CN114106851A - Fireproof stock solution, fireproof solution, preparation method of fireproof solution and vacuum fireproof glass - Google Patents

Abstract

The invention discloses a fireproof stock solution, a fireproof solution, a preparation method of the fireproof solution and vacuum fireproof glass. The fireproof stock solution comprises the following components in percentage by weight: 89.0-99.9 wt% of second base liquid; 0.1-10 wt% of glass powder; 0.01-0.5 wt% of glass powder dispersant; 0.01-0.5 wt% of powder surface modifier; the second base liquid comprises the following components in percentage by weight: 45-65 wt% of first base liquid; 35-55 wt% of hydrophilic gas-phase nano-silica particles; the first base liquid comprises the following components in percentage by weight: 0.1 to 3.0 weight percent of carbon forming agent; 0.01 to 0.8 weight percent of dehydrating agent; 0.01-0.5 wt% of foaming agent; 0-30 wt% of antifreeze agent; 0.1-1.0 wt% of mildew inhibitor; 0.001 to 0.05 weight percent of defoaming agent; 0.01 to 0.5 weight percent of thickening agent; 0.01-0.5 wt% of pH regulator; 70-90 wt% of deionized water. The fire-proof liquid comprises the fire-proof stock solution. According to the invention, the glass powder is added into the fireproof stock solution, so that on one hand, the glass powder is taken as an additive to obviously increase the hardness of the fireproof adhesive layer, and on the other hand, when a fire disaster occurs, the fireproof adhesive layer is heated to expand, and the low-temperature glass powder is melted, softened and soaked between the expanded carbon layers, so that the strength of the expansion layer can be increased, and the flame impact strength can be improved.

Description

Fireproof stock solution, fireproof solution, preparation method of fireproof solution and vacuum fireproof glass

Technical Field

The invention belongs to the technical field of glass preparation, and particularly relates to a fireproof stock solution, a fireproof solution, a preparation method of the fireproof solution and vacuum fireproof glass.

Background

At present, a plurality of outdoor composite fireproof glass are generally in a structure compounded with hollow glass when applied, but the temperature inside a cavity of the hollow glass is rapidly increased under illumination, particularly the temperature in the cavity of the hollow glass in hot summer is even up to 80 ℃, the fluidity of a fireproof adhesive layer is enhanced under the condition of long-term high temperature, the strength is reduced, the hollow glass seriously falls down, the glass is integrally deformed and light distortion occurs, objects are seen through the glass, the objects are deformed, and people feel dizzy. In cold winter, the low-temperature resistance of the fireproof adhesive layer is poor, and particularly in northeast cold areas of China, the fireproof adhesive layer freezes at about-20 ℃ and loses the transparency of glass. These severely limit the application scenarios and the service life of the fire-resistant glass.

Disclosure of Invention

In view of the above, the main purpose of the present invention is to provide a fire-proof stock solution, a fire-proof solution, a preparation method thereof, and vacuum fire-proof glass, and to solve the technical problems of improving the strength of a glue layer in the fire-proof glass, improving the fire resistance limit, and prolonging the service life of the glass by introducing glass powder.

The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. According to the fire-proof stock solution provided by the invention, the fire-proof stock solution comprises the following components in percentage by weight: 89.0-99.9 wt% of second base liquid; 0.1-10 wt% of glass powder; 0.01-0.5 wt% of glass powder dispersant; 0.01-0.5 wt% of powder surface modifier; the second base liquid comprises the following components in percentage by weight: 45-65 wt% of first base liquid; 35-55 wt% of hydrophilic gas-phase nano-silica particles; the first base liquid comprises the following components in percentage by weight: 0.1 to 3.0 weight percent of carbon forming agent; 0.01 to 0.8 weight percent of dehydrating agent; 0.01-0.5 wt% of foaming agent; 0-30 wt% of antifreeze agent; 0.1-1.0 wt% of mildew inhibitor; 0.001 to 0.05 weight percent of defoaming agent; 0.01 to 0.5 weight percent of thickening agent; 0.01-0.5 wt% of pH regulator; 70-90 wt% of deionized water.

Preferably, in the fire-proof stock solution, the diameter of the glass powder is less than 50 μm; the glass powder is at least one of soda-lime-silica glass powder, borosilicate glass powder, phosphate glass powder, quartz glass powder, lead glass powder and bismuth glass powder.

Preferably, in the fire-proof stoste, the nano silica particles are hydrophilic gas-phase nano silica particles.

Preferably, in the fire-proof stock solution, the pH of the first base solution is 9 to 10; the char-forming agent comprises at least one of monosaccharide, polysaccharide, pentaerythritol and dipentaerythritol; the dehydrating agent comprises at least one of boric acid, phosphoric acid, ammonium phosphate and sodium borate; the foaming agent comprises at least one of melamine, ammonium bicarbonate, sodium bicarbonate and ammonium hydrogen phosphate; the antifreeze agent comprises at least one of glycerol, ethylene glycol, 1,2 propylene glycol and 1,3 propylene glycol; the mildew preventive comprises at least one of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The preparation method of the fireproof stock solution provided by the invention comprises the following steps:

1) fully dispersing a char forming agent, a dehydrating agent, a foaming agent, an antifreeze agent, a mildew preventive, a defoaming agent, a thickening agent and a pH regulator in deionized water to obtain a first base liquid;

2) mixing nano silicon dioxide particles with the base liquid, and standing for sufficient reaction to obtain a second base liquid;

3) and uniformly dispersing the glass powder, the glass powder dispersing agent and the powder surface modifier in the second base liquid to obtain the fireproof stock solution.

