CN112662317B - Transparent fireproof glue, preparation method thereof and composite fireproof glass comprising transparent fireproof glue - Google Patents
Transparent fireproof glue, preparation method thereof and composite fireproof glass comprising transparent fireproof glue Download PDFInfo
- Publication number
- CN112662317B CN112662317B CN202011559130.0A CN202011559130A CN112662317B CN 112662317 B CN112662317 B CN 112662317B CN 202011559130 A CN202011559130 A CN 202011559130A CN 112662317 B CN112662317 B CN 112662317B
- Authority
- CN
- China
- Prior art keywords
- glass
- fire
- glass layer
- fireproof
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a transparent fireproof adhesive, a preparation method thereof and composite fireproof glass containing the transparent fireproof adhesive, wherein the transparent fireproof adhesive comprises the following raw materials in parts by weight: 45-55 parts of nano silicon dioxide sol, 25-40 parts of water glass solution, 0.5-1.0 part of carbon forming agent, 0.1-0.3 part of carbon forming auxiliary agent, 0.3-0.8 part of heat-resistant stabilizer, 0-5 parts of organic anti-condensing agent, 10-15 parts of inorganic anti-condensing agent, 0.05-0.1 part of ion fixing agent, 0.3-0.5 part of storage stabilizer, 0.1-0.5 part of defoaming agent and 0.15-0.3 part of cross-linking agent; wherein the water content of the transparent fireproof glue is 30-50%. The water content of the transparent fireproof glue is as low as 30-50%, the fireproof performance of the composite fireproof glass is effectively improved, and a certain flowing performance is ensured to facilitate pouring. The heat-insulation type composite fireproof glass and the non-heat-insulation type composite fireproof glass prepared by using the transparent fireproof glue have the characteristics of good appearance quality, good weather resistance, high visible light transmittance, excellent cold flow resistance and the like.
Description
Technical Field
The invention relates to the technical field of fireproof glue, in particular to transparent fireproof glue, a preparation method thereof and composite fireproof glass containing the transparent fireproof glue.
Background
The fire-proof glass has certain properties of common glass, and also has the properties of controlling fire spread, insulating smoke, insulating heat and the like, thereby providing valuable rescue time for effective rescue in case of fire and reducing the loss of personnel, property and buildings to the maximum extent. The fireproof glass can prevent escape and rescue personnel from being damaged by heat radiation and reduce the destructive power of fire to the minimum degree. Due to the recent frequent occurrence of certain well-known fire disasters of large buildings at home and abroad, people pay more and more attention to the research, development, production and use effects of the composite fireproof glass.
The earliest research on composite fire-resistant glass was organic grouting composite fire-resistant glass. The organic grouting composite fireproof glass has good low-temperature resistance, but poor ultraviolet radiation resistance, high-temperature resistance, hardness and cold flow resistance. The inorganic composite fireproof glass is divided into inorganic airing plate composite fireproof glass and inorganic grouting composite fireproof glass, wherein the airing plate composite fireproof glass has good low-temperature resistance and particularly outstanding hardness and cold flow resistance, but has poor ultraviolet irradiation resistance and high-temperature resistance, is difficult to apply to relatively complex and severe environments such as outdoor environment and the like, has a complex production process, and easily generates micro bubbles in the production process to influence the appearance quality; the inorganic grouting composite fireproof glass has excellent ultraviolet radiation resistance and high temperature resistance, the hardness and the rheostatic resistance are better than those of organic grouting composite fireproof glass, the low temperature resistance is far higher than the national standard although being inferior to that of the organic grouting composite fireproof glass and inorganic airing plate composite fireproof glass, and the low temperature resistance is greatly improved through the development of recent years.
Disclosure of Invention
The invention mainly aims to provide a transparent fireproof glue, a preparation method thereof and composite fireproof glass containing the transparent fireproof glue, and aims to solve the technical problems of reducing the water content in the transparent fireproof glue, effectively improving the fireproof performance of the composite fireproof glass, and ensuring certain flowing performance so as to facilitate pouring.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The transparent fireproof glue provided by the invention comprises the following raw materials in parts by weight: 45-55 parts of nano silicon dioxide sol, 25-40 parts of water glass solution, 0.5-1.0 part of carbon forming agent, 0.1-0.3 part of carbon forming auxiliary agent, 0.3-0.8 part of heat-resistant stabilizer, 0-5 parts of organic anti-condensing agent, 10-15 parts of inorganic anti-condensing agent, 0.05-0.1 part of ion fixing agent, 0.3-0.5 part of storage stabilizer, 0.1-0.5 part of defoaming agent and 0.15-0.3 part of cross-linking agent; wherein the water content of the transparent fireproof glue is 30-50 wt%.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the transparent fireproof glue is prepared by mixing the nano silica sol and the transparent fireproof glue, wherein the mass concentration of the nano silica sol is 45-50%; the particle size of the silicon dioxide in the nano silicon dioxide sol is 50-180 nm.
Preferably, the transparent fireproof glue is characterized in that the modulus of the water glass solution is 1.0-1.5; the mass concentration of the water glass solution is 40-45%.
Preferably, the transparent fire-proof glue is prepared by mixing sodium silicate solution, potassium silicate solution and lithium silicate solutionOne kind of the material is selected; the charring agent is at least one of sucrose, fructose, glucose, granulated sugar and maltose; the char-forming auxiliary agent is at least one selected from potassium dihydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate and sodium hydrogen phosphate; the heat stabilizer is selected from at least one of borax and boric acid; the organic anti-condensation agent is selected from at least one of ethanol, ethylene glycol, propylene glycol, glycerol, isopropanol and pentaerythritol; the inorganic anti-condensing agent is selected from MgCl2And CaCl2At least one of; the ionic fixing agent is at least one selected from zinc oxide, aluminum oxide and starch; the storage stabilizer is at least one of sodium polyphosphate and potassium polyphosphate; the defoaming agent is at least one selected from polyether modified organic silicon, polyoxyethylene polyoxypropylene pentaerythritol ether and polyoxypropylene ethylene oxide glycerol ether; the selected cross-linking agent is selected from at least one of sodium fluorosilicate, potassium fluorosilicate, aluminum fluoride, potassium carbonate, potassium bicarbonate and ammonium bicarbonate.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the preparation method of the transparent fireproof glue provided by the invention, the preparation method comprises the following steps:
sequentially adding a carbon forming agent, a carbon forming auxiliary agent, a heat-resistant stabilizer, an inorganic anti-condensing agent, an ion fixing agent, a storage stabilizer, a defoaming agent and a cross-linking agent into the nano-silica sol, and uniformly stirring to obtain a first solution;
mixing the water glass solution with the first solution, stirring for 30-60min at the temperature of 20-60 ℃, degassing in vacuum, and filtering to obtain transparent fireproof glue;
wherein, by weight, the nano-silica sol is 45 to 55 parts, the water glass solution is 25 to 40 parts, the carbon forming agent is 0.5 to 1.0 part, the carbon forming auxiliary agent is 0.1 to 0.3 part, the heat-resistant stabilizer is 0.3 to 0.8 part, the organic anti-condensing agent is 0 to 5 parts, the inorganic anti-condensing agent is 10 to 15 parts, the ion fixing agent is 0.05 to 0.1 part, the storage stabilizer is 0.3 to 0.5 part, the defoaming agent is 0.1 to 0.5 part and the cross-linking agent is 0.15 to 0.3 part; the water content of the transparent fireproof glue is 30-50 wt%.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the preparation method of the transparent fireproof glue comprises the following steps: degassing under vacuum of less than-0.096 MPa for 30-40 min;
the filtering comprises the following steps: filtering with 150-200 mesh sieve.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the present invention, a heat insulation type composite fireproof glass is provided, which comprises: the fireproof glass comprises a fire-facing surface glass layer, a back fire-facing surface glass layer and at least one middle glass layer positioned between the fire-facing surface glass layer and the back fire-facing surface glass layer, sealing strips along the edge parts of the glass layers are arranged between the adjacent glass layers, structural adhesive is filled in grooves formed by the outer sides of the sealing strips and the adjacent glass layers, and a sealed cavity defined by the inner sides of the sealing strips and the adjacent glass layers is filled with the transparent fireproof adhesive.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the glass layer of the fire-facing surface is float glass or toughened glass, and the thickness of the glass layer of the fire-facing surface is 3-10 mm;
the back fire surface glass layer is made of toughened glass, and the thickness of the back fire surface glass layer is 5-10 mm;
the middle glass layer is float glass or toughened glass, and the thickness of the middle glass layer is 3-10 mm;
the sealing strip is selected from an acrylic acid adhesive tape, a butyl adhesive tape or a glass strip coated with sealing glass adhesive, and the thickness of the sealing strip is 2-10 mm;
the structural adhesive is selected from silicone adhesive or polysulfide adhesive, and the thickness of the structural adhesive is 2-10 mm;
the thickness of the transparent fireproof glue is 2-10 mm.
