Production method of nano-silicon composite fireproof glass

Abstract

The invention discloses a production method of nano-silicon composite fireproof glass, which comprises the following steps: compounding amino nano-silicon dioxide with a modified zinc-aluminum flame retardant to prepare a coated silicon-based filler, and compounding the coated silicon-based filler with nickel-titanium bimetal MOF to obtain a composite silicon-based flame-retardant filler; the preparation method comprises the following steps: mixing a mixed solution of silica sol, water-soluble silicone oil, a composite silicon-based flame-retardant filler, potassium hydroxide and sodium hydroxide with ethylene glycol, filling laminated glass with the mixed solution, and sealing and curing to obtain the nano-silicon composite fireproof glass. The nano-silicon composite fireproof glass has high light transmittance and high fire resistance, the zinc-aluminum flame retardant and the nickel-titanium bimetal MOF which have flame retardance are compounded on the nano-silicon dioxide to obtain a composite silicon-based flame-retardant filler, and the zinc-aluminum flame retardant and the nickel-titanium bimetal MOF generate a synergistic effect through compounding of a multi-layer core-shell structure, so that the flame-retardant performance of the nano-silicon composite fireproof glass is improved, and the flame-retardant performance of the nano-silicon composite fireproof glass is improved. The flame-retardant and fire-resistant performance of the composite silicon-based flame-retardant filler is improved, and the influence of the flame retardant on the light transmission of the nano-silicon composite fireproof glass is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of glass manufacturing, relates to fireproof glass, and specifically relates to a production method of nano-silicon composite fireproof glass. Background Art

[0002] Fireproof glass is a measure-type fireproof material. It is a special glass that has been processed and treated with special technology and can maintain its integrity and even have heat-insulating properties in the prescribed fire resistance test. Fireproof glass can be divided into laminated composite fireproof glass, grouting fireproof glass, wired fireproof glass, special fireproof glass, hollow fireproof glass, high-strength single-layer cesium potassium fireproof glass, etc. according to its composition and preparation process; nano-silicon fireproof glass is a fireproof glass with high-performance silicon-based materials as the core. It has excellent fire resistance and light transmittance. It is widely used in the field of building fire protection. Its core advantage lies in its excellent thermal insulation effect and stable optical properties.

[0003] Patent CN109824280A discloses a layered composite fireproof glass based on a multi-component fireproof adhesive, which is composed of three layers of glass sheets and two layers of fireproof adhesive. By preparing a fireproof adhesive A containing a hydrotalcite / silicon composite sol and a fireproof adhesive B containing carbon nanotube / alumina core-shell fiber, the prepared fireproof glass has high strength and good fireproof performance; however, the five-layer composite fireproof glass has poor light transmittance and high application limitations.

[0004] Patent CN116903265A discloses a method for preparing high borosilicate fireproof glass, which effectively improves the heat resistance stability and resistance to drastic temperature changes by subjecting the pretreated substrate to two plasma treatments and filling the pretreated substrate with a composite fireproof liquid after heat treatment and rapid cooling. However, the single filler nano-silicon dioxide in the composite fireproof liquid in this scheme is prone to agglomeration, and after agglomeration, it is easy to settle under the action of gravity in the composite fireproof liquid, affecting the fire resistance of the composite fireproof liquid. Summary of the invention

[0005] The purpose of the present invention is to solve the problem that the fireproof performance of the heat-resistant filler in the fireproof intermediate layer of the composite fireproof glass is insufficient and the excessive addition affects the light transmittance of the fireproof glass, and to provide a production method for nano-silicon composite fireproof glass.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A method for producing nano-silicon composite fire-proof glass comprises the following steps: Step 1: Ultrasonic disperse amino nano-silica in deionized water in a reactor, add 50wt% glutaraldehyde, stir and react for 1-2h, then add modified zinc-aluminum flame retardant and stir and react for 20-24h, wash the precipitate after centrifugation, and vacuum dry to obtain the coated silicon-based filler.

[0007] Step 2: Ultrasonic disperse the coated silicon-based filler in deionized water in a reactor, add 50wt% glutaraldehyde, stir and react for 1-2h, then add nickel-titanium bimetallic MOF, stir and react for 20-24h, wash the precipitate after centrifugation, and vacuum dry to obtain a composite silicon-based flame retardant filler.

