CN116574520A - Fireproof gel and preparation method and application thereof - Google Patents

Fireproof gel and preparation method and application thereof Download PDF

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Publication number
CN116574520A
CN116574520A CN202310519835.7A CN202310519835A CN116574520A CN 116574520 A CN116574520 A CN 116574520A CN 202310519835 A CN202310519835 A CN 202310519835A CN 116574520 A CN116574520 A CN 116574520A
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fireproof
fire
gel
flame retardant
crosslinking reaction
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CN116574520B (en
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颜龙
廖玉荣
蔡萌涛
周龙夏娣
赵雯筠
李佳乐
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Hunan Shengniu Safety Technology Co ltd
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Hunan Shengniu Safety Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant

Abstract

The invention discloses a fireproof gel and a preparation method and application thereof, wherein the fireproof gel comprises the following components: preparing a flame retardant aqueous solution; neutralizing acrylic acid or methacrylic acid with sodium hydroxide to obtain partially neutralized acrylic acid-sodium acrylate solution or methacrylic acid-sodium methacrylate solution, and then adding acrylamide and a crosslinking agent to perform a crosslinking reaction to obtain a crosslinking reaction solution; and mixing the fire retardant aqueous solution with the crosslinking reaction solution to obtain a fireproof liquid, adding an initiator, and curing to obtain the fireproof gel. The high-efficiency durable transparent fireproof gel improves the fireproof and weather-resistant properties of fireproof glass on the basis of ensuring the transparency and mechanical properties of the gel, and solves the problems of complex preparation process, easy sedimentation, poor weather-resistant properties, easy generation of microbubbles, insufficient fireproof properties and the like of the existing products.

Description

Fireproof gel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite fireproof glass, and particularly relates to fireproof gel and a preparation method and application thereof.
Background
Fire-resistant glass refers to a special type of glass that is capable of maintaining its integrity, even thermal insulation, in a fire-resistance test that specifies a temperature rise profile. The composite fireproof glass is one kind of fireproof glass, and fireproof glue solution is added between two or more pieces of glass to cure into transparent gel and to bond with glass to form fireproof glass member. The composite fireproof glass has excellent heat insulation performance, can meet the corresponding fire-resistant grade requirement, and is the most effective and safer fireproof glass product at present. The grouting type composite fireproof glass is a type of composite fireproof glass which is relatively simple and convenient to prepare, and mainly comprises organic grouting type composite fireproof glass and inorganic grouting type composite fireproof glass.
At present, the organic grouting type composite fireproof glass which takes polyacrylamide gel as a fireproof heat insulation layer is commonly used in China, has excellent heat insulation performance, but has poor ultraviolet irradiation resistance, and can generate phenomena of yellowing, foaming and the like after long-time use, so that the service life of the glass is greatly limited.
The existing preparation process of the composite fireproof glass is complex and has high cost; meanwhile, according to research and study of products at home and abroad, the fire resistance limit of the products is still generally lower, and related products with low price, low overall thickness and higher fire resistance limit hardly exist, so that the industrialized development of the composite fire-proof glass is restricted. It is therefore critical to develop a fire-resistant glass gel interlayer that is highly efficient and durable to address the above problems.
Disclosure of Invention
The invention aims to solve the technical problems, overcome the defects and shortcomings in the background art, provide the high-efficiency durable transparent fireproof gel and the preparation method thereof, and simultaneously provide the composite fireproof glass with excellent fireproof and ageing-resistant properties.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method of preparing a fire-resistant gel comprising the steps of:
(1) Preparation of an aqueous flame retardant solution: dissolving the composite flame retardant in water to obtain a flame retardant aqueous solution;
(2) Preparation of a crosslinking reaction solution: neutralizing acrylic acid or methacrylic acid with sodium hydroxide to a neutralization degree of 70% -80% to obtain a partially neutralized acrylic acid-sodium acrylate solution or methacrylic acid-sodium methacrylate solution, and then adding acrylamide and a crosslinking agent to carry out a crosslinking reaction to obtain a crosslinking reaction solution;
(3) Preparation of the fire-retardant gel: and (3) mixing the fire retardant aqueous solution obtained in the step (1) with the crosslinking reaction solution obtained in the step (2) to obtain a fireproof liquid, and then adding an initiator to obtain the fireproof gel after curing.
As a further improvement, the composite flame retardant of step (1) comprises: (a) a char source; (b) an acid source; (c) a gas source.
As a further improvement, the carbon source comprises glycerol and/or urea, the acid source comprises monoammonium phosphate, and the gas source comprises at least one of ammonium polyphosphate, monoammonium phosphate, or urea.
As a further improvement, the composite flame retardant comprises ammonium dihydrogen phosphate, magnesium chloride, glycerol and urea, wherein the mass ratio of the ammonium dihydrogen phosphate to the magnesium chloride to the glycerol is (2-4): 5-10): 1-3): 1.
As a further improvement, the mass ratio of the acrylic acid or the methacrylic acid to the acrylamide in the step (2) is 1 (0.5-4).
As a further improvement, the reaction temperature of the crosslinking reaction in the step (2) is 70-80 ℃ and the reaction time is 0.5-1 h.
As a further improvement, the fire retardant aqueous solution and the crosslinking reaction solution in the step (3) are mixed according to the mass ratio of 1 (0.5-2); and/or
The dosage ratio of the composite flame retardant to the acrylic acid or the methacrylic acid is 13 (1.8-6).
The invention also provides a fireproof gel, which is mainly prepared from the following components:
a composite flame retardant comprising soluble metal ions;
the crosslinking reaction component is prepared by crosslinking reaction of acrylic acid-sodium acrylate or methacrylic acid-sodium methacrylate with the neutralization degree of 70-80 percent, acrylamide and a crosslinking agent;
an initiator;
and solvent water.
The invention also provides composite fireproof glass which is grouting type composite fireproof glass, and the fireproof gel prepared by the method is used for bonding the glass. Specifically, an initiator is added into the fireproof liquid, and then the fireproof liquid is poured into the composite fireproof glass and is solidified.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the fireproof gel disclosed by the invention, the copolymer is prepared by adopting the acrylic acid (methacrylic acid) and the acrylamide through a chemical method, and the acrylic acid (methacrylic acid) is introduced into a matrix, so that the problems of reduced coating transparency, poor migration and compatibility of the flame retardant and the like caused by adding the flame retardant are effectively avoided.
2. The fireproof gel is added with the composite flame retardant, integrates a carbon source, an acid source and an air source of an intumescent flame retardant system, and introduces acrylic acid (methacrylic acid), so that the fireproof gel has better fireproof performance, ageing resistance and flexibility.
3. The invention has the advantages of wide raw material sources, low cost, simple preparation process and convenient operation.
Therefore, the high-efficiency durable transparent fireproof gel improves the fireproof and weather-resistant properties of the fireproof glass on the basis of ensuring the transparency and mechanical properties of the gel, and solves the problems of complex preparation process, easy sedimentation, poor weather-resistant properties, easy generation of microbubbles, insufficient fireproof properties and the like of the existing products.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of the present invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Aiming at the problems that the organic grouting type composite fireproof glass which adopts polyacrylamide gel as a fireproof heat-insulating layer at present has poor ultraviolet irradiation resistance, yellowing, foaming and the like can occur after long-time use, the invention provides the high-efficiency durable transparent fireproof gel and the preparation method thereof.
In some embodiments, the method of preparing a fire-resistant gel of the present invention comprises the steps of:
step (1), preparation of a flame retardant aqueous solution: and dissolving the composite flame retardant in water to obtain a flame retardant aqueous solution.
In some embodiments, the composite flame retardant comprises: (a) a char source; (b) an acid source; (c) a gas source. The composite flame retardant is dissolved in water to be uniformly dispersed.
In the flame-retardant system, the carbon source comprises glycerol and/or urea, the acid source comprises ammonium dihydrogen phosphate, and the gas source comprises at least one of ammonium polyphosphate, ammonium dihydrogen phosphate or urea. When the fireproof gel is heated, an acid source releases an acidic substance, the acidic substance and a carbon source are subjected to esterification reaction at a higher temperature, dehydration is carried out to form carbon, a carbon layer is formed, and the system starts to melt; the gases such as water vapor, ammonia gas, carbon dioxide and the like generated by the esterification reaction and incombustible gas generated by an air source are filled into the carbon layer, so that the system is expanded and foamed, and when the reaction is nearly completed, the carbon layer of the system is solidified, and finally a porous foam carbon layer is formed, and heat is prevented from being transferred to the back surface of the fireproof glass, thereby achieving the purpose of improving the fireproof performance.
Preferably, the flame retardant contains soluble metal ions, such as Mg 2+ . In some embodiments, the flame retardant contains magnesium chloride, has better solubility, can improve the fire-resistant flame retardant performance of the fire-resistant glass under the condition of not affecting the light transmittance of the fire-resistant glass, and can strengthen the crosslinking degree of the gel due to the existence of metal ions, so that the hydrogel has stronger stability.
In some embodiments, the composite flame retardant comprises ammonium dihydrogen phosphate, magnesium chloride, glycerol and urea in a mass ratio of (2-4): 5-10): 1-3): 1.
Step (2), preparing a crosslinking reaction solution: neutralizing acrylic acid or methacrylic acid with sodium hydroxide to obtain partially neutralized acrylic acid-sodium acrylate solution or methacrylic acid-sodium methacrylate solution, and then adding acrylamide and a crosslinking agent to carry out crosslinking reaction to obtain a crosslinking reaction solution.
The acrylamide-acrylic acid copolymer synthesized by taking acrylic acid and acrylamide as monomers has a large number of hydroxyl groups, and can form more hydrogen bonds in the gel, so that the thermal stability of the gel is enhanced; acrylic acid also enhances the char formation ability of the gel and exhibits good synergy with the flame retardant of the present invention, so that its fire resistance properties can be improved.
The addition of the acrylic acid not only improves the water absorption and water retention performance of the hydrogel so that the gel is more difficult to degrade, but also introduces highly stable carboxylate and carboxylic acid into the gel, thereby effectively increasing the ageing resistance of the fireproof gel.
In addition, the acrylic acid molecular chain contains flexible hydrophilic groups, so that better flexibility can be provided for the gel.
The optical clarity of the fire-resistant glass is related to the dispersion of the solute in the matrix and the compatibility of the flame retardant particles with the matrix, which can affect the transparency of the coating if the flame retardant is selected improperly or added in too much amount; the mutual rejection phenomenon is very easy to occur when the interaction between the flame retardant and the matrix is weak or the compatibility is poor, and the migration and precipitation of the flame retardant occur. Therefore, when the fire-proof gel is prepared, the problems of reduced coating transparency, poor compatibility of the fire retardant, migration and precipitation and the like occur when the fire retardant is added.
The invention can avoid the occurrence of the problems mainly for two reasons by adding the acrylic acid: on one hand, the acrylic acid has good compatibility with the flame retardant disclosed by the invention, so that the influence of the flame retardant on the transparency of the coating can be reduced; on the other hand, the polymer network formed by copolymerization of acrylic acid and acrylamide is more compact and stable, and can absorb the flame retardant into the gaps of the polymer gel network, so that the migration and precipitation of the flame retardant are prevented.
In some embodiments, the acrylic acid or methacrylic acid has a degree of neutralization of 70% -80%. The neutralization degree of the acrylic acid has an influence on the water absorption performance of the hydrogel, and the sodium hydroxide is used for neutralizing the acrylic acid to convert carboxyl groups in the monomer into sodium carboxylate groups with stronger hydrophilicity, so that the water absorption capacity of the hydrogel is improved. When the neutralization degree of the acrylic acid is less than 75%, the water absorption of the prepared hydrogel is increased along with the increase of the neutralization degree, and when the neutralization degree is more than 75%, the water absorption is reduced along with the increase of the neutralization degree, so that the neutralization degree of the sodium acrylate solution is controlled to be 70% -80%, and partial free acrylic acid is reserved, so that the hydrogel has better water absorption and water retention capacity, and the fire resistance of the fireproof glass is effectively improved.
In some embodiments, the mass ratio of the acrylic acid or the methacrylic acid to the acrylamide is 1 (0.5-4), and the acrylic acid or the methacrylic acid can better cooperate with the acrylamide and the flame retardant to play the role in the mass ratio.
In some embodiments, the crosslinker is added in an amount of 0.5 to 1% of the total mass of the monomers (i.e., the total mass of the acrylic/methacrylic acid and acrylamide starting materials). The crosslinking reaction temperature is 70-80 ℃ and the reaction time is 0.5-1 h. The acrylamide-acrylic acid copolymer is cross-linked to form a network.
Step (3), preparation of fireproof gel: and (3) mixing the fire retardant aqueous solution obtained in the step (1) with the crosslinking reaction solution obtained in the step (2) to obtain a fireproof liquid, and then adding an initiator to obtain the fireproof gel after curing.
In some embodiments, the flame retardant aqueous solution and the crosslinking reaction solution are mixed according to the mass ratio of (0.5-2), and the using amount ratio of the composite flame retardant to the acrylic acid or the methacrylic acid is 13 (1.8-6).
In some embodiments, the initiator comprises ammonium persulfate and sodium metabisulfite, 8-15 wt% of aqueous solution is prepared respectively, and ammonium persulfate solution and sodium metabisulfite solution which account for 0.3-0.8% of the total mass of the monomers are sequentially added into the fireproof liquid, so that the ammonium persulfate and the ammonium metabisulfite undergo redox reaction to generate primary free radicals, and the unreacted monomer solution is initiated to continue to initiate polymerization reaction, so that hydrogel formation is accelerated.
In some embodiments, after the fire-protecting liquid is added with the initiator, the fire-protecting liquid is mixed and stirred, and then poured into the composite fire-protecting glass (namely poured between two or more pieces of glass), and solidified into transparent gel at normal temperature, and the transparent gel and the glass are bonded into a whole to form the composite fire-protecting glass.
In some embodiments, a coupling agent (e.g., 85wt% absolute ethyl alcohol, 10wt% acrylamide, and 5wt% silane coupling agent a151 may be used as the coupling agent) is brushed onto the inner surface of the glass, and then a fire-blocking liquid is poured in, so that the coupling agent can improve the interface characteristics between the inorganic filler and the organic polymer matrix, and can bond the fire-blocking gel and the glass more tightly.
The fire resistance limit of the composite fireproof glass with the thickness of 10mm prepared by the transparent fireproof gel can reach 60-75min.
Some of the reagents used in the examples below were as follows:
acrylonitrile (AM) purity not less than 99% Ala Ding Shiji (Shanghai Co., ltd.)
Acrylic Acid (AA) purity of 99% or more of Ala Ding Shiji (Shanghai Co., ltd.)
Methacrylic acid (MAA) purity of 99% or more of Ala Ding Shiji (Shanghai Co., ltd.)
Methylene Bisacrylamide (MBA) purity of not less than 99.5% of Ala Ding Shiji (Shanghai Co., ltd.)
Sodium hydroxide (NaOH) purity not less than 98% Chengdu Colon chemical Co., ltd
Sodium metabisulfite (Na) 2 S 2 O 5 ) Tianjin far chemical reagent Co., ltd. With purity of not less than 96%
Ammonium persulfate ((NH) 4 ） 2 S 2 O 8 ) Shanghai Miclin Biochemical technology Co.Ltd with purity of not less than 98.5%
Ammonium polyphosphate (APP) n < 20 Shanghai Michlin Biochemical technologies Co., ltd
Ammonium Dihydrogen Phosphate (ADP) purity not less than 99% Tianjin far chemical reagent Co., ltd
Urea purity not less than 99% Tianjin far chemical reagent Co.Ltd
Magnesium chloride hexahydrate with purity not less than 98% of national medicine group chemical reagent Co., ltd
Glycerol (glycerol) purity is not less than 98% of Tianjin far chemical reagent Co.
Example 1:
in this embodiment, the preparation method of the high-efficiency durable fireproof gel includes the following steps:
(1) Preparation of the Components
a. Preparation of an aqueous flame retardant solution: sequentially dissolving flame retardant monoammonium phosphate, magnesium chloride, glycerol and urea in deionized water according to a mass ratio of 3:7:2:1 in a beaker, stirring and dissolving, standing for 24 hours, and then settling and filtering to obtain a flame retardant aqueous solution.
b. Preparation of a crosslinking reaction solution: acrylic acid (raw material) and sodium hydroxide are neutralized at normal temperature according to a molar ratio of 1:0.75, and an acrylic acid-sodium acrylate solution with a neutralization degree of 75% is obtained. Then, in a three-neck flask with a stirrer, a thermometer, a reflux condenser and a water separator, adding acrylamide (the mass ratio of the acrylic acid raw material to the acrylamide is 2:1) into an acrylic acid-sodium acrylate solution for mixing reaction, and adding a cross-linking agent accounting for 0.8 percent of the total mass of monomers (namely the total mass of the acrylic acid and the acrylamide raw material)N’N-methylene bisacrylamide), wherein the reaction temperature is 70 ℃, and the reaction time is 0.5-1h, so as to prepare transparent crosslinking reaction liquid;
c. preparing an initiator solution: preparing 10wt% aqueous solution of ammonium persulfate and sodium metabisulfite respectively;
(2) Preparation of high-efficiency durable fireproof gel
Uniformly mixing the fire retardant aqueous solution prepared in the step (1) and the crosslinking reaction solution according to the mass ratio of 1:1 to prepare the transparent fireproof liquid. And sequentially adding an initiator solution accounting for 0.5% of the total mass of the monomers into the transparent fireproof liquid, uniformly mixing and stirring, and then pouring the mixture into the composite fireproof glass (namely, pouring the mixture between two or more pieces of glass), curing the mixture into transparent gel at normal temperature, and bonding the transparent gel and the glass into a whole.
In this example, the mass ratio of the raw materials used is that the flame retardant is acrylic acid and acrylamide=13:6:3.
(3) Characterization of Performance of high Performance durable transparent fire-resistant gels
The high-efficiency durable composite fireproof glass prepared in the embodiment is measured on the fire resistance and ageing resistance by using GB15763.1-2009 safety glass for building: as shown in Table 1, the transmittance of the composite fireproof glass is 81.3%, the fire-resistant time can reach 71min, the transmittance of the composite fireproof glass after 168h accelerated aging is 77%, and the fire-resistant time can reach 67min.
TABLE 1
Example 2:
this embodiment differs from embodiment 1 in that: the mass ratio of the acrylic acid raw material to the acrylamide in the preparation step of the crosslinking reaction liquid is 1:4;
in this example, the mass ratio of the raw materials used is that the flame retardant is acrylic acid and acrylamide=13:1.8:7.2.
The high-efficiency durable composite fireproof glass prepared in the embodiment is measured on the fire resistance and ageing resistance by using GB15763.1-2009 safety glass for building: the light transmittance of the composite fireproof glass is 85.4%, the fire-resistant time can reach 65min, the light transmittance of the composite fireproof glass after 168h accelerated aging is 82.9%, and the fire-resistant time can reach 63min.
TABLE 2
Example 3:
this embodiment differs from embodiment 1 in that: in the embodiment, methacrylic acid and acrylamide are used as raw materials to prepare the high-efficiency durable fireproof gel, and the flame retardant adopts ammonium polyphosphate, monoammonium phosphate, urea, glycerol and silicon phosphate.
(1) Preparation of the Components
a. Preparation of an aqueous flame retardant solution: and (3) sequentially dissolving glycerol, ammonium polyphosphate, monoammonium phosphate and urea in deionized water according to a mass ratio of 2:7:3:1 in a beaker, stirring and dissolving, standing for 24 hours, and then settling and filtering to obtain the flame retardant aqueous solution.
b. Preparation of a crosslinking reaction solution: methacrylic acid (raw material) and sodium hydroxide are neutralized at normal temperature according to a molar ratio of 1:0.75, and a methacrylic acid-sodium methacrylate solution with a neutralization degree of 75% is obtained. Then, in a three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a water separator, acrylamide (the mass ratio of methacrylic acid raw material to acrylamide is 1:4) is added into a methacrylic acid-sodium methacrylate solution for mixing reaction, and a cross-linking agent accounting for 0.8 percent of the total mass of the monomers is added into the three-neck flask to obtain the productN’N-methylene bisacrylamide), wherein the reaction temperature is 70 ℃, and the reaction time is 0.5-1h, so as to prepare transparent crosslinking reaction liquid;
c. preparing an initiator solution: the same as in example 1;
(2) Preparation of high-efficiency durable fireproof gel: the same as in example 1.
In this example, the mass ratio of the raw materials used is that the flame retardant is acrylic acid and acrylamide=13:1.8:7.2.
(3) Characterization of Performance of high Performance durable transparent fire-resistant gels
The high-efficiency durable composite fireproof glass prepared in the embodiment is measured on the fire resistance and ageing resistance by using GB15763.1-2009 safety glass for building: the light transmittance of the composite fireproof glass is 86.1%, the fire-resistant time can reach 69min, the light transmittance of the composite fireproof glass after 168h accelerated aging is 83.6%, and the fire-resistant time can reach 67min.
TABLE 3 Table 3
Example 4:
the difference between this example and example 3 is that the mass ratio of methacrylic acid raw material to acrylamide in the preparation step of the crosslinking reaction liquid is 1:0.5;
in this example, the mass ratio of the raw materials used is that the flame retardant is acrylic acid and acrylamide=13:6:3.
The high-efficiency durable composite fireproof glass prepared in the embodiment is measured on the fire resistance and ageing resistance by using GB15763.1-2009 safety glass for building: the light transmittance of the composite fireproof glass is 85.6%, the fire-resistant time can reach 63min, the light transmittance of the composite fireproof glass after 168h accelerated aging is 83.4%, and the fire-resistant time can reach 61min.
TABLE 4 Table 4
Comparative example 1:
this comparative example differs from example 1 in that: no acrylic acid was added.
(1) Preparation of the Components
a. Preparation of an aqueous flame retardant solution: sequentially dissolving flame retardant monoammonium phosphate, magnesium chloride, glycerol and urea in deionized water according to a mass ratio of 3:7:2:1 in a beaker, stirring and dissolving, standing for 24 hours, and then settling and filtering to obtain a flame retardant aqueous solution.
b. Preparation of a crosslinking reaction solution: adding acrylamide into water in a three-neck flask with a stirrer, a thermometer, a reflux condenser pipe and a water separator, and adding a cross-linking agent accounting for 0.8 percent of the total mass of the monomersN’N-methylene bisacrylamide), wherein the reaction temperature is 70 ℃, and the reaction time is 0.5-1h, so as to prepare transparent crosslinking reaction liquid;
c. preparing an initiator solution: preparing 10wt% aqueous solution of ammonium persulfate and sodium metabisulfite respectively;
(2) Preparation of high-efficiency durable fireproof gel
Uniformly mixing the fire retardant aqueous solution prepared in the step (1) and the crosslinking reaction solution according to the mass ratio of 1:1 to prepare the transparent fireproof liquid. And sequentially adding an initiator solution accounting for 0.5% of the total mass of the monomers into the transparent fireproof liquid, uniformly mixing and stirring, and then pouring the mixture into the composite fireproof glass (namely, pouring the mixture between two or more pieces of glass), curing the mixture into transparent gel at normal temperature, and bonding the transparent gel and the glass into a whole.
In this example, the mass ratio of the raw materials used is that of the flame retardant, namely acrylamide=13:3.
(3) Characterization of Performance of high Performance durable transparent fire-resistant gels
The high-efficiency durable composite fireproof glass prepared in the embodiment is measured on the fire resistance and ageing resistance by using GB15763.1-2009 safety glass for building: the light transmittance of the composite fireproof glass is 86.6%, the fire-resistant time can reach 53min, the light transmittance of the composite fireproof glass after 168h accelerated aging is 64.8%, and the fire-resistant time can reach 40min.
TABLE 5
Comparative example 2
This comparative example differs from example 1 in that: the degree of neutralization of the acrylic acid-sodium acrylate solution was 50%.
(1) Preparation of the Components
a. Preparation of an aqueous flame retardant solution: sequentially dissolving flame retardant monoammonium phosphate, magnesium chloride, glycerol and urea in deionized water according to a mass ratio of 3:7:2:1 in a beaker, stirring and dissolving, standing for 24 hours, and then settling and filtering to obtain a flame retardant aqueous solution.
b. Preparation of a crosslinking reaction solution: acrylic acid (raw material) and sodium hydroxide are neutralized at normal temperature according to a molar ratio of 1:0.5, and an acrylic acid-sodium acrylate solution with a neutralization degree of 50% is obtained. Then, in a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a water separator, acrylamide (the mass ratio of the acrylic acid raw material to the acrylamide is 2:1) was added to the acrylic acid-sodium acrylate solution to carry out a mixing reactionAdding cross-linking agent accounting for 0.8 percent of the total mass of the monomers (namely the total mass of the raw materials of the acrylic acid and the acrylamide)N’N-methylene bisacrylamide), wherein the reaction temperature is 70 ℃, and the reaction time is 0.5-1h, so as to prepare transparent crosslinking reaction liquid;
c. preparing an initiator solution: preparing 10wt% aqueous solution of ammonium persulfate and sodium metabisulfite respectively;
(2) Preparation of high-efficiency durable fireproof gel
Uniformly mixing the fire retardant aqueous solution prepared in the step (1) and the crosslinking reaction solution according to the mass ratio of 1:1 to prepare the transparent fireproof liquid. And sequentially adding an initiator solution accounting for 0.5% of the total mass of the monomers into the transparent fireproof liquid, uniformly mixing and stirring, and then pouring the mixture into the composite fireproof glass (namely, pouring the mixture between two or more pieces of glass), curing the mixture into transparent gel at normal temperature, and bonding the transparent gel and the glass into a whole.
In this example, the mass ratio of the raw materials used is that the flame retardant is acrylic acid and acrylamide=13:6:3.
(3) Characterization of Performance of high Performance durable transparent fire-resistant gels
The high-efficiency durable composite fireproof glass prepared in the embodiment is measured on the fire resistance and ageing resistance by using GB15763.1-2009 safety glass for building: as shown in Table 6, the transmittance of the composite fireproof glass is 80.9%, the fire-resistant time can reach 55min, the transmittance of the composite fireproof glass after 168h accelerated aging is 75.4%, and the fire-resistant time can reach 43min.
TABLE 6
Comparative example 3
This comparative example differs from example 1 in that: the flame retardant is free of magnesium chloride.
(1) Preparation of the Components
a. Preparation of an aqueous flame retardant solution: sequentially dissolving flame retardant monoammonium phosphate, glycerol and urea in deionized water according to a mass ratio of 3:2:1 in a beaker, stirring and dissolving, standing for 24 hours, and then settling and filtering to obtain a flame retardant aqueous solution.
b. Preparation of a crosslinking reaction solution: acrylic acid (raw material) and sodium hydroxide are neutralized at normal temperature according to a molar ratio of 1:0.75, and an acrylic acid-sodium acrylate solution with a neutralization degree of 75% is obtained. Then, in a three-neck flask with a stirrer, a thermometer, a reflux condenser and a water separator, adding acrylamide (the mass ratio of the acrylic acid raw material to the acrylamide is 2:1) into an acrylic acid-sodium acrylate solution for mixing reaction, and adding a cross-linking agent accounting for 0.8 percent of the total mass of monomers (namely the total mass of the acrylic acid and the acrylamide raw material)N’N-methylene bisacrylamide), wherein the reaction temperature is 70 ℃, and the reaction time is 0.5-1h, so as to prepare transparent crosslinking reaction liquid;
c. preparing an initiator solution: preparing 10wt% aqueous solution of ammonium persulfate and sodium metabisulfite respectively;
(2) Preparation of high-efficiency durable fireproof gel
Uniformly mixing the fire retardant aqueous solution prepared in the step (1) and the crosslinking reaction solution according to the mass ratio of 1:1 to prepare the transparent fireproof liquid. And sequentially adding an initiator solution accounting for 0.5% of the total mass of the monomers into the transparent fireproof liquid, uniformly mixing and stirring, and then pouring the mixture into the composite fireproof glass (namely, pouring the mixture between two or more pieces of glass), curing the mixture into transparent gel at normal temperature, and bonding the transparent gel and the glass into a whole.
In this example, the mass ratio of the raw materials used is that the flame retardant is acrylic acid and acrylamide=6:6:3.
(3) Characterization of Performance of high Performance durable transparent fire-resistant gels
The high-efficiency durable composite fireproof glass prepared in the embodiment is measured on the fire resistance and ageing resistance by using GB15763.1-2009 safety glass for building: as shown in Table 7, the transmittance of the composite fireproof glass is 83.2%, the fire-resistant time can reach 62min, the transmittance of the composite fireproof glass after 168h accelerated aging is 78.5%, and the fire-resistant time can reach 50min.
TABLE 7
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall fall within the scope of the technical solution of the present invention.

Claims (10)

1. A method of preparing a fire-resistant gel comprising the steps of:
(1) Preparation of an aqueous flame retardant solution: dissolving the composite flame retardant in water to obtain a flame retardant aqueous solution;
(2) Preparation of a crosslinking reaction solution: neutralizing acrylic acid or methacrylic acid with sodium hydroxide to a neutralization degree of 70% -80% to obtain a partially neutralized acrylic acid-sodium acrylate solution or methacrylic acid-sodium methacrylate solution, and then adding acrylamide and a crosslinking agent to carry out a crosslinking reaction to obtain a crosslinking reaction solution;
(3) Preparation of the fire-retardant gel: and (3) mixing the fire retardant aqueous solution obtained in the step (1) with the crosslinking reaction solution obtained in the step (2) to obtain a fireproof liquid, and then adding an initiator to obtain the fireproof gel after curing.
2. The method of preparing a fire resistant gel according to claim 1, wherein the composite flame retardant of step (1) comprises: (a) a char source; (b) an acid source; (c) a gas source.
3. The method of preparing a fire resistant gel according to claim 2, wherein the char source comprises glycerol and/or urea, the acid source comprises monoammonium phosphate, and the gas source comprises at least one of ammonium polyphosphate, monoammonium phosphate, or urea.
4. The method for preparing the fireproof gel according to claim 3, wherein the composite flame retardant comprises ammonium dihydrogen phosphate, magnesium chloride, glycerol and urea in a mass ratio of (2-4): 5-10): 1-3): 1.
5. The method for preparing a fire-resistant gel according to any one of claims 1 to 3, wherein the mass ratio of the acrylic acid or the methacrylic acid to the acrylamide in the step (2) is 1 (0.5 to 4).
6. The method for preparing a fireproof gel according to any one of claims 1 to 3, wherein the reaction temperature of the crosslinking reaction in the step (2) is 70 ℃ to 80 ℃ and the reaction time is 0.5h to 1h.
7. The method for preparing a fireproof gel according to any one of claims 1 to 3, wherein the aqueous solution of the flame retardant and the crosslinking reaction solution in the step (3) are mixed according to a mass ratio of 1 (0.5 to 2); and/or
The dosage ratio of the composite flame retardant to the acrylic acid or the methacrylic acid is 13 (1.8-6).
8. A fire-resistant gel, characterized in that it is mainly made of the following components:
a composite flame retardant comprising soluble metal ions;
the crosslinking reaction component is prepared by crosslinking reaction of acrylic acid-sodium acrylate or methacrylic acid-sodium methacrylate with the neutralization degree of 70-80 percent, acrylamide and a crosslinking agent;
an initiator;
and solvent water.
9. A composite fire-proof glass which is grouting type composite fire-proof glass, characterized in that the glass is bonded by fire-proof gel prepared by any one of claims 1-7.
10. A method of preparing a composite fire-resistant glazing as claimed in claim 9, wherein the fire-resistant liquid is filled with an initiator and cured.
CN202310519835.7A 2023-05-10 2023-05-10 Fireproof gel and preparation method and application thereof Active CN116574520B (en)

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