Preferably, the strength of the intermediate glass layer close to the back fire surface glass layer is less than or equal to that of the back fire surface glass layer.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the invention, the non-heat-insulation type composite fireproof glass comprises: the fireproof glass comprises a fire-facing glass layer and a back-fire glass layer, wherein a sealing strip along the edge of the glass layer is arranged between the fire-facing glass layer and the back-fire glass layer, a groove formed by the outer side of the sealing strip and the fire-facing glass layer and the back-fire glass layer is filled with structural adhesive, and a closed cavity enclosed by the inner side of the sealing strip and the fire-facing glass layer and the back-fire glass layer is filled with the transparent fireproof adhesive.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the non-heat-insulation type composite fireproof glass, the glass layer of the fire-facing side is float glass or toughened glass, and the thickness of the glass layer of the fire-facing side is 3-10 mm;
the back fire surface glass layer is made of toughened glass, and the thickness of the back fire surface glass layer is 5-10 mm;
the middle glass layer is float glass or toughened glass, and the thickness of the middle glass layer is 3-10 mm;
the sealing strip is selected from an acrylic acid adhesive tape, a butyl adhesive tape or a glass strip coated with sealing glass adhesive, and the thickness of the sealing strip is 0.5-10 mm;
the structural adhesive is selected from silicone adhesive or polysulfide adhesive, and the thickness of the structural adhesive is 2-10 mm;
the thickness of the transparent fireproof glue is 0.5-10 mm.
Preferably, the strength of the glass layer on the fire-facing side is less than or equal to that of the glass layer on the fire-back side.
By the technical scheme, the transparent fireproof glue, the preparation method thereof and the composite fireproof glass comprising the transparent fireproof glue have the following advantages:
1. the water content of the transparent fireproof glue is as low as 30-50%, so that the fireproof performance of the composite fireproof glass can be improved by one grade; the main raw materials adopted by the method are nano silicon dioxide sol and water glass solution, compared with the prior artThe reaction of the aqueous alkali, the water glass solution and the silicon dioxide dispersion liquid is slower, and the process is better controlled; although the solid content of the fireproof glue solution is up to 45-50% before curing after reaction, the fireproof glue solution has low viscosity and still has good fluidity, and the viscosity is only 45-50mm measured by a coating-4 cup2S, after 6 hours at room temperature, the viscosity only rises to 50-55mm2S, after 24 hours at room temperature, the viscosity rises to 120-2And/s, still has better fluidity, can realize smooth pouring, and the window period of grouting operation at room temperature can reach 24 h. If the solid phase content of the fireproof glue solution prepared by the fumed silica dispersion reaches about 45 percent, the viscosity can reach 150mm2The window period of grouting operation at room temperature is only 1-2 h. In addition, due to the addition of the inorganic anti-condensation agent, the aqueous solution of the inorganic anti-condensation agent has a lower freezing point, so that the low-temperature resistance of the fireproof glue is integrally improved, and the heat preservation at minus 25 ℃ can be realized for 6 hours without change.
2. When a fire disaster occurs, the glass layer on the fire-facing surface is cracked by heat, the first layer of transparent fireproof glue foams and expands after absorbing heat to form an opaque fireproof layer, and the second layer of transparent fireproof glue and the rear layer of transparent fireproof glue gradually foam and expand to form the fireproof layer along with the time extension, so that the spread of flame is effectively prevented, and the conduction and radiation of heat can be prevented.
3. When a fire disaster occurs, the glass layer on the fire-facing surface is cracked by heat, the transparent fireproof glue foams and expands after absorbing heat to form an opaque fireproof layer, so that the flame is effectively prevented from spreading, and the conduction and radiation of partial heat can be prevented, thereby keeping the integrity of the glass layer on the fire-facing surface, playing a role in protecting the safety of life and property of people, and being suitable for building external window fireproof glass, refuge room fireproof glass, indoor partition fireproof glass and the like.
4. The transparent fireproof glue has the advantages of high production safety and simple production process, and the prepared heat-insulation type composite fireproof glass and non-heat-insulation type composite fireproof glass have the characteristics of good appearance quality, good weather resistance, high visible light transmittance, high hardness of the transparent fireproof glue, excellent cold flow resistance and the like.
At present, the main stream of inorganic grouting composite fireproof glass adopts the in-situ reaction of a dispersion liquid of silicon dioxide powder and an alkali solution as a fireproof glue layer material, the alkali solution belongs to a strong alkaline dangerous product, personal injury is easily caused to operators in the production process, and meanwhile, the reaction process is not easy to control; the invention adopts the sodium silicate to replace the alkali solution, so that the production process is simpler, the reaction process is more controllable, and the occurrence of danger in the production process can be reduced.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic structural diagram of a heat-insulating composite fire-resistant glass provided by an embodiment of the invention;
FIG. 2 is a schematic structural view of another heat-insulating composite fire-resistant glass provided by an embodiment of the invention;
fig. 3 shows a schematic structural diagram of a non-thermal insulation type composite fireproof glass provided by an embodiment of the invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the transparent fire-proof glue and the preparation method thereof and the composite fire-proof glass comprising the same according to the present invention, and the specific implementation manner, structure, characteristics and effects thereof, with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
One embodiment of the invention provides a transparent fireproof adhesive which comprises the following raw materials in parts by weight: 45-55 parts of nano silicon dioxide sol, 25-40 parts of water glass solution, 0.5-1.0 part of carbon forming agent, 0.1-0.3 part of carbon forming auxiliary agent, 0.3-0.8 part of heat-resistant stabilizer, 0-5 parts of organic anti-condensing agent, 10-15 parts of inorganic anti-condensing agent, 0.05-0.1 part of ion fixing agent, 0.3-0.5 part of storage stabilizer, 0.1-0.5 part of defoaming agent and 0.15-0.3 part of cross-linking agent; wherein the water content of the transparent fireproof glue is 30-50 wt%.
The water content of the transparent fireproof glue is lower and is as low as 30-50 wt%, so that the fireproof performance of the composite fireproof glass can be improved by one grade; but the viscosity is not high and still has good fluidity. In addition, due to the addition of the inorganic anti-condensation agent, the aqueous solution of the inorganic anti-condensation agent has a lower freezing point, so that the low-temperature resistance of the fireproof glue is integrally improved, and the heat preservation at minus 25 ℃ can be realized for 6 hours without change.
In the embodiment, the transparent fireproof glue can keep higher transparency and has higher hardness by limiting the weight ratio of the nano silica sol to the water glass solution; the larger the weight ratio, the higher the hardness, the better the resistance to flow, but the light transmittance is too poor; the smaller the weight ratio, the higher the light transmittance, but the lower the hardness, the worse the resistance to flow. Therefore, the weight ratio of the nano silica sol to the water glass solution is 9-11: and when the thickness is 5-8, the high transparency of the fireproof adhesive can be ensured, and the fireproof adhesive has high hardness and good rheologic resistance.
In some embodiments, the nanosilica sol has a mass concentration of 45-50%;
the particle size of the silicon dioxide in the nano silicon dioxide sol is 50-180 nm.
In the present embodiment, the mass concentration of the nano silica sol is 45-50%, and the concentration is too low, such as below 45%, which cannot satisfy the requirement of the present application for the water content, while the concentration is too high, such as above 50%, which may affect the fluidity of the waterproof adhesive.
The nano-silica sol is prepared by wet chemistry, wherein the wet chemistry method comprises ion exchange resin treatment, acid neutralization or silicate hydrolysis; the smaller the particle size of the nano silicon dioxide sol is, the larger the specific surface area is, the larger the surface energy is, and the higher the reaction activity is; conversely, the larger the particle size, the smaller the specific surface area, the smaller the surface energy, and the lower the reactivity. When the particle size of the nano silicon dioxide sol is too small and less than 50nm, the reaction is too rapid, and the slurry becomes viscous quickly, which is not beneficial to perfusion; when the particle size of the nano-silica sol is too large and is larger than 180nm, the reaction activity is too low, the nano-silica sol is difficult to be transparent in the curing process of an oven, and the energy consumption is greatly increased. The liquid phase method silica sol is preferred because: the particle size distribution of the liquid phase method silica sol is more uniform, and the unimodal distribution accords with the normal distribution.
