Organic / Inorganic Hybrid Nanomaterials, Fireproof Pre-Reaction Liquid and Their Preparation Methods and Applications

Abstract

The present invention relates to an organic / inorganic hybrid nanomaterial, a fireproof pre-reaction solution, and their preparation methods and applications. Among them, the organic / inorganic hybrid nanoparticles include first polyacrylamide-based organic / inorganic hybrid nanoparticles and second polyacrylamide-based organic / inorganic hybrid nanoparticles. Both the first polyacrylamide-based organic / inorganic hybrid nanoparticles and the second polyacrylamide-based organic / inorganic hybrid nanoparticles include a flexible core layer, a shell layer, and a reinforcing transition layer, and the reinforcing transition layer is disposed between the flexible core layer and the shell layer. The pre-reaction solution of the present invention has the characteristics of low viscosity and can form an interpenetrating network structure with cellulose, and can be coated on the surface of a transparent cellulose-modified soda-lime glass product to form a fireproof layer. At the same time, the low-temperature use temperature can reach -25°C ± 1°C, and the coating has a UV irradiation resistance time exceeding 2000 hours.

Description

Technical Field

[0001] The present invention relates to the field of glass safety, and particularly to organic / inorganic hybrid nanomaterials, fireproof pre-reaction liquid and their preparation methods and applications. Background Art

[0002] With the accelerating pace of urbanization, the building windows of houses are becoming larger and larger. Elegant, beautiful, functional and safe glass components are gradually favored by designers at home and abroad, which directly leads to the rapid development of various safety glasses and special glasses in the architectural glass industry. Architectural glass has gradually developed from a simple lighting and decoration material to a multi-functional composite material with functions such as light control, room temperature adjustment, noise reduction, and improvement of living environment. Special coatings have gradually developed from simple anti-corrosion and decoration materials to a multi-functional composite material with functions such as flame retardancy, heat insulation, wear resistance, damping, and noise reduction.

[0003] As a safety coating, the flame-retardant fireproof transparent coating pre-reaction liquid has, in addition to some properties of ordinary coatings, properties such as controlling the spread of fire and heat insulation, providing valuable rescue time for effective rescue in case of fire, minimizing the losses of personnel, property and vehicles, and reducing the destructive power of fire to the minimum. Coating on the glass surface can form fireproof glass. The coated fireproof glass has, in addition to some properties of ordinary glass, the ability to protect escape and rescue personnel from heat radiation damage. Due to frequent fires in some well-known large buildings at home and abroad recently, people have gradually paid attention to the research, production and use effects of new flame-retardant coatings. Poor ultraviolet radiation resistance is one of the main factors restricting the application of flame-retardant coatings. Therefore, developing a high-performance flame-retardant fireproof transparent coating pre-reaction liquid with excellent ultraviolet radiation resistance, realizing a qualitative leap in product performance, and expanding the application area of the product is an important direction for the industrial development of special coatings.

[0004] At present, the work on the special flame-retardant fireproof transparent coating pre-reaction liquid for glass in China is in the basic research stage. The existing flame-retardant fireproof transparent coating pre-reaction liquid has poor ultraviolet radiation resistance and needs to be coated frequently at regular intervals, using a large amount of fireproof coatings. At the same time, most products will crack and fall off from the glass surface under long-term ultraviolet radiation outdoors and cannot meet the requirements for long-term outdoor use in rainy areas in the south. The existing flame-retardant coatings also have poor solvent resistance, hardness, low temperature resistance and impact resistance, reducing the actual fireproof effect of the fireproof layer and seriously affecting the use effect and service life of the flame-retardant fireproof transparent coating pre-reaction liquid. Summary of the Invention

[0005] The main object of the present invention is to provide a polyacrylamide-based organic / inorganic hybrid nanomaterial with a "rosa roxburghii" - shaped multi - layer core - shell structure and capable of multiple cross - linking, a fire - proof pre - reaction liquid, and their preparation methods and applications, which overcome the drawbacks that the fire - proof layer materials in the prior art cannot meet the ultraviolet test, and avoid the disadvantages such as cracking of the fire - proof layer, mismatch between impact resistance and hardness, and poor water resistance.

[0006] The object of the present invention and the technical problems to be solved are achieved by the following technical solutions.

[0007] The organic / inorganic hybrid nanomaterial includes a first polyacrylamide - based organic / inorganic hybrid nanoparticle and a second polyacrylamide - based organic / inorganic hybrid nanoparticle. Both the first polyacrylamide - based organic / inorganic hybrid nanoparticle and the second polyacrylamide - based organic / inorganic hybrid nanoparticle include a flexible core layer, a shell layer, and a reinforcing transition layer, and the reinforcing transition layer is arranged between the flexible core layer and the shell layer. Among them, the shell layer of the first polyacrylamide - based organic / inorganic hybrid nanoparticle is a polymer layer of a phosphorus - containing polymer, and linear ammonium polyphosphate is grafted on the surface of the shell layer of the first polyacrylamide - based organic / inorganic hybrid nanoparticle. The shell layer of the second polyacrylamide - based organic / inorganic hybrid nanoparticle is a polymer layer of an epoxy - containing polymer, and linear glycidyl methacrylate is grafted on the surface of the shell layer of the second polyacrylamide - based organic / inorganic hybrid nanoparticle. The flexible core layers of both the first polyacrylamide - based organic / inorganic hybrid nanoparticle and the second polyacrylamide - based organic / inorganic hybrid nanoparticle are polyacrylamide latex particles. The reinforcing transition layers of both the first polyacrylamide - based organic / inorganic hybrid nanoparticle and the second polyacrylamide - based organic / inorganic hybrid nanoparticle are polymer layers containing melamine - formaldehyde materials with a cross - linked network structure. The polymers in the shell layer of the first polyacrylamide - based organic / inorganic hybrid nanoparticle and the polymers in the shell layer of the second polyacrylamide - based organic / inorganic hybrid nanoparticle each contain at least one polymer capable of forming an interpenetrating network structure with cellulose. In the present invention, both linear glycidyl methacrylate and linear ammonium polyphosphate can form an interpenetrating network structure with cellulose.

[0008] Among them, the material composed of the first polyacrylamide-based organic / inorganic hybrid nanoparticles is made from the following components: 7 to 26 parts by weight of the third mixed solution and 51 to 327 parts by weight of the second polymer template emulsion; the third mixed solution is formed by mixing 5 to 15 parts by weight of ammonium polyphosphate, 0.1 to 1 part by weight of ethanol, and 2 to 10 parts by weight of deionized water; the second polymer template emulsion is made from 0.1 to 18 parts by weight of the second mixed solution, 15 to 40 parts by weight of deionized water, 10 to 26 parts by weight of an amine-functionalized silica dispersion, 0.003 to 0.03 parts by weight of an initiator, and 26 to 243 parts by weight of the first polymer template emulsion; the second mixed solution is formed by mixing 0.1 to 6 parts by weight of butyl acrylate, 0.1 to 6 parts by weight of methyl methacrylate, 0.1 to 6 parts by weight of methacrylic acid, and 0.01 to 0.02 parts by weight of a reactive emulsifier; the first polymer template emulsion is made from 0.5 to 80 parts by weight of the first mixed solution, 6 to 12 parts by weight of deionized water, 0.005 to 1 part by weight of an initiator, and 20 to 150 parts by weight of a polyacrylamide emulsion with a particle size of 40 nm to 200 nm and a solids content of 15 wt% to 55 wt%; the first mixed solution is formed by mixing 0.1 to 20 parts by weight of butyl acrylate, 0.1 to 20 parts by weight of melamine, 0.1 to 20 parts by weight of styrene, 0.01 to 0.03 parts by weight of divinyl sulfone, 0.05 to 0.2 parts by weight of 20 wt% ammonia water, 0.1 to 20 parts by weight of 2,4-methyl-3-cyclohexenecarboxaldehyde, and 0.002 to 0.08 parts by weight of a reactive emulsifier; the hydrophilic amine-functionalized silica dispersion is made from 10 to 25 parts by weight of a silica seed solution, 0.1 to 1 part by weight of an amine-silane coupling agent, and 0.001 to 0.02 parts by weight of ethanol; the silica seed solution is made from 2 to 3 parts by weight of tetraethyl orthosilicate, 0.02 to 0.04 parts by weight of 25 wt% concentrated ammonia water, and 8 to 22 parts by weight of deionized water;

[0009] The material composed of the second polyacrylamide-based organic / inorganic hybrid nanoparticles is made from the following components: 10 to 25 parts by weight of the fourth mixed solution and 51 to 327 parts by weight of the fourth polymer template emulsion; the fourth mixed solution is formed by mixing 5 to 15 parts by weight of glycidyl methacrylate, 0.01 to 0.2 parts by weight of an initiator, and 5 to 10 parts by weight of deionized water; the fourth polymer template emulsion is made from 0.1 to 18 parts by weight of the second mixed solution, 15 to 40 parts by weight of deionized water, 10 to 26 parts by weight of a silica dispersion with double bonds on its surface, 0.003 to 0.03 parts by weight of an initiator, and 26 to 243 parts by weight of the first polymer template emulsion; the second mixed solution is composed of 0.1 to 6 parts by weight of butyl acrylate, 0.1 to 6 parts by weight of methyl methacrylate, 0.1 to 6 parts by weight of methacrylic acid, and 0.01 to 0.02 parts by weight of a reactive emulsifier; the first polymer template emulsion is made from 0.1 to 80 parts by weight of the first mixed solution, 6 to 12 parts by weight of deionized water, 0.005 to 1 part by weight of an initiator, and 20 to 150 parts by weight of a polyacrylamide emulsion with a particle size of 40 nm to 200 nm and a solid content of 15 wt% to 55 wt%; the first mixed solution is formed by mixing 0.1 to 20 parts by weight of butyl acrylate, 0.1 to 20 parts by weight of melamine, 0.1 to 20 parts by weight of styrene, 0.01 to 0.03 parts by weight of divinyl sulfone, 0.05 to 0.2 parts by weight of 20 wt% ammonia water, 0.1 to 20 parts by weight of 2,4-methyl-3-cyclohexenecarboxaldehyde, and 0.002 to 0.08 parts by weight of a reactive emulsifier; the hydrophilic silica dispersion with double bonds on its surface is made from 10 to 25 parts by weight of a silica seed solution, 0.1 to 1 part by weight of an alkenyl silane coupling agent, and 0.001 to 0.02 parts by weight of ethanol; the silica seed solution is made from 2 to 3 parts by weight of tetraethyl orthosilicate, 0.02 to 0.04 parts by weight of 25 wt% concentrated ammonia water, and 8 to 22 parts by weight of deionized water.

[0010] For the above-mentioned organic / inorganic hybrid nanomaterial, the degree of polymerization of the polyacrylamide particles in the polyacrylamide emulsion is 10,000 to 100,000, the particle size is 40 nm to 200 nm, and the particle size distribution is a unimodal narrow distribution.

[0011] For the above-mentioned organic / inorganic hybrid nanomaterial, the alkenyl silane coupling agent is one or more of vinyltri(tert-butylperoxy)silane, vinyltriethoxysilane, butadienyltriethoxysilane, vinyltrimethoxysilane, isobutenyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane.

[0012] For the above-mentioned organic / inorganic hybrid nanomaterials, the amino-silane coupling agent is one or more of phenylaminomethyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.

[0013] For the above-mentioned organic / inorganic hybrid nanomaterials, the initiator is one or two of a thermal initiator and a redox initiator.

[0014] The preparation method of the above-mentioned organic / inorganic hybrid nanomaterials includes the following steps:

[0015] S11) Prepare a silica seed solution: Mix tetraethyl orthosilicate, concentrated ammonia water with a concentration of 25 wt%, and deionized water according to a weight ratio of 2 - 3:0.02 - 0.04:8 - 22, and let it stand for aging for 36 h. After the alcoholysis of tetraethyl orthosilicate, a silica seed solution is formed, and the particle size of the silica particles is 20 nm - 30 nm;

[0016] S12-1) Prepare a silica dispersion with an amino group on the surface: Put the silica seed solution, amino-silane coupling agent, and ethanol into a high-pressure homogenizer according to a weight ratio of 10 - 25:0.1 - 1:0.001 - 0.02, circulate and disperse for 10 min to obtain a first primary dispersion. Put the first primary dispersion into a three-necked flask, and then put the three-necked flask into a water bath at 70°C - 90°C, stir and disperse at a stirring speed of 100 - 150 r / min for 30 min, and then cool to 20°C to obtain a silica dispersion with an amino group on the surface; among them, the silica seed solution is the silica seed solution prepared in step S11);

[0017] S12-2) Prepare a silica dispersion with a double bond on the surface: Put the silica seed solution, alkenyl-silane coupling agent, and ethanol into a high-pressure homogenizer according to a weight ratio of 10 - 25:0.1 - 1:0.001 - 0.02, circulate and disperse for 10 min to obtain a second primary dispersion. Put the second primary dispersion into a three-necked flask, and then put the three-necked flask into a water bath at 70°C - 90°C, stir and disperse at a stirring speed of 100 - 150 r / min for 30 min, and then cool to 20°C to obtain a silica dispersion with a double bond on the surface; among them, the silica seed solution is the silica seed solution prepared in step S11);

[0018] S13) Prepare the first polymer template emulsion, and the specific steps are as follows:

[0019] S13-1) Mix butyl acrylate, melamine, styrene, divinyl sulfone, ammonia water with a concentration of 20 wt%, 2,4-methyl-3-cyclohexene formaldehyde and a reactive emulsifier in a weight ratio of 0.1 - 20:0.1 - 20:0.1 - 20:0.01 - 0.03:0.05 - 0.2:0.1 - 20:0.002 - 0.08 to obtain a first mixed solution;

[0020] S13-2) By means of starvation polymerization, at a temperature of 60 - 65 °C, drop 0.5 - 80 parts by weight of the first mixed solution, 6 - 12 parts by weight of deionized water and 0.005 - 1 part by weight of an initiator into 20 - 150 parts by weight of a polyacrylamide emulsion with a particle size of 40 nm - 200 nm and a solid content of 15 wt% - 55% at a constant rate. After polymerization is completed, a layer of poly(butyl acrylate - styrene - divinyl sulfone - 2,4-methyl-3-cyclohexene melamine formaldehyde) material is coated on the surface of the polyacrylamide latex particles to obtain a first polymer template emulsion with a crosslinked core-shell structure;

[0021] S14) Prepare an emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles, and the specific steps are as follows:

[0022] S14-1) Mix butyl acrylate, methyl methacrylate, methacrylic acid and a reactive emulsifier in a weight ratio of 0.1 - 6:0.1 - 6:0.1 - 6:0.01 - 0.02 to obtain a second mixed solution;

[0023] S14-2) Prepare a second polymer template emulsion: By means of starvation polymerization, at a temperature of 60 - 65 °C, drop 0.1 - 18 parts by weight of the second mixed solution, 15 - 40 parts by weight of deionized water, 10 - 26 parts by weight of a silica dispersion with amine groups on the surface, and 0.003 - 0.03 parts by weight of an initiator into 26 - 243 parts by weight of the first polymer template emulsion at a constant rate. After polymerization is completed, a layer of poly(butyl acrylate - methyl methacrylate - methacrylic acid) material embedded with silica particles with a particle size of 20 nm - 30 nm and amine groups is coated on the surface of the polyacrylamide latex particles to obtain a second polymer template emulsion with a bayberry-like multi-layer core-shell structure;

[0024] S14-3) Prepare a third mixed solution: Mix ammonium polyphosphate, ethanol and deionized water in a weight ratio of 5 - 15:0.5 - 1:2 - 10 to obtain a third mixed solution;

[0025] S14-4) Preparation of an emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles: By means of an ion exchange reaction, 7-26 parts by weight of a third mixed solution was added dropwise to 51-327 parts by weight of a second polymer template emulsion at a constant rate under a temperature condition of 30-40 °C, stirred at a stirring speed of less than 80 r / min, and refluxed and condensed for 4 h under this temperature condition to form a polymer with linear ammonium polyphosphate as the outermost branch on the surface of the latex particles, obtaining an emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles;

[0026] S15) Preparation of an emulsion containing second polyacrylamide-based organic / inorganic hybrid nanoparticles, and the specific steps are as follows:

[0027] S15-1) Preparation of a third polymer template emulsion: By means of a starvation polymerization method, 0.1-18 parts by weight of a second mixed solution, 15-40 parts by weight of deionized water, 10-26 parts by weight of a silica dispersion with double bonds on the surface, and 0.003-0.03 parts by weight of an initiator were added dropwise to 26-242 parts by weight of a first polymer template emulsion at a constant rate under a temperature condition of 60-65 °C. After polymerization was completed, a poly(butyl acrylate-methyl methacrylate-methacrylic acid) material with silica particles with a particle size of 20 nm-30 nm and double bonds embedded on the surface of the polyacrylamide latex particles was coated, obtaining a third polymer template emulsion with a multi-layer core-shell structure;

[0028] S15-2) Preparation of a fourth mixed solution: Glycidyl methacrylate, an initiator, and deionized water were prepared into a fourth mixed solution according to a weight ratio of 5-15:0.01-0.2:5-10;

[0029] S15-3) Preparation of an emulsion containing second polyacrylamide-based organic / inorganic hybrid nanoparticles: 10-25 parts by weight of the fourth mixed solution was added dropwise to 51-327 parts by weight of the third polymer template emulsion at a constant rate under a temperature condition of 60-65 °C, stirred at a stirring speed of less than 80 r / min, and refluxed and condensed for 3 h under this temperature condition to form a second polymer with linear polyglycidyl methacrylate as the branch on the surface of the latex particles, obtaining an emulsion containing second polyacrylamide-based organic / inorganic hybrid nanoparticles;

[0030] S16) Composite the emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles and the emulsion containing second polyacrylamide-based organic / inorganic hybrid nanoparticles to obtain an organic / inorganic hybrid nanomaterial.

[0031] Fire prevention pre-reaction liquid, comprising at least the following components: 58 to 353 parts by weight of first polyacrylamide-based organic / inorganic hybrid nanoparticles, 61 to 352 parts by weight of second polyacrylamide-based organic / inorganic hybrid nanoparticles, 0.5 to 4 parts by weight of cellulose solvent, 0.5 to 2.5 parts by weight of catalyst, and 10 to 30 parts by weight of deionized water; the first polyacrylamide-based organic / inorganic hybrid nanoparticles are the first polyacrylamide-based organic / inorganic hybrid nanoparticles described in claim 1, and the second polyacrylamide-based organic / inorganic hybrid nanoparticles are the second polyacrylamide-based organic / inorganic hybrid nanoparticles described in claim 1.

[0032] The above fire prevention pre-reaction liquid further comprises: 1 to 5 parts by weight of charring agent, 0.001 to 0.05 parts by weight of defoaming agent, and 0.1 to 1 part by weight of rheology aid; the charring agent is prepared by compounding pentaerythritol with one or more of sucrose, fructose, glucose, and maltose; the rheology aid is one or more of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose; the antifreeze plasticizer is one or more of ethylene glycol, glycerol, and 1,4-butanediol; the cellulose solvent is one or two of dipropylene glycol methyl ether and N-methyl morpholine N-oxide; the catalyst is prepared by compounding a dilute hydrochloric acid solution with a mass concentration less than or equal to 20 wt% with one or two of aluminum diethyl phosphinate and inorganic aluminum hypophosphite; the defoaming agent is one or two of polysiloxane defoaming agents and polyether defoaming agents.

[0033] The preparation method of the above fire prevention pre-reaction liquid comprises the following steps:

[0034] Step S21), mixing the charring agent, rheology aid, and deionized water according to a weight ratio of 1 to 5: 0.1 to 1: 10 to 25, stirring at a stirring speed of less than 100 r / min for 40 minutes to form a uniform suspension, and standing and aging for 12 h to obtain a transparent and dynamically reversible gel material;

[0035] Step S22), mixing the first polyacrylamide-based organic / inorganic hybrid nanoparticles, the second polyacrylamide-based organic / inorganic hybrid nanoparticles, the cellulose solvent, the catalyst, and deionized water according to a weight ratio of 58 to 353: 61 to 352: 0.5 to 4: 0.5 to 2.5: 10 to 30 to obtain a first fire prevention mixture,

[0036] Stir at a stirring speed of less than 80 r / min for 40 minutes at room temperature to form a uniform suspension; then add 11-30 parts by weight of the gelling material to the first fireproof mixture, and stir at a stirring speed of less than 80 r / min for 80 minutes at room temperature to obtain a clear or slightly turbid second fireproof mixture; then add 0.5-2.5 parts by weight of the catalyst and 0.001-0.05 parts by weight of the defoamer to the second fireproof mixture in sequence, stir at a stirring speed of less than 80 r / min for 40 minutes at room temperature to obtain a fireproof pre-reaction liquid, and let it stand for use.

[0037] The application of the above fireproof pre-reaction liquid is used for the flame retardant treatment of transparent cellulose-modified soda-lime glass products and forms a fireproof layer with a thickness of 0.02-0.3 mm on the surface layer of the glass products. The specific operation is as follows: spray the fireproof pre-reaction liquid on the surface of the transparent cellulose-modified soda-lime glass products, let it stand for 50 minutes, and after the surface of the glass products is surface-dried, put it into an oven at 50 °C and bake for 4 hours, then raise the temperature to 80 °C and bake for 3 hours, so that the cellulose on the glass surface and the fireproof pre-reaction liquid covering it form a multiple cross-linking system to form an interpenetrating network structure.

[0038] The technical solution of the present invention has achieved the following beneficial technical effects:

[0039] 1. By introducing double bonds (vinyl silane coupling agent) and amino groups (amino silane coupling agent) on the surface of hydrophilic silica, reaction sites are provided for grafting two kinds of linear polymers (ammonium polyphosphate, glycidyl methacrylate) on the surface of the core-shell polymer: the amino groups in the functional shell polymer can graft ammonium polyphosphate on the surface of the functional shell through an ion exchange reaction in an ethanol solution to obtain linearly grafted ammonium polyphosphate; at the same time, the vinyl groups in the functional shell can polymerize with glycidyl methacrylate to form a linear glycidyl methacrylate polymer, providing a precursor for the ring-opening curing of epoxy groups with ionic reaction activity in the later stage, and then forming a material with a multiple network structure; cellulose substances are used as rheological aids in the fireproof pre-reaction liquid. On the one hand, it can improve the leveling property of the system during brushing, and at the same time, it can penetrate into the multiple cross-linking network to form physical cross-links, so as to further entangle with the cellulose on the surface of the transparent cellulose-modified soda-lime glass for building, and improve the cross-linking degree of the coating.

[0040] 2. The introduction of polyacrylamide in the flexible core layer, silica particles in the functional shell layer, and cross-linking agent divinyl sulfone guarantees the toughness, impact strength, hardness, and environmental adaptability of the coating: due to the requirements of wiping, wind-induced deformation, and weather resistance during the use of glass window structures, the silica particles in the polymer functional shell layer further improve the toughness and impact strength of the system on the basis of the original multiple cross-linking, and at the same time, the introduction of the multiple cross-linking system also provides conditions for improving the weather resistance of the organic coating for glass window structures.

[0041] 3. Gradually polymerize by means of soap-free emulsification technology, and further optimize the dosage of emulsifier by introducing reactive emulsifier; at the same time, compared with the blended fire-proof pre-reaction liquid, by means of the particle design principle, the hydrophilic groups in the monomer are effectively distributed in each layer of the latex particles, reducing the number of hydrophilic groups aggregated and distributed in the outermost layer, thereby reducing the viscosity of the solution and making it easier to penetrate into the interior of the transparent lignin layer on the glass surface, improving the flame retardancy of the product; using the ion exchange method and the low-temperature polycondensation method, graft ammonium polyphosphate and melamine formaldehyde onto the surface of the latex particles and the reinforcing transition layer respectively under the condition of below 50 °C, avoiding the premature formation of cross-linked network structure in the pre-reaction liquid. At the same time, after being coated on the glass surface in the later stage, using the gradient heating method, the components in the fire-proof pre-reaction liquid produce a synergistic effect, ensuring the realization of the functions of the multiple cross-linked system, and preparing a high-performance flame-retardant fire-proof glass material that can reach -25 °C ± 1 °C in a low-temperature use environment, the coating has a UV irradiation resistance time of more than 2000 hours, and the flame retardancy grade meets the B1 low-flammability material standard (German standard) specified in DIN4102 and the UL94-V0 high-flame-retardant material standard (American Insurance Association standard).

[0042] 4. The reasons why the fire-proof layer formed after the curing of the fire-proof pre-reaction liquid of the present invention has low temperature resistance, UV irradiation resistance, impact resistance, high hardness and water flushing resistance are as follows: The specially designed multi-layer core-shell structure and preparation process optimize the effective cross-linking between the particles themselves and between the particles, reduce the swelling degree of the multi-layer core-shell latex particles and the film layer such as solvents in the system and moisture in the use environment, further improve the density of the particles during the film-forming process, reduce the water content in the film layer on the basis of improving the strength of the film layer polymer. Correspondingly, it avoids the damage of the internal structure of the film layer by ice crystals at low temperature; the multiple cross-linked system also increases the UV irradiation resistance of the film layer; at the same time, silica particles with double bonds and amine groups are polymerized in the functional shell layer, realizing the uniform distribution of "prickly pear"-shaped linear ammonium polyphosphate and poly(glycidyl methacrylate) molecular chains on the outer surface of the latex particles. At the same time, by virtue of the high hardness of the silica inorganic particles, the advantages of "soft core and hard shell" of the latex particles are realized. The soft core can ensure that the coating has excellent impact resistance, and the cross-linked organic / inorganic composite hard shell endows the coating with scratch resistance and can also improve the UV irradiation resistance of the coating; the "prickly pear" structure increases the entanglement between the film layer and the transparent cellulose on the glass surface, and at the same time the multiple network cross-linked structure firmly fixes these entanglements together, improving the adhesion of the coating. At the same time, this "prickly pear" structure can endow the coating with a "lotus leaf effect", further improving the water flushing resistance of the coating.

[0043] The above description is only an overview of the technical solution of the present invention. In order to understand the technical means of the present invention more clearly and be able to implement it according to the content of the description, the following describes in detail with reference to the preferred embodiments of the present invention and the accompanying drawings. Description of the Drawings

[0044] Figure 1 Schematic diagram of the structure of the first polyacrylamide-based organic / inorganic hybrid nanoparticle.

[0045] Figure 2 Schematic diagram of the structure of the second polyacrylamide-based organic / inorganic hybrid nanoparticle.

[0046] 1 - flexible core layer; 2 - reinforcing transition layer; 3 - shell layer; 4 - silica particles; 5 - linear ammonium polyphosphate polymer; 6 - linear glycidyl methacrylate polymer. Detailed Description of the Invention

[0047] The organic / inorganic hybrid nanomaterial in the present invention is composed of two polyacrylamide-based organic / inorganic hybrid nanoparticles compounded, such as Figure 1 and Figure 2As shown, in the multi-layer core-shell structure of each polyacrylamide-based organic / inorganic hybrid nanoparticle, a reinforcing transition layer is provided between the flexible core layer and the outermost shell layer. The reinforcing transition layer is a polymer layer containing a melamine formaldehyde material with a cross-linked network structure. Among the two polyacrylamide-based organic / inorganic hybrid nanoparticles, the outermost layer of the first polyacrylamide-based organic / inorganic hybrid nanoparticle is a graft formed from a phosphorus-containing polymer, and the outermost layer of the second polyacrylamide-based organic / inorganic hybrid nanoparticle is a graft formed from an epoxy-containing polymer. Among them, the graft on the outermost layer of the polyacrylamide-based organic / inorganic hybrid nanoparticle is similar to the thorns on the surface of a prickly pear; at least one polymer in the two polyacrylamide-based organic / inorganic hybrid nanoparticles can form a fireproof layer with interpenetrating network structure with cellulose. Among them, the polyacrylamide-based organic / inorganic hybrid nanoparticle with a multi-layer core-shell structure is a narrow-distribution particle prepared by a soap-free emulsion polymerization method with the aid of the particle design principle. For the first polyacrylamide-based organic / inorganic hybrid nanoparticle, the flexible core layer material is polyacrylamide particles and their aggregates, and the materials wrapped on the polyacrylamide particles are respectively a reinforcing transition layer of poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer with a cross-linked structure, a shell layer of poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer inlaid with silica particles with a particle size of 20 nm to 30 nm and an amine group, and a graft on the shell layer surface composed of linear ammonium polyphosphate; for the second polyacrylamide-based organic / inorganic hybrid nanoparticle, the flexible core layer material is polyacrylamide particles and their aggregates, and the materials wrapped on the polyacrylamide particles are respectively a reinforcing transition layer of poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer with a cross-linked structure, a shell layer of poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer inlaid with silica particles with a particle size of 20 nm to 30 nm and a double bond, and a graft on the shell layer composed of linear polyglycidyl methacrylate copolymer.The fireproof pre-reaction liquid containing the organic / inorganic hybrid nanomaterial consists of the following substances in parts by weight: 4 to 6 parts of tetraethyl orthosilicate, 0.04 to 0.08 parts of concentrated ammonia water with a concentration of 25 wt%, 55 to 138 parts of deionized water, 0.1 to 1 part of alkenyl silane coupling agent, 0.1 to 1 part of amino silane coupling agent, 0.502 to 1.04 parts of ethanol, 40 to 300 parts of polyacrylamide solution, 0.4 to 52 parts of butyl acrylate, 1.2 to 14 parts of methyl methacrylate, 0.2 to 40 parts of melamine, 0.2 to 40 parts of styrene, 0.02 to 0.06 parts of divinyl sulfone, 0.1 to 0.4 parts of ammonia water with a concentration of 20 wt%, 0.2 to 40 parts of 2,4-methyl-3-cyclohexene formaldehyde, 0.2 to 12 parts of methacrylic acid, 5 to 15 parts of ammonium polyphosphate, 5 to 15 parts of glycidyl methacrylate, 0.024 to 0.2 parts of emulsifier, 0.026 to 2.26 parts of initiator, 1 to 5 parts of charring agent, 0.1 to 1 part of rheological aid, 0.5 to 4 parts of cellulose solvent, 0.5 to 2.5 parts of catalyst, 0.001 to 0.05 parts of defoamer. The polyacrylamide-based organic / inorganic hybrid nanoparticles are single-peak and narrow-distribution particles; the polyacrylamide-based organic / inorganic hybrid nanoparticles with a nano core-shell structure are narrow-distribution particles prepared by means of a soap-free emulsion polymerization method and particle design principle. For the first polyacrylamide-based organic / inorganic hybrid nanoparticles, the flexible core layer material is polyacrylamide particles and their aggregates, the reinforcing transition layer material is a poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer with a crosslinked structure, the shell layer material is a poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer inlaid with silica particles with a particle size of 20 nm to 30 nm and carrying amino groups, and the shell layer surface graft is linear ammonium polyphosphate; for the second polyacrylamide-based organic / inorganic hybrid nanoparticles, the flexible core layer material is polyacrylamide particles and their aggregates, the reinforcing transition layer material is a poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer with a crosslinked structure, the shell layer material is a poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer inlaid with silica particles with a particle size of 20 nm to 30 nm and carrying double bonds, and the shell layer surface graft is linear polyglycidyl methacrylate copolymer; the pH value of the fireproof material pre-reaction liquid is between 5.5 and 8.5.

[0048] Such as Figure 1 And Figure 2As shown, there are silica particles in the shell layer of the first polyacrylamide-based organic / inorganic hybrid nanoparticles and the shell layer of the second polyacrylamide-based organic / inorganic hybrid nanoparticles in the present invention. Since the hardness of the silica particles is relatively greater than that of the organic matter, the silica in the shell layer of the first polyacrylamide-based organic / inorganic hybrid nanoparticles and the shell layer of the second polyacrylamide-based organic / inorganic hybrid nanoparticles can further improve the strength of the shell layer. While providing toughness to the inner layer structure, it can ensure that the material has beneficial impact resistance performance and at the same time ensure the strength of the material.

[0049] As a preferred embodiment, the fireproof pre-reaction liquid, in parts by weight, is composed of the following raw materials: 4.5 - 5.5 parts of tetraethyl orthosilicate, 0.05 - 0.07 parts of concentrated ammonia water with a concentration of 25 wt%, 60 - 120 parts of deionized water, 0.2 - 0.8 parts of alkenyl silane coupling agent, 0.2 - 0.8 parts of amino silane coupling agent, 0.6 - 0.9 parts of ethanol, 30 - 120 parts of polyacrylamide solution, 5 - 35 parts of butyl acrylate, 3 - 10 parts of methyl methacrylate, 3 - 20 parts of melamine, 3 - 20 parts of styrene, 0.03 - 0.05 parts of divinyl sulfone, 0.15 - 0.35 parts of ammonia water with a concentration of 20 wt%, 3 - 20 parts of 2,4-methyl-3-cyclohexenecarboxaldehyde, 3 - 10 parts of methacrylic acid, 7.5 - 12 parts of ammonium polyphosphate, 7.5 - 12 parts of glycidyl methacrylate, 0.04 - 0.16 parts of emulsifier, 0.5 - 1.5 parts of initiator, 1.5 - 3.5 parts of charring agent, 0.2 - 0.8 parts of rheological aid, 1 - 3.5 parts of cellulose solvent, 0.8 - 2 parts of catalyst, and 0.005 - 0.04 parts of defoamer.

[0050] As a preferred embodiment, the solid content of the polyacrylamide emulsion is 35 wt% - 45 wt%, the degree of polymerization of the polyacrylamide particles is 15000 - 25000, the particle size is 50 nm - 80 nm, the particle size distribution is a single-peak narrow distribution, and the thicknesses of the reinforcement transition layer, shell layer, and shell layer surface grafted substance of the first polyacrylamide-based organic / inorganic hybrid nanoparticles and the second polyacrylamide-based organic / inorganic hybrid nanoparticles are 35 nm - 45 nm, 25 nm - 35 nm, and 40 nm - 120 nm respectively.

[0051] The present invention uses two kinds of polyacrylamide-based organic / inorganic hybrid nanoparticles as the main raw materials of the fireproof material. The particle size of the polyacrylamide particles in the polyacrylamide emulsion is 40 nm to 200 nm, and the solid content is 15 wt% to 55 wt%. The particle sizes of the flexible core layers of the two kinds of polyacrylamide-based organic / inorganic hybrid nanoparticles are both 40 nm to 200 nm, and the particle size distributions are both single-peak narrow distributions. For the first polyacrylamide-based organic / inorganic hybrid nanoparticle: the reinforcing transition layer material is a poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer containing a melamine formaldehyde material with a crosslinked network structure, and the thickness of the reinforcing transition layer is 35 nm to 45 nm; the shell layer material is a poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer embedded with silica particles with a particle size of 20 nm to 30 nm, and the thickness of the shell layer is 25 nm to 35 nm; and the grafted substance on the shell surface is linear ammonium polyphosphate, and the thickness of the grafted substance on the shell surface is 40 nm to 120 nm. For the second polyacrylamide-based organic / inorganic hybrid nanoparticle: the reinforcing transition layer material is a first shell layer of a poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer containing a melamine formaldehyde material with a crosslinked network structure, and the thickness of the reinforcing transition layer is 20 nm to 30 nm; the shell layer material is a poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer embedded with silica particles with a particle size of 20 nm to 30 nm, and the thickness of the shell layer is 25 nm to 35 nm; and the grafted substance on the shell surface is a linear glycidyl methacrylate polymer, and the thickness of the grafted substance on the shell surface is 40 nm to 120 nm. The two kinds of polyacrylamide-based organic / inorganic hybrid nanoparticles are narrow-distribution particles. The present invention has the characteristics of a multiple crosslinking system, small viscosity of the pre-reaction solution, good impact resistance of the coating, and resistance to water flushing. At the same time, the low-temperature use temperature can reach -35°C ± 1°C, the coating has a UV irradiation resistance time of more than 2000 hours, and the flame retardancy level meets the B1-level low-flammability material standard (German standard) specified in DIN4102 and the UL94-V0-level high flame retardancy material standard (American Insurance Association standard).

[0052] The reasons for the low-temperature resistance, UV irradiation resistance, impact resistance, and water flushing resistance of the organic / inorganic hybrid nanomaterial itself are as follows:

[0053] 1. The specially designed multi-layer core-shell structure and preparation process optimize the effective crosslinking between the particles themselves and between the particles, reduce the swelling degree of the multi-layer core-shell latex particles and the film layer such as solvents in the system and moisture in the use environment, further improve the density of the particles during the film formation process, reduce the moisture content in the film layer on the basis of improving the strength of the film layer polymer. Correspondingly, it avoids the damage of the internal structure of the film layer by ice crystals at low temperatures;

[0054] 2. The multi-crosslinking system also enhances the UV irradiation resistance of the film layer;

[0055] 3. Silica particles with double bonds and amino groups are polymerized in the two functional shell layers respectively, realizing the uniform distribution of "rosa roxburghii" - shaped ammonium polyphosphate and polymethacrylic acid molecular chains on the outer surfaces of the two kinds of latex particles. By virtue of the high hardness of the silica inorganic particles, the advantage of "soft core and hard shell" of the latex particles is achieved. The soft core can ensure that the coating has excellent impact resistance, and the crosslinked organic / inorganic composite hard shell endows the coating with scratch resistance and can also improve the UV irradiation resistance of the coating;

[0056] 4. The "rosa roxburghii" - shaped structure increases the entanglement between the film layer and the cellulose on the glass surface, and at the same time, the multi - network crosslinking structure firmly fixes these entanglements together, improving the adhesion of the coating. At the same time, this "rosa roxburghii" - shaped structure can endow the coating with a "lotus leaf effect", further improving the water - rinsing resistance of the coating.

[0057] The fire - proof pre - reaction liquid of the present invention exists in the form of a dispersion liquid, and the mass concentration of the dispersion liquid is 40% - 60%.

[0058] As a preferred embodiment, the emulsifier is at least one of reactive emulsifiers (such as ammonium nonylphenol allyl polyoxyethylene ether sulfate, ammonium allyloxy decyl polyoxyethylene ether sulfate, etc.); the initiator is at least one of thermal initiators (such as benzoyl peroxide, azobisisobutyronitrile, etc.), redox initiators (such as ammonium persulfate and sodium bisulfite, etc.); the alkenyl silane coupling agent is at least one of vinyl tri-tert-butylperoxysilane, vinyl triethoxysilane, butadienyl triethoxysilane, vinyl trimethoxysilane, isobutenyl triethoxysilane, vinyl tris(β-methoxyethoxy)silane; the amino silane coupling agent is at least one of phenylaminomethyl triethoxysilane, γ-aminopropyl trimethoxysilane, N-β(aminoethyl)-γ-aminopropyl triethoxysilane, and 3-aminopropyl triethoxysilane; the charring agent is a material obtained by compounding at least one of sucrose, fructose, glucose, and maltose with pentaerythritol; the rheology aid is at least one of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose; the cellulose solvent is at least one of dipropylene glycol methyl ether and N-methylmorpholine N-oxide solution; the pigment is at least one of organic pigments and inorganic pigments; the pigment aid is at least one of N-methylpyrrolidone, N-ethylpyrrolidone, N-d butylpyrrolidone, and N-octylpyrrolidone; the catalyst is a material obtained by compounding at least one of aluminum diethyl hypophosphite and inorganic hypophosphite with a dilute hydrochloric acid solution (≤20 wt%); the defoamer is at least one of polysiloxane defoamers (such as BYK024, BYK088) and polyether defoamers (such as GP type glycerol polyether, GPE type polyoxyethylene (polyoxypropylene) ether, and PPG type polypropylene glycol).

[0059] The functions of the respective raw materials used in the fireproof pre-reaction liquid of the present invention are as follows:

[0060] Two kinds of polyacrylamide-based organic / inorganic hybrid nanoparticles are mixed with a solvent to form a fireproof pre-reaction liquid of polyacrylamide-based organic / inorganic hybrid latex particles with a "rosa roxburghii" - like multi-layer core-shell structure and capable of multiple cross-linking. After this fireproof pre-reaction liquid contacts with transparent cellulose-modified soda-lime glass, it can penetrate into the multiple cross-linking network to form physical cross-linking, thereby further entangling with the cellulose on the glass surface to improve the cross-linking degree of the coating; at the same time, this "rosa roxburghii" - like structure can endow the coating with a "lotus leaf effect", further improving the water rinsing resistance of the coating.

[0061] The two polyacrylamide-based organic / inorganic hybrid nanoparticles used in the embodiments of the present invention have a core-shell structure, which means that two or more monomers are polymerized in stages or in multiple segments under certain conditions, so that different components are enriched on the inner or outer side of the particles, that is, core-shell type particles, thereby endowing the core and the shell with different functions and obtaining particles with excellent performance; among them, the flexible core layer material is polyacrylamide particles and their aggregates. For the first polyacrylamide-based organic / inorganic hybrid nanoparticle: its reinforcing transition layer material is a first shell layer of poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer containing melamine formaldehyde material with a crosslinked network structure, the functional shell layer material is a second shell layer of poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer inlaid with silicon dioxide particles with a particle size of 20 nm to 30 nm, and the grafted substance on the shell surface is linear ammonium polyphosphate. For the second polyacrylamide-based organic / inorganic hybrid nanoparticle: its reinforcing transition layer material is a first shell layer of poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer containing melamine formaldehyde material with a crosslinked network structure, the functional shell layer material is a second shell layer of poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer inlaid with silicon dioxide particles with a particle size of 20 nm to 30 nm, and the grafted substance on the shell surface is linear polyglycidyl methacrylate copolymer. This specially designed multi-layer core-shell structure and preparation process optimize the effective crosslinking between the particles themselves and among the particles, reduce the swelling degree of multi-layer core-shell latex particles and film layers such as solvents in the system and moisture in the use environment, further improve the density of the particles during the film-forming process, reduce the water content in the film layer on the basis of improving the strength of the film layer polymer. Correspondingly, it avoids the damage of the internal structure of the film layer by ice crystals at low temperatures; the multiple crosslinking system also increases the ultraviolet radiation resistance of the film layer; at the same time, silicon dioxide particles with double bonds and amine groups are polymerized in the functional shell layer to realize the uniform distribution of "rosaceae roxbunghii tratt" linear ammonium polyphosphate and polyglycidyl methacrylate molecular chains on the outer surface of the latex particles. With the help of the high hardness of silicon dioxide inorganic particles, the advantage of "soft core and hard shell" of the latex particles is realized. The soft core can ensure that the coating has excellent impact resistance, and the crosslinked organic / inorganic composite hard shell endows the coating with scratch resistance, and can also improve the hardness and ultraviolet radiation resistance of the coating.

[0062] Both of the above two polyacrylamide-based organic / inorganic hybrid nanoparticles are narrow-distribution nanoparticles with a particle size of 140 nm - 400 nm. It is found that: by virtue of the "particle design" principle, the fireproof pre-reaction liquid composed of polyacrylamide-based organic / inorganic hybrid nanoparticles with a multi-layer core-shell structure and low viscosity has the property of shear thinning because the entanglement between the outermost branched polymers is only physical entanglement. By optimizing other additives, the addition of other additives does not affect the shear thinning property of the system. Therefore, the prepared fireproof pre-reaction liquid also has the property of shear thinning.

[0063] Since the two polyacrylamide-based organic / inorganic hybrid nanoparticles are narrow-distribution nanoparticles, they have the characteristics of a multi-crosslinking system, low viscosity of the pre-reaction liquid, good impact resistance of the coating, and water-washing resistance. At the same time, the low-temperature service temperature can reach -25°C ± 1°C, the coating's ultraviolet radiation resistance time exceeds 2000 hours, and the flame retardancy grade meets the B1 low-flammability material standard (German standard) specified in DIN4102 and the UL94-V0 high-flame-retardant material standard (American Insurance Association standard). For the above two polyacrylamide-based organic / inorganic hybrid nanoparticles, by introducing double bonds (vinyl silane coupling agent) and amino groups (amino silane coupling agent) on the surface of hydrophilic silica, reaction sites are provided for grafting the two outermost linear polymers (ammonium polyphosphate, glycidyl methacrylate) onto the surface of the core-shell polymer respectively: the amino groups in the functional shell polymer of the first polyacrylamide-based organic / inorganic hybrid nanoparticles can graft ammonium polyphosphate onto the shell surface through an ion exchange reaction in an ethanol solution to obtain linearly grafted ammonium polyphosphate; at the same time, the vinyl groups in the functional shell of the second polyacrylamide-based organic / inorganic hybrid nanoparticles can polymerize with glycidyl methacrylate to form a linear glycidyl methacrylate polymer, providing a precursor for the ring-opening curing of the epoxy groups with ionic reaction activity in the later stage, and then forming a material with a multi-network structure; in the fireproof pre-reaction liquid, cellulose substances are used as rheological aids. On the one hand, it can improve the leveling property of the system during brushing, and at the same time, it can penetrate into the multi-crosslinking network to form physical crosslinks, so as to further entangle with the cellulose on the surface of the cellulose-modified sodium calcium glass for building use, and improve the crosslinking degree of the coating.

[0064] It should be emphasized that in the fireproof pre-reaction liquid of the present invention, the nano core-shell structure organic-inorganic hybrid particles themselves have the properties of low-temperature resistance, ultraviolet radiation resistance, impact resistance, and water-washing resistance.

[0065] The fireproof pre-reaction liquid containing two polyacrylamide-based organic / inorganic hybrid nanoparticles with a "rosa roxburghii" - like multi-layer core-shell structure in the present invention is prepared by the following steps:

[0066] Tetraethyl orthosilicate, concentrated ammonia water with a concentration of 25 wt%, and deionized water are mixed according to a weight ratio of 2 - 3:0.02 - 0.04:8 - 22, and left to age for 36 h. After the tetraethyl orthosilicate undergoes alcoholysis to form a silica seed solution, the particle size of the silica particles is 20 nm - 30 nm;

[0067] The silica seed solution, amino silane coupling agent, and ethanol are put into a high-pressure homogenizer and circulated and dispersed for 10 min according to 10 - 25:0:0.1 - 0.5:0.001 - 0.02. Then it is put into a three-necked flask, and the three-necked flask is placed in a water bath at 70°C - 90°C and stirred and dispersed at a stirring speed of 100 - 150 r / min for 30 min and then cooled to 20°C to obtain a silica dispersion with amino groups on the surface;

[0068] The silica seed solution, alkenyl silane coupling agent, and ethanol are put into a high-pressure homogenizer and circulated and dispersed for 10 min according to 10 - 25:0.1 - 1:0.001 - 0.02. Then it is put into a three-necked flask, and the three-necked flask is placed in a water bath at 70°C - 90°C and stirred and dispersed at a stirring speed of 100 - 150 r / min for 30 min and then cooled to 20°C to obtain a silica dispersion with double bonds on the surface; wherein, the silica seed solution is the silica seed solution prepared in step S11);

[0069] Butyl acrylate, melamine, styrene, divinyl sulfone, ammonia water with a concentration of 20 wt%, 2,4-methyl-3-cyclohexene formaldehyde and a reactive emulsifier are mixed in weight parts of 0.1-20:0.1-20:0.1-20:0.01-0.03:0.05-0.2:0.1-20:0.002-0.08 to obtain a first mixed solution; by means of the starvation polymerization method, at a temperature of 60-65 °C, 0.5-80 weight parts of the first mixed solution, 6-12 weight parts of deionized water and 0.005-1 weight part of an initiator are added dropwise at a constant speed to 20-150 weight parts of a polyacrylamide emulsion with a particle size of 40 nm-200 nm and a solid content of 15 wt%-55 wt%. After the polymerization is completed, a layer of poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) material is coated on the surface of the polyacrylamide latex particles to obtain a first polymer template emulsion with a crosslinked core-shell structure; butyl acrylate, methyl methacrylate, methacrylic acid and a reactive emulsifier are mixed in weight parts of 0.1-6:0.1-6:0.1-6:0.01-0.02 to obtain a second mixed solution; by means of the starvation polymerization method, at a temperature of 60-65 °C, 0.1-18 weight parts of the second mixed solution, 15-40 weight parts of deionized water, 10-26 weight parts of a silica dispersion with amino groups on the surface and 0.003-0.03 weight part of an initiator are added dropwise at a constant speed to 26-243 weight parts of the first polymer template emulsion. After the polymerization is completed, a layer of poly(butyl acrylate-methyl methacrylate-methacrylic acid) material embedded with silica particles with a particle size of 20 nm-30 nm and amino groups is coated on the surface of the polyacrylamide latex particles to obtain a second polymer template emulsion with a bayberry-like multi-layer core-shell structure; preparing an emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles: by means of an ion exchange reaction, at a temperature of 30-40 °C, 7-26 weight parts of a third mixed solution are added dropwise at a constant speed to 51-327 weight parts of the second polymer template emulsion, stirred at a stirring speed of less than 80 r / min, and refluxed and condensed at this temperature for 4 h to form a polymer with linear ammonium polyphosphate as the outermost branched chain on the surface of the latex particles, obtaining an emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles; furthermore, first polyacrylamide-based organic / inorganic hybrid nanoparticles with a "rosaceae roxburghii tratt" -like multi-layer core-shell structure and capable of multiple crosslinking can be obtained.

[0070] By means of starvation polymerization, at a temperature of 60 - 65 °C, 0.1 - 18 parts by weight of a second mixed solution, 15 - 40 parts by weight of deionized water, 10 - 26 parts by weight of a silica dispersion with double bonds on the surface, and 0.003 - 0.03 parts by weight of an initiator are added dropwise to 26 - 242 parts by weight of a first polymer template emulsion at a constant rate. After polymerization is completed, a poly(butyl acrylate-methyl methacrylate-methacrylic acid) material in which silica particles with a particle size of 20 nm - 30 nm and double bonds are embedded is coated on the surface of the polyacrylamide latex particles, and a third polymer template emulsion with a multi-layer core-shell structure is obtained. A fourth mixed solution is prepared from glycidyl methacrylate, an initiator, and deionized water according to a weight ratio of 5 - 15:0.01 - 0.2:5 - 10. At a temperature of 60 - 65 °C, 10 - 25 parts by weight of the fourth mixed solution are added dropwise to 51 - 327 parts by weight of the third polymer template emulsion, stirred at a stirring speed of less than 80 r / min, and subjected to reflux condensation reaction at this temperature for 3 h to form a second polymer with linear polyglycidyl methacrylate as the side chain on the surface of the latex particles, obtaining second polyacrylamide-based organic / inorganic hybrid nanoparticles with a "prickly pear" - shaped multi-layer core-shell structure and capable of multiple crosslinking.

[0071] The charring agent, rheological aid, and deionized water are mixed according to a weight ratio of 1 - 5:0.1 - 1:10 - 25, stirred at a stirring speed of less than 100 r / min for 40 minutes to form a homogeneous suspension, and left to age for 12 h to obtain a transparent and dynamically reversible gelation material;

[0072] The first polyacrylamide-based organic / inorganic hybrid nanoparticles, the second polyacrylamide-based organic / inorganic hybrid nanoparticles, a cellulose solvent, a catalyst, and deionized water are mixed according to a weight ratio of 58 - 353:61 - 352:0.5 - 4:0.5 - 2.5:10 - 30 to obtain a first fireproof mixed solution, and stirred at a stirring speed of less than 80 r / min at room temperature for 40 minutes to form a homogeneous suspension; then 11 - 30 parts by weight of the gelation material are added to the first fireproof mixed solution, and stirred at a stirring speed of less than 80 r / min at room temperature for 80 minutes to obtain a clear or slightly turbid second fireproof mixed solution; then 0.5 - 2.5 parts by weight of the catalyst and 0.001 - 0.05 parts by weight of an antifoaming agent are successively added to the second fireproof mixed solution, and stirred at a stirring speed of less than 80 r / min at room temperature for 40 minutes to obtain a fireproof pre-reaction solution, which is left standing for use;

[0073] According to the standard requirements of XF 159-2011 "Water-based Flame Retardants", spray the fire prevention pre-reaction liquid onto the surface of the transparent cellulose-modified soda-lime glass product, let it stand for 50 minutes, and after the surface of the glass product is surface-dried, put it into an oven at 50°C and bake for 4 hours, then raise the temperature to 80°C and bake for 3 hours, so that the cellulose on the glass surface and the fire prevention pre-reaction liquid covering it form a multiple cross-linking system to form an interpenetrating network structure.

[0074] Further, in the above steps, the particle size of the polyacrylamide particles in the polyacrylamide emulsion is 40 nm to 200 nm, and the solid content is 15 wt% to 55 wt%. The particle sizes of the flexible core layers of the two polyacrylamide-based organic / inorganic hybrid nanoparticles are both 40 nm to 200 nm, and the particle size distributions are both single-peak narrow distributions; the reinforcing transition layer materials of the two polyacrylamide-based organic / inorganic hybrid nanoparticles are the first shell layer of poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) copolymer containing melamine formaldehyde material with a cross-linked network structure, and the functional shell layer material is poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer embedded with silica particles with a particle size of 20 nm to 30 nm, and the shell layer thicknesses are both 25 nm to 35 nm; the grafted substances on the shell layer surface are linear ammonium polyphosphate or linear poly(glycidyl methacrylate