阅读说明：本技术 一种夹层隔热防火玻璃的改性方法 (Modification method of interlayer heat-insulating fireproof glass ) 是由 张猛 于 2019-09-26 设计创作，主要内容包括：本发明公开了一种夹层隔热防火玻璃的改性方法,将纳米羟基磷灰石粉体分散在去离子水中超声分散,加多巴胺充分搅拌后超声,得聚多巴胺包覆改性的羟基磷灰石,将其均匀分散在乙醇溶液中,磁力搅拌下加二氧化硅气凝胶粉末、莫来石微球隔热组分,搅匀得复合隔热组分；将氧化石墨烯加入缓冲溶液中,与氮化硼纳米片分散液混匀,加盐酸多巴胺水溶液反应,离心、水洗得复合防火组分；将纳米二氧化硅微粒分散液水浴加热,磁力搅拌,加氢氧化钾溶液混合,恒温反应,加复合隔热组分、复合防火组分及抗冷凝剂、防冻剂,搅拌,抽真空并接入冷却水进行降温,得隔热防火浆料,将其倒入夹层玻璃中,将灌好的玻璃在电热鼓风干燥箱中完全固化,得夹层隔热防火玻璃。(The invention discloses a method for modifying interlayer heat-insulating fireproof glass, which comprises the steps of dispersing nano hydroxyapatite powder in deionized water for ultrasonic dispersion, adding dopamine, fully stirring, then performing ultrasonic treatment to obtain polydopamine-coated modified hydroxyapatite, uniformly dispersing the polydopamine-coated modified hydroxyapatite in an ethanol solution, adding silicon dioxide aerogel powder and mullite microsphere heat-insulating components under magnetic stirring, and uniformly stirring to obtain composite heat-insulating components; adding graphene oxide into a buffer solution, uniformly mixing the graphene oxide with the boron nitride nanosheet dispersion solution, adding a dopamine hydrochloride aqueous solution for reaction, centrifuging, and washing to obtain a composite fireproof component; heating the nano silicon dioxide particle dispersion liquid in a water bath, stirring by magnetic force, mixing with a potassium hydroxide solution, reacting at constant temperature, adding a composite heat insulation component, a composite fireproof component, an anti-condensing agent and an antifreezing agent, stirring, vacuumizing, adding cooling water, cooling to obtain heat insulation fireproof slurry, pouring the heat insulation fireproof slurry into laminated glass, and completely curing the poured glass in an electric heating air blast drying oven to obtain the laminated heat insulation fireproof glass.)

1. The method for modifying the interlayer heat-insulating fireproof glass is characterized by comprising the following steps of:

(1) preparation of composite heat insulation component:

dispersing 6-9 parts of nano hydroxyapatite powder 1:10 in deionized water, performing ultrasonic dispersion for 20-30min, adding 0.36-0.54 part of dopamine, performing sufficient stirring, performing ultrasonic treatment for 30-40min to obtain polydopamine-coated modified hydroxyapatite, uniformly dispersing 1:5 in an ethanol solution, adding 4-7 parts of silica aerogel powder and 5-10 parts of mullite microsphere heat insulation components under magnetic stirring, and uniformly stirring to obtain a composite heat insulation component;

preparation of the composite fireproof component:

dispersing 3-5 parts of boron nitride nanosheets in deionized water, and ultrasonically and uniformly obtaining a boron nitride nanosheet dispersion liquid; adding 1-2 parts of graphene oxide 1:100 into a buffer solution, uniformly mixing with a boron nitride nanosheet dispersion solution, dropwise adding 7-11 parts of dopamine hydrochloride aqueous solution, reacting at 60-65 ℃ for 2-4h, centrifuging, and washing for 3-5 times to obtain a composite fireproof component;

(3) preparing the interlayer heat-insulating fireproof glass:

heating 25-50 parts of nano silicon dioxide particle dispersion liquid in a water bath at 75-85 ℃, magnetically stirring, adding 10-20 parts of potassium hydroxide solution, mixing, reacting at constant temperature for 20-25min, adding the materials obtained in (1) and (2), 2.8-5.6 parts of anti-condensing agent and 1.75-3.5 parts of anti-freezing agent, stirring for 15-25min, vacuumizing, and adding cooling water for cooling to obtain heat-insulating fireproof slurry; and pouring the obtained slurry into the laminated glass, putting the poured glass into an electric heating forced air drying box, and completely curing to obtain the laminated heat-insulating fireproof glass.