Further, the silica has a particle size distribution index PDI of 0.02 to 0.04, preferably 0.03.
In some embodiments, the water glass solution has a modulus of 1.0 to 1.5; the mass concentration of the water glass solution is 40-45%.
In this embodiment, the water glass solution includes at least one of a sodium water glass solution, a potassium water glass solution, and a lithium water glass solution; when used, different types of water glass, especially lithium water glass, can be used with the same mechanism, with some differences in concentration. In the present embodiment, commercially available water glass may be generally selected, or home-made water glass may be selected, and the concentration of water glass is preferably adjusted to 40 to 45%.
In some preferred embodiments, the water glass solution is a sodium water glass solution.
In some preferred embodiments, the water glass solution is a potassium water glass solution.
In some preferred embodiments, the water glass solution is a mixed solution of a sodium water glass solution and a potassium water glass solution, and the molar ratio of the sodium water glass solution to the potassium water glass solution is 1: 1-5.
In the embodiment, the modulus of the water glass solution is 1.0-1.5, and the lower the modulus, the lower the viscosity of the water glass, so that the water glass is more convenient to use and has better storage stability. The prior art is obtained by reacting a silica dispersion with an alkali solution having a content of less than 50%. Taking a potassium water glass solution as an example, when the content of the alkali solution is higher than 50%, KOH is very dissolved out, so that the proportioning of the raw materials is inaccurate. This also limits the water content in the caustic solution to not less than 50%. Adopt the water glass solution of higher concentration in this embodiment, can show the solid content who improves transparent fire prevention glue, reduce its moisture content to effectively promote fire prevention glass's fire behavior.
In some embodiments, the char-forming agent is selected from at least one of sucrose, fructose, glucose, granulated sugar, and maltose;
the char-forming auxiliary agent is at least one selected from potassium dihydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate and sodium hydrogen phosphate;
the heat stabilizer is selected from at least one of borax and boric acid;
the organic anti-condensation agent is selected from at least one of ethanol, ethylene glycol, propylene glycol, glycerol, isopropanol and pentaerythritol;
the inorganic anti-condensing agent is selected from MgCl2And CaCl2At least one of;
the ionic fixing agent is at least one selected from zinc oxide, aluminum oxide and starch;
the storage stabilizer is at least one of sodium polyphosphate and potassium polyphosphate;
the defoaming agent is at least one selected from polyether modified organic silicon, polyoxyethylene polyoxypropylene pentaerythritol ether and polyoxypropylene ethylene oxide glycerol ether;
the selected cross-linking agent is selected from at least one of sodium fluorosilicate, potassium fluorosilicate, aluminum fluoride, potassium carbonate, potassium bicarbonate and ammonium bicarbonate.
Compared with the single use of the organic anti-condensation agent, the inorganic anti-condensation agent with the same concentration has a lower freezing point, so that the fireproof glue has more excellent low-temperature resistance.
The foaming principle of the transparent fireproof glue provided by the embodiment of the invention is as follows:
when the transparent fireproof glue meets fire, the evaporation of water is the driving force for foaming the fireproof glue, and the whole foaming process can be divided into four stages:
in the first stage, analysis of TG-DSC (thermogravimetric-differential scanning calorimetry) shows that evaporation of a large amount of molecular water is an initial driving force for foaming of the fireproof adhesive when encountering fire, and the fireproof adhesive almost cannot play a heat insulation role after being foamed and expanded into a spherical hollow shell; the spherical hollow shell formed by the method is too large in volume due to the fact that the content of free water is too high, the whole volume can be larger in foaming at the later stage, but the porosity is reduced, and the heat insulation performance is reduced. Therefore, the water content in the fireproof glue has great influence on the heat preservation and insulation performance. According to the invention, by controlling the water content to be 30-50 wt%, the foaming porosity is small and dense, and the heat insulation effect is good under the premise of ensuring that the fireproof glue has enough foaming driving force and fluidity.
The second stage, which is the stage where the foaming volume increases the fastest, is mainly caused by the hydrolytic evaporation due to the polymerization of adsorbed water and silanol groups in the fire-proof glue. At this stage, a large number of dense closed air holes are formed, and the heat preservation effect is good;
in the third stage, the absorbed water completely disappears, but the polymerization of silanol groups still proceeds, so that the foaming volume is further maximized, and the heat preservation and insulation effects of the fireproof glue are best;
the fourth stage, the volume shrinkage stage, is the stage where the foaming volume is drastically reduced due to the significant densification of the region reaching the glass transition temperature, at which the thermal insulation properties of the fire-proof glue gradually decrease.
One embodiment of the invention also provides a preparation method of the transparent fireproof glue, which specifically comprises the following steps:
sequentially adding a carbon forming agent, a carbon forming auxiliary agent, a heat-resistant stabilizer, an inorganic anti-condensing agent, an ion fixing agent, a storage stabilizer, a defoaming agent and a crosslinking agent into the nano silica sol, stirring while adding, and uniformly stirring to obtain a first solution;
adding a water glass solution into the first solution, or adding the first solution into a potassium water glass solution, transferring the solution into a vacuum stirring kettle, controlling the system temperature within 60 ℃, preferably 20-60 ℃, stirring for 30-60min, degassing for 30-40min under the vacuum of less than-0.096 MPa, and filtering the solution by using a 150-mesh and 200-mesh screen after pressure relief to obtain the transparent fireproof adhesive;
wherein, the raw materials in the method are the same as the raw materials of the transparent fireproof glue, specifically, by weight, 45-55 parts of nano silicon dioxide sol, 25-40 parts of water glass solution, 0.5-1.0 part of char forming agent, 0.1-0.3 part of char forming auxiliary agent, 0.3-0.8 part of heat-resistant stabilizer, 10-20 parts of inorganic anti-condensation agent, 0.05-0.1 part of ion fixing agent, 0.3-0.5 part of storage stabilizer, 0.1-0.5 part of defoaming agent and 0.15-0.3 part of cross-linking agent; the water content of the transparent fireproof glue is 30-50 wt%.
As shown in fig. 1 and 2, an embodiment of the present invention provides a heat-insulating composite fire-resistant glass, which includes: the fireproof glass comprises a fire-facing surface glass layer 11, a fire-facing surface glass layer 12 and at least one middle glass layer 13 positioned between the fire-facing surface glass layer 11 and the fire-facing surface glass layer 12, as shown in fig. 1, the middle glass layer 13 is one layer, as shown in fig. 2, the middle glass layer 13 is two layers, a plurality of middle glass layers 13 can be arranged according to needs, 1-5 layers are preferred, the thicknesses of the middle glass layers can be the same or different, and the specific thickness can be designed according to the thickness and the fire-resistant limit time of the whole glass. The sealing strips 14 along the edge parts of the glass layers are arranged between the adjacent glass layers, the distance between each sealing strip 14 and the edge of each glass layer is about 5-10mm, the height of each sealing strip 14 is about 2-10mm, each sealing strip 14 can be of an integral structure, and can also be formed by splicing a plurality of small sealing strips according to the shape requirement, for example, when the glass is rectangular, the sealing strips are formed by sequentially connecting four small sealing strips end to form a rectangular structure, when the glass is triangular, the sealing strips are formed by sequentially connecting three small sealing strips end to form a triangular structure, and when the glass is hexagonal, the sealing strips are formed by sequentially connecting three small sealing strips end to form a hexagonal structure; the groove formed by the outer side of the sealing strip 14 and the adjacent glass layer is filled with structural adhesive 15, and the closed cavity enclosed by the inner side of the sealing strip 14 and the adjacent glass layer is filled with transparent fireproof adhesive 16. The specific formulation and preparation method of the transparent fire-proof adhesive 16 can be used in the foregoing embodiments, and are not described herein again. The heat-insulating composite fireproof glass made of the transparent fireproof glue has high fire resistance and heat insulation, and as the water content of the used transparent fireproof glue is as low as 30-50 wt%, the foaming layer is uniformly foamed, the porosity is high, the fire resistance and heat insulation are good, and the fire resistance grade of the fireproof glass can be improved by one grade. The reason is that: 1. the water content of the transparent fireproof glue layer is as low as 30-50 wt%, the hardness at room temperature is high, and in the temperature rising process, the transparent fireproof glue has stronger adhesiveness, is easier to adhere to the surface of glass and is difficult to fall off, a formed foaming layer is relatively thicker, and the fireproof and heat-insulating properties are better; 2. in the foaming process of the transparent fireproof glue layer, because the content of free water is less, the initially formed bubbles are smaller, and the expansion of the later-stage bubbles is limited, the bubbles of the transparent fireproof glue foaming layer are small, uniform and compact, the porosity is higher, and the fireproof and heat-insulating properties are better; 3. the transparent fireproof glue layer has the advantages of low water content, low water vapor formed during foaming of the transparent fireproof glue layer, low pressure and capability of reducing the risk of breakage of the glass layer of the back fire surface when the outermost transparent fireproof glue layer is foamed, so that the fireproof and heat-insulating properties of the fireproof glue layer are improved.