[0008] Step 3: Heat 45-50% silica sol to 40-45°C in a reactor, stir magnetically at 10-15rpm for 10-15min, add water-soluble silicone oil to the reactor and continue stirring for 10-15min, then add composite silicon-based flame retardant filler, stir and react for 10-15min, add 1M potassium hydroxide and 1M sodium hydroxide in equal volumes to obtain a mixed solution, heat to 70-80°C, stir at 40-50rpm for 50-60min, add ethylene glycol, stir for 10-15min, pour into laminated glass, seal the laminated glass with butyl tape, fill the gap next to the butyl tape with silicone tape, dry and cure at 70-80°C in a drying oven for 2-3h to obtain nano-silicon composite fireproof glass.

[0009] Furthermore, in step 1, the dosage ratio of amino nano-silica, deionized water, glutaraldehyde and modified zinc-aluminum flame retardant is 20-30g: 300-500mL: 50-60mL: 10-15g.

[0010] Furthermore, in step 2, the usage ratio of the coated silicon-based filler, deionized water, glutaraldehyde and nickel-titanium bimetallic MOF is 20-30 g: 300-500 mL: 50-60 mL: 10-15 g.

[0011] Furthermore, in step three, the dosage ratio of silica sol, water-soluble silicone oil, composite silicon-based flame retardant filler, mixed liquid and ethylene glycol is 60-65g: 8-10g: 5-7g: 15-20mL: 5-6mL.

[0012] Further, amino nano-silica is prepared by the following steps: In a reaction kettle, hexadecyltrimethylammonium bromide was dissolved in deionized water, 0.2M sodium hydroxide aqueous solution was added, the mixture was stirred and heated to 70-80°C, ethyl orthosilicate was added and reacted for 15-20min, (3-aminopropyl)triethoxysilane was added, the reaction was stirred for 2-3h, the precipitate was collected by centrifugation, washed, and dried in vacuo to obtain amino nano-silica.

[0013] Furthermore, the usage ratio of hexadecyltrimethylammonium bromide, deionized water, sodium hydroxide aqueous solution, ethyl orthosilicate and (3-aminopropyl)triethoxysilane is 10-12 g: 1.8-2 L: 300-500 mL: 50-100 mL: 10-20 mL.

[0014] Furthermore, the modified zinc-aluminum flame retardant is prepared by the following steps: In a reaction kettle, tannic acid is dissolved in a 1M sodium hydroxide aqueous solution, zinc nitrate hexahydrate and aluminum nitrate nonahydrate are dissolved in deionized water, and then dripped into the reaction kettle drop by drop under stirring conditions. During the dripping process, the pH value in the reaction kettle is controlled to be 11-11.5 with a 1M sodium hydroxide solution, and the temperature of the reaction kettle is 50-60° C. After the dripping is completed, the stirring reaction is continued for 40-60 minutes, the temperature is raised to 70-80° C. and the stirring reaction is carried out for 16-18 hours, the precipitate is washed after centrifugation, and vacuum drying is performed to obtain a modified zinc-aluminum flame retardant.

[0015] Furthermore, the usage ratio of tannic acid, sodium hydroxide aqueous solution, zinc nitrate hexahydrate, aluminum nitrate nonahydrate and deionized water is 12-20 g: 200-300 mL: 12-15 g: 8-12 g: 500-600 mL.

[0016] Further, the nickel-titanium bimetallic MOF is prepared by the following steps: In a reaction kettle, 2-aminophthalic acid, titanium isopropoxide and nickel nitrate hexahydrate are mixed in a mixed solution of N,N-dimethylacetamide and methanol, ultrasonically dispersed for 10-20 minutes, then heated to 150-160°C for reaction for 20-24 hours, washed and precipitated after centrifugation, and dried to obtain a nickel-titanium bimetallic MOF.

[0017] Furthermore, the usage ratio of 2-aminophthalic acid, titanium isopropoxide, nickel nitrate hexahydrate, N,N-dimethylacetamide and methanol is 7-9 g: 40-50 mL: 11-12 g: 700-800 mL: 300-400 mL.

