A kind of heat-insulating composite fire-proof glass and its preparation process

Abstract

The present application relates to the field of glass product manufacturing technology, specifically disclosing a heat-insulating composite fireproof glass and a preparation process thereof. A heat-insulating composite fireproof glass comprises a hollow glass structure and a gel interlayer, wherein the gel interlayer comprises the following raw materials in parts by weight: 10-15 parts of silica sol, 3-5 parts of disodium hydrogen phosphate, 2-4 parts of hollow silica microspheres, 1-3 parts of zirconium dioxide, 5-8 parts of borate, 2-4 parts of mullite fiber, 6-10 parts of modified polydimethylsiloxane, and 2-5 parts of a toughening agent; the preparation method comprises the following steps: adding silica sol, disodium hydrogen phosphate, borate, mullite fiber, modified polydimethylsiloxane, and a toughening agent to deionized water in sequence, heating the mixture to react, adding the remaining raw materials, stirring evenly at room temperature, standing, and filtering to obtain a filtrate, pouring the filtrate into the interlayer of the hollow glass structure, and curing and sealing the glass. The composition of the present application can be used in special scenarios such as fireproof glass partitions, fireproof doors, elevator doors, fireproof windows, and fireproof skylights, and has the advantages of good thermal insulation and high strength.

Description

Technical Field

[0001] The present application relates to the technical field of glass product manufacturing, and more specifically, to a heat-insulating composite fire-resistant glass and a preparation process thereof. Background Art

[0002] Fire prevention is a crucial aspect of building safety design. With the implementation of fire prevention regulations worldwide and the development of the construction industry, various fireproofing materials for buildings are receiving increasing attention. Glass is an essential building material. When ordinary glass encounters fire, a temperature difference develops between its two surfaces. The side facing the fire experiences a higher temperature, causing it to expand due to the heat. This causes the glass to bend inward due to the internal stress generated by the temperature difference. Microcracks on the surface facing the fire gradually expand due to the thermal stress, leading to glass breakage and resulting in numerous casualties. This is why fireproof glass came into being.

[0003] Fireproof glass is divided into composite fireproof glass and single-piece fireproof glass. Composite fireproof glass is composed of two or more layers of glass with one or more layers of water-soluble inorganic fireproof adhesive interlayer. Nano-silicon composite fireproof glass with inorganic hydrogel as the main body has played an important role in the field of fireproof glass due to its excellent radiation resistance, green environmental protection, high light transmittance and strong heat insulation. Among them, when the grouting glass encounters high temperature, the fireproof transparent adhesive layer in the middle will quickly foam, expand and spread to form an opaque fireproof insulation board. The insulation board can not only prevent the spread of flames, but also prevent the high temperature from the fire-facing side from being transmitted to the back-fire side, protecting the objects and personnel on the back-fire side. However, the middle adhesive layer is soft and has low impact strength, which can easily cause the glass to break. Summary of the Invention

[0004] In order to improve the mechanical properties of insulating glass, the present application provides an insulating composite fireproof glass and a preparation process thereof.

[0005] In a first aspect, the present application provides a heat-insulating composite fire-resistant glass, which adopts the following technical solution:

[0006] A heat-insulating composite fireproof glass is composed of a hollow glass structure and a gel interlayer, wherein the gel interlayer comprises the following raw materials in parts by weight:

[0007] 10-15 parts of silica sol, 3-5 parts of disodium hydrogen phosphate, 2-4 parts of hollow silicon dioxide microspheres, 1-3 parts of zirconium dioxide, 5-8 parts of borate, 2-4 parts of mullite fiber, 6-10 parts of modified polydimethylsiloxane, and 2-7 parts of toughening agent.

[0008] By adopting the above technical solution, silica sol serves as a binder, mullite fibers connect the various components, and strengthen the binding capacity of the gel layer. Borates react with active hydrogen atoms in the system to form borate bonds, which can form strong chemical bonds between molecules and form a stable three-dimensional cross-linked structure with polydimethylsiloxane, improving the material's impact strength, hardness, and heat resistance. Zirconium dioxide further improves the mechanical properties of the gel after curing. The addition of hollow silica microspheres reduces the material's weight and provides good fluidity, facilitating the operation of gel grouting. The hollow structure can form a continuous cavity structure in the gel, further improving the material's ability to block heat and enhance the thermal insulation capacity of the glass. Disodium hydrogen phosphate serves as a stabilizer, improving the gel's thermal stability and preventing microorganisms in the interlayer from corroding the gel's organic matter, which would lead to a decrease in thermal insulation and affect the glass's light transmittance.