Furthermore, as the tin surface side of the glass layer has stronger corrosion resistance, the tin surface sides of the glass layer on the fire facing side and the glass layer on the back fire facing side face towards the transparent fireproof glue. This is because the film layer of the coated glass is located on the non-tin surface (air surface), which can enhance the corrosion resistance of the non-tin surface. The glass of the interlayer is preferably coated glass to enhance the overall corrosion resistance of the glass.
In some embodiments, the fire-facing glass layer is float glass or toughened glass, and the thickness of the fire-facing glass layer is 3-10 mm;
the back fire surface glass layer is made of toughened glass, and the thickness of the back fire surface glass layer is 5-10 mm;
the middle glass layer is float glass or toughened glass, and the thickness of the middle glass layer is 3-10 mm;
the sealing strip is selected from an acrylic acid adhesive tape, a butyl adhesive tape or a glass strip coated with sealing glass adhesive, and the thickness of the sealing strip is 2-10 mm;
the structural adhesive is selected from silicone adhesive or polysulfide adhesive, and the thickness of the structural adhesive is 2-10 mm;
the thickness of the transparent fireproof glue is 2-10 mm.
In this embodiment, the final thickness of the sealing strip is 1-10mm, i.e. the thickness of the cavity is 1-10 mm. The situation of the sealing strip is different, and if the sealing strip is a glass strip or an acrylic rubber strip, the relevant size can be directly selected; if the adhesive tape is a butyl adhesive tape, the adhesive tape with the thickness being a little larger than the final size needs to be selected, and the required final size is achieved after hot pressing.
The silicone adhesive or polysulfide adhesive is fluid before curing, and has no thickness, but after the polysulfide adhesive or the silica sol is injected into the cavity, the thickness of the cavity is the same, and the thickness of the structural adhesive is the same.
In some embodiments, the strength of the intermediate glass layer adjacent to the back fire side glass layer is less than or equal to the strength of the back fire side glass layer.
The intensity of the middle glass layer close to the back fire surface glass layer is less than or equal to that of the back fire surface glass layer, and when the last layer of transparent fireproof glue layer begins to foam and expand, the back fire surface glass layer is prevented from being broken due to low intensity, so that the glass loses integrity and the whole fire-resistant and heat-insulating performance of the glass is reduced.
Furthermore, one embodiment of the present invention further provides a method for preparing a heat insulation type composite fireproof glass, which specifically comprises the following steps:
(1) the method comprises the following steps of obtaining a required fire-facing glass layer, an intermediate glass layer and a back fire glass layer through cutting, edging, chamfering and other treatments, toughening the glass layer to be toughened, preferably toughening the back fire glass layer, and ensuring that the thickness of the intermediate glass layer close to the back fire glass layer is not more than that of the back fire glass layer;
(2) cleaning a fire-facing glass layer, an intermediate glass layer and a back fire surface glass layer, wherein the following steps can be started from any glass layer without strict requirements, but the sequence of each glass layer is required to be strictly designed and can not be changed randomly, the specific steps are described below by taking the glass layer from the back fire surface as an example, sealing strips are stacked along the edge of the back fire surface glass layer, a grouting opening is reserved at one corner of glass, and the intermediate glass layer and the back fire surface glass layer are aligned to the edge and then are adhered and fixed through a sealing adhesive to form a cavity with the grouting opening; continuously stacking sealing strips on the edge part of the middle glass layer, reserving a grouting opening at the same position, aligning the edges of the second middle glass layer and the first middle glass layer, and then adhering and fixing the second middle glass layer and the first middle glass layer through a sealant to form a second cavity with the grouting opening; … … bonding and fixing the middle glass layer and the back fire surface glass layer to form a multi-glass and multi-cavity structure;
if the sealing strip is a butyl strip, hot pressing is needed to reach the required thickness; if the sealing strip is an acrylic acid adhesive tape or a glass strip coated with sealing glass cement, only pressing is needed;
filling structural adhesive in a groove formed by the outer side of the sealing strip and the adjacent glass layer;
(3) preparing transparent fireproof glue: obtaining the transparent fireproof glue for perfusion by adopting the preparation method of the transparent fireproof glue;
(4) pouring the transparent fireproof glue prepared in the step (3) into a cavity formed by the inner side of the sealing strip and the adjacent glass layer in the step (2), and quantitatively pouring according to the density of the transparent fireproof glue and the volume of the cavity; filling the whole cavity with the transparent fireproof glue, and sealing the grouting opening with sealant and structural glue to obtain a semi-finished product of the heat-insulating composite fireproof glass;
(5) and (4) transferring the semi-finished product of the heat-insulating composite fireproof glass prepared in the step (4) into an oven, and reacting for 6-36h at the temperature of 60-80 ℃ to react and solidify the transparent fireproof collagen in the cavity, thereby finally obtaining the heat-insulating composite fireproof glass.
As shown in fig. 3, an embodiment of the present invention also provides a non-thermal insulation type composite fire-resistant glass, which includes: the glass comprises a fire-facing glass layer 21 and a back-fire glass layer 22, wherein a sealing strip 23 along the edge of the glass layer is arranged between the fire-facing glass layer 21 and the back-fire glass layer 22, the distance between the sealing strip 23 and the edge of the glass layer is about 5-10mm, the height of the sealing strip 23 is about 2-10mm, the sealing strip 23 can be of an integral structure, or can be formed by splicing a plurality of small sealing strips according to the shape requirement, for example, when the glass is rectangular, the sealing strip is of a rectangular structure formed by sequentially connecting four small sealing strips end to end, when the glass is of a trilateral shape, the sealing strip is of a triangular structure formed by sequentially connecting three small sealing strips end to end, and when the glass is of a hexagonal shape, the sealing strip is of a hexagonal structure formed by sequentially connecting three small sealing strips end to end; the groove formed by the outer side of the sealing strip 23 and the glass layer 21 and the glass layer 22 on the fire facing side is filled with structural adhesive 24, and the sealed cavity surrounded by the inner side of the sealing strip 23 and the glass layer 21 and the glass layer 22 on the fire facing side is filled with transparent fireproof adhesive 25. The specific formulation and preparation method of the transparent fire-proof adhesive 26 can be used in the foregoing embodiments, and are not described herein again.
The non-heat-insulation composite fireproof glass manufactured by the transparent fireproof glue has higher fire resistance integrity, and the fire resistance grade of the fireproof glass can be improved by one grade due to the fact that the water content of the used transparent fireproof glue is low, the foaming layer is uniformly foamed, the porosity is high, and the fire resistance and heat insulation are good. The reason is that: 1. the transparent fireproof glue layer has low water content and high hardness at room temperature, and has stronger transparent fireproof glue adhesiveness, is easier to adhere to the surface of glass and is difficult to fall off in the temperature rising process, so that a formed foaming layer is relatively thicker, and has better fire resistance and heat insulation; 2. in the foaming process of the transparent fireproof glue layer, because the content of free water is less, the initially formed bubbles are smaller, and the expansion of the later-stage bubbles is limited, the bubbles of the transparent fireproof glue foaming layer are small, uniform and compact, the porosity is higher, and the fireproof and heat-insulating properties are better; 3. the transparent fireproof glue layer has the advantages of low water content, low water vapor formed during foaming of the transparent fireproof glue layer, low pressure and capability of reducing the risk of breakage of the glass layer of the back fire surface when the outermost transparent fireproof glue layer is foamed, so that the fireproof and heat-insulating properties of the fireproof glue layer are improved.