Preferably, in the preparation method of the fire-retardant liquid, in step 3), the dispersing method is at least one selected from the group consisting of high-speed stirring, ultrasonic dispersing, grinding, ball milling and roll milling.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. According to the fireproof liquid provided by the invention, the fireproof liquid comprises 70-85 wt% of the fireproof stock solution and 15-30 wt% of alkali solution in percentage by weight, and the mass concentration of the alkali solution is 50-80 wt%.

Preferably, in the fire-fighting liquid, the alkali solution is at least one of potassium hydroxide solution and sodium hydroxide solution.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The preparation method of the fireproof liquid provided by the invention comprises the following steps: adding the alkali solution into the fireproof stock solution, and mixing, reacting and vacuum degassing to obtain the fireproof liquid.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. According to the vacuum fireproof glass provided by the invention, the vacuum fireproof glass comprises at least one vacuum cavity and at least one fireproof glue cavity which are mutually connected, and the fireproof glue cavity is filled with the fireproof liquid.

Preferably, in the vacuum fireproof glass, two or more fireproof glue cavities are arranged on the same side of the vacuum cavity.

Preferably, in the vacuum fireproof glass, two or more fireproof glue cavities are arranged on two sides of the vacuum cavity.

Preferably, in the vacuum fireproof glass, two or more vacuum chambers are disposed on the same side of the fireproof chamber.

Preferably, in the vacuum fireproof glass, two or more vacuum cavities are arranged on two sides of the fireproof cavity.

By the technical scheme, the fireproof stock solution, the fireproof solution, the preparation method thereof and the vacuum fireproof glass provided by the invention at least have the following advantages:

1. the glass powder is added into the fireproof liquid, so that on one hand, the glass powder is used as an additive to remarkably increase the hardness of a fireproof adhesive layer, on the other hand, when a fire disaster occurs, the fireproof adhesive layer is heated to expand, and the low-temperature glass powder is melted, softened and soaked between the expanded carbon layers, so that the strength of the expanded layer can be increased, and the flame impact strength can be improved. Meanwhile, the fireproof glass with different colors can be prepared according to different colors of the added glass powder, so that the fireproof effect and the decorative effect are achieved;

2. when the vacuum fireproof glass is used in hot summer, the vacuum layer faces outdoors, the fireproof layer faces indoors, the vacuum layer can effectively prevent outdoor heat conduction, if the vacuum fireproof glass is provided with Low-E glass, solar radiation and infrared radiation can be effectively blocked, the temperature of the inner fireproof glue layer is far lower than that of the currently and commonly adopted hollow structure, aging and discoloration and high-temperature falling of the fireproof glue layer can be effectively prevented, and the service life of the glass is prolonged;

3. when the vacuum fireproof glass is used in cold winter, the phenomenon of icing exists in the inner part of the existing fireproof glass adhesive layer, the outdoor temperature is lower, and particularly in the area with the low temperature of below-20 ℃, the vacuum fireproof glass can effectively prevent heat conduction, so that the temperature difference between the temperature of the inner fireproof adhesive layer and the indoor temperature is below 10 ℃, and if the temperature of the indoor fireproof adhesive layer is calculated according to 25 ℃, the temperature of the fireproof adhesive layer is above 15 ℃, and the fireproof adhesive layer can be ensured not to be iced;

4. the vacuum cavity of the vacuum fireproof glass has excellent heat preservation and insulation effects, can effectively block heat conduction and heat radiation, reduces the power consumption of an air conditioner in summer and the heating load in winter, and plays a role in energy conservation and environmental protection; the introduction of the vacuum cavity enables the glass to have the fireproof performance of fireproof glass and the heat and sound insulation characteristic of vacuum glass, so that ultraviolet rays, heat radiation and heat conduction can be effectively blocked, a fireproof adhesive layer is protected, aging is delayed, the service life of the glass is greatly prolonged, meanwhile, the adhesive layer formed after the fireproof liquid is cured is directly bonded with the vacuum glass to form the laminated glass, and the impact resistance of the vacuum glass is also improved;

5. the vacuum fireproof glass disclosed by the invention also belongs to laminated glass, belongs to safe glass, and can be widely applied to projects such as doors and windows, curtain walls, daylighting roofs and the like, a sealed hollow cavity is arranged in the hollow glass, the glass can bulge and deform in a plateau area, the vacuum fireproof glass does not have the problem, and the application scene is wide;

6. the vacuum fireproof glass disclosed by the invention greatly improves the energy-saving effect of the glass on the basis of overcoming the defects that the fireproof adhesive layer of the existing fireproof glass is easy to drop and deform and has poor low-temperature performance.

The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.

Drawings

FIG. 1 is a schematic view of a vacuum fire-proof glass with a single fire-proof chamber according to a preferred embodiment of the present invention;

FIG. 2 is a schematic structural view of a dual-fire-proof-cavity vacuum fire-proof glass according to a preferred embodiment of the present invention;

fig. 3 is a schematic structural view of a fire-proof vacuum fireproof glass with fire-proof cavity according to a preferred embodiment of the present 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 given to the embodiments, structures, features and effects of a fire-proof stock solution, a fire-proof solution and a preparation method thereof, and vacuum fire-proof glass according to the present invention with reference to the preferred embodiments.

Unless otherwise specified, the following materials, reagents and the like are commercially available products well known to those skilled in the art; unless otherwise specified, all methods are well known in the art. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The following procedures or conditions, which are not specifically mentioned, may be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the art.