[0009] Optionally, the modified polydimethylsiloxane is prepared by the following method:

[0010] (1) Allyl polyoxyethylene ether, vinyl triethoxysilane and polydimethylsiloxane are mixed and added to isopropyl alcohol, heated to 80-90° C., and a catalyst is added while stirring;

[0011] (2) The reaction is carried out at 110-120° C. to obtain a crude product, which is then subjected to alcohol removal and drying to obtain modified polydimethylsiloxane.

[0012] By adopting the above technical solution, the addition of polydimethylsiloxane can react with other components in the raw materials to form a network structure, but the dispersibility of polydimethylsiloxane in the solution is poor and the compatibility is not good, resulting in reduced impact strength and visible light transmittance of the fire-resistant glass. Modification of polydimethylsiloxane to introduce more active hydrogen groups and hydrophilic groups improves the dispersibility of polydimethylsiloxane in the system, making the network structure more stable, and ensuring that the fire-resistant glass still has good impact strength when facing low temperatures.

[0013] Optionally, the weight ratio of the allyl polyoxyethylene ether, vinyl triethoxysilane and polydimethylsiloxane is 2:(0.5-1):1.

[0014] Optionally, the catalyst is sulfuric acid or hydrochloric acid.

[0015] By adopting the above technical solution, when preparing modified polydimethylsiloxane, by controlling the addition ratio of raw materials and the type of catalyst, the occurrence of side reactions during the modification process is reduced, the conversion rate is increased, and the dispersibility of polydimethylsiloxane in the system is improved.

[0016] Optionally, the borate ester is any one of triphenyl borate and ferrocenyl borate.

[0017] By adopting the above technical solution, triphenylborate and ferrocenylborate are both borate esters with rigid structures, which can undergo esterification reaction with polydimethylsiloxane with active hydrogen to form a network structure. The presence of the rigid structure and the tough network structure can increase the hardness of the gel material after curing and improve the impact strength of the glass.

[0018] Optionally, the toughening agent is epoxy resin.

[0019] By adopting the above technical solution, epoxy resin can undergo a cross-linking reaction with polydimethylsiloxane having active hydrogen to form a network structure, thereby improving the stability of the network structure molding and further improving the toughness and impact strength of the material.

[0020] Optionally, the gel interlayer further comprises 2-6 parts of 2-hydroxyethyl methacrylate phosphate.

[0021] By adopting the above technical solution, the addition of 2-hydroxyethyl methacrylate phosphate can, on the one hand, improve the bonding ability between zirconium dioxide and polydimethylsiloxane and improve the stability of inorganic materials in the network structure; on the other hand, it can improve the adhesion and bonding strength of the gel to the glass structural parts, has a low shrinkage rate, and has stable performance even at low temperatures, thereby ensuring the stability of the performance of the fire-resistant glass.

[0022] In a second aspect, the present application provides a process for preparing heat-insulating composite fire-resistant glass, which adopts the following technical solution:

[0023] A preparation process of heat-insulating composite fire-resistant glass comprises the following steps:

[0024] (1) Preparation of gel interlayer: Add silica sol, disodium hydrogen phosphate, borate, mullite fiber, modified polydimethylsiloxane and toughening agent in order by weight, dissolve in deionized water and heat to 40-50°C for reaction, then add hollow silica microspheres and zirconium dioxide and stir at room temperature until a colorless transparent solution is obtained. Let stand for 12 hours, filter the solution and set the filtrate aside;

[0025] (2) The filtrate is poured into the middle interlayer of the insulating glass structure. After the poured filtrate is completely solidified into glue, the grouting port is sealed with glass strips and transparent flame retardant glue to obtain the heat-insulating composite fireproof glass.