Furthermore, as the tin surface side of the glass layer has stronger corrosion resistance, the tin surface sides of the glass layer on the fire facing side and the glass layer on the back fire facing side face towards the transparent fireproof glue. This is because the film layer of the coated glass is located on the non-tin surface (air surface), which can enhance the corrosion resistance of the non-tin surface. The glass of the interlayer is preferably coated glass to enhance the overall corrosion resistance of the glass.
In some embodiments, the fire-facing glass layer is float glass or toughened glass, and the thickness of the fire-facing glass layer is 3-10 mm;
the back fire surface glass layer is made of toughened glass, and the thickness of the back fire surface glass layer is 5-10 mm;
the middle glass layer is float glass or toughened glass, and the thickness of the middle glass layer is 3-10 mm;
the sealing strip is selected from an acrylic acid adhesive tape, a butyl adhesive tape or a glass strip coated with sealing glass adhesive, and the thickness of the sealing strip is 0.5-10 mm;
the structural adhesive is selected from silicone adhesive or polysulfide adhesive, and the thickness of the structural adhesive is 2-10 mm;
the thickness of the transparent fireproof glue is 0.5-10 mm.
In some embodiments, the strength of the fire-facing glass layer is ≦ the strength of the fire-back glass layer.
Under normal conditions, the glass layer on the fire-facing surface is firstly burst when meeting fire, and the transparent fireproof glue layer begins to foam and expand. Under special conditions, the temperature rises slowly, the glass layer on the fire-facing surface cannot be burst in time, and the transparent fireproof glue layer begins to foam. If the strength of the glass layer on the back fire surface is lower than that of the glass layer on the front fire surface, the glass layer on the back fire surface can be broken, so that the integrity of the fireproof glass is invalid, and the fireproof performance of the non-heat-insulation type composite fireproof glass is not up to the standard.
Further, an embodiment of the present invention also provides a method for preparing a non-thermal insulation type composite fireproof glass, which includes:
(1) the required glass layer of the fire-facing surface and the glass layer of the back fire-facing surface are obtained through cutting, edging, chamfering and other treatments, the glass layer to be toughened is preferably toughened, the glass layer of the back fire-facing surface is ensured to be thinner than or equal to the thickness of the glass layer of the back fire-facing surface, the strength of the glass layer of the back fire-facing surface is ensured to be larger than that of the glass layer of the fire-facing surface, the situation that the back fire-facing surface is broken and loses integrity due to expansion of transparent fireproof glue when encountering fire is prevented, and in some embodiments, the toughening strength of the glass layer of the fire-facing surface is smaller than or equal to 75% of the toughening strength of the glass layer of the back fire-facing surface; however, in consideration of the necessity of double-sided fire protection, in some embodiments, the glass layer of the fire-facing side is simultaneously tempered, and the tempered glass with the same thickness is selected for the glass layer of the fire-facing side and the glass layer of the back fire-facing side.
(2) Cleaning a glass layer on the fire facing side and a glass layer on the back fire side, wherein the following steps can be started from the glass layer on the fire facing side or the glass layer on the back fire side, the specific steps are described by taking the glass layer on the back fire side as an example, a sealing strip is arranged along the edge part of the glass layer on the back fire side, a grouting opening is reserved at one corner of the glass, and the glass layer on the fire facing side and the glass layer on the back fire side are aligned to the edge and then are bonded and fixed through a sealing adhesive to form a cavity with the grouting opening; if the sealant is a butyl adhesive tape, hot pressing is required to reach the required thickness; if the sealing strip is an acrylic acid adhesive tape or a glass strip coated with sealing glass cement, only pressing is needed; filling structural adhesive in a groove formed by the outer side of the sealing strip and the glass layer on the fire-facing surface and the glass layer on the back fire surface;
(3) preparing transparent fireproof glue: obtaining the transparent fireproof glue for perfusion by adopting the preparation method of the transparent fireproof glue;
(4) pouring the transparent fireproof glue prepared in the step (3) into a cavity formed by the inner side of the sealing strip, the fire-facing surface glass layer and the back fire surface glass layer in the step (2), and quantitatively pouring according to the density of the transparent fireproof glue and the volume of the cavity; filling the whole cavity with the transparent fireproof glue, and sealing the grouting opening with sealant and structural glue to obtain a semi-finished product of the non-heat-insulation composite fireproof glass;
(5) and (4) transferring the semi-finished product of the non-heat-insulation type composite fireproof glass obtained in the step (4) into an oven, reacting for 2-8h at the temperature of 60-90 ℃, and reacting and curing the transparent fireproof collagen in the cavity to finally obtain the non-heat-insulation type composite fireproof glass.
The transparent fireproof glue can be used for preparing heat-insulation type composite fireproof glass and can also be used for preparing non-heat-insulation type composite fireproof glass. The heat-insulation composite fireproof glass needs to play a heat-insulation effect, so that the fireproof interlayer is thick, the foaming thickness is larger when fire occurs, and the heat-insulation effect is better. The non-heat-insulation type composite fireproof glass layer only needs to protect the glass layer of the back fire surface from cracking, so that the glass layer is generally thinner and lighter in weight when being used for an outer window, and the condition of being thick is certainly not eliminated.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
In the following examples of the present invention, all reagents used are commercially available unless otherwise specified, and the methods involved are conventional unless otherwise specified.
In the following examples of the present invention, the components referred to are all commercially available products well known to those skilled in the art unless otherwise specified.
Example 1
The transparent fireproof glue is prepared from the following raw materials in parts by weight: 50kg of nano silica sol with the mass concentration of 45 percent, 38kg of potassium water glass solution with the mass concentration of 40 percent, 0.5kg of cane sugar, 0.1kg of monopotassium phosphate, 0.3kg of boric acid, 5kg of glycerol and MgCl210kg, starch 0.05kg, sodium polyphosphate 0.4kg, polyether modified organic silicon 0.5kg and sodium fluosilicate 0.15 kg.
The preparation method of the transparent fireproof glue specifically comprises the following steps: sequentially adding a carbon forming agent, a carbon forming auxiliary agent, a heat-resistant stabilizer, an inorganic anti-condensing agent, an ion fixing agent, a storage stabilizer, a defoaming agent and a cross-linking agent into the nano-silica sol, and uniformly stirring to obtain a first solution; mixing the potassium water glass solution with the first solution, stirring at 40 ℃ for 50min, degassing under-0.08 MPa for 40min, and filtering by using a screen with 180 meshes of 160-.
The method for preparing the heat-insulating composite fireproof glass by using the transparent fireproof glue comprises the following specific steps:
(1) obtaining a glass layer of a fire-facing surface, a glass layer of a middle glass layer and a glass layer of a back fire surface through cutting, edging, chamfering and tempering treatment;
(2) adopting a butyl adhesive tape with the thickness of 7mm as a sealing strip, stacking the butyl adhesive tape on the surface of the glass layer of the fire-facing surface at a position 6-10mm away from the edge of the glass along the periphery of the glass, leaving a grouting opening at one corner, and then placing the middle glass layer on the glass layer of the fire-facing surface on which the butyl adhesive tape is stacked; then stacking another butyl rubber strip with the thickness of 7mm on the surface of the middle glass layer along the periphery of the glass at a position 6-10cm away from the edge of the glass, reserving a grouting opening at the same position, then placing the back-fire surface glass layer on the middle glass layer on which the butyl rubber strip is stacked, and placing a plurality of fixed-thickness blocks with the thickness of 5mm at intervals close to the butyl rubber strip on the edge of the glass; laminating the laminated glass by a heatable laminating machine until the thickness of the cavity is 5mm, and simultaneously bonding the glass layer on the fire-facing surface, the middle glass layer and the glass layer on the fire-facing surface together by using a butyl adhesive tape; the mixed double-component silicone adhesive is injected into a groove formed between a butyl adhesive tape and an adjacent glass layer by a glue injector, the two-component silicone adhesive is placed overnight, after the silicone adhesive is solidified, the prepared transparent fireproof adhesive is respectively injected into two closed cavities, the quantitative injection is carried out according to the volume of the cavity, the transparent fireproof adhesive is used for filling the whole cavity, after the injection is finished, the butyl adhesive tape is used for sealing, and the silicone adhesive is respectively used for filling at the sealing position, so that a composite fireproof glass semi-finished product is obtained;
(3) and (3) sending the semi-finished product of the composite fireproof glass obtained in the step (2) into an oven, carrying out curing reaction for 8 hours at the temperature of 75 ℃, and forming a transparent fireproof glue layer after in-situ reaction and curing to obtain the heat-insulation type composite fireproof glass finished product.
