be optimized in terms of fiber dispersibility, interfacial compatibility, and crosslinking efficiency. Therefore, it is of great significance to develop an impact-resistant tempered glass with high performance, environmental friendliness, and the ability to solve the above problems. Summary of the Invention

[0003] The purpose of the present invention is to provide an impact-resistant tempered glass and a preparation method thereof to solve the problems existing in the prior art.

[0004] To solve the above technical problems, the present invention provides the following technical solution: An impact-resistant tempered glass, and the preparation method of the impact-resistant tempered glass includes the following steps:

[0005] (1) Raw bamboo is subjected to raw material pretreatment to make nanofibers, and the nanofibers are degummed and bleached with a biological enzyme solution, and vacuum dried at -50°C for 12 h to obtain nano transparent bamboo fibers; the nano transparent fibers are thiolated, and at room temperature, the thiolated fibers and mixed solvent 1 are mixed at a mass ratio of 1-2:19 and ultrasonically dispersed at 20 kHz for 30 min, and nanofiber mats are prepared by electrospinning. The fiber mats are stacked layer by layer with rotation, the rotation angle is 15°, after stacking 4-6 layers, hot pressing is carried out at 120°C and 0.5 MPa for 5 min, and vacuum drying is carried out at 60-80°C for 12 h and then pulverized to obtain self-made modified spiral bamboo fiber powder;

[0006] (2) The honeycomb silica template was fabricated by the photolithography template method, coated with silane coupling agent 1 on the surface, cured at 120 °C for 30 min. Polyethylene glycol divinyl ether, polyethylene glycol diacrylate, self-made modified spiral bamboo fiber powder, photoinitiator and mixed solvent 2 were mixed at a mass ratio of 5-7:5-7:3-5:1-2:80-83, ultrasonically dispersed at 200-300 rpm and 20 kHz for 30 min, injected into the silica template, degassed under vacuum at -0.1 MPa for 10 min at room temperature, covered with a glass slide, and pre-cured by UV at 365 nm and 500 mJ / cm 2 for 10 s, and then completely cured by irradiation at 254 nm and 2000 mJ / cm 2 for 30 s to obtain the honeycomb buffer layer;

[0007] (3) After the honeycomb buffer layer was frozen at -50 °C for 30 min, a Teflon thin sheet was inserted into the edge for mechanical peeling of the silica template, ultrasonically cleaned with an organic solvent at 40 kHz for 5 min, washed 2-4 times with deionized water and then dried with nitrogen; the surface of the tempered glass was cleaned by plasma, coated with a double silane coupling agent for compounding, and then hot-pressed at 120 °C and 0.5 MPa for 10 min according to the "glass-honeycomb buffer layer-glass" structure, and cooled to room temperature to obtain the impact-resistant tempered glass.

[0008] Furthermore, the raw material pretreatment in step (1) is as follows: The fresh bamboo was sliced into 2 mm thick slices, and the mass ratio of bamboo to water was 2:1, and then steam exploded at 100 °C and 2.2 MPa for 4 min, and a continuous fiber bundle was obtained by a spiral fiber opening machine at 2000 rpm and a gap of 0.1 mm; the fiber bundle was pulverized by a supersonic airflow pulverizer with an N2 pressure of 0.8 MPa and a nozzle speed of 300 m / s to obtain fibers with a length of 100 nm and a diameter of 50 nm.

[0009] Furthermore, the biological enzyme solution in step (1) is a mixed solution with a pH of 4.5-5.5 at 40-50 °C, 10 U / g of ligninase, and 5 U / g of xylanase.

[0010] Furthermore, the degumming and bleaching treatment in step (1) is as follows: The nanofibers were dispersed in a mixed solution with a pH of 4.5-5.5 at 40-50 °C, 10 U / g of ligninase, and 5 U / g of xylanase, stirred at 200 rpm for 4-8 h, and then centrifuged and washed 2-4 times with deionized water; then bleached with 0.1-0.2 times the mass of the fibers of NaClO2 at 60 °C for 2 h, and freeze-dried at -50 °C to obtain the nano transparent fibers.

[0011] Further, the mercapto group formation in step (1) is as follows: The nano transparent fibers and an ethanol solution of 20 wt% 2-mercaptoacetic acid are mixed at a mass ratio of 1-2:20, and then stirred and reacted at 60°C and 200 rpm for 4-8 h under a nitrogen atmosphere, washed with ethanol 2-4 times, and vacuum dried at 60°C to constant weight.