[0018] Beneficial effects of the present invention: (1) The nano-silicon composite fireproof glass produced by the production method of the present invention has high light transmittance and high fire resistance. The composite silicon-based flame retardant filler is obtained by compounding a zinc-aluminum flame retardant and a nickel-titanium bimetallic MOF with flame retardant ability on nano-silicon dioxide. The zinc-aluminum flame retardant and the nickel-titanium bimetallic MOF produce a synergistic effect through a multi-layer core-shell structure, thereby improving the flame retardant and fire resistance of the composite silicon-based flame retardant filler, reducing the amount of flame retardant added, and reducing the influence of the flame retardant on the light transmittance of the nano-silicon composite fireproof glass.

[0019] (2) The present invention modifies the surface of zinc-aluminum flame retardant by tannic acid, grafts the modified zinc-aluminum flame retardant onto the surface of amino nano-silica, and uses the modified zinc-aluminum flame retardant as a connecting layer to graft and composite the nickel-titanium bimetallic MOF onto the surface of the zinc-aluminum flame retardant. The obtained composite silicon-based flame retardant filler has good flame retardant and fire resistant properties, is evenly dispersed in silica sol, and has little effect on the light transmittance of nano-silicon composite fireproof glass. DETAILED DESCRIPTION

[0020] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Embodiment 1: A method for producing nano-silicon composite fire-resistant glass, comprising the following steps: S1. Dissolve 10 g of hexadecyltrimethylammonium bromide in 1.8 L of deionized water in a reactor, add 300 mL of 0.2 M sodium hydroxide aqueous solution, stir and mix, heat to 70 ° C, add 50 mL of tetraethyl orthosilicate and react for 15 min, then add 10 mL of (3-aminopropyl)triethoxysilane, stir and react for 2 h, collect the precipitate after centrifugation at 7000 rpm for 5 min, mix 300 mL of 40 wt% hydrochloric acid solution with 5 L of methanol to obtain a hydrochloric acid methanol solution, wash with hydrochloric acid methanol solution, methanol and deionized water respectively, and dry in vacuo at 70 ° C for 20 h to obtain amino nano-silica.

[0022] S2. In a reactor, 7 g of 2-aminophthalic acid, 40 mL of titanium isopropoxide and 11 g of nickel nitrate hexahydrate were mixed in a mixed solution of 700 mL of N,N-dimethylacetamide and 300 mL of methanol, and ultrasonically dispersed for 10 min. The mixture was then heated to 150°C and reacted for 20 h. After centrifugation at 6000 rpm, the precipitate was washed with N,N-dimethylacetamide and vacuum dried at 70°C for 8 h to obtain a nickel-titanium bimetallic MOF.

[0023] S3. Dissolve 12 g of tannic acid in 200 mL of 1 M sodium hydroxide aqueous solution in a reactor, dissolve 12 g of zinc nitrate hexahydrate and 8 g of aluminum nitrate nonahydrate in 500 mL of deionized water, and drip them dropwise into the reactor under stirring. During the dripping process, the pH value in the reactor is controlled to be 11 with 1 M sodium hydroxide solution, and the temperature of the reactor is 50° C. After the dripping is completed, continue to stir the reaction for 40 min, heat to 70° C. and stir the reaction for 16 h. After centrifugation at 6000 rpm, wash the precipitate with deionized water, and vacuum dry at 70° C. for 8 h to obtain a modified zinc-aluminum flame retardant.

[0024] S4. In a reactor, 20 g of amino nano-silica was ultrasonically dispersed in 300 mL of deionized water, 50 mL of 50 wt% glutaraldehyde was added, the reaction was stirred for 1 h, and then 10 g of modified zinc-aluminum flame retardant was added and the reaction was stirred for 20 h. After centrifugation, the precipitate was washed with deionized water, and vacuum dried at 40 ° C for 8 h to obtain a coated silicon-based filler; In a reactor, 20 g of the coated silicon-based filler was ultrasonically dispersed in 300 mL of deionized water, 50 mL of 50 wt% glutaraldehyde was added, the reaction was stirred for 1 h, and then 10 g of nickel-titanium bimetallic MOF was added, the reaction was stirred for 20 h, the precipitate was washed with deionized water after centrifugation, and vacuum dried at 40 ° C for 8 h to obtain a composite silicon-based flame retardant filler.