2. The method for modifying the laminated heat-insulating fireproof glass according to claim 1, wherein the preparation of the mullite microsphere heat-insulating component in the step (1): uniformly mixing 5-10 parts of aggregate mullite microspheres, 0.25-0.5 part of binding agent calcium aluminate cement and 0.3-0.8 part of active alpha-alumina micropowder, adding 4-8 parts of deionized water, and uniformly stirring to obtain the mullite microsphere heat insulation component.

3. The method for modifying the interlayer heat-insulating fireproof glass according to claim 1, wherein in the step (2), the solid content of the boron nitride nanosheet dispersion is 3-5 mg/mL; the buffer solution is Tris buffer solution with the pH value of 8-9; 0.5-1 part of dopamine hydrochloride powder 1:10 is dissolved in deionized water to obtain dopamine hydrochloride aqueous solution.

4. The method for modifying the laminated heat-insulating fireproof glass as claimed in claim 1, wherein the solid content of the nano silica particle dispersion liquid in the step (3) is 45-55%; the concentration of the potassium hydroxide solution is 45-55%; the antifreezing agent is ethylene glycol or propylene glycol; the curing process comprises the steps of firstly reacting for 4-6h at 60-65 ℃, then heating to 70-75 ℃ and continuing to react for 7-10 h.

Technical Field

The invention belongs to the field of glass deep processing, and particularly relates to a method for modifying interlayer heat-insulating fireproof glass.

Background

With the development of urbanization, more and more people move into cities, various buildings with comprehensive functions, such as large buildings, underground buildings, high-rise buildings, super high-rise buildings and the like, emerge in large numbers, new fire safety problems also occur when new buildings fall, and the fire prevention problem of urban buildings becomes the most important problem. The safety level of the fireproof glass is improved, the fireproof glass is applied on a large scale, the requirements of modern building laws and regulations are met, the research on a high-performance fireproof glass material system and the research on the industrial production process of the fireproof glass are developed, and the method has important theoretical significance and practical requirements.

Fire-resistant glass is a special type of glass that maintains its integrity and even thermal insulation during a specified fire resistance test. There are many types of fire-resistant glass in terms of composition and manufacturing process, and among them, silicate-based fire-resistant glass is currently the safest fire-resistant glass in terms of fire protection. Not only has reliable fire-resistant integrity, but also can form a heat barrier and has excellent heat insulation property.

The preparation method comprises the following steps of mixing polydopamine-coated and modified hydroxyapatite, silicon dioxide aerogel powder and mullite microsphere heat insulation components uniformly to obtain a composite heat insulation component, carrying out coating reaction on a graphene oxide solution, a boron nitride nanosheet dispersion solution and a dopamine hydrochloride aqueous solution to obtain a composite fire insulation component, mixing a nano silicon dioxide particle dispersion solution, a potassium hydroxide solution, the composite heat insulation component and the composite fire insulation component uniformly to prepare a heat insulation fire prevention slurry, pouring the slurry into laminated glass, putting the laminated glass into an electrothermal blowing drying box, and completely curing to obtain the laminated heat insulation fire prevention glass; the obtained modified laminated glass has excellent heat-insulating property and fireproof property.

Disclosure of Invention

The invention aims to solve the existing problems and provides a method for modifying laminated heat-insulating fireproof glass, and the laminated glass modified according to the method has excellent heat-insulating property and fireproof performance.