[0012] Further, the mixed solvent 1 in step (1) is a mixed solvent of polyvinylpyrrolidone, N,N-dimethylformamide, and ethanol at a mass ratio of 1:6:2.

[0013] Further, the silane coupling agent 1 in step (2) is an ethanol solution of 1 wt% heptadecafluorodecyltrimethoxysilane.

[0014] Further, the photolithography template method in step (2) is as follows: After using a Klayout device to draw a regular hexagonal honeycomb, a laser direct writing system is used to expose the pattern point by point at 405 nm and 200 mJ / cm 2 Then, it is spin-coated with PDMS at 2000 rpm and pre-baked at 60°C for 30 min. A Karl Suss MA6 alignment lithography machine is used with a 365 nm high-pressure mercury lamp and 1000 mJ / cm 2 Develop for 5 min with n-butanol, post-bake at 120°C for 2 h. After cooling to room temperature, cut along the edge of the silicon wafer with a scalpel, and use PDMS elastic peeling to obtain a honeycomb-shaped silica template.

[0015] Further, the polyethylene glycol divinyl ether in step (2) has a molecular weight of 400.

[0016] Further, the polyethylene glycol diacrylate in step (2) has a molecular weight of 700.

[0017] Further, the photoinitiator in step (2) is Irgacure 2959.

[0018] Further, the mixed solvent 2 in step (2) is an ethanol aqueous solution with a volume ratio of 1:1.

[0019] Further, the organic solvent in step (3) is a mixed solvent of n-hexane and ethanol with a volume ratio of 3:1.

[0020] Further, the double silane coupling agent compounding in step (3) is as follows: γ-glycidoxypropyltriethoxysilane and 1,2-bis(triethoxysilyl)ethane are mixed at a mass ratio of 1:1, and then the pH is adjusted to 4.5 with glacial acetic acid for hydrolysis, and uniformly coated on the glass surface at a coating amount of 0.1-0.3 mg / cm 2

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0022] The present invention cures self-made modified spiral bamboo fibers and self-made transparent resin into a tempered glass buffer layer to achieve the effect of impact resistance.

[0023] First, the present invention subjects pretreated raw bamboo to a spiral fiber opening device to obtain a fiber bundle. After the fiber bundle is cut into nano-length by a fiber cutting machine, it undergoes bio-enzymatic degumming and bleaching to obtain nano-transparent bamboo fibers. After introducing mercapto groups into the cellulose to form high-density thiol groups, a spiral composite structure imitating the appendage of a mantis shrimp is formed through electrospinning, spiral laying, and interfacial toughening. This can effectively disperse impact energy, prevent crack propagation, and achieve the characteristics of "transparent and tough", endowing the self-made modified bamboo fibers with excellent impact resistance.

[0024] Secondly, a transparent cross-linked resin is formed using polyethylene glycol divinyl ether and polyethylene glycol diacrylate as the main raw materials. Polyethylene glycol divinyl ether, polyethylene glycol diacrylate, self-made modified spiral bamboo fibers, a photoinitiator, and an ethanol aqueous solution are mixed and added to a silica gel template with a micron-scale honeycomb structure prepared by a photolithographic template method. The surface of the template is hydrophobic-treated, and UV curing is carried out. The mercapto group and the double bond of acrylate undergo a click chemical reaction to form a covalent bond; the double bond of acrylate and the double bond of divinyl ether copolymerize under the photoinitiator to form a cross-linked network; the double bond of divinyl ether can also participate in the mercapto reaction to further enhance the network density; after curing, the silica gel template is peeled off to obtain a transparent honeycomb-shaped cross-linked polymer layer, which is placed in the interlayer of tempered glass. The surface of the tempered glass is subjected to plasma cleaning, and after coating with a bis-silane coupling agent, it is hot-pressed and compounded to form a buffer layer. This structure greatly improves the impact resistance through four-level coordination of molecule-nano-micro-macro: the molecular layer is a three-dimensional network structure formed by mercapto-double bond and double bond polymerization, the nano layer is a three-dimensional multi-directional distribution of spiral fiber spring mechanism, the micro layer is a composite structure of honeycomb-fiber, and the macro layer is a "glass-buffer-glass" sandwich structure. And this buffer layer also has good light transmittance, sound insulation, and heat insulation properties. Specific Embodiments

[0025] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

[0026] In order to more clearly illustrate the method provided by the present invention, the following embodiments are used for detailed description. The test methods for each index of the impact-resistant tempered glass manufactured in the following embodiments are as follows:

[0027] Impact resistance test: The prepared tempered glass was made into a square specimen with a size of 500mm×500mm, and the specimen was tested according to GB / T2843-1981 "Test Method for Impact Resistance of Tempered Glass (227g Steel Ball Test)", and the improvement rate of impact resistance was recorded.