[0025] S5. Heat 60g of 45% silica sol to 40°C in a reactor, stir magnetically at 10rpm for 10min, add 8g of water-soluble silicone oil to the reactor and continue stirring for 10min, then add 5g of composite silicon-based flame retardant filler, stir and react for 10min, then add 15mL of an equal volume mixture of 1M potassium hydroxide and 1M sodium hydroxide, heat to 70°C, stir at 40rpm for 50min, add 5mL of ethylene glycol, stir for 10min, then pour into laminated glass, seal the laminated glass with butyl tape, fill the gap next to the butyl tape with silicone tape, dry and cure at 70°C in a drying oven for 2h to obtain nano-silicon composite fireproof glass.

[0026] Embodiment 2: A method for producing nano-silicon composite fire-resistant glass, comprising the following steps: S1. Dissolve 11 g of hexadecyltrimethylammonium bromide in 1.9 L of deionized water in a reactor, add 400 mL of 0.2 M sodium hydroxide aqueous solution, stir and mix, heat to 75 ° C, add 75 mL of ethyl orthosilicate and react for 17 min, then add 15 mL of (3-aminopropyl)triethoxysilane, stir and react for 2.5 h, collect the precipitate after centrifugation at 7500 rpm for 6 min, mix 400 mL of 40 wt% hydrochloric acid solution with 5.5 L of methanol to obtain a hydrochloric acid methanol solution, wash with hydrochloric acid methanol solution, methanol and deionized water respectively, and dry under vacuum at 75 ° C for 22 h to obtain amino nano-silica.

[0027] S2. In a reactor, 8 g of 2-aminophthalic acid, 45 mL of titanium isopropoxide and 11.5 g of nickel nitrate hexahydrate were mixed in a mixed solution of 750 mL of N,N-dimethylacetamide and 350 mL of methanol, and ultrasonically dispersed for 15 min. The temperature was then raised to 155° C. for reaction for 22 h. After centrifugation at 6500 rpm, the precipitate was washed with N,N-dimethylacetamide and vacuum dried at 75° C. for 9 h to obtain a nickel-titanium bimetallic MOF.

[0028] S3. In a reactor, 16 g of tannic acid was dissolved in 250 mL of 1 M sodium hydroxide aqueous solution. 13.5 g of zinc nitrate hexahydrate and 10 g of aluminum nitrate nonahydrate were dissolved in 550 mL of deionized water and then added dropwise into the reactor under stirring. During the addition, the pH value in the reactor was controlled to be 11.2 with 1 M sodium hydroxide solution. The temperature of the reactor was 55° C. After the addition was completed, the reaction was continued to be stirred for 50 min. The temperature was raised to 75° C. and the reaction was stirred for 17 h. After centrifugation at 6500 rpm, the precipitate was washed with deionized water and dried in vacuo at 75° C. for 9 h to obtain a modified zinc-aluminum flame retardant.

[0029] S4. In a reactor, 25 g of amino nano-silica was ultrasonically dispersed in 400 mL of deionized water, 55 mL of 50 wt% glutaraldehyde was added, the reaction was stirred for 1.5 h, and then 12.5 g of modified zinc-aluminum flame retardant was added and the reaction was stirred for 22 h. After centrifugation, the precipitate was washed with deionized water, and vacuum dried at 45 ° C for 9 h to obtain a coated silicon-based filler; In a reactor, 25 g of the coated silicon-based filler was ultrasonically dispersed in 400 mL of deionized water, 55 mL of 50 wt% glutaraldehyde was added, the reaction was stirred for 1.5 h, and then 12.5 g of nickel-titanium bimetallic MOF was added, the reaction was stirred for 22 h, the precipitate was washed with deionized water after centrifugation, and vacuum dried at 45 ° C for 9 h to obtain a composite silicon-based flame retardant filler.