[0026] By adopting the above technical solution, the reaction raw materials are mixed at high temperature, which is conducive to the reaction, accelerates the reaction rate and conversion rate, and is grouting into the hollow structural member to seal the insulating composite fireproof glass.

[0027] In summary, this application has the following beneficial effects:

[0028] 1. Since the present application uses borate with a rigid structure and polydimethylsiloxane capable of forming a network structure, the obtained gel has both good hardness and good toughness after curing, high impact strength, good thermal insulation ability, and still maintains good performance at low temperatures.

[0029] 2. In this application, allyl polyoxyethylene ether and vinyl triethoxysilane are preferably used to modify polydimethylsiloxane. The modified polydimethylsiloxane not only has good dispersibility and increases the reaction points for generating a network structure, but also has good defoaming properties, preventing the occurrence of microbubbles during grouting, which affects the appearance. DETAILED DESCRIPTION

[0030] The present application is further described in detail below with reference to the embodiments.

[0031] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0032] 2-Hydroxyethyl methacrylate phosphate was purchased from Hubei Qianmosheng Biotechnology Co., Ltd., CAS: 52628-03-2; polydimethylsiloxane was purchased from Shandong Juneng Chemical Co., Ltd., model GB201-350; the glass structural parts were silicate glass, and the prepared hollow structural parts had a size of 200 mm × 200 mm × 20 mm, and a hollow interlayer thickness of 10 mm. Transparent flame retardant adhesive was purchased from Langfang Jun Energy Saving Technology Co., Ltd.; silica sol was purchased from Jinan Quanxing New Materials Co., Ltd.; triphenyl borate was purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., CAS: 1095-03-0; ferrocenyl borate was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS: 737776-93-1.

[0033] Preparation examples of raw materials and / or intermediates

[0034] Preparation Example 1

[0035] A modified polydimethylsiloxane, the preparation of which comprises the following steps:

[0036] (1) 20 kg of allyl polyoxyethylene ether, 5 kg of vinyl triethoxysilane and 10 kg of polydimethylsiloxane were mixed and added to 30 kg of isopropanol, heated to 80°C, and 3 kg of ammonia water as a catalyst was added while stirring;

[0037] (2) The reaction was carried out at 110° C. for 4 h to obtain a crude product, which was then dried in a rotary evaporator to obtain modified polydimethylsiloxane.

[0038] Preparation Example 2

[0039] A modified polydimethylsiloxane is prepared, which is different from Preparation Example 1 in that the catalyst used in this Preparation Example is hydrochloric acid.

[0040] Preparation Example 3

[0041] A modified polydimethylsiloxane is prepared, which is different from Preparation Example 1 in that the catalyst used in this Preparation Example is sulfuric acid.

[0042] Preparation Example 4

[0043] A modified polydimethylsiloxane is different from Preparation Example 3 in that the ratio of allyl polyoxyethylene ether, vinyl triethoxysilane and polydimethylsiloxane added in this Preparation Example is 1.5:1:1.

[0044] Preparation Example 5

[0045] A modified polydimethylsiloxane is different from Preparation Example 3 in that the ratio of allyl polyoxyethylene ether, vinyl triethoxysilane and polydimethylsiloxane added in this Preparation Example is 1.65:0.85:1.

[0046] Comparative Preparation Example 1

[0047] A modified polydimethylsiloxane is different from Preparation Example 3 in that the ratio of allyl polyoxyethylene ether, vinyl triethoxysilane and polydimethylsiloxane added in this Preparation Example is 3:1.5:1.

[0048] Example

[0049] Example 1

[0050] A heat-insulating composite fire-resistant glass, the preparation of which comprises the following steps:

[0051] (1) Preparation of gel interlayer: silica sol, disodium hydrogen phosphate, borate, mullite fiber, modified polydimethylsiloxane and toughening agent epoxy resin were sequentially added and dissolved in deionized water and heated to 45°C for reaction. Then, hollow silica microspheres and zirconium dioxide were added and stirred at room temperature until a colorless and transparent solution was obtained. The solution was allowed to stand for 12 hours, and the filtrate was filtered and the filtrate was set aside.

[0052] (2) The filtrate is poured into the middle interlayer of the insulating glass structure. After the poured filtrate is completely solidified into glue, the grouting opening is sealed with glass strips and transparent flame retardant glue to produce the insulating composite fireproof glass. The modified polydimethylsiloxane prepared in Preparation Example 1 is used, and the borate is triisopropyl borate.

[0053] Example 2-3

[0054] A heat-insulating composite fireproof glass, which is different from Example 1 in that the raw material components and their corresponding weight parts are shown in Table 1.

[0055] Table 1 Raw materials and their weights in Examples 1-3 (kg)

[0056] Example 1 Example 2 Example 3 Silica Sol 10 12.5 15 Disodium hydrogen phosphate 5 4 3 borate esters 6.5 8 5 Mullite fiber 2 3 4 Modified polydimethylsiloxane 8 10 6 Toughener 3.5 2 5 Silica hollow microspheres 3 4 2 Zirconium dioxide 3 2 1

[0057] Example 4

[0058] A heat-insulating composite fireproof glass is different from Example 1 in that the modified polydimethylsiloxane prepared in Preparation Example 2 is used in this example.

[0059] Example 5

[0060] A heat-insulating composite fireproof glass is different from Example 1 in that the modified polydimethylsiloxane prepared in Preparation Example 3 is used in this embodiment.

[0061] Example 6

[0062] A heat-insulating composite fireproof glass is different from Example 1 in that the modified polydimethylsiloxane prepared in Preparation Example 4 is used in this embodiment.

[0063] Example 7

[0064] A heat-insulating composite fireproof glass is different from Example 1 in that the modified polydimethylsiloxane prepared in Preparation Example 5 is used in this example.

[0065] Example 8

[0066] A heat-insulating composite fireproof glass, which is different from Example 7 in that the borate used in this example is triphenyl borate.

[0067] Example 9

[0068] A heat-insulating composite fireproof glass, which is different from Example 7 in that the borate used in this example is ferrocenyl borate.

[0069] Example 10

[0070] A heat-insulating composite fireproof glass, which differs from Example 9 in that 4 kg of 2-hydroxyethyl methacrylate phosphate is further added in this example, and the preparation comprises the following steps:

[0071] (1) Preparation of gel interlayer: silica sol, disodium hydrogen phosphate, borate, mullite fiber, modified polydimethylsiloxane, 2-hydroxyethyl methacrylate phosphate and toughening agent epoxy resin were sequentially added and dissolved in deionized water and heated to 45°C for reaction. Then, hollow silica microspheres and zirconium dioxide were added and stirred at room temperature until a colorless and transparent solution was obtained. The solution was allowed to stand for 12 hours, and the filtrate was filtered and the filtrate was set aside.

[0072] (2) The filtrate is poured into the middle interlayer of the insulating glass structure. After the poured filtrate is completely solidified into glue, the grouting opening is sealed with glass strips and transparent flame retardant glue to produce the insulating composite fireproof glass. The modified polydimethylsiloxane prepared in Preparation Example 1 is used, and the borate is triisopropyl borate.

[0073] Comparative Example

[0074] Comparative Example 1

[0075] A heat-insulating composite fireproof glass is different from Example 1 in that the polydimethylsiloxane added in this comparative example is not modified.

[0076] Comparative Example 2

[0077] A heat-insulating composite fireproof glass is different from Example 1 in that the polydimethylsiloxane added in this comparative example is prepared according to Comparative Preparation Example 1.

[0078] Comparative Example 3

[0079] A heat-insulating composite fireproof glass, which is different from Example 1 in that the solution poured into the hollow structure is replaced with an equal amount of silica sol.

[0080] Performance testing

[0081] Detection method

[0082] Light transmittance test: Test the transmittance according to GB / T 2680-2021 "Determination of visible light transmittance, direct solar transmittance, total solar transmittance, ultraviolet transmittance and related window glass parameters of architectural glass".

[0083] Impact strength: The impact strength test is carried out in accordance with the "Impact Strength" method of the national standard GB15763.2-2005 "Safety Glass for Construction Part 2: Tempered Glass". A smooth steel ball with a diameter of 63.5mm and a mass of approximately 1040g is placed at a height of 1000mm from the surface of the fireproof glass sample and allowed to fall freely. The impact point is within 25mm from the center of the sample. Each sample is impacted once. If the surface of the composite fireproof glass is not damaged, the height of the steel ball is increased to 1500mm and 1900mm respectively. The impact strength is rated on a scale of 1 to 6. The higher the score, the stronger the impact strength.