[0028] Light transmittance test: The visible light transmittance of the prepared tempered glass in the range of 380 - 780nm was tested with an ultraviolet-visible spectrophotometer.

[0029] Example 1

[0030] (1) Cut the raw bamboo into slices with a thickness of 2mm, and perform steam explosion at 100°C and 2.2MPa for 4min with a water mass ratio of 2:1. Obtain continuous fiber bundles through a spiral fiber opening machine with a speed of 2000rpm and a gap of 0.1mm; obtain nanofibers with a length of 100nm and a diameter of 50nm through a supersonic airflow pulverizer with an N2 pressure of 0.8MPa and a nozzle speed of 300m / s; disperse the nanofibers in a mixed solution at 40°C with a pH of 4.5, 10U / g of ligninase, and 5U / g of xylanase, stir at 200rpm for 4h, and then wash twice with centrifuged deionized water; then bleach with 0.1 times the fiber mass of NaClO2 at 60°C for 2h and vacuum dry at -50°C for 12h to obtain nano transparent bamboo fibers; mix the nano transparent fibers with an ethanol solution of 20wt% 2-mercaptoacetic acid at a mass ratio of 1:20, stir and react at 60°C and 200rpm for 4h under a nitrogen atmosphere, wash twice with ethanol, and vacuum dry at 60°C to constant weight to obtain mercapto-functionalized fibers; at room temperature, mix the mercapto-functionalized fibers with a mixed solvent of polyvinylpyrrolidone, N,N-dimethylformamide, and ethanol at a mass ratio of 1:6:2 at a mass ratio of 1∶19 and ultrasonically disperse at 20kHz for 30min, prepare a nanofiber mat through electrospinning, stack the fiber mats layer by layer with a rotation angle of 15°, after stacking 4 layers, hot press at 120°C and 0.5MPa for 5min, vacuum dry at 60°C for 12h and then pulverize to obtain self-made modified spiral bamboo fiber powder with a particle size of 30nm;

[0031] (2) After drawing a regular hexagon honeycomb with a Klayout device, use a laser direct writing system to expose the pattern point by point at 405nm and 200mJ / cm 2 Spin coat with PDMS at 2000rpm and pre-bake at 60°C for 30min. Use a Karl Suss MA6 alignment photolithography machine with a 365nm high-pressure mercury lamp and 1000mJ / cm 2Develop for 5 min with n-butanol, post-bake at 120 °C for 2 h. After cooling to room temperature, cut along the edge of the silicon wafer with a scalpel. After obtaining a honeycomb-shaped silica template by elastic peeling with PDMS, coat the surface with an ethanol solution of 1 wt% heptadecafluorodecyltrimethoxysilane and cure at 120 °C for 30 min. Mix polyethylene glycol divinyl ether, polyethylene glycol diacrylate, self-made modified spiral bamboo fiber powder, Irgacure 2959 with an ethanol aqueous solution with a volume ratio of 1:1 according to a mass ratio of 5:5:3:1:80, disperse ultrasonically at 200 rpm and 20 kHz for 30 min, inject into the silica template, degas under vacuum at -0.1 MPa at room temperature for 10 min, cover with a glass slide, and perform UV pre-curing at 365 nm and 500 mJ / cm 2 for 10 s, and then irradiate at 254 nm and 2000 mJ / cm 2 for 30 s to completely cure to obtain a honeycomb-shaped buffer layer;

[0032] (3) After freezing the honeycomb-shaped buffer layer at -50 °C for 30 min, insert the edge of a Teflon sheet for mechanical peeling of the silica template, ultrasonically clean with a mixed solvent of n-hexane and ethanol with a volume ratio of 3:1 at 40 kHz for 5 min, wash twice with deionized water and then dry with nitrogen to obtain a buffer layer with a thickness of 0.2 mm; After plasma cleaning the surface of the tempered glass, mix γ-glycidoxypropyltriethoxysilane and 1,2-bis(triethoxysilyl)ethane according to a mass ratio of 1:1, adjust the pH to 4.5 with glacial acetic acid to obtain a hydrolysis solution for glass surface coating, and the coating amount is 0.1 mg / cm 2 , and hot press at 120 °C and 0.5 MPa for 10 min according to the "glass-buffer layer-glass" structure, and cool to room temperature to obtain impact-resistant tempered glass.