[0030] S5. Heat 62.5 g of 47% silica sol to 42.5°C in a reactor, stir magnetically at 13 rpm for 12.5 min, add 9 g of water-soluble silicone oil to the reactor and continue stirring for 12.5 min, then add 6 g of composite silicon-based flame retardant filler, stir and react for 12.5 min, then add 17.5 mL of an equal volume mixture of 1 M potassium hydroxide and 1 M sodium hydroxide, heat to 75°C, stir at 45 rpm for 55 min, add 5.5 mL of ethylene glycol, stir for 12.5 min, then pour into laminated glass, seal the laminated glass with butyl tape, fill the gap next to the butyl tape with silicone tape, dry and cure at 75°C in a drying oven for 2.5 h to obtain nano-silicon composite fireproof glass.

[0031] Embodiment 3: A method for producing nano-silicon composite fire-resistant glass, comprising the following steps: S1. Dissolve 12 g of hexadecyltrimethylammonium bromide in 2 L of deionized water in a reactor, add 500 mL of 0.2 M sodium hydroxide aqueous solution, stir and mix, heat to 80 ° C, add 100 mL of ethyl orthosilicate and react for 20 min, then add 20 mL of (3-aminopropyl)triethoxysilane, stir and react for 3 h, collect the precipitate after centrifugation at 8000 rpm for 7 min, mix 500 mL of 40 wt% hydrochloric acid solution with 6 L of methanol to obtain a hydrochloric acid methanol solution, wash with hydrochloric acid methanol solution, methanol and deionized water respectively, and dry in vacuo at 80 ° C for 24 h to obtain amino nano-silica.

[0032] Nano-silica is prepared by a solvent-gel method, and a surfactant, hexadecyltrimethylammonium bromide, is used to graft a silane coupling agent (3-aminopropyl) triethoxysilane onto the surface of the nano-silica to obtain amino nano-silica.

[0033] S2. In a reactor, 9 g of 2-aminophthalic acid, 50 mL of titanium isopropoxide and 12 g of nickel nitrate hexahydrate were mixed in a mixed solution of 800 mL of N,N-dimethylacetamide and 400 mL of methanol, and ultrasonically dispersed for 20 min. The mixture was then heated to 160° C. and reacted for 24 h. After centrifugation at 7000 rpm, the precipitate was washed with N,N-dimethylacetamide and vacuum dried at 80° C. for 10 h to obtain a nickel-titanium bimetallic MOF.

[0034] A nickel-titanium bimetallic MOF containing a small amount of titanium is synthesized through a one-pot method. Titanium can be added as an active metal to the formation of metal oxides, thereby promoting the improvement of the flame retardant ability of the nickel-titanium bimetallic MOF.

[0035] S3. Dissolve 20 g of tannic acid in 300 mL of 1 M sodium hydroxide aqueous solution in a reactor, dissolve 15 g of zinc nitrate hexahydrate and 12 g of aluminum nitrate nonahydrate in 600 mL of deionized water, and drip them dropwise into the reactor under stirring. During the dripping process, the pH value in the reactor is controlled to be 11.5 with 1 M sodium hydroxide solution, and the temperature of the reactor is 60° C. After the dripping is completed, the stirring reaction is continued for 60 min, the temperature is raised to 80° C. and the stirring reaction is carried out for 18 h. After centrifugation at 7000 rpm, the precipitate is washed with deionized water, and vacuum dried at 80° C. for 10 h to obtain a modified zinc-aluminum flame retardant.

[0036] Zinc-aluminum hydrotalcite is generated as a flame retardant by a coprecipitation method, and tannic acid groups are grafted onto the surface of the zinc-aluminum flame retardant by adding tannic acid modification during the coprecipitation process.

[0037] S4. Ultrasonic disperse 30 g of amino nano-silica in 500 mL of deionized water in a reactor, add 60 mL of 50 wt% glutaraldehyde, stir to react for 2 h, then add 15 g of modified zinc-aluminum flame retardant and stir to react for 24 h, wash the precipitate with deionized water after centrifugation, and vacuum dry at 50 ° C for 10 h to obtain a coated silicon-based filler; Ultrasonic disperse 30 g of coated silicon-based filler in 500 mL of deionized water in a reactor, add 60 mL of 50 wt% glutaraldehyde, stir to react for 2 h, then add 15 g of nickel-titanium bimetallic MOF, stir to react for 24 h, wash the precipitate with deionized water after centrifugation, and vacuum dry at 50 ° C for 10 h to obtain a composite silicon-based flame retardant filler.