As shown in fig. 1, the heat-insulating composite fire-proof glass a1 obtained in the step (3) includes: the fireproof glass comprises a fire-facing glass layer 11, a back fire-facing glass layer 12 and an intermediate glass layer 13, wherein each glass layer is toughened glass with the thickness of 5mm, and the thickness of two transparent fireproof glue layers 16 is also 5 mm.
In the following detection, the thickness is measured by a vernier caliper; the transmittance is measured by a transmittance tester; the fire-resistant and heat-insulating performance standard is that a professional burning detection furnace is adopted; the cold resistance is detected by a high-low temperature box; detecting the heat resistance by using an oven; the ultraviolet irradiation resistance is carried out in an ultraviolet irradiation resistance tester.
Through detection, the performance indexes of the heat-insulating composite fireproof glass obtained in the embodiment 1 are as follows: total thickness: 25mm, visible light transmittance: 82.3%, fire resistance and heat insulation: 113min, cold resistance: no change in appearance at constant temperature of-25 ℃ for 6h, heat resistance: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 2.1 percent.
The method for preparing the non-heat-insulation type composite fireproof glass by using the transparent fireproof glue comprises the following specific steps:
(1) respectively carrying out cutting, edge grinding, chamfering and toughening treatment on each glass layer;
(2) a butyl adhesive tape with the thickness of 2mm is used as a sealant, the butyl adhesive tape is stacked on the surface of 5mm toughened glass at a position 6-10mm away from the edge along the periphery of the glass, a grouting opening is reserved at one corner, then 3mm non-toughened glass is placed on the 5mm toughened glass stacked with the butyl adhesive tape, the glass is pressed to the thickness of 1mm of a cavity through a heatable laminating machine, and meanwhile, the two pieces of glass are bonded together by the butyl adhesive tape. And then, driving the mixed double-component silicone adhesive into a groove between the butyl adhesive and the glass plate by using a gluing machine, placing the mixed double-component silicone adhesive for one night, pouring inorganic fireproof liquid into the two closed cavities after the silicone adhesive is solidified, carrying out quantitative pouring according to the volume of the cavities, filling the fireproof liquid into the whole cavity after pouring, sealing the cavities by using the butyl adhesive, and respectively filling the sealing parts by using the silicone adhesive to obtain the non-heat-insulation type composite fireproof glass semi-finished product.
(3) And (3) sending the semi-finished product of the non-heat-insulation type composite fireproof glass obtained in the step (2) into an oven, curing and reacting for 8 hours at 60 ℃, and curing the semi-finished product of the non-heat-insulation type composite fireproof glass by an inorganic fireproof liquid in-situ reaction method to form a transparent fireproof glue layer so as to obtain a finished product of the non-heat-insulation type composite fireproof glass.
As shown in fig. 3, the non-heat-insulating composite fire-proof glass B1 obtained in the step (3) includes: a fire-facing glass layer 21 and a fire-backing glass layer 22. Wherein the glass layer 21 on the fire facing side is float glass with the thickness of 3mm, and the glass layer on the fire back side is toughened glass with the thickness of 5 mm. The thickness of the transparent fireproof glue layer 25 is 1 mm.
Through detection, the performance indexes of the non-heat-insulation type composite fireproof glass obtained in the embodiment 1 are as follows: total thickness: 9mm, visible light transmittance: 85.8%, refractory integrity: 115min, cold resistance: no change in appearance at constant temperature of-25 ℃ for 6h, heat resistance: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 2.4 percent.
Example 2
The transparent fireproof glue is prepared from the following raw materials in parts by weight: 55kg of nano silica sol with the mass concentration of 48 percent, 28kg of sodium water glass solution with the mass concentration of 42 percent, 0.3kg of fructose, 0.2kg of potassium hydrogen phosphate, 0.5kg of borax, 2kg of ethylene glycol and MgCl213kg, zinc oxide 0.1kg, potassium polyphosphate 0.5kg, polyoxyethylene polyoxypropylene pentaerythritol ether 0.2kg and aluminum fluoride 0.3 kg.
The preparation method of the transparent fireproof glue specifically comprises the following steps: sequentially adding a carbon forming agent, a carbon forming auxiliary agent, a heat-resistant stabilizer, an inorganic anti-condensing agent, an ion fixing agent, a storage stabilizer, a defoaming agent and a cross-linking agent into the nano-silica sol, and uniformly stirring to obtain a first solution; mixing the potassium water glass solution with the first solution, stirring at 60 ℃ for 30min, degassing under-0.06 MPa for 30min, and filtering by using a screen with 150-mesh and 170-mesh to obtain the transparent fireproof glue.
The same preparation method as that of example 1 was used to prepare heat-insulating composite fire-resistant glass a2, which is different from that of example 1 in that: the obtained heat-insulating composite fireproof glass, as shown in fig. 2, comprises: the fire-resistant glass layer comprises a fire-facing surface glass layer 11, a fire-facing surface glass layer 12 and two middle glass layers 13, and transparent fireproof glue prepared in the front is poured into three formed closed cavities. The glass layer 11 of the fire-facing side and the glass layer 12 of the back fire-facing side are both made of toughened glass with the thickness of 8mm, the two middle glass layers 13 are both made of toughened glass with the thickness of 5mm, and the three transparent fireproof glue layers 16 are both 5mm in thickness.
Through detection, the same detection method as that of the embodiment 1 is adopted, and the performance indexes of the heat-insulating composite fireproof glass of the embodiment 2 are as follows: total thickness: 41mm, visible light transmittance: 78.8%, fire-resistant and heat-insulating property: 148min, cold resistance: no change in appearance at constant temperature of-25 ℃ for 6h, heat resistance: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 2.7 percent.
The non-heat-insulation type composite fire-resistant glass B2 was prepared by the same preparation method as in example 1, and as shown in FIG. 3, it included: a fire-facing glass layer 21 and a fire-backing glass layer 22. Wherein the glass layer 21 of the fire-facing surface and the glass layer 22 of the back fire-facing surface are both toughened glass with the thickness of 8 mm. The thickness of the transparent fireproof glue layer 25 is 2 mm.
Through detection, the performance indexes of the non-heat-insulation type composite fireproof glass obtained in the embodiment 2 are as follows: total thickness: 18mm, visible light transmittance: 82.5%, refractory integrity: 132min, cold resistance: no change in appearance at constant temperature of-25 ℃ for 6h, heat resistance: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 1.6 percent.
Example 3
The transparent fireproof glue is prepared from the following raw materials in parts by weight: 45kg of nano silica sol with the mass concentration of 50 percent, 40kg of sodium water glass solution and potassium water glass solution which are mixed according to the molar ratio of 1:3 and have the mass concentration of 45 percent, 1.0kg of glucose, 0.3kg of sodium dihydrogen phosphate, 0.8kg of borax, MgCl2 7kg、CaCl28kg, 2kg of isopropanol, 3kg of pentaerythritol, 0.08kg of alumina, 0.3kg of potassium polyphosphate, 0.1kg of polyoxypropylene ethylene oxide glycerol ether and 0.2kg of potassium bicarbonate.
The same preparation method as that of example 1 is adopted to prepare the heat-insulation type composite fireproof glass A3, and the structure of the heat-insulation type composite fireproof glass in the embodiment is as follows: the glass layer of the fire-facing side and the glass layer of the back fire-facing side both adopt toughened glass with the thickness of 5mm, the three middle glass layers are all toughened glass with the thickness of 5mm, and the thicknesses of the four transparent fireproof glue layers are all 5 mm.
The performance indexes of the heat-insulating composite fireproof glass of the embodiment 3 are as follows: total thickness 45mm, visible light transmittance: 76.9%, fire-resistant and heat-insulating properties: 177min, cold resistance: no change in appearance at constant temperature of-25 ℃ for 6h, heat resistance: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 1.9 percent.
The non-heat-insulation type composite fire-resistant glass B3 was prepared by the same preparation method as in example 1, and as shown in FIG. 3, it included: a fire-facing glass layer 21 and a fire-backing glass layer 22. Wherein the glass layer 21 of the fire-facing surface and the glass layer 22 of the back fire-facing surface are both toughened glass with the thickness of 8 mm. The thickness of the transparent fireproof glue layer 25 is 4 mm.
Through detection, the performance indexes of the non-heat-insulation type composite fireproof glass obtained in the embodiment 3 are as follows: total thickness: 20mm, visible light transmittance: 81.7%, refractory integrity: 152min, cold resistance: no change in appearance at constant temperature of-25 ℃ for 6h, heat resistance: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 1.1 percent.
Comparative example 1
The transparent fireproof glue is prepared from the following raw materials in parts by weight: 45kg of nano silica sol with the mass concentration of 45%, 38kg of potassium water glass solution with the mass concentration of 45%, 0.5kg of cane sugar, 0.1kg of monopotassium phosphate, 0.3kg of boric acid, 15kg of glycerol, 0.05kg of starch, 0.4kg of sodium polyphosphate, 0.5kg of polyether modified organic silicon and 0.15kg of sodium fluosilicate.
The transparent flameproof adhesive of comparative example 1 was used to obtain a heat-insulating type composite flameproof glass D1 having the same glass structure and the same production process as those of example 1 except that the transparent flameproof adhesive was different.
Through detection, the performance indexes of the heat-insulation type composite fireproof glass obtained in the comparative example 1 are as follows: total thickness: 25mm, visible light transmittance: 83.4%, fire resistance and heat insulation: 104min, cold resistance: the appearance is unchanged at the constant temperature of-20 ℃ for 6h, and the heat resistance is as follows: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 2.1 percent.
The transparent fire-proof adhesive of comparative example 1 was used to obtain a non-heat insulating type composite fire-proof glass E1 having the same glass structure and the same production process as those of example 1. Through detection, the performance indexes of the non-heat-insulation type composite fireproof glass obtained in the comparative example 1 are as follows: total thickness: 9mm, visible light transmittance: 86.1%, refractory integrity: 112min, cold resistance: the appearance is unchanged at the constant temperature of-20 ℃ for 6h, and the heat resistance is as follows: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 2.5 percent.
Comparative example 2
The transparent fireproof glue is prepared from the following raw materials in parts by weight: 13kg of nano silica sol with the mass concentration of 45%, 34kg of potassium water glass solution with the mass concentration of 45%, 36kg of deionized water, 0.3kg of cane sugar, 0.1kg of monopotassium phosphate, 0.5kg of borax, 15kg of ethylene glycol, 0.05kg of zinc oxide, 0.5kg of potassium polyphosphate, 0.5kg of polyether modified organic silicon and 0.15kg of sodium fluosilicate.
The transparent fire-retardant adhesive of comparative example 2 was used to obtain a heat-insulating composite fire-retardant glass D2 having the same glass structure as that of example 2 and the same production process. Through detection, the performance indexes of the heat-insulation type composite fireproof glass obtained in the comparative example 2 are as follows: total thickness: 41mm, visible light transmittance: 79.8 percent, fire resistance and heat insulation: 109min, cold resistance: the appearance is unchanged at the constant temperature of-20 ℃ for 6h, and the heat resistance is as follows: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 2.4 percent.
The transparent fire-retardant adhesive of comparative example 2 was used to obtain a non-heat-insulating composite fire-retardant glass E2 having the same glass structure and the same production process as those of example 2. Through detection, the performance indexes of the non-heat-insulation type composite fireproof glass obtained in the comparative example 2 are as follows: total thickness: 18mm, visible light transmittance: 83.7%, refractory integrity: 96min, cold resistance: the appearance is unchanged at the constant temperature of-20 ℃ for 6h, and the heat resistance is as follows: the appearance is unchanged at the constant temperature of 50 ℃ for 6h, and the ultraviolet resistance is as follows: after the ultraviolet irradiation for 100h, the change of the visible light transmittance is only 2.2 percent.
The properties of the heat-insulating composite fire-resistant glass and the properties of the non-heat-insulating composite fire-resistant glass of the above examples and comparative examples are shown in tables 1 and 2, respectively.
TABLE 1 Properties of heat-insulating type composite fire-resistant glasses of examples and comparative examples
TABLE 2 Properties of non-heat-insulating type composite fire-resistant glasses of examples and comparative examples
As can be seen from tables 1 and 2, reducing the water content in the transparent fire-retardant adhesive can significantly improve the fire resistance of the fire-retardant glass, mainly due to: the transparent fireproof glue has high water content, and is particularly easy to soften and fall when meeting fire at the temperature of 100-plus-150 ℃, so that the transparent fireproof glue on the surface of the glass is greatly reduced, the thickness of a later foaming layer is influenced, and the fireproof and heat-insulating properties of the foaming layer are reduced; in addition, when the moisture content of the transparent fireproof glue is high, a large amount of water vapor is easily generated in the temperature rising process, so that the air pressure in the cavity is increased, the probability of breakage of the glass layer on the back fire surface is increased, and the glass loses the fire-resistant integrity.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
It will be appreciated that the relevant features of the devices described above may be referred to one another. In addition, "first", "second", and the like in the above embodiments are for distinguishing the embodiments, and do not represent merits of the embodiments.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (12)
1. The transparent fireproof glue is characterized by comprising the following raw materials in parts by weight: 45-55 parts of nano silicon dioxide sol, 25-40 parts of water glass solution, 0.5-1.0 part of carbon forming agent, 0.1-0.3 part of carbon forming auxiliary agent, 0.3-0.8 part of heat-resistant stabilizer, 0-5 parts of organic anti-condensing agent, 10-15 parts of inorganic anti-condensing agent, 0.05-0.1 part of ion fixing agent, 0.3-0.5 part of storage stabilizer, 0.1-0.5 part of defoaming agent and 0.15-0.3 part of cross-linking agent; wherein the water content of the transparent fireproof glue is 30-50 wt%.
2. The transparent fire-proof adhesive according to claim 1,
the mass concentration of the nano-silica sol is 45-50%;
the particle size of the silicon dioxide in the nano silicon dioxide sol is 50-180 nm.
3. The transparent fire-proof adhesive according to claim 1,
the modulus of the water glass solution is 1.0-1.5;
the mass concentration of the water glass solution is 40-45%.
4. The transparent fire-proof adhesive according to claim 1,
the water glass solution is at least one of sodium water glass solution, potassium water glass solution and lithium water glass solution;
the charring agent is at least one of sucrose, fructose, glucose, granulated sugar and maltose;
the char-forming auxiliary agent is at least one selected from potassium dihydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate and sodium hydrogen phosphate;
the heat stabilizer is selected from at least one of borax and boric acid;
the organic anti-condensation agent is selected from at least one of ethanol, ethylene glycol, propylene glycol, glycerol, isopropanol and pentaerythritol;
the inorganic anti-condensing agent is selected from MgCl2And CaCl2At least one of;
the ionic fixing agent is at least one selected from zinc oxide, aluminum oxide and starch;
the storage stabilizer is at least one of sodium polyphosphate and potassium polyphosphate;
the defoaming agent is at least one selected from polyether modified organic silicon, polyoxyethylene polyoxypropylene pentaerythritol ether and polyoxypropylene ethylene oxide glycerol ether;
the selected cross-linking agent is selected from at least one of sodium fluorosilicate, potassium fluorosilicate, aluminum fluoride, potassium carbonate, potassium bicarbonate and ammonium bicarbonate.
5. A preparation method of transparent fireproof glue is characterized by comprising the following steps:
sequentially adding a carbon forming agent, a carbon forming auxiliary agent, a heat-resistant stabilizer, an inorganic anti-condensing agent, an ion fixing agent, a storage stabilizer, a defoaming agent and a cross-linking agent into the nano-silica sol, and uniformly stirring to obtain a first solution;
mixing the water glass solution with the first solution, stirring for 30-60min at the temperature of 20-60 ℃, degassing in vacuum, and filtering to obtain transparent fireproof glue;
wherein, by weight, the nano-silica sol is 45 to 55 parts, the water glass solution is 25 to 40 parts, the carbon forming agent is 0.5 to 1.0 part, the carbon forming auxiliary agent is 0.1 to 0.3 part, the heat-resistant stabilizer is 0.3 to 0.8 part, the inorganic anti-condensing agent is 10 to 20 parts, the ion fixing agent is 0.05 to 0.1 part, the storage stabilizer is 0.3 to 0.5 part, the defoaming agent is 0.1 to 0.5 part, and the cross-linking agent is 0.15 to 0.3 part; the water content of the transparent fireproof glue is 30-50 wt%.
6. The method for preparing transparent fire-proof adhesive according to claim 5,
the vacuum degassing comprises: degassing under vacuum of less than-0.096 MPa for 30-40 min;
the filtering comprises the following steps: filtering with 150-200 mesh sieve.
7. A kind of heat-insulating type compounds the fire-proof glass, characterized by comprising: the fireproof glass comprises a fire-facing glass layer, a back-fire glass layer and at least one middle glass layer positioned between the fire-facing glass layer and the back-fire glass layer, wherein sealing strips along the edge parts of the glass layers are arranged between the adjacent glass layers, structural adhesive is filled in grooves formed by the outer sides of the sealing strips and the adjacent glass layers, and transparent fireproof adhesive according to any one of claims 1 to 4 is filled in a closed cavity defined by the inner sides of the sealing strips and the adjacent glass layers.
8. The insulating composite fire-resistant glass according to claim 7,
the glass layer of the fire-facing side is float glass or toughened glass, and the thickness of the glass layer of the fire-facing side is 3-10 mm;
the back fire surface glass layer is made of toughened glass, and the thickness of the back fire surface glass layer is 5-10 mm;
the middle glass layer is float glass or toughened glass, and the thickness of the middle glass layer is 3-10 mm;
the sealing strip is selected from an acrylic acid adhesive tape, a butyl adhesive tape or a glass strip coated with sealing glass adhesive, and the thickness of the sealing strip is 2-10 mm;
the structural adhesive is selected from silicone adhesive or polysulfide adhesive, and the thickness of the structural adhesive is 2-10 mm;
the thickness of the transparent fireproof glue is 2-10 mm.
9. The heat-insulating composite fireproof glass according to claim 7 or 8, wherein the strength of the middle glass layer close to the back fire surface glass layer is less than or equal to that of the back fire surface glass layer.
10. A non-insulating composite fire-resistant glass, comprising: the fireproof glass comprises a fire-facing glass layer and a back-fire glass layer, wherein a sealing strip along the edge of the glass layer is arranged between the fire-facing glass layer and the back-fire glass layer, a groove formed by the outer side of the sealing strip and the fire-facing glass layer and the back-fire glass layer is filled with structural adhesive, and a sealed cavity defined by the inner side of the sealing strip and the fire-facing glass layer and the back-fire glass layer is filled with the transparent fireproof adhesive according to any one of claims 1 to 4.
11. The non-insulating composite fire-resistant glass according to claim 10,
the glass layer of the fire-facing side is float glass or toughened glass, and the thickness of the glass layer of the fire-facing side is 3-10 mm;
the back fire surface glass layer is made of toughened glass, and the thickness of the back fire surface glass layer is 5-10 mm;
the sealing strip is selected from an acrylic acid adhesive tape, a butyl adhesive tape or a glass strip coated with sealing glass adhesive, and the thickness of the sealing strip is 0.5-10 mm;
the structural adhesive is selected from silicone adhesive or polysulfide adhesive, and the thickness of the structural adhesive is 2-10 mm;
the thickness of the transparent fireproof glue is 0.5-10 mm.
12. The non-insulating composite fire-resistant glass according to claim 10 or 11,
the intensity of the glass layer on the fire-facing side is less than or equal to that of the glass layer on the fire-backing side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011559130.0A CN112662317B (en) | 2020-12-25 | 2020-12-25 | Transparent fireproof glue, preparation method thereof and composite fireproof glass comprising transparent fireproof glue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011559130.0A CN112662317B (en) | 2020-12-25 | 2020-12-25 | Transparent fireproof glue, preparation method thereof and composite fireproof glass comprising transparent fireproof glue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112662317A CN112662317A (en) | 2021-04-16 |
| CN112662317B true CN112662317B (en) | 2022-04-08 |
Family
ID=75408813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011559130.0A Active CN112662317B (en) | 2020-12-25 | 2020-12-25 | Transparent fireproof glue, preparation method thereof and composite fireproof glass comprising transparent fireproof glue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112662317B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113512363A (en) * | 2021-05-28 | 2021-10-19 | 海南大学 | Fireproof adhesive and preparation method thereof |
| US11654663B2 (en) * | 2021-06-07 | 2023-05-23 | GM Global Technology Operations LLC | Polymer-metal sandwich structure having in situ-formed flame retardant and method of manufacturing the same |
| CN113185149A (en) * | 2021-06-08 | 2021-07-30 | 中国科学院长春应用化学研究所 | Fireproof glass and preparation method thereof |
| CN114045112B (en) * | 2021-11-12 | 2023-09-08 | 中国建筑材料科学研究总院有限公司 | Temperature-changing light-adjusting fireproof adhesive and thermochromic glass |
| CN114015362B (en) * | 2021-11-12 | 2023-07-18 | 中国建筑材料科学研究总院有限公司 | Fireproof glue and fireproof glass |
| CN114106851B (en) * | 2021-11-19 | 2022-10-18 | 中国建筑材料科学研究总院有限公司 | Fireproof stock solution, fireproof solution, preparation method of fireproof solution and vacuum fireproof glass |
| CN114409279B (en) * | 2022-01-24 | 2024-03-29 | 广东卫屋防火科技有限公司 | Fireproof interlayer adhesive, preparation method thereof and fireproof glass comprising fireproof interlayer adhesive |
| CN114854328A (en) * | 2022-05-27 | 2022-08-05 | 广东标达新材料有限公司 | Inorganic adhesive composite reinforcing agent for building and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3682781B2 (en) * | 1992-06-19 | 2005-08-10 | 日本電気硝子株式会社 | Fireproof glass panel |
| CN105131868B (en) * | 2015-09-07 | 2016-11-30 | 中国建筑材料科学研究总院 | Fire-resistant fluid of composite fireproof glass and preparation method thereof and composite fireproof glass |
| CN107226626A (en) * | 2017-07-21 | 2017-10-03 | 日照市华业玻璃有限公司 | A kind of non-insulated type composite fireproof glass and its manufacture method |
| CN107640915A (en) * | 2017-10-23 | 2018-01-30 | 秦皇岛玻璃工业研究设计院有限公司 | A kind of refractory heat-insulating glass and preparation method thereof |
-
2020
- 2020-12-25 CN CN202011559130.0A patent/CN112662317B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112662317A (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112662317B (en) | Transparent fireproof glue, preparation method thereof and composite fireproof glass comprising transparent fireproof glue | |
| CN112724840B (en) | Fireproof adhesive, preparation method thereof and composite fireproof glass containing fireproof adhesive | |
| CN105295741A (en) | Fire-proof glue of fire-proof glass, preparation method thereof and composite fire-proof glass | |
| CN105295742A (en) | Fire-proof glue of fire-proof glass, preparation method thereof and composite fire-proof glass | |
| CN109679537B (en) | Fireproof layer material, preparation method thereof and fireproof glass | |
| CN112320807B (en) | Modified silica sol, fireproof liquid, composite fireproof glass and preparation method and application thereof | |
| SK187892A3 (en) | Transparebnt heatproof glass panel and method of its production | |
| CN107235645B (en) | Heat-insulation type composite fireproof glass and manufacturing method thereof | |
| CN109721915B (en) | Fireproof layer material, preparation method thereof and fireproof glass | |
| CN107226626A (en) | A kind of non-insulated type composite fireproof glass and its manufacture method | |
| RU2214372C2 (en) | Transparent thermoswelling material and fire- resistant panel | |
| CN107151547A (en) | A kind of preparation method of fireproof gum for flame resistant glass | |
| CN206955908U (en) | A kind of non-insulated type composite fireproof glass | |
| CN107640915A (en) | A kind of refractory heat-insulating glass and preparation method thereof | |
| CN113929841B (en) | Fireproof layer material, preparation method thereof and fireproof glass | |
| CN207685141U (en) | A kind of refractory heat-insulating glass | |
| CN210454024U (en) | Heat-preserving toughened glass | |
| CN115593048B (en) | Fireproof layer material, preparation method thereof and heat-insulating fireproof glass | |
| CN115521081B (en) | Fireproof layer material and preparation method thereof and non-heat-insulation composite fireproof glass | |
| CN206955907U (en) | A kind of heat insulation type composite fireproof glass | |
| CN114106851B (en) | Fireproof stock solution, fireproof solution, preparation method of fireproof solution and vacuum fireproof glass | |
| CN216305771U (en) | Fireproof anti-riot glass | |
| CN212222803U (en) | Ultralow-temperature pouring sealant fireproof glass | |
| CN214646593U (en) | High-radiation-resistance fireproof glass | |
| CN212400522U (en) | Fire-resistant laminated glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |