High-performance composite fireproof glass and preparation method thereof

Abstract

The present application relates to the technical field of composite fireproof glass, and particularly relates to a high-performance composite fireproof glass and a preparation method thereof. The high-performance composite fireproof glass comprises a fireproof layer and at least two layers of glass, and the fireproof layer is arranged between the two adjacent layers of glass. The fireproof layer is a material layer containing a fireproof agent, and the fireproof agent is composite modified nano-SiO2. The composite modified nano-SiO2 is prepared by condensation copolymerization reaction of n-propyl trialkoxysilane, phenyl trialkoxysilane and vinyl trialkoxysilane in the presence of nano-SiO2 and water. The composite modified nano-SiO2 is reacted with KOH to obtain a potassium water glass (K2O.nSiO2) fireproof layer material. The finally prepared composite fireproof glass has high fire resistance and heat insulation. At the same time of high solid content, the viscosity of the system is effectively reduced, so that the light transmittance, ultraviolet resistance and cold resistance of the composite fireproof glass can be simultaneously improved under the condition of high modulus.

Description

Technical Field

[0001] This invention relates to the technical field of composite fireproof glass, and specifically to a high-performance composite fireproof glass and its preparation method. Background Technology

[0002] Fire-resistant glass is a type of building exterior wall or window glass with fire-resistant properties. It can remain unshaken for a long time under the impact of a 1000℃ flame, thus effectively preventing the spread of flames and smoke. This facilitates the early detection of fires, ensures that affected people have enough time to evacuate the scene, and buys time for disaster relief work. It is currently the most effective and safest fire-resistant glass product.

[0003] Fire-resistant glass is structurally classified into composite and monolithic types. Compared to monolithic fire-resistant glass, composite fire-resistant glass offers superior heat insulation, fire resistance, and sound insulation. Composite fire-resistant glass is a fire-resistant material used to control the spread of fire or isolate smoke; it belongs to the category of heat-insulating fire-resistant glass and can simultaneously meet the requirements of fire resistance integrity and fire-resistant heat insulation. Composite fire-resistant glass refers to glass made by bonding two or more pieces of ordinary flat glass with a transparent fire-resistant adhesive. The fire-resistant adhesive is the fire-resistant layer, which is formed by the curing of a fire-retardant liquid. Therefore, the performance of the fire-retardant liquid determines the fire resistance performance of the composite fire-resistant glass.

[0004] Fire retardant liquids mainly fall into two categories: organic fire retardant liquids based on polyacrylamide and inorganic fire retardant liquids based on silicate water glass. Currently, the fire-retardant layer material in composite inorganic fire-retardant glass both domestically and internationally is primarily a mixture based on potassium water glass (K2O·nSiO2), including charring agents, charring aids, plasticizers, and other related additives. Potassium water glass (K2O·nSiO2) with a SiO2 / K2O ratio of approximately 3.4 is used as the fire-retardant layer material. This material has a low degree of silicon-oxygen bond crosslinking and poor chemical stability. During use, especially under ultraviolet light, it is prone to -Si-O-Si- bridging oxygen bonds breaking and hydroxylation, resulting in a decrease in visible light transmittance and the formation of bubbles, affecting the appearance quality of the fire-retardant glass. When the modulus of the inorganic fireproof layer material K2O·nSiO2 increases to above 5, the degree of cross-linking of silicon-oxygen bonds in the fireproof layer material increases, the chemical stability is significantly improved, and the thermal stability and fireproof performance are also improved. However, due to its high viscosity, the process of debubbling and spreading during the preparation of fireproof glass is extremely difficult. This not only significantly reduces the visible light transmittance, thereby increasing the defect rate, but also causes UV resistance and easy freezing at low temperatures, gel cracking due to bubbles. Furthermore, the discontinuity and uneven thickness of the fireproof layer lead to differences in the fireproof performance of different parts of the same piece of glass. Summary of the Invention

[0005] Therefore, the purpose of this invention is to provide a high-performance composite fireproof glass and its preparation method, so as to solve the problem that fireproof liquid cannot simultaneously improve the light transmittance, UV resistance, fire resistance and cold resistance of composite fireproof glass under high modulus conditions.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A high-performance composite fireproof glass includes a fireproof layer and at least two glass layers, wherein the fireproof layer is disposed between two adjacent glass layers; the fireproof layer is a material layer containing a fire retardant, wherein the fire retardant is a composite modified nano-SiO2, which is prepared by a condensation copolymerization reaction of n-propyltrialkoxysilane, phenyltrialkoxysilane and vinyltrialkoxysilane in the presence of nano-SiO2 and water.

[0008] This invention uses a composite modified nano-SiO2 containing propyl, phenyl, and vinyl groups as the main component of the fire retardant liquid, ensuring that it can simultaneously improve the light transmittance, UV resistance, fire resistance, and cold resistance of the composite fire-resistant glass even with a high modulus.

[0009] To further improve the reaction rate and reduce the viscosity of the system, preferably, the components are subjected to condensation copolymerization in the following weight proportions: 280-310 parts of nano-SiO2, 10-20 parts of n-propyltrimethoxysilane, 3-5 parts of phenyltriethoxysilane and 10-20 parts of vinyltrimethoxysilane; wherein the particle size of the nano-SiO2 is 250-450 nm.

[0010] To ensure the basic performance of the fire-resistant glass, preferably, the fire retardant further includes triethanolamine, an antifreeze agent, a charring agent, a charring aid, a heat stabilizer, an ion fixative, a storage stabilizer, KOH, an antifoaming agent, and water; the fire retardant comprises the following components in parts by weight: 303-355 parts of composite modified nano-SiO2, 10-20 parts of triethanolamine, 50-70 parts of antifreeze agent, 12-20 parts of charring agent, 12-20 parts of charring aid, and 8-15 parts of heat stabilizer. The composite modified nano-SiO2 comprises the following components in parts by weight: 280-310 parts nano-SiO2, 10-20 parts n-propyltrimethoxysilane, 3-5 parts phenyltriethoxysilane, and 10-20 parts vinyltrimethoxysilane; the nano-SiO2 has a particle size of 250-450 nm.

[0011] Preferably, the antifreeze is glycerol, the charring agent is glucose, the charring aid is potassium dihydrogen phosphate, the heat stabilizer is borax, the ion fixative is sodium aluminate, the storage stabilizer is potassium polyphosphate, and the defoamer is a polyether-modified silicone defoamer, specifically BYK-024w.

[0012] Preferably, the method for preparing the fire retardant includes the following steps:

[0013] (I) Preparation of nano-SiO2 aqueous slurry: 280~310 parts by weight of SiO2 and 190~240 parts by weight of water are thoroughly mixed and stirred to obtain SiO2 aqueous slurry;

[0014] (II) Mix 150-340 parts by weight of water with 10-20 parts by weight of n-propyltrimethoxysilane, and then slowly add the SiO2 aqueous slurry prepared in step (I) while stirring. Then add 10-20 parts by weight of triethanolamine for the first reaction, followed by 3-5 parts by weight of phenyltriethoxysilane for the second reaction, and then add 10-20 parts by weight of vinyltrimethoxysilane to continue the reaction. After the third reaction, the first mixture is obtained, which is the initial product of the fire retardant.

[0015] To further improve the efficiency of dehydration condensation and ensure complete reaction, preferably, the reaction temperature of the first reaction, the second reaction, and the third reaction are all 40~43℃ and the time is 38~40min.

[0016] Preferably, the method for preparing the fire retardant further includes the following steps:

[0017] (III) Disperse 50-70 parts by weight of antifreeze, 12-20 parts by weight of charring agent, 12-20 parts by weight of charring aid, 8-15 parts by weight of heat stabilizer, 8-15 parts by weight of ion fixative, and 5-10 parts by weight of storage stabilizer in 90-120 parts by weight of water and stir to form a second mixture.

[0018] (IV) Dissolve 75-85 parts by weight of KOH in the remaining water to form a third mixture;

[0019] (V) Under high-speed shearing conditions, the second mixture is added to the first mixture and stirred evenly. Then, the third mixture and 1.5 to 3 parts by weight of defoamer are gradually and slowly added to it. Vacuum is drawn and the reaction is carried out for 3 hours until no bubbles are generated, thus obtaining the finished fire retardant.

[0020] Preferably, the fireproof layer is formed by injecting a fire retardant between two adjacent glass layers and curing it, wherein the curing temperature is 75~85℃ and the time is 15~30h.

[0021] More preferably, the thickness of the glass is 5-6 mm, and the thickness of the fireproof layer is 5-6 mm.

[0022] The second technical solution of the present invention is:

[0023] A method for preparing high-performance composite fireproof glass includes the following steps:

[0024] (1) The glass sheet is cut, edged, cleaned and tempered, and then cleaned thoroughly;

[0025] (2) After cleaning, the glass is glued to the frame with adhesive strips, hot-pressed, and then glued according to the requirements of the glue applicator. The sealing around the frame is checked to obtain a well-sealed glass frame.

[0026] (3) Move at least two sealed glass frames onto the grouting platform and fix them in place. Then, input the prepared fireproof liquid into the injection machine and connect the outlet pipe to the glass frame inlet for fireproof liquid injection. Ensure that the glass frame is filled and free of air bubbles. After the injection is completed, seal the injection port with sealing glue.

[0027] (4) Move the glass frame filled with fire retardant liquid into the baking oven and bake it at a temperature of 75~85℃ for 15~30 h to ensure that the glass becomes completely transparent and obtain the composite fire retardant glass.

[0028] The technical solution of the present invention achieves the following beneficial technical effects:

[0029] 1. The composite fireproof glass of the present invention has high fire resistance and heat insulation properties, with a fire resistance and heat insulation performance of more than 176 minutes.

[0030] 2. The fire retardant liquid of the present invention effectively reduces the viscosity of the system while ensuring a high solids content, with a viscosity of 40.1~41.2 mm. 2 / s, which does not affect the fire resistance of composite fireproof glass, and also ensures that it has high light transmittance, high UV resistance and high cold resistance. Attached Figure Description

[0031] Figure 1 This is a particle size distribution diagram of the nano-SiO2 aqueous slurry in Example 1 of the present invention;

[0032] Figure 2 This is a SEM image of the nano-SiO2 aqueous slurry in Example 1 of the present invention;

[0033] Figure 3 This is a physical image of the composite fireproof glass of Embodiment 4 of the present invention. Detailed Implementation

[0034] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0035] Specific embodiments of the fire retardant liquid and its preparation method of the present invention are as follows:

[0036] Example 1

[0037] The fire retardant liquid of this embodiment is composed of the following components in parts by weight: 167 kg of trialkoxysilane composite modified nano-SiO2, 30 kg of glycerol, 9 kg of glucose, 9 kg of potassium dihydrogen phosphate, 5 kg of borax, 6 kg of sodium aluminate, 3 kg of potassium polyphosphate, 40 kg of KOH, 1 kg of BYK-024w, and 260 kg of deionized water; wherein the trialkoxysilane composite modified nano-SiO2 is prepared by condensation copolymerization of n-propyltrimethoxysilane, phenyltriethoxysilane, and vinyltrimethoxysilane in the presence of nano-SiO2 and water, and the mass ratio of n-propyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and nano-SiO2 is 3.75:1:3.75:75; the mass of nano-SiO2 is 150 kg, and the average particle size is 300 nm.

[0038] The method for preparing the fire retardant liquid in this embodiment includes the following steps:

[0039] (1) Add 150 kg of deionized water and 7.5 kg of n-propyltrimethoxysilane to the reaction vessel according to the formula ratio. Then, while stirring, slowly add nano-SiO2 aqueous slurry (SiO2 mass ratio is about 58.7%). Add 8 kg of triethanolamine and stir at 40 °C for 40 min. After the reaction, add 2 kg of phenyltriethoxysilane and stir at 40 °C for 40 min. Then add 7.5 kg of vinyltrimethoxysilane and continue to stir at 40 °C for 40 min to form the first mixture containing trialkoxysilane composite modified nano-SiO2.

[0040] (2) Disperse glycerol, glucose, potassium dihydrogen phosphate, borax, sodium aluminate and potassium polyphosphate in 50 kg of water and stir to form a second mixture;

[0041] (3) Dissolve KOH in 60 kg of deionized water to form a third mixture;

[0042] (4) Under high-speed shearing conditions, add the second mixture to the first mixture and stir evenly. Then, continue to add the third mixture and defoamer to the solution gradually and slowly, evacuate the vacuum, and react for 3 hours until no bubbles are generated to obtain the fireproof liquid.

[0043] Example 2

[0044] The composition, proportion, and preparation method of the fire retardant liquid in this embodiment are basically the same as those in Example 1, except that the mass ratio of n-propyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and nano-SiO2 is 3.75:1:3.75:70, and the mass of nano-SiO2 is 140 kg.

[0045] Example 3

[0046] The composition, proportion, and preparation method of the fire retardant liquid in this embodiment are basically the same as those in Example 1, except that the mass ratio of n-propyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and nano-SiO2 is 3.75:1:3.75:77.5, and the mass of nano-SiO2 is 155 kg.

[0047] Specific embodiments of the high-performance composite fireproof glass and its preparation method of the present invention are as follows;

[0048] Example 4

[0049] The high-performance composite fireproof glass of this embodiment consists of two tempered glass panes and a fireproof layer. The fireproof layer is formed by injecting the fireproof liquid from Example 1 into the cavity of the laminated glass and curing it at 80°C. The thickness of the glass cavity is 5mm, and the laminated glass panes forming the cavity are all 5mm thick. A physical image of this composite fireproof glass is shown below. Figure 3 As shown.

[0050] The method for preparing the composite fireproof glass in this embodiment includes the following steps:

[0051] (1) Cut, grind, clean and temper the glass sheet, and clean the tempered glass.

[0052] (2) Use adhesive strips to glue the cleaned tempered glass to the frame, then press it with heat, and finally apply glue according to the requirements of the glue applicator, and check the sealing around the frame.

[0053] (3) Move the two sealed glass frames onto the grouting platform and fix them in place. Then output the fireproof liquid of Example 1 to the injection machine. Connect the outlet pipe to the glass frame inlet for fireproof liquid injection. Ensure that it is filled and free of air bubbles. After the injection is completed, seal the injection port with sealing glue.

[0054] (4) Move the glass frame filled with fire retardant liquid into the baking oven and bake it at 80°C for 15-30 hours to ensure that the glass becomes completely transparent and obtain high-performance composite fire retardant glass.

[0055] Example 5

[0056] The composition and preparation method of the high-performance composite fireproof glass in this embodiment are basically the same as those in Example 4, except that the fireproof liquid used in the fireproof layer is the same as that in Example 2.

[0057] Example 6

[0058] The composition and preparation method of the high-performance composite fireproof glass in this embodiment are basically the same as those in Example 4, except that the fireproof liquid used in the fireproof layer is the same as that in Example 3.

[0059] Comparative Examples 1-6

[0060] The composition and preparation method of the composite fireproof glass in this comparative example are basically the same as those in Example 4, except that the fireproof liquid used for the fireproof layer is the fireproof liquid shown in Table 1. The preparation method of the fireproof liquid in this comparative example is the same as that in Example 1.

[0061] Table 1. Formulations of comparative fire retardant liquids

[0062]

[0063] Experimental Example 1

[0064] This experimental example tested the particle size of the nano-SiO2 aqueous slurry used in Example 1, and the results are as follows: Figure 1 The test results showed that the SiO2 particle size distribution in the nano-SiO2 aqueous slurry ranged from 0.256 μm to 0.517 μm, with an average particle size of approximately 300 nm. Further SEM analysis of the SiO2 yielded the following results: Figure 2 As shown in the figure, the nano-SiO2 is approximately spherical and uniformly distributed.

[0065] In addition, XRF testing was performed on the SiO2 slurry in this experiment, where the mass fraction of SiO2 in the slurry was approximately 58.7%, and the specific results are shown in Table 2.

[0066] Table 2 XRF test results of SiO2 slurry

[0067]

[0068] Experiment Example 2

[0069] This experiment tested the appearance, light transmittance, UV resistance, fire resistance, heat insulation, and cold resistance (-20℃) of the high-performance composite fire-resistant glass in Examples 4-6 and Comparative Examples 1-6. The results are shown in Table 3. Specific experimental procedures were performed in accordance with GB / T 9978.1-2008 "Fire Resistance Test Methods for Building Components - Part 1: General Requirements", GB / T 12513-2006 "Fire Resistance Test Methods for Glass-Plated Components", and GB / T15763.1-2009 "Safety Glass for Buildings - Part 1: Fire-Resistant Glass".

[0070] A comparison of Comparative Examples 1 and 2 and Examples 4-6 shows that when the particle size of SiO2 is 50nm or 700nm, the light transmittance, UV resistance, fire resistance, heat insulation, and cold resistance of the composite fireproof glass are all poor. However, when the particle size of SiO2 is 300nm, these properties are improved. A comparison with Comparative Examples 3-6 reveals that using only two of n-propyltrimethoxysilane, phenyltriethoxysilane, or vinyltrimethoxysilane to modify SiO2 cannot simultaneously improve the light transmittance, UV resistance, fire resistance, heat insulation, and cold resistance of the composite fireproof glass, nor reduce the system viscosity. In contrast, the fire retardant liquid in Examples 4-6 of this invention effectively reduces the viscosity of the system while maintaining a high solids content, thereby enabling the composite fireproof glass to possess high modulus, high light transmittance, high UV resistance, high fire resistance, and cold resistance.

[0071] Table 3 Performance test results of composite fireproof glass

[0072]

[0073] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of the claims of this patent application.

Claims

1. A high-performance composite fireproof glass, characterized in that, It includes a fireproof layer and at least two layers of glass, with the fireproof layer disposed between two adjacent layers of glass; the fireproof layer is a material layer containing a fire retardant, the fire retardant being a composite modified nano-SiO2, which is prepared by a condensation copolymerization reaction of n-propyltrialkoxysilane, phenyltrialkoxysilane and vinyltrialkoxysilane in the presence of nano-SiO2 and water.

2. The high-performance composite fireproof glass according to claim 1, characterized in that, The components are subjected to condensation copolymerization reaction in the following weight parts: 280-310 parts of nano-SiO2, 10-20 parts of n-propyltrimethoxysilane, 3-5 parts of phenyltriethoxysilane and 10-20 parts of vinyltrimethoxysilane; the particle size of the nano-SiO2 is 250-450 nm.

3. The high-performance composite fireproof glass according to claim 1, characterized in that, The fire retardant further includes triethanolamine, antifreeze, charring agent, charring aid, heat stabilizer, ion fixation agent, storage stabilizer, KOH, defoamer, and water; the fire retardant comprises the following components in parts by weight: 303-355 parts composite modified nano-SiO2, 10-20 parts triethanolamine, 50-70 parts antifreeze, 12-20 parts charring agent, 12-20 parts charring aid, 8-15 parts heat stabilizer, 8-15 parts ion fixation agent, and water. The composite modified nano-SiO2 comprises the following components in parts by weight: 280-310 parts nano-SiO2, 10-20 parts n-propyltrimethoxysilane, 3-5 parts phenyltriethoxysilane, and 10-20 parts vinyltrimethoxysilane; the nano-SiO2 has a particle size of 250-450 nm.

4. The high-performance composite fireproof glass according to claim 3, characterized in that, The antifreeze agent is glycerol, the charring agent is glucose, the charring aid is potassium dihydrogen phosphate, the heat stabilizer is borax, the ion fixative is sodium aluminate, the storage stabilizer is potassium polyphosphate, and the defoamer is a polyether-modified silicone defoamer, specifically BYK-024w.

5. The high-performance composite fireproof glass according to claim 3, characterized in that, The method for preparing the fire retardant includes the following steps: (I) Preparation of nano-SiO2 aqueous slurry: 280~310 parts by weight of SiO2 and 190~240 parts by weight of water are thoroughly mixed and stirred to obtain SiO2 aqueous slurry; (II) Mix 150-340 parts by weight of water with 10-20 parts by weight of n-propyltrimethoxysilane, and then slowly add the SiO2 aqueous slurry prepared in step (I) while stirring. Then add 10-20 parts by weight of triethanolamine for the first reaction, followed by 3-5 parts by weight of phenyltriethoxysilane for the second reaction, and then add 10-20 parts by weight of vinyltrimethoxysilane to continue the reaction. After the third reaction, the first mixture is obtained, which is the initial product of the fire retardant.

6. The high-performance composite fireproof glass according to claim 5, characterized in that, The reaction temperature for the first, second, and third reactions is 40-43℃, and the reaction time is 38-40 min.

7. The high-performance composite fireproof glass according to claim 6, characterized in that, The method for preparing the fire retardant further includes the following steps: (III) Disperse 50-70 parts by weight of antifreeze, 12-20 parts by weight of charring agent, 12-20 parts by weight of charring aid, 8-15 parts by weight of heat stabilizer, 8-15 parts by weight of ion fixative, and 5-10 parts by weight of storage stabilizer in 90-120 parts by weight of water and stir to form a second mixture. (IV) Dissolve 75-85 parts by weight of KOH in the remaining water to form a third mixture; (V) Under high-speed shearing conditions, the second mixture is added to the first mixture and stirred evenly. Then, the third mixture and 1.5 to 3 parts by weight of defoamer are gradually and slowly added to it. Vacuum is drawn and the reaction is carried out for 3 hours until no bubbles are generated, thus obtaining the finished fire retardant.

8. The high-performance composite fireproof glass according to any one of claims 1-7, characterized in that, The fireproof layer is formed by injecting a fire retardant between two adjacent glass layers and curing it. The curing temperature is 75~85℃ and the time is 15~30h.

9. The high-performance composite fireproof glass according to any one of claims 1-7, characterized in that, The thickness of the glass is 5-6 mm, and the thickness of the fireproof layer is 5-6 mm.

10. A method for preparing high-performance composite fireproof glass, characterized in that, Includes the following steps: (1) The glass sheet is cut, edged, cleaned and tempered, and then cleaned thoroughly; (2) After cleaning, the glass is glued to the frame with adhesive strips, hot-pressed, and then glued according to the requirements of the glue applicator. The sealing around the frame is checked to obtain a well-sealed glass frame. (3) Move at least two sealed glass frames onto the grouting platform and fix them in place. Then, input the prepared fireproof liquid into the injection machine and connect the outlet pipe to the glass frame inlet for fireproof liquid injection. Ensure that the glass frame is filled and free of air bubbles. After the injection is completed, seal the injection port with sealing glue. (4) The glass frame filled with fire retardant liquid is moved to the baking oven and baked at a temperature of 75~85℃ for 15~30 h to ensure that the glass becomes completely transparent, thereby obtaining the composite fire retardant glass as described in any one of claims 1-9.

Images