[0038] The tannic acid groups on the surface of the modified zinc-aluminum flame retardant were used as a connection. Under the cross-linking action of glutaraldehyde, the modified zinc-aluminum flame retardant and the nickel-titanium bimetallic MOF in the ligand were coated layer by layer on the surface of amino nano-silica by utilizing the addition and cross-linking reactions of amino groups and glutaraldehyde, and glutaraldehyde and tannic acid, to form a composite silicon-based flame retardant filler with the core of amino nano-silica, the inner shell of the modified zinc-aluminum flame retardant, and the outer shell of the nickel-titanium bimetallic MOF.

[0039] When nickel-titanium bimetallic MOF is used alone as a nano flame retardant, the nickel-titanium bimetallic MOF undergoes a chemical reaction after flame retardant combustion to produce metal oxides, thereby promoting carbonization to form a flame retardant layer. However, the gaps left by the thermal decomposition of nickel-titanium bimetallic MOF in the polymer will accelerate the transfer of heat, and the flame retardant effect is not good. The flame retardant effect is improved by coating the nickel-titanium bimetallic MOF with a modified zinc-aluminum flame retardant. The oxide layer formed by the modified zinc-aluminum flame retardant will further block the transfer of heat. The zinc-aluminum flame retardant and nickel-titanium bimetallic MOF will also form aluminum-nickel composite metal compounds at high temperatures, further enhancing the flame retardant effect of the composite silicon-based flame retardant filler. At the same time, the tannic acid groups between the nickel-titanium bimetallic MOF and the modified zinc-aluminum flame retardant will carbonize and expand, thereby compensating for the volume loss caused by the decomposition of the nickel-titanium bimetallic MOF and slowing down the transfer of heat. The core layer structure composed of amino nano-silica also has flame retardant properties. The core, inner layer and outer layer materials of the composite silicon-based flame retardant filler produce a synergistic effect to improve the flame retardant ability. The surface of the composite silicon-based flame retardant filler contains amino groups, which improves the compatibility with silica sol, reduces the agglomeration of the composite silicon-based flame retardant filler in silica sol, and reduces the influence of the composite silicon-based flame retardant filler on the light transmittance of nano-silicon composite fire-resistant glass.

[0040] S5. Heat 65g of 50% silica sol to 45°C in a reactor, stir magnetically at 15rpm for 15min, add 10g of water-soluble silicone oil to the reactor and continue stirring for 15min, then add 7g of composite silicon-based flame retardant filler, stir and react for 15min, then add 20mL of an equal volume mixture of 1M potassium hydroxide and 1M sodium hydroxide, heat to 80°C, stir at 50rpm for 60min, add 6mL of ethylene glycol, stir for 15min, then pour into laminated glass, seal the laminated glass with butyl tape, fill the gap next to the butyl tape with silicone tape, dry and cure at 80°C in a drying oven for 3h to obtain nano-silicon composite fireproof glass.

[0041] Comparative Example 1: The difference from Example 1 is that titanium isopropoxide is not added to S2 to prepare nickel MOF, and nickel MOF is used to replace nickel-titanium bimetallic MOF to prepare nano-silicon composite fire-resistant glass.

[0042] Comparative Example 2: The difference from Example 1 is that in S3, tannic acid is not added to prepare the zinc-aluminum flame retardant, and the zinc-aluminum flame retardant is used to replace the modified zinc-aluminum flame retardant to prepare the nano-silicon composite fire-proof glass.

[0043] Comparative Example 3: The difference from Example 1 is that S2 is: 7 g of 2-aminophthalic acid, 40 mL of titanium isopropoxide, 11 g of nickel nitrate hexahydrate and 20 g of nano-silica are mixed in a mixed solution of 700 mL of N,N-dimethylacetamide and 300 mL of methanol in a reactor, ultrasonically dispersed for 10 min, then heated to 150°C for reaction for 20 h, centrifuged at 6000 rpm, washed with N,N-dimethylacetamide, and dried to obtain nano-silica coated with nickel-titanium bimetallic MOF.