[0033] Example 2

[0034] (1) Cut the raw moso bamboo into slices with a thickness of 2 mm, and carry out steam explosion at 100 °C and 2.2 MPa for 4 min with a mass ratio of 2:1 to water. Obtain continuous fiber bundles through a spiral fiber opening machine with a speed of 2000 rpm and a gap of 0.1 mm. Use a supersonic airflow pulverizer with a N₂ pressure of 0.8 MPa and a nozzle speed of 300 m / s to obtain nanofibers with a length of 100 nm and a diameter of 50 nm. Disperse the nanofibers in a mixed solution at 45 °C with a pH of 5.0, 10 U / g of ligninase, and 5 U / g of xylanase, stir at 200 rpm for 6 h, and then wash 3 times with centrifuged deionized water. Then bleach with 0.15 times the mass of the fiber of NaClO₂ at 60 °C for 2 h and vacuum dry at -50 °C for 12 h to obtain nano transparent bamboo fibers. Mix the nano transparent fibers with an ethanol solution of 20 wt% 2-mercaptoacetic acid at a mass ratio of 1.5:20, stir and react at 60 °C and 200 rpm for 6 h in a nitrogen atmosphere, wash 3 times with ethanol, and vacuum dry at 60 °C to constant weight to obtain mercapto-functionalized fibers. At room temperature, mix the mercapto-functionalized fibers with a mixed solvent of polyvinylpyrrolidone, N,N-dimethylformamide, and ethanol with a mass ratio of 1:6:2 at a mass ratio of 1.5∶19 and ultrasonically disperse at 20 kHz for 30 min. Prepare a nanofiber mat by electrospinning. Stack the fiber mats layer by layer with a rotation angle of 15°. After stacking 5 layers, hot press at 120 °C and 0.5 MPa for 5 min, vacuum dry at 70 °C for 12 h, and then crush to obtain self-made modified spiral bamboo fiber powder with a particle size of 30 nm;

[0035] (2) After drawing a regular hexagon honeycomb with a Klayout device, use a laser direct writing system to expose the pattern point by point at 405 nm and 200 mJ / cm 2 Spin coat with PDMS at 2000 rpm and pre-bake at 60 °C for 30 min. Use a Karl Suss MA6 alignment mask aligner with a 365 nm high-pressure mercury lamp and 1000 mJ / cm 2 Develop with n-butanol for 5 min and post-bake at 120 °C for 2 h. After cooling to room temperature, cut along the edge of the silicon wafer with a scalpel, and use the elastic peeling of PDMS to obtain a honeycomb-shaped silica template. Then coat the surface with an ethanol solution of 1 wt% heptadecafluorodecyltrimethoxysilane and cure at 120 °C for 30 min. Mix polyethylene glycol divinyl ether, polyethylene glycol diacrylate, self-made modified spiral bamboo fiber powder, Irgacure 2959 with an ethanol aqueous solution with a volume ratio of 1:1 at a mass ratio of 6:6:4:1.5:82, ultrasonically disperse at 250 rpm and 20 kHz for 30 min, inject into the silica template, degas at -0.1 MPa vacuum at room temperature for 10 min, cover with a glass slide, and carry out UV pre-curing at 365 nm and 500 mJ / cm 2 for 10 s, and then irradiate at 254 nm and 2000 mJ / cm 2 for 30 s to completely cure to obtain a honeycomb-shaped buffer layer;

[0036] (3) After placing the honeycomb buffer layer at -50°C for 30 minutes, insert the edge of a Teflon sheet to mechanically peel the silicone template, and ultrasonically clean it in a mixed solvent of n-hexane and ethanol with a volume ratio of 3:1 at 40 kHz for 5 minutes. Wash it three times with deionized water and then dry it with nitrogen to obtain a buffer layer with a thickness of 0.3 mm. After plasma cleaning the surface of tempered glass, mix γ-glycidoxypropyltriethoxysilane and 1,2-bis(triethoxysilyl)ethane in a mass ratio of 1:1, and adjust the pH to 4.5 with glacial acetic acid to obtain a hydrolysis solution for glass surface coating, with a coating amount of 0.2 mg / cm 2 , and press it at 120°C and 0.5 MPa for 10 minutes according to the "glass-buffer layer-glass" structure, and cool it to room temperature to obtain impact-resistant tempered glass.

[0037] Example 3

[0038] (1) Cut the raw moso bamboo into slices with a thickness of 2 mm, and perform steam explosion at 100°C and 2.2 MPa for 4 minutes with a mass ratio of bamboo to water of 2:1. Obtain continuous fiber bundles through a spiral fiber opening machine with a speed of 2000 rpm and a gap of 0.1 mm. Crush the fiber bundles through a supersonic airflow crusher with an N2 pressure of 0.8 MPa and a nozzle speed of 300 m / s to obtain nanofibers with a length of 100 nm and a diameter of 50 nm. Disperse the nanofibers in a mixed solution at 50°C with a pH of 5.5, 10 U / g of ligninase, and 5 U / g of xylanase, stir at 200 rpm for 8 hours, and then wash 4 times with centrifuged deionized water. Then bleach with 0.2 times the mass of the fiber of NaClO2 at 60°C for 2 hours and vacuum dry at -50°C for 12 hours to obtain nano transparent bamboo fibers. After mixing the nano transparent fibers with an ethanol solution of 20 wt% 2-mercaptoacetic acid in a mass ratio of 2:20, stir and react at 60°C and 200 rpm for 8 hours in a nitrogen atmosphere, wash 4 times with ethanol, and vacuum dry at 60°C to constant weight to obtain mercapto-functionalized fibers. At room temperature, mix the mercapto-functionalized fibers with a mixed solvent of polyvinylpyrrolidone, N,N-dimethylformamide, and ethanol in a mass ratio of 1:6:2 in a mass ratio of 2:19 and ultrasonically disperse at 20 kHz for 30 minutes. Prepare a nanofiber mat by electrospinning, stack the fiber mats layer by layer with a rotation angle of 15°, stack 6 layers, press at 120°C and 0.5 MPa for 5 minutes, vacuum dry at 80°C for 12 hours, and then crush to obtain self-made modified spiral bamboo fiber powder with a particle size of 30 nm;

[0039] (2) After drawing a regular hexagon honeycomb with a Klayout device, use a laser direct writing system to expose the pattern point by point at 405 nm and 200 mJ / cm 2 Spin-coat with PDMS at 2000 rpm and pre-bake at 60°C for 30 minutes. Use a Karl Suss MA6 alignment mask aligner with a 365 nm high-pressure mercury lamp and 1000 mJ / cm 2Develop for 5 min with n-butanol, post-bake at 120 °C for 2 h. After cooling to room temperature, cut along the edge of the silicon wafer with a scalpel. After obtaining a honeycomb-shaped silica template by elastic peeling with PDMS, coat the surface with an ethanol solution of 1 wt% heptadecafluorodecyltrimethoxysilane and cure at 120 °C for 30 min. Mix polyethylene glycol divinyl ether, polyethylene glycol diacrylate, self-made modified spiral bamboo fiber powder, Irgacure 2959 with an ethanol aqueous solution with a volume ratio of 1:1 according to a mass ratio of 7:7:5:2:83, ultrasonically disperse at 300 rpm and 20 kHz for 30 min, inject into the silica template, degas at -0.1 MPa vacuum for 10 min at room temperature, cover with a glass slide, and perform UV pre-curing at 365 nm and 500 mJ / cm 2 for 10 s, and then irradiate at 254 nm and 2000 mJ / cm 2 for 30 s to completely cure to obtain a honeycomb-shaped buffer layer;

[0040] (3) Place the honeycomb-shaped buffer layer in a freezer at -50 °C for 30 min, then insert the edge of a Teflon sheet for mechanical peeling of the silica template, ultrasonically clean with a mixed solvent of n-hexane and ethanol with a volume ratio of 3:1 at 40 kHz for 5 min, wash 4 times with deionized water and then dry with nitrogen to obtain a buffer layer with a thickness of 0.4 mm; After the surface of the tempered glass is cleaned by plasma, mix γ-glycidoxypropyltriethoxysilane and 1,2-bis(triethoxysilyl)ethane according to a mass ratio of 1:1, adjust the pH to 4.5 with glacial acetic acid to obtain a hydrolysis solution for glass surface coating, and the coating amount is 0.3 mg / cm 2 , and hot press at 120 °C and 0.5 MPa for 10 min according to the "glass-buffer layer-glass" structure, and cool to room temperature to obtain impact-resistant tempered glass.

[0041] Comparative Example 1

[0042] The difference between Comparative Example 1 and Example 2 lies in step (1), that is, the continuous fiber bundle is not made into nanofibers by a supersonic airflow pulverizer, and the remaining steps are the same as those in Example 2.

[0043] Comparative Example 2

[0044] The difference between Comparative Example 2 and Example 2 lies in step (1), that is, the nanofibers are not subjected to bio-enzymatic degumming and bleaching, and the remaining steps are the same as those in Example 2.

[0045] Comparative Example 3

[0046] The difference between Comparative Example 3 and Example 2 lies in step (1), that is, the nano transparent fibers are not mercapto-functionalized, and the remaining steps are the same as those in Example 2.

[0047] Comparative Example 4

[0048] The difference between Comparative Example 4 and Example 2 lies in step (1), specifically, the nanofiber mat is not stacked layer by layer in a rotating manner, and the remaining steps are the same as those in Example 2.

[0049] Comparative Example 5

[0050] The difference between Comparative Example 5 and Example 2 lies in step (2). Specifically, in step (2), polyethylene glycol divinyl ether, polyethylene glycol diacrylate, self-made modified spiral bamboo fiber powder, Irgacure 2959, and an ethanol aqueous solution with a volume ratio of 1:1 are mixed at a mass ratio of 6:6:4:1.5:82, ultrasonically dispersed at 250 rpm and 20 kHz for 30 min, injected into a template, and after vacuum degassing at -0.1 MPa for 10 min at room temperature, a glass slide is covered, and after UV pre-curing at 365 nm and 500 mJ / cm 2 for 10 s, and then irradiated at 254 nm and 2000 mJ / cm 2 for 30 s to obtain a complete cured buffer layer, and the remaining steps are the same as those in Example 2.

[0051] Comparative Example 6

[0052] The difference between Comparative Example 6 and Example 2 lies in step (2). Specifically, polyethylene glycol divinyl ether is not added, and the remaining steps are the same as those in Example 2.

[0053] Comparative Example 7

[0054] The difference between Comparative Example 7 and Example 2 lies in step (2). Specifically, polyethylene glycol diacrylate is not added, and the remaining steps are the same as those in Example 2.

[0055] Comparative Example 8

[0056] The difference between Comparative Example 8 and Example 2 lies in step (2). Specifically, self-made modified spiral bamboo fiber powder is not added, and the remaining steps are the same as those in Example 2.

[0057] Comparative Example 9

[0058] The difference between Comparative Example 9 and Example 2 lies in step (3). Specifically, the bis-silane coupling agent is not coated, and the remaining steps are the same as those in Example 2.

[0059] Comparative Example 10

[0060] The difference between Comparative Example 10 and Example 2 is that tempered glass with twice the thickness of the tempered glass layer in Example 2 is selected as the blank group.

[0061] The performance analysis results of the impact-resistant tempered glass using Examples 1 to 3 and Comparative Examples 1 to 10 of the present invention are given in Table 1 below.

[0062] Table 1

[0063]

[0064]

[0065] From the comparison of the experimental data of the impact resistance improvement rate between the examples and the comparative examples, it can be found that after mixing the self-made modified spiral bamboo fibers with the self-made transparent resin and injecting them into a honeycomb silica gel template to obtain a buffer layer, the surface of the tempered glass is subjected to plasma cleaning, coated with a bis-silane coupling agent, and then hot-pressed and compounded according to the structure of "glass-buffer layer-glass" to obtain the tempered glass. This structure realizes a great improvement in impact resistance through the four-level coordination of molecule-nano-micro-macro: the molecular layer is a three-dimensional network structure formed by the polymerization of mercapto-double bonds and double bonds, the nano-layer is a three-dimensional multi-directional spiral fiber spring mechanism, the micro-layer is a composite structure of honeycomb-fiber, and the macro-layer is a "glass-buffer-glass" sandwich structure; from the comparison of the experimental data of the visible light transmittance between the examples and the comparative examples, it can be found that the transparent nano-bamboo fibers obtained by pretreating raw bamboo and then performing bio-enzymatic degumming and bleaching have good light transmittance, and in the coexistence of the self-made transparent resin and a small amount of bis-silane coupling agent, there is no obvious influence on the light transmittance of the tempered glass, and it still has a very high light transmittance performance.

[0066] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be construed as limiting the claimed rights.

Claims

1. An impact-resistant tempered glass, characterized in that, It includes the following steps: (1) Pretreat raw moso bamboo to make nanofibers, degum and bleach the nanofibers with a biological enzyme solution, and vacuum dry at -50°C for 12 h to obtain nano transparent bamboo fibers; subject the nano transparent fibers to mercapto group modification, mix the mercapto group modified fibers with mixed solvent 1 at a mass ratio of 1-2:19 at room temperature and ultrasonically disperse for 30 min at 20 kHz, prepare a nanofiber mat by electrospinning, stack the fiber mats layer by layer with a rotation angle of 15°, after stacking 4-6 layers, hot press at 120°C and 0.5 MPa for 5 min, vacuum dry at 60-80°C for 12 h and then pulverize to obtain self-made modified spiral bamboo fiber powder; (2) Fabricate a honeycomb silica gel template using the photolithography template method, coat the surface with silane coupling agent 1, cure at 120 °C for 30 min, mix polyethylene glycol divinyl ether, polyethylene glycol diacrylate, self-made modified spiral bamboo fiber powder, photoinitiator and mixed solvent 2 in a mass ratio of 5 - 7:5 - 7:3 - 5:1 - 2:80 - 83, disperse ultrasonically at 200 - 300 rpm and 20 kHz for 30 min, inject into the silica gel template, after vacuum degassing at -0.1 MPa for 10 min at room temperature, cover with a glass slide, and perform UV pre-curing at 365 nm and 500 mJ / cm 2 for 10 s, and then irradiate at 254 nm and 2000 mJ / cm 2 for 30 s to obtain a completely cured honeycomb buffer layer; (3) Place the honeycomb buffer layer at -50°C and freeze for 30 min, insert the edge of a Teflon sheet to mechanically peel the silicone template, ultrasonically clean with an organic solvent at 40 kHz for 5 min, wash with deionized water 2-4 times and then dry with nitrogen; after plasma cleaning the surface of tempered glass, coat with a double silane coupling agent for compounding, and then press at 120°C and 0.5 MPa for 10 min according to the structure of "glass-honeycomb buffer layer-glass", and cool to room temperature to obtain impact-resistant tempered glass.

2. The impact-resistant toughened glass according to claim 1, wherein The biological enzyme solution described in step (1) is a mixed solution with a pH of 4.5-5.5 at 40-50°C, 10 U / g of lignin enzyme, and 5 U / g of xylanase.

3. An impact-resistant tempered glass according to claim 1, wherein, The mixed solvent 1 described in step (1) is a mixed solvent of polyvinylpyrrolidone, N,N-dimethylformamide, and ethanol at a mass ratio of 1:6:

2.

4. An impact-resistant tempered glass according to claim 1, characterized in that, The silane coupling agent 1 described in step (2) is an ethanol solution of 1 wt% heptadecafluorodecyltrimethoxysilane.

5. An impact-resistant tempered glass according to claim 1, characterized in that, The polyethylene glycol divinyl ether described in step (2) has a molecular weight of 400-600.

6. An impact-resistant tempered glass according to claim 1, characterized in that, The polyethylene glycol diacrylate described in step (2) has a molecular weight of 400-700.

7. An impact-resistant tempered glass according to claim 1, characterized in that, The photoinitiator described in step (2) is Irgacure 2959.

8. An impact-resistant tempered glass according to claim 1, characterized in that, The mixed solvent 2 described in step (2) is an ethanol aqueous solution with a volume ratio of 1:

1.

9. An impact-resistant tempered glass according to claim 1, wherein, The organic solvent described in step (3) is a mixed solvent of n-hexane and ethanol with a volume ratio of 3:

1.

10. An impact-resistant tempered glass according to claim 1, characterized in that, The double silane coupling agent described in step (3) is γ-glycidoxypropyltriethoxysilane and 1,2-bis(triethoxysilyl)ethane.

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