[0084] Fire resistance (surface stress) test: The surface stress value of fire glass is one of the important data indicators for measuring the fire resistance of the product. The larger the surface stress value, the better its thermal shock resistance, physical shock resistance, and fire resistance integrity. A glass surface stress meter (SMM-2 glass surface stress meter) is used for measurement. The glass to be tested is placed on the measuring table of the glass surface stress meter with the tin-impregnated surface facing up. The measurement point is determined according to Section 6.4.1 of the national standard GB17841-1999 "Tempered Glass and Semi-Tempered Glass for Curtain Walls". The measured glass surface position is wiped with alcohol. After 1 minute, a drop of refractive oil is added to the measurement position and the bottom of the glass surface stress meter prism is placed on the refractive oil. The eyepiece of the glass surface stress meter is adjusted to read the values ​​of the horizontal axis of the micrometer eyepiece coordinate line along the upper and lower ends of the step within the field of view. The difference is calculated (i.e., the measured step height D). The stress value is equal to the measured step height D × 3. The measurement results are shown in Table 2.

[0085] Table 2 Performance test results

[0086] Transmittance / % Impact strength Surface stress / Mpa Thermal conductivity (W / (m·K)) Example 1 74.3 4 235.5 0.41 Example 2 74.6 4 235.9 0.43 Example 3 74.4 4 235.6 0.42 Example 4 76.9 4 236.6 0.35 Example 5 77.1 4 236.9 0.34 Example 6 77.0 5 236.7 0.33 Example 7 77.2 5 237.0 0.32 Example 8 77.4 6 239.2 0.27 Example 9 77.5 6 239.9 0.28 Example 10 77.6 6 241.5 0.21 Comparative Example 1 61.2 2 198.4 1.12 Comparative Example 2 66.4 3 214.3 0.67 Comparative Example 3 44.7 1 135.6 1.56

[0087] Combining Examples 1-3 with Comparative Example 1 and Table 2, it can be seen that the experimental data of Examples 1-3 are all better than those of Comparative Example 1, indicating that the polydimethylsiloxane modified using the scheme of the present application has more active hydrogen groups and hydrophilic groups, thereby improving the dispersibility of polydimethylsiloxane in the system and making the network structure more stable, thereby improving the various properties of the fire-resistant glass.

[0088] Combining Examples 1-7 with Comparative Example 2 and Table 2, it can be seen that the experimental data of Examples 1-3 are better than those of Comparative Example 2, and the various data of Examples 4-7 are better than those of Examples 1-3, indicating that the modified polydimethylsiloxane reduces the occurrence of side reactions during the modification process, improves the conversion rate, improves the dispersibility of polydimethylsiloxane in the system, and further improves the impact strength and visible light transmittance of the fire-resistant glass by controlling the addition ratio of the modified raw materials 2: (0.5-1): 1 and the type of catalyst.

[0089] Combining Example 7 with Examples 8-9 and Table 2, it can be seen that the experimental data of Examples 8-9 are better than those of Example 7, indicating that the selection of borate affects the final performance of the fireproofing ratio, especially the impact resistance and surface stress of the glass.

[0090] Combining Example 9 with Example 10 and Table 2, it can be seen that the experimental data of Example 10 is better than that of Example 8, indicating that the addition of 2-hydroxyethyl methacrylate phosphate is beneficial to improving the adhesion of the gel to the glass, ensuring the stability of the gel, and further improving the thermal insulation and impact resistance of the glass.

[0091] The fireproof glass prepared in Example 1, Example 11, Example 12 and Comparative Examples 1-2 was tested for heat resistance and cold resistance according to the testing method of GB15763.1-2009 "Safety of Buildings - Part 1 - Fireproof Glass".

[0092] Table 3 Test results of heat and cold resistance

[0093] Heat resistance test phenomenon Cold resistance experiment phenomenon Example 1 A 0.5mm bubble is generated A 0.5mm bubble is generated Example 11 A 0.5mm bubble is generated A 0.5mm bubble is generated Example 12 No change No change Comparative Example 1 Gel interlayer and glass create pores Gap between gel interlayer and glass Comparative Example 2 Gel interlayer and glass create pores Gap between gel interlayer and glass

[0094] The above experimental results show that when unmodified polydimethylsiloxane or the modified polydimethylsiloxane prepared in Comparative Preparation Example 1 is used, defects of varying degrees will occur in the heat resistance test and the cold resistance test. This is because the gel layer has poor adhesion to the glass under high and low temperature conditions, and its volume shrinks, resulting in the gel layer gradually separating from the glass, further causing the transmittance and aesthetics of the fire-resistant glass to decrease. When the modified polydimethylsiloxane prepared in this scheme is used, the obtained gel has good adhesion to the glass, its volume shrinkage is less affected by temperature, and it maintains good performance at both high and low temperatures.

[0095] According to GB / T12513-2006, "Test Methods for Fire Resistance of Glazed Components," the fire-resistant glasses prepared in the examples were vertically mounted in a refractory furnace and heated according to the heating curve specified in GB / T9978.1-2008, "Test Methods for Fire Resistance of Building Components - Part 1: General Requirements." The glass breakage time was measured during the heating process. The fire-resistant glass of Comparative Example 3 broke within 10 minutes, the fire-resistant glass of Comparative Examples 1-2 shattered within 30 minutes, and the fire-resistant glass prepared in the present invention remained intact for 1.5 hours.

[0096] Weather resistance: The test equipment is an irradiation chamber that meets the requirements of the national standard GB15763.2-2009. The test conditions are 45°C and 750W UV lamp irradiation for 100 hours. The transmittance is tested before and after irradiation; there is almost no change before and after, indicating that the fire-retardant gel prepared by this scheme has strong radiation stability and good weather resistance.

[0097] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A heat-insulating composite fire-resistant glass, characterized in that: It includes a hollow glass structure and a gel interlayer, and the gel interlayer includes the following raw materials in parts by weight: 10-15 parts of silica sol, 3-5 parts of disodium hydrogen phosphate, 2-4 parts of hollow silicon dioxide microspheres, 1-3 parts of zirconium dioxide, 5-8 parts of borate, 2-4 parts of mullite fiber, 6-10 parts of modified polydimethylsiloxane, and 2-5 parts of a toughening agent; the borate has a rigid structure; The modified polydimethylsiloxane is prepared by the following method: (1) Mix allyl polyoxyethylene ether, vinyl triethoxysilane and polydimethylsiloxane and add them to isopropyl alcohol, heat to 80-90°C, and add catalyst while stirring; (2) Keeping the reaction at 110-120°C to obtain a crude product, which is then subjected to alcohol removal and drying to obtain modified polydimethylsiloxane; The weight ratio of the allyl polyoxyethylene ether, vinyl triethoxysilane and polydimethylsiloxane is (1.5-2): (0.5-1): 1; The catalyst is sulfuric acid or hydrochloric acid.

2. The heat-insulating composite fire-resistant glass according to claim 1, characterized in that: The borate ester is any one of triphenyl borate and ferrocenyl borate.

3. The heat-insulating composite fire-resistant glass according to claim 1, characterized in that: The toughening agent is epoxy resin.

4. The heat-insulating composite fire-resistant glass according to claim 1, characterized in that: The gel interlayer also includes 2-6 parts of 2-hydroxyethyl methacrylate phosphate.

5. A process for preparing a heat-insulating composite fire-resistant glass according to any one of claims 1 to 3, characterized in that: The steps include: (1) Preparation of gel interlayer: Add silica sol, disodium hydrogen phosphate, borate, mullite fiber, modified polydimethylsiloxane and toughening agent in order by weight, dissolve in deionized water and heat to 40-50 ° C for reaction, then add silica hollow microspheres and zirconium dioxide and stir at room temperature until a colorless transparent solution is obtained. Let it stand for 12 hours, filter the solution and set the filtrate aside; (2) The filtrate is poured into the middle interlayer of the insulating glass structure. After the poured filtrate is completely solidified into glue, the grouting port is sealed with glass strips and transparent flame retardant glue to obtain the heat-insulating composite fireproof glass.