The invention is realized by the following technical scheme:

a method for modifying interlayer heat-insulating fireproof glass comprises the following steps of:

(1) preparation of composite heat insulation component:

dispersing 6-9 parts of nano hydroxyapatite powder 1:10 in deionized water, performing ultrasonic dispersion for 20-30min, adding 0.36-0.54 part of dopamine, performing sufficient stirring, performing ultrasonic treatment for 30-40min to obtain polydopamine-coated modified hydroxyapatite, uniformly dispersing 1:5 in an ethanol solution, adding 4-7 parts of silica aerogel powder and 5-10 parts of mullite microsphere heat insulation components under magnetic stirring, and uniformly stirring to obtain a composite heat insulation component;

the hydrophilic modifier dopamine is selected to carry out surface modification on the hydroxyapatite, so that the dispersibility of the hydroxyapatite is improved, the particle size of the modified hydroxyapatite is obviously increased, and the hydrophilic modifier dopamine is oxidized and self-polymerized to generate polydopamine so as to realize coating modification on the hydroxyapatite; mixing mullite microspheres serving as aggregate, calcium aluminate cement serving as a bonding agent and active alpha-alumina micropowder serving as fine powder with water to obtain a mullite microsphere heat insulation component; uniformly mixing and stirring the polydopamine-coated modified hydroxyapatite, the silicon dioxide aerogel powder and the mullite microsphere heat insulation component to obtain a composite heat insulation component;

(2) preparation of the composite fireproof component:

dispersing 3-5 parts of boron nitride nanosheets in deionized water, and ultrasonically and uniformly obtaining a boron nitride nanosheet dispersion liquid; adding 1-2 parts of graphene oxide 1:100 into a buffer solution, uniformly mixing with a boron nitride nanosheet dispersion solution, dropwise adding 7-11 parts of dopamine hydrochloride aqueous solution, reacting at 60-65 ℃ for 2-4h, centrifuging, and washing for 3-5 times to obtain a composite fireproof component;

preparing a polydopamine-coated reduced graphene oxide-boron nitride nanosheet composite fireproof component by utilizing the self-polymerization reaction of the dopamine hydrochloride in a weakly alkaline environment; after the graphene oxide is coated by the polydopamine, some oxygen-containing functional groups on the surface of the graphene oxide are removed, which shows that the graphene oxide is partially reduced while being coated by the polydopamine, and the thermal stability is improved; the composite fireproof component is added into the laminated glass, so that the heat release rate and the primary peak value of the toxic gas CO yield can be reduced to the maximum extent, the secondary peak value release of the heat release rate and the CO yield is delayed and inhibited, and the total smoke release amount of a sample during combustion can be effectively reduced;

(3) preparing the interlayer heat-insulating fireproof glass:

heating 25-50 parts of nano silicon dioxide particle dispersion liquid in a water bath at 75-85 ℃, magnetically stirring, adding 10-20 parts of potassium hydroxide solution, mixing, reacting at constant temperature for 20-25min, adding the materials obtained in (1) and (2), 2.8-5.6 parts of anti-condensing agent and 1.75-3.5 parts of anti-freezing agent, stirring for 15-25min, vacuumizing, and adding cooling water for cooling to obtain heat-insulating fireproof slurry; pouring the obtained slurry into laminated glass, putting the poured glass into an electric heating forced air drying box, and completely curing to obtain the laminated heat-insulating fireproof glass;

mixing the high-solid-content nano silicon dioxide particle dispersion liquid and a potassium hydroxide solution to prepare a fireproof base material, adding a composite heat-insulating component and a composite fireproof component to obtain heat-insulating fireproof slurry, pouring the obtained slurry into laminated glass, putting the laminated glass into an electric heating air blast drying box, and completely curing to obtain the laminated heat-insulating fireproof glass;

further, the preparation of the mullite microsphere heat insulation component in the step (1): uniformly mixing 5-10 parts of aggregate mullite microspheres, 0.25-0.5 part of binding agent calcium aluminate cement and 0.3-0.8 part of active alpha-alumina micropowder, adding 4-8 parts of deionized water, and uniformly stirring to obtain the mullite microsphere heat insulation component.

Further, in the step (2), the solid content of the boron nitride nanosheet dispersion liquid is 3-5 mg/mL; the buffer solution is Tris buffer solution with the pH value of 8-9; 0.5-1 part of dopamine hydrochloride powder 1:10 is dissolved in deionized water to obtain dopamine hydrochloride aqueous solution.

Further, the solid content of the nano silicon dioxide particle dispersion liquid in the step (3) is 45-55%; the concentration of the potassium hydroxide solution is 45-55%; the antifreezing agent is ethylene glycol or propylene glycol; the curing process comprises the steps of firstly reacting for 4-6h at 60-65 ℃, then heating to 70-75 ℃ and continuing to react for 7-10 h.

Compared with the prior art, the invention has the following advantages:

(1) the hydrophilic modifier dopamine is selected to carry out surface modification on the hydroxyapatite, so that the dispersibility of the hydroxyapatite is improved, the particle size of the modified hydroxyapatite is obviously increased, and the hydrophilic modifier dopamine is oxidized and self-polymerized to generate polydopamine so as to realize coating modification on the hydroxyapatite; mixing mullite microspheres serving as aggregate, calcium aluminate cement serving as a bonding agent and active alpha-alumina micropowder serving as fine powder with water to obtain a mullite microsphere heat insulation component; and uniformly mixing and stirring the polydopamine-coated modified hydroxyapatite, the silicon dioxide aerogel powder and the mullite microsphere heat insulation component to obtain the composite heat insulation component.

(2) Preparing a polydopamine-coated reduced graphene oxide-boron nitride nanosheet composite fireproof component by utilizing the self-polymerization reaction of the dopamine hydrochloride in a weakly alkaline environment; after the graphene oxide is coated by the polydopamine, some oxygen-containing functional groups on the surface of the graphene oxide are removed, which shows that the graphene oxide is partially reduced while being coated by the polydopamine, and the thermal stability is improved; the composite fireproof component is added into the laminated glass, so that the heat release rate and the primary peak value of the toxic gas CO yield can be reduced to the maximum extent, the secondary peak value release of the heat release rate and the CO yield is delayed and inhibited, and the total smoke release amount of a sample during combustion can be effectively reduced;

the flame retardant mechanism is: the large-sheet structure of the reduced graphene oxide is very favorable for forming a protective layer in the laminated glass, the graphene oxide is reduced while being coated by the polydopamine, the thickness of the sheet layer is increased, the thermal stability of the sheet layer is improved, a polydopamine-coated reduced graphene oxide carbon skeleton with good thermal stability is used as a carbon forming template in the combustion process to promote the surface of the laminated glass to form a stable protective carbon layer, and the undegraded polymer at the bottom is effectively protected; when the composite fireproof component is added into the laminated glass, a good physical barrier can be formed, and the mutual permeation of oxygen, heat and volatile combustible components between a gas phase and a solidified phase is effectively prevented; in addition, the anisotropic nature of the composite fire-blocking component sheet promotes rapid lateral heat dissipation along the plane of the sheet, and the rate of penetration into the underlying polymer is slow, thereby slowing down the rate of thermal degradation of the underlying polymer.

(3) Mixing the high-solid-content nano silicon dioxide particle dispersion liquid and a potassium hydroxide solution to prepare a fireproof base material, adding a composite heat-insulating component and a composite fireproof component to obtain heat-insulating fireproof slurry, pouring the obtained slurry into laminated glass, putting the laminated glass into an electric heating air blast drying oven, and completely curing to obtain the laminated heat-insulating fireproof glass.

Detailed Description