The invention provides a fireproof stock solution, which comprises the following components in percentage by weight: 89.0-99.9 wt% of second base liquid; 0.1-10 wt% of glass powder; 0.01-0.5 wt% of glass powder dispersant; 0.01-0.5 wt% of powder surface modifier; the formula design can ensure that the glass powder is uniformly dispersed, the fire-proof stock solution has good stability, and the viscosity is suitable for process operation; preferably, the second stock solution comprises 89-94 wt% of the first stock solution, 5-10 wt% of glass powder, 0.1-0.5 wt% of glass powder dispersant and 0.1-0.5 wt% of powder surface modifier; therefore, the second stock solution is more stable and has more proper viscosity;

the second base liquid comprises the following components in percentage by weight: 45-65 wt% of first base liquid; 35-55 wt% of hydrophilic gas-phase nano-silica particles; the silicon dioxide particles can be uniformly dispersed by the formula design, and the viscosity of the second base liquid is suitable for process operation; in order to ensure the viscosity of the fire-retardant liquid and the strength of the fire-retardant adhesive layer, the first stock solution may preferably comprise 45-60 wt% of the base liquid and 40-55 wt% of the hydrophilic fumed nano-silica particles.

The first base liquid comprises the following components in percentage by weight: 0.1 to 3.0 weight percent of carbon forming agent; 0.01 to 0.8 weight percent of dehydrating agent; 0.01-0.5 wt% of foaming agent; 0-30 wt% of antifreeze agent; 0.1-1.0 wt% of mildew inhibitor; 0.001 to 0.05 weight percent of defoaming agent; 0.01 to 0.5 weight percent of thickening agent; 0.01-0.5 wt% of pH regulator; 70-90 wt% of deionized water.

In the technical scheme, the proportion of each component is changed according to different temperatures in different climatic regions at home and abroad, for example, in a hot region, the content of the antifreeze agent can be reduced, and in a cold region, the antifreeze agent needs to be increased. Too little glass powder addition amount can not play the effect, and too high addition amount can increase the viscosity of fire-proof liquid, is unfavorable for filling in the production, and too little glass powder dispersant and powder surface modification agent play a role in the same way, and the volume is too big to influence the viscosity of fire-proof liquid, and the operation is inconvenient, and the cost is improved.

The components of the char forming agent, the dehydrating agent and the foaming agent have certain solubility, and cannot be dissolved when exceeding the respective upper limits, on the one hand, crystalline solids are separated out in the fireproof adhesive layer prepared finally when exceeding the upper limits, the glass light transmittance is influenced, the addition amount of the antifreeze agent exceeds the upper limits, and the adhesive layer cannot be solidified; the viscosity and the pH value of the solution are influenced when the mildew preventive, the defoaming agent, the thickening agent and the pH regulator exceed the upper limit, so that the process operation is not facilitated; all components are added too little above the lower limit and do not function, and deionized water functions to dilute and dissolve the components.

In some embodiments of the invention, the glass frit has a diameter of 50 μm or less; the fire-proof liquid is too large in particle size and easy to settle, and the fire-proof liquid is too large in viscosity due to too small particle size, so that the pouring is inconvenient to operate. The nano glass powder is at least one of soda-lime-silica glass powder, borosilicate glass powder, phosphate glass powder, quartz glass powder, lead glass powder and bismuth glass powder. The introduction of the glass powder obviously improves the Shore hardness and the fire resistance limit of the adhesive layer. The glass powder can be used for fire-proof liquid, wherein the components of the soda-lime-silica glass powder and the components of the plate glass powder are consistent, and the soda-lime-silica glass powder and the plate glass powder play a role of a filler after being added, so that the strength is increased; the borosilicate glass powder and the quartz glass powder are low-expansion-coefficient glass, and have certain fireproof effect besides the function of the filler; phosphate glass powder, lead glass powder and bismuth glass powder are mostly low-temperature glass powder, and the low-temperature glass powder is melted, softened and soaked between the expanded carbon layers after being heated, so that the strength and the flame impact resistance of the carbon layers can be effectively improved, and the fire resistance limit is improved.

In some embodiments of the present invention, the glass frit dispersant may be selected from at least one of VOK-KD21, BYK190, and DS-195; the function is to disperse and prevent agglomeration, if not, a gradual change layering can be formed; the powder surface modifier can be selected from at least one of AD8058, AD8059 and AD 8099; its function is to modify the surface to increase compatibility and if not, to form a dense precipitate.

In some embodiments of the invention, the nanosilica particles are hydrophilic fumed nanosilica particles. The content of the silicon dioxide is equivalent to the solid content in the fireproof liquid, so that the fireproof liquid is preferably solidified into a fireproof glue layer to achieve better strength.

In some embodiments of the invention, the pH of the first base liquid is 9-10; the char-forming agent comprises at least one of monosaccharide, polysaccharide, pentaerythritol and dipentaerythritol;

in some embodiments of the invention, the dehydrating agent may include at least one of boric acid, phosphoric acid, ammonium phosphate, and sodium borate, which is used to facilitate the dehydrating carbonization of the char-forming agent; preferably, the dehydrating agent comprises boric acid, phosphoric acid and ammonium phosphate, wherein the decomposition temperature of the boric acid and the phosphoric acid has a good synergistic effect with the charring agent, the charring agent is promoted to be carbonized after decomposition, and the ammonium phosphate can be decomposed to generate ammonia gas besides the dehydration effect of the ammonium phosphate and has a certain foaming agent effect.

In some embodiments of the present invention, the foaming agent includes at least one of melamine, ammonium bicarbonate, sodium bicarbonate and ammonium hydrogen phosphate, which decomposes to generate gas after being heated, so as to foam the carbon layer to form compact closed pores, and the honeycomb structure has a better heat insulation effect; in consideration of water solubility and glass light transmittance, the foaming agent preferably comprises at least one of melamine, ammonium bicarbonate and ammonium hydrogen phosphate, after the carbon forming agent is softened, the temperature is continuously increased to reach the decomposition temperature of the foaming agent, and the foaming agent is decomposed and foamed, so that the thickness of the foamed carbon layer can be remarkably increased, and uniform and compact bubbles are formed.

In some embodiments of the present invention, the antifreeze agent comprises at least one of glycerol, ethylene glycol, 1, 2-propanediol, and 1, 3-propanediol, which acts to prevent freezing. Preferably, the antifreeze comprises at least one of glycerol and 1, 3-propylene glycol, has better water solubility, low viscosity and lower freezing point, is convenient to produce and operate and has good low-temperature resistance.

In some embodiments of the invention, the mold inhibitor comprises at least one of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, calcium hydroxide, magnesium oxide, and magnesium hydroxide. Preferably sodium hydroxide or potassium hydroxide, and the two have good water solubility and convenient operation.

In some embodiments of the invention, the defoaming agent comprises an aqueous defoaming agent such as BYK-028, BYK-188, SDJ6011, FoamStar ST2454, and the like, preferably BYK-028, BYK-188, which when used herein, exhibit a more pronounced defoaming effect.

In some embodiments of the invention, the thickener comprises an aqueous thickener such as TT935, VISCOATEX46, UH-450VF, preferably TT935, which acts to thicken more significantly.

In some embodiments of the invention, the pH adjusting agent comprises at least one of potassium hydroxide, sodium hydroxide, magnesium hydroxide and sodium bicarbonate, preferably potassium hydroxide or sodium hydroxide.

The invention also provides a preparation method of the fireproof stock solution, which comprises the following steps:

1) fully dispersing a char forming agent, a dehydrating agent, a foaming agent, an antifreeze agent, a mildew preventive, a defoaming agent, a thickening agent and a pH regulator in deionized water to obtain a first base liquid;

2) mixing nano silicon dioxide particles with the base liquid, and standing for sufficient reaction to obtain a second base liquid;

3) and uniformly dispersing the nano glass powder, the glass powder dispersing agent and the powder surface modifier in the second base liquid to obtain the fireproof stock solution.

In some embodiments of the invention, in step 3), the dispersing method is selected from at least one of high speed stirring, ultrasonic dispersing, milling, ball milling, and roll milling. The dispersion method is selected from high-speed stirring or grinding in consideration of convenience and dispersibility of the nano-powder, wherein high-speed stirring is convenient to operate and is a common powder dispersion method, and grinding can better promote the dispersion of the nano-powder.

The invention also provides a fireproof liquid, which comprises 70-85 wt% of the fireproof stock solution and 15-30 wt% of alkali solution in percentage by weight, wherein the mass concentration of the alkali solution is 50-80 wt%. Preferably, the fireproof liquid comprises 72-82 wt% of fireproof stock solution and 18-28 wt% of alkali solution, and the mass concentration of the alkali solution is 50-70 wt%. The high concentration of the alkali solution can obviously improve the curing amount and the hardness of the fireproof adhesive layer, but the viscosity can be improved, so that the production operation is influenced, and therefore, a proper proportion needs to be selected according to the concrete application. Within the proportion setting range, the viscosity of the fireproof liquid is low on the premise of ensuring high solid content, and the pouring and bubble discharge during the production of the fireproof glass are convenient.

In some embodiments of the invention, the alkali solution is at least one of a potassium hydroxide and sodium hydroxide solution. Preferably, the alkali solution is a potassium hydroxide solution, and the strength of the fireproof glue layer prepared by the potassium hydroxide is better than that of the fireproof glue layer prepared by the sodium hydroxide.

The invention also provides the vacuum fireproof glass, which comprises at least one vacuum cavity and at least one fireproof glue cavity which are mutually connected, wherein the fireproof glue cavity is filled with the fireproof liquid, and the fireproof liquid is solidified to form a fireproof glue layer.

In still other embodiments of the present invention, two or more of the fire-retardant glue cavities are disposed on the same side of the vacuum cavity.

In still other embodiments of the present invention, two or more fire-retardant glue cavities are disposed on two sides of the vacuum cavity.

In still other embodiments of the present invention, as shown in fig. 1, the vacuum fireproof glass includes a vacuum cavity 3 and a fireproof glue cavity 2 connected to each other, and the fireproof glue cavity 2 is filled with the fireproof liquid; solidifying the fireproof liquid to form a fireproof glue layer; the vacuum cavity 3 comprises A, B pieces of glass, and the fireproof glue cavity 2 comprises B, C pieces of glass.

Furthermore, at least one of the A, B pieces of glass can be Low-E glass, if the Low-E glass is used, the Low-E surface faces the vacuum cavity 3, and the energy-saving effect of the glass can be improved by using the Low-E glass. And the C sheet glass can be ordinary flat glass.

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.

Example 1

Referring to fig. 1, a method for preparing vacuum fireproof glass with a single fireproof cavity comprises the following specific steps: punching a glass sheet A, punching a glass sheet B, uniformly distributing supports on the glass sheet B, uniformly coating low-temperature glass powder (low-temperature lead glass powder at 380 ℃ with the coating thickness of 2mm and the coating width of 3mm) on the periphery of the glass sheet A or the glass sheet B, then heating A, B glass sheets to 380 ℃ to melt sealing solder, cooling, solidifying the sealing glass powder to bond the two glass sheets together, finally placing the whole glass at 250 ℃, sucking air through an air suction port 1 on the glass sheet A for 4 hours, sintering and sealing an air suction pipe, and then activating a barium-aluminum getter (2g) through a high-frequency motor 5s to finish the manufacture of the vacuum glass. And bonding the glass surface A of the prepared vacuum glass with the glass surface C of the vacuum glass by using a butyl adhesive tape, and then sealing by using a silicone structural adhesive for two times, wherein a liquid filling opening is reserved at one corner.

The fire-proof liquid is prepared according to the following steps:

sequentially adding 800g of deionized water, 120g of glycerol, 10g of cane sugar, 0.8g of boric acid, 1.2g of ammonium hydrogen phosphate, 1.5g of potassium hydroxide, 0.15g of defoaming agent BYK028, 0.8g of thickening agent TT935 and 1g of sodium hydroxide into a large beaker, and dissolving and uniformly mixing the raw materials to form a first base solution;

adding 800g of nano silicon dioxide particles into the base liquid, and fully stirring and mixing the mixture by a high-speed stirrer at the rotating speed of 1000r/min for 20min to obtain a second base liquid;

adding 0.8g of glass powder dispersing agent BYK190 and 1.2g of powder surface modifier AD8058 into the second base solution, stirring for 30min by using a high-speed stirrer, slowly adding 80g of soda-lime-silica glass powder sieved by a 325-mesh sieve while stirring, and continuously stirring for 30min to obtain a fireproof stock solution;

weighing 520g of 50 wt% potassium hydroxide aqueous solution into a vacuum stirring kettle, slowly adding the fireproof stock solution into the vacuum stirring kettle, mixing and reacting with the potassium hydroxide aqueous solution, starting stirring simultaneously, controlling the system temperature below 60 ℃, stirring for 60min, starting a vacuum pump, starting vacuumizing and degassing, wherein the vacuum degree is-0.095 MPa, the vacuum time is 30min, discharging the negative pressure after the vacuum is finished, and discharging the liquid, namely the fireproof liquid.

And pouring the fireproof liquid into a cavity between two pieces of glass, removing air between the cavities, sealing the liquid pouring port, heating to 75 ℃, preserving heat for 12 hours to solidify the fireproof liquid, and finally treating the edge (beautifying) to obtain the vacuum fireproof glass. The vacuum fireproof glass comprises a vacuum cavity 3 and a fireproof glue cavity 2 which are connected with each other, and the fireproof glue cavity 2 is filled with the fireproof liquid; solidifying the fireproof liquid to form a fireproof glue layer; the vacuum cavity 3 comprises A, B pieces of glass, and the fireproof glue cavity 2 comprises B, C pieces of glass. The glass A is Low-E glass, and the glass B is common plate glass.

Example 2

Referring to fig. 2, a method for preparing vacuum fireproof glass with double fireproof cavities comprises the following specific steps:

punching a glass sheet A, punching a glass sheet B, uniformly distributing supports on the glass sheet B, uniformly coating low-temperature glass powder (380 ℃ low-temperature lead glass powder with the thickness of 2mm and the width of 3mm) on the periphery of the glass sheet A or the glass sheet B, then heating A, B glass sheets to 380 ℃ to melt a sealing solder, cooling, solidifying the sealing glass powder to bond the two glass sheets together, finally performing vacuum air suction for 4 hours at the temperature of 250 ℃ through an air suction port 1 on the glass sheet A, finally sintering and sealing an air suction pipe, and then activating a barium-aluminum getter (2g) through 5s of electrification of a high-frequency machine to complete the manufacture of the vacuum glass. Bonding the glass surface A of the prepared vacuum glass with the periphery of the glass sheet C by using a butyl adhesive tape, bonding the glass sheet D with the glass sheet C by using the butyl adhesive tape, and then performing secondary sealing by using silicone adhesive, wherein two cavities are reserved with 2cm of liquid filling ports.

The fire-proof liquid is prepared according to the following steps:

sequentially adding 800g of deionized water, 150g of 1,3 g of propylene glycol, 20g of glucose, 0.5g of sodium borate, 3.5g of ammonium bicarbonate, 1.5g of potassium hydroxide, 0.1g of defoaming agent BYK028, 0.5g of thickening agent TT935 and 1g of sodium hydroxide into a large beaker, and dissolving and uniformly mixing the raw materials to form a first base solution;

adding 750g of hydrophilic gas phase nano silicon dioxide particles into the first base liquid, then putting the mixture into a ball milling tank, carrying out ball milling for 20min at the rotating speed of 100r/min, and filtering to obtain a second base liquid;

adding 1.5g of glass powder dispersing agent BYK190 and 1.5g of powder surface modifier AD8058 into the second base solution, stirring for 30min at the speed of 1000r/min, then slowly adding 100g of borosilicate glass powder which is sieved by a 400-mesh sieve while stirring, and continuously stirring for 30min to obtain a fireproof stock solution;

weighing 490g of 52 wt% potassium hydroxide aqueous solution into a vacuum stirring kettle, slowly adding the fireproof stock solution into the vacuum stirring kettle, mixing and reacting with the potassium hydroxide aqueous solution, simultaneously starting stirring, controlling the system temperature below 60 ℃, stirring for 60min, then starting a vacuum pump, starting vacuumizing and degassing, wherein the vacuum degree is-0.095 MPa, the vacuum time is 30min, discharging the negative pressure after the vacuum is finished, and discharging the liquid, namely the fireproof liquid.

And pouring the fireproof liquid into a cavity between two pieces of glass, removing air between the cavities, sealing the liquid pouring port, heating to 75 ℃, preserving heat for 18 hours to solidify the fireproof liquid, and finally treating the edge (beautifying) to obtain the vacuum fireproof glass. The vacuum fireproof glass comprises a vacuum cavity 3 and two fireproof glue cavities 2 which are mutually connected, and the fireproof liquid is filled in the two fireproof glue cavities 2; solidifying the fireproof liquid to form a fireproof glue layer; the vacuum cavity 3 comprises A, B pieces of glass, and the two fireproof glue cavities 2 comprise B, C, D three pieces of glass. The two fireproof glue cavities 2 are arranged on the same side of the vacuum cavity 3. The glass A is Low-E glass, and the B, C, D glass plates are common plate glass.

Example 3

Referring to fig. 3, a preparation method of vacuum fireproof glass with double fireproof cavities comprises the following specific steps: : punching a glass sheet A, punching a glass sheet B, uniformly distributing supports on the glass sheet B, uniformly coating low-temperature glass powder (380 ℃ low-temperature lead glass powder with the thickness of 2mm and the width of 3mm) on the periphery of the glass sheet A or the glass sheet B, then heating A, B glass sheets to 380 ℃ to melt a sealing solder, cooling, solidifying the sealing glass powder to bond the two glass sheets together, finally performing vacuum air suction for 4 hours at the temperature of 250 ℃ through an air suction port 1 on the glass sheet A, finally sintering and sealing an air suction pipe, and then activating a barium-aluminum getter (2g) through 5s of electrification of a high-frequency machine to complete the manufacture of the vacuum glass. And adhering the glass surface A of the prepared vacuum glass to the periphery of the glass sheet C by using a butyl adhesive tape, adhering the glass sheet D to the glass sheet C by using the butyl adhesive tape, adhering the glass surface B to the periphery of the glass sheet E by using the butyl adhesive tape, and then finishing two sealing steps by using silicone adhesive on the outside. Wherein, the three cavities are reserved with 2cm of liquid filling ports.

The fire-proof liquid is prepared according to the following steps:

sequentially adding 800g of deionized water, 200g of ethylene glycol, 2g of pentaerythritol, 1g of melamine, 0.8g of borax, 1.5g of potassium hydroxide, 0.05g of defoaming agent BYK028, 0.2g of thickening agent TT935 and 1g of sodium hydroxide into a large beaker, and dissolving and uniformly mixing the raw materials to form a first base solution;

adding 800g of hydrophilic gas phase nano silicon dioxide particles into the first base liquid, and fully stirring and mixing by a high-speed stirrer at the rotating speed of 1000r/min for 20min to obtain a second base liquid;

adding 4.0g of glass powder dispersing agent BYK190 and 4.0g of powder surface modifier AD8058 into the second base solution, stirring for 30min at the speed of 1000r/min, then slowly adding 100g of light green lead glass powder which is sieved by a 500-mesh sieve while stirring, and continuously stirring for 30min to obtain a fireproof stock solution;

weighing 430g of 60 wt% potassium hydroxide aqueous solution into a vacuum stirring kettle, slowly adding the fireproof stock solution into the vacuum stirring kettle, mixing and reacting with the potassium hydroxide aqueous solution, simultaneously starting stirring, controlling the system temperature below 60 ℃, stirring for 60min, then starting a vacuum pump, starting vacuumizing and degassing, wherein the vacuum degree is-0.095 MPa, the vacuum time is 30min, discharging the negative pressure after the vacuum is finished, and discharging the liquid, namely the fireproof liquid.

And pouring the fireproof liquid into a cavity between two pieces of glass, removing air between the cavities, sealing the liquid pouring port, heating to 75 ℃, preserving heat for 24 hours to solidify the fireproof liquid, and finally treating the edge part to obtain the vacuum fireproof glass. The vacuum fireproof glass comprises a vacuum cavity 3 and three fireproof glue cavities 2 which are mutually connected, and the three fireproof glue cavities 2 are filled with the fireproof liquid; solidifying the fireproof liquid to form a fireproof glue layer; the vacuum cavity 3 comprises A, B pieces of glass, and the two fireproof glue cavities 2 comprise A, B, C, D, E five pieces of glass. The three fireproof glue cavities 2 are arranged on different sides of the vacuum cavity 3. The A glass sheets are Low-E glass, and the B, C, D, E four glass sheets are common flat glass.

Example 4

The difference between this example and example 1 is that the glass frit used in this example is 60g of soda-lime-silica glass frit that was sieved through a 325 mesh sieve.

Example 5

The difference between this example and example 1 is that the glass frit used in this example is 100g of soda-lime-silica glass frit that was sieved through a 325 mesh sieve.

Example 6

The difference between this example and example 1 is that 80g of borosilicate glass powder sieved by 325 mesh is used as the glass powder in this example.

Example 7

The difference between the present example and example 1 is that the glass powder used in the present example is 380 ℃ low-temperature lead glass powder which is 80g and passes through a 325-mesh sieve.

Example 8

The difference between the present example and example 1 is that the glass powder used in the present example is 100g of 380 ℃ low-temperature lead glass powder passing through a 325-mesh sieve.

Example 9

The difference between this example and example 1 is that the glass frit used in this example is 80g of soda lime glass frit which is sieved with a 500 mesh sieve.

Example 10

This example differs from example 1 in that this example uses 0.5g of a glass frit dispersant BYK 190.

Example 11

This example differs from example 1 in that 0.5g of the glass frit dispersant BYK190 was used, and 80g of soda lime glass frit sieved with a 500 mesh sieve was used in this example.

Example 12

This example differs from example 1 in that 0.5g of the glass frit dispersant BYK190 was used, and 50g of soda lime glass frit sieved with a 500 mesh sieve was used in this example.

Example 13

This example differs from example 1 in that this example uses 0.5g of a glass frit dispersant BYK190, and 50g of a 500 mesh-sieved silica glass frit.

Example 14

The difference between this example and example 1 is that 0.8g of powder surface modifier AD8058 was used in this example.

Example 15

The difference between this example and example 1 is that 2.0g of powder surface modifier AD8058 was used in this example.

Example 16

This example differs from example 1 in that 80g of low temperature lead glass frit glass powder of 380 c, which was sieved through a 500 mesh sieve, was used in this example.

Example 17

The difference between this example and example 1 is that this example uses 100g of 380 ℃ low temperature lead glass frit sieved with 325 mesh.

Example 18

This example differs from example 1 in that this example uses 100g of 380 ℃ low temperature lead glass frit that was passed through a 500 mesh screen.

Example 19

The difference between this example and example 1 is that 0.9g of BYK190 as a glass powder dispersant is used in this example, and 100g of 380 ℃ low-temperature lead glass powder which is sieved with a 500-mesh sieve is used.

Example 20

The difference between the present example and example 1 is that 0.9g of glass powder dispersant BYK190, 2.0g of powder surface modifier AD8058 and 100g of 380 ℃ low-temperature lead glass powder sieved by a 500-mesh sieve are used in the present example.

Comparative example 1

The difference of the comparative example 1 is that the soda-lime-silica glass powder sieved by a 325-mesh sieve, the glass dispersant BYK190 and the powder surface modifier AD8058 are not added in the comparative example.

Comparative example 2

The comparative example is different from example 1 in that the glass dispersant BYK190 and the powder surface modifier AD8058 are not added in the comparative example.

Comparative example 3

The comparative example is different from example 1 in that soda-lime-silica glass powder sieved by a 325-mesh sieve and a glass dispersant BYK190 are not added in the comparative example.

Comparative example 4

The difference between the comparative example and the example 1 is that the soda-lime-silica glass powder which is sieved by a 325-mesh sieve and the powder surface modifier AD8058 are not added in the comparative example.

Comparative example 5

The comparative example differs from example 1 in that no soda-lime-silica glass frit that was sieved through a 325 mesh sieve was added.

Comparative example 6

This comparative example is different from example 1 in that the glass dispersant BYK190 was not added.

Comparative example 7

The comparative example is different from example 1 in that the powder surface modifier AD8058 is not added in the comparative example.

Comparative example 8

The difference between the comparative example and the example 1 is that the comparative example does not add the glass powder dispersing agent BYK190 and the powder surface modifier AD8058, and 100g of 380 ℃ low-temperature lead glass powder which is sieved by a 500-mesh sieve is used.

Comparative example 9

The difference between the comparative example and the example 1 is that the comparative example does not add the glass powder dispersing agent BYK190 and the powder surface modifier AD8058, and 150g of 380 ℃ low-temperature lead glass powder which is sieved by a 500-mesh sieve is used.

Comparative example 10

This comparative example differs from example 1 in that: this comparative example used 1.0g of glass frit dispersant BYK190 without the addition of powder surface modifier AD 8058.

Comparative example 11

This comparative example differs from example 1 in that: in the comparative example, 1.0g of BYK190 as a glass powder dispersant, no AD8058 as a powder surface modifier, and 100g of 380 ℃ low-temperature lead glass powder which is sieved by a 500-mesh sieve were used.

Comparative example 12

This comparative example differs from example 1 in that: in this comparative example, 100g of a low-temperature lead glass frit of 380 ℃ sieved with a 325 mesh sieve was used without adding BYK190 as a glass frit dispersant.

Test example

The storage states, the adhesive layer strengths of the fireproof liquid and the fireproof original liquid of the vacuum fireproof glass provided by examples 1-20 and comparative examples 1-12 of the invention, and the fire endurance were tested, wherein the storage time of the fireproof original liquid was determined by a method of standing for 10 days and then observing sedimentation and delamination phenomena, the adhesive layer strength of the fireproof liquid was determined by hardness shore-a (LX-a) (shore hardness is determined by the adhesive layer strength in the fireproof glass), and the fire endurance was determined by the method specified in GB/T15763.1. The specific test results are shown in table 1 below.

TABLE 1

As can be seen from the data in Table 1, the second stock solutions of examples 1-20 of the present invention were uniformly dispersed without sedimentation upon storage; the glue line strength of the prepared fireproof liquid reaches more than 91-96HA, and the fire resistance limit reaches more than 82 min; the glass powder is uniformly dispersed, so that the strength of the fireproof glue layer and the fire resistance limit of the fireproof glass can be effectively improved, and the glass surface modifier and the glass powder dispersant can obviously improve the dispersion uniformity of the glass powder in the stock solution and prevent sedimentation. Particularly, the low-temperature glass powder is added, the temperature of the glass powder which is softened and melted by heating is higher than the decomposition temperature of the dehydrating agent, the charring agent and the foaming agent, and after the expanded carbonaceous layer is formed, the uniformly dispersed glass powder is melted again, softened and soaked between the expanded carbonaceous layers, so that the flame impact strength of the expanded carbonaceous layer is improved, and the fire resistance limit of the fireproof glass is obviously improved.

It can be seen from the data of comparative examples 7 and 10-11 that the glass powder has poor compatibility with the solution without the addition of the powder surface modifier, and the glass powder will settle and form a compact precipitate after a long time, because the powder surface modifier modifies the surface of the glass powder to promote the compatibility of the glass powder with the solution; as can be seen from the data of comparative examples 6, 8, 9 and 12, the glass powder is layered, because the glass powder dispersing agent is used for better dispersing the glass particles and preventing agglomeration, and the glass powder particles are agglomerated into large particles and are easy to sink gradually under the action of gravity without adding the glass powder dispersing agent; as can be seen from comparison of the data of comparative examples 1 to 12 with example 1, the presence of the powder surface modifier and the glass frit dispersant can better promote uniform dispersion of the glass powder in the solution, preventing sedimentation and delamination. The glass powder is uniformly dispersed in the second base liquid, and the glass powder is uniformly dispersed in the glue layer prepared by final curing. When the glass with fire disaster is heated, firstly, the dehydrating agent is melted, the charring agent is dehydrated and carbonized under the action of the dehydrating agent, the foaming agent is decomposed to generate gas along with the continuous temperature rise, the softened charcoal layer is foamed to form a honeycomb structure, and the glass powder is melted and soaked between the expanded charcoal layers along with the continuous temperature rise, so that the flame resistance impact strength of the expanded charcoal layer is improved; compared with the fire-proof glass without adding glass powder, the fire-proof limit of the fire-proof glass is obviously improved. Meanwhile, due to the addition of the glass powder, the Shore hardness of the fireproof adhesive layer is obviously improved compared with that of the fireproof adhesive layer without the glass powder, the hardness of the adhesive layer is high, the glass is effectively prevented from falling after being put on a wall, and the service life of the glass is further prolonged.

The vacuum fireproof glass prepared in the embodiment 1 is applied to doors and windows of high-grade villa subdistricts of Harbin at present, and conventional temperature tests show that when the outdoor temperature of the Harbin is-21 ℃ and the indoor temperature is 22 ℃, the measured indoor surface glass temperature is 18 ℃, which shows that the vacuum fireproof glass structure can effectively preserve heat and insulate heat, and prevent a fireproof adhesive layer from being frozen below zero.

In the description of the present invention, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some embodiments, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (10)

1. A fire protection stock solution, characterized in that the fire protection stock solution comprises, in weight percent: 89.0-99.9 wt% of second base liquid; 0.1-10 wt% of glass powder; 0.01-0.5 wt% of glass powder dispersant; 0.01-0.5 wt% of powder surface modifier; the second base liquid comprises the following components in percentage by weight: 45-65 wt% of first base liquid; 35-55 wt% of hydrophilic gas-phase nano-silica particles; the first base liquid comprises the following components in percentage by weight: 0.1 to 3.0 weight percent of carbon forming agent; 0.01 to 0.8 weight percent of dehydrating agent; 0.01-0.5 wt% of foaming agent; 0-30 wt% of antifreeze agent; 0.1-1.0 wt% of mildew inhibitor; 0.001 to 0.05 weight percent of defoaming agent; 0.01 to 0.5 weight percent of thickening agent; 0.01-0.5 wt% of pH regulator; 70-90 wt% of deionized water.

2. The fire protection dope of claim 1,

the diameter of the glass powder is less than 50 mu m; the glass powder is at least one of soda-lime-silica glass powder, borosilicate glass powder, phosphate glass powder, quartz glass powder, lead glass powder and bismuth glass powder;

the nano silicon dioxide particles are hydrophilic gas phase nano silicon dioxide particles;

the pH value of the first base liquid is 9-10; the char-forming agent comprises at least one of monosaccharide, polysaccharide, pentaerythritol and dipentaerythritol; the dehydrating agent comprises at least one of boric acid, phosphoric acid, ammonium phosphate and sodium borate; the foaming agent comprises at least one of melamine, ammonium bicarbonate, sodium bicarbonate and ammonium hydrogen phosphate; the antifreeze agent comprises at least one of glycerol, ethylene glycol, 1,2 propylene glycol and 1,3 propylene glycol; the mildew preventive comprises at least one of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide.

3. A method of preparing a fire protection dope according to claim 1 or 2, comprising the steps of:

1) fully dispersing a char forming agent, a dehydrating agent, a foaming agent, an antifreeze agent, a mildew preventive, a defoaming agent, a thickening agent and a pH regulator in deionized water to obtain a first base liquid;

2) mixing nano silicon dioxide particles with the base liquid, and standing for sufficient reaction to obtain a second base liquid;

3) and uniformly dispersing the glass powder, the glass powder dispersing agent and the powder surface modifier in the second base liquid to obtain the fireproof stock solution.

4. The method of preparing a fire-retardant stock solution according to claim 3, wherein in the step 3), the dispersion method is at least one selected from the group consisting of high-speed stirring, ultrasonic dispersion, milling, ball milling, and roll milling.

5. A fire-proof liquid, characterized in that, the fire-proof liquid comprises 70-85 wt% of the fire-proof stock solution of claim 1 or 2 and 15-30 wt% of alkali solution, and the mass concentration of the alkali solution is 50-80 wt%.

6. The fire protection fluid of claim 5, wherein the alkali solution is at least one of a potassium hydroxide solution and a sodium hydroxide solution.

7. A method for preparing the fire-retardant liquid according to claim 5 or 6, comprising the steps of: adding the alkali solution into the fireproof stock solution, and mixing, reacting and vacuum degassing to obtain the fireproof liquid.

8. The vacuum fireproof glass is characterized by comprising at least one vacuum cavity and at least one fireproof glue cavity which are connected with each other, wherein the fireproof glue cavity is filled with the fireproof liquid.

9. The vacuum fire-retardant glass of claim 8, wherein more than two fire-retardant adhesive cavities are disposed on the same side or both sides of the vacuum cavity.

10. The vacuum fire-retardant glass of claim 8, wherein more than two vacuum chambers are disposed on the same side or both sides of the fire-retardant chamber.

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