[0044] S4 is, in a reactor, 30g of nano-silica coated with nickel-titanium bimetallic MOF is ultrasonically dispersed in 300mL of deionized water, 50mL of 50wt% glutaraldehyde is added, the reaction is stirred for 1h, and then 10g of modified zinc-aluminum flame retardant is added and the reaction is stirred for 20h. After centrifugation, the precipitate is washed with deionized water and vacuum dried at 40°C for 8h to obtain a composite silicon-based flame retardant filler.

[0045] Nano-silicon composite fireproof glass is prepared by using the composite silicon-based flame-retardant filler.

[0046] The performance test was performed on the nano-silicon composite fireproof glass samples prepared in Example 1 to Example 3 and Comparative Example 1 to Comparative Example 3. The glass sample size was 200 mm × 80 mm × 15 mm, and the interlayer thickness was 5 mm. The sample was placed on a BTR-1S visible light transmittance / reflectance tester for transmittance test. The test was performed under light-proof conditions. The transmittance test method was in accordance with the standard GB15763.1-2009. The fire resistance of the glass sample was tested in accordance with the standard GB / T 12513-2006. The temperature was increased at a heating rate of 5°C / min, and the time for the single point temperature on the back of the glass sample to reach 180°C or the average temperature to reach 140°C was measured. The results are shown in Table 1: Table 1 Test results of light transmittance and fire resistance of glass samples

[0047] It can be seen from Table 1 that the nano-silicon composite fire-proof glass prepared by the present invention has high light transmittance and a fire-resistant time of more than 120 minutes, indicating that the composite silicon-based flame-retardant filler of the present invention is well dispersed, has little effect on light transmittance, and has good fire-resistant performance; in Comparative Example 1, since titanium element is not incorporated into the nickel MOF structure, the activity of the composite silicon-based flame-retardant filler prepared is low, and the rate of generating metal oxide is slow, so the fire-resistant time is lower than that of Examples 1 to 3; in Comparative Example 2, since tannic acid is not used to modify the zinc-aluminum flame retardant, the bonding force between the composite silicon-based flame-retardant fillers prepared is poor, and it is easy to fall off and produce when preparing the nano-silicon composite fire-proof glass. Agglomeration affects the transmittance, and the synergistic effect of the flame retardant filler is lost, and the fire resistance time is also greatly reduced; in Comparative Example 3, the nickel-titanium bimetallic MOF is directly generated in situ on the surface of nano-silica, and then the modified zinc-aluminum flame retardant is compounded on the nano-silica coated with the nickel-titanium bimetallic MOF by the grafting effect of glutaraldehyde. However, since the nickel-titanium bimetallic MOF is between the nano-silica and the modified zinc-aluminum flame retardant, and the decomposition temperature of the nickel-titanium bimetallic MOF is lower than that of the modified zinc-aluminum flame retardant, the gaps generated after the decomposition of the nickel-titanium bimetallic MOF can easily cause the modified zinc-aluminum flame retardant to fall off, thereby reducing the fire resistance time of Comparative Example 3.

[0048] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0049] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for producing nano-silicon composite fire-resistant glass, characterized in that: The steps include: Step 1: Ultrasonic dispersion of amino nano-silica in deionized water in a reaction kettle, adding 50 wt% glutaraldehyde, stirring and reacting for 1-2 hours, then adding a modified zinc-aluminum flame retardant and stirring and reacting for 20-24 hours, washing the precipitate after centrifugation, and vacuum drying to obtain a coated silicon-based filler; Step 2: Ultrasonic dispersion of the coated silicon-based filler in deionized water in a reactor, adding 50 wt% glutaraldehyde, stirring for 1-2 hours, then adding nickel-titanium bimetallic MOF, stirring for 20-24 hours, washing the precipitate after centrifugation, and vacuum drying to obtain a composite silicon-based flame-retardant filler; Step 3: Heat 45-50% silica sol to 40-45°C in a reactor, stir magnetically at 10-15rpm for 10-15min, add water-soluble silicone oil to the reactor and continue stirring for 10-15min, then add composite silicon-based flame retardant filler, stir and react for 10-15min, add 1M potassium hydroxide and 1M sodium hydroxide in equal volumes to obtain a mixed solution, heat to 70-80°C, stir at 40-50rpm for 50-60min, add ethylene glycol, stir for 10-15min, pour into laminated glass, seal the laminated glass with butyl tape, fill the gap next to the butyl tape with silicone tape, dry and cure at 70-80°C in a drying oven for 2-3h to obtain nano-silicon composite fireproof glass.

2. The method for producing a nano-silicon composite fireproof glass according to claim 1, characterized in that: The dosage ratio of the amino nano-silica, deionized water, glutaraldehyde and modified zinc-aluminum flame retardant in step 1 is 20-30g: 300-500mL: 50-60mL: 10-15g.

3. The method for producing a nano-silicon composite fireproof glass according to claim 1, characterized in that: The usage ratio of the coated silicon-based filler, deionized water, glutaraldehyde and nickel-titanium bimetallic MOF in step 2 is 20-30 g: 300-500 mL: 50-60 mL: 10-15 g.

4. The method for producing a nano-silicon composite fire-resistant glass according to claim 1, characterized in that: The amount ratio of the silica sol, water-soluble silicone oil, composite silicon-based flame-retardant filler, mixed liquid and ethylene glycol in step three is 60-65g: 8-10g: 5-7g: 15-20mL: 5-6mL.

5. The method for producing a nano-silicon composite fireproof glass according to claim 2, characterized in that: The amino nano-silica is prepared by the following steps: In a reaction kettle, hexadecyltrimethylammonium bromide was dissolved in deionized water, 0.2M sodium hydroxide aqueous solution was added, the mixture was stirred and heated to 70-80°C, ethyl orthosilicate was added and reacted for 15-20min, (3-aminopropyl)triethoxysilane was added, the reaction was stirred for 2-3h, the precipitate was collected by centrifugation, washed, and dried in vacuo to obtain amino nano-silica.

6. The method for producing a nano-silicon composite fireproof glass according to claim 5, characterized in that: The usage ratio of the hexadecyltrimethylammonium bromide, deionized water, sodium hydroxide aqueous solution, ethyl orthosilicate and (3-aminopropyl)triethoxysilane is 10-12g:1.8-2L:300-500mL:50-100mL:10-20mL.

7. The method for producing a nano-silicon composite fireproof glass according to claim 2, characterized in that: The modified zinc-aluminum flame retardant is prepared by the following steps: In a reaction kettle, tannic acid is dissolved in a 1M sodium hydroxide aqueous solution, zinc nitrate hexahydrate and aluminum nitrate nonahydrate are dissolved in deionized water, and then dripped into the reaction kettle drop by drop under stirring conditions. During the dripping process, the pH value in the reaction kettle is controlled to be 11-11.5 with a 1M sodium hydroxide solution, and the temperature of the reaction kettle is 50-60° C. After the dripping is completed, the stirring reaction is continued for 40-60 minutes, the temperature is raised to 70-80° C. and the stirring reaction is carried out for 16-18 hours, the precipitate is washed after centrifugation, and vacuum drying is performed to obtain a modified zinc-aluminum flame retardant.

8. The method for producing nano-silicon composite fire-resistant glass according to claim 7, characterized in that: The dosage ratio of the tannic acid, the sodium hydroxide aqueous solution, the zinc nitrate hexahydrate, the aluminum nitrate nonahydrate and the deionized water is 12-20 g: 200-300 mL: 12-15 g: 8-12 g: 500-600 mL.

9. The method for producing a nano-silicon composite fire-resistant glass according to claim 3, characterized in that: The nickel-titanium bimetallic MOF is prepared by the following steps: In a reaction kettle, 2-aminophthalic acid, titanium isopropoxide and nickel nitrate hexahydrate are mixed in a mixed solution of N,N-dimethylacetamide and methanol, ultrasonically dispersed for 10-20 minutes, then heated to 150-160°C for reaction for 20-24 hours, washed and precipitated after centrifugation, and dried to obtain a nickel-titanium bimetallic MOF.

10. The method for producing nano-silicon composite fire-resistant glass according to claim 9, characterized in that: The usage ratio of the 2-aminophthalic acid, titanium isopropoxide, nickel nitrate hexahydrate, N,N-dimethylacetamide and methanol is 7-9 g: 40-50 mL: 11-12 g: 700-800 mL: 300-400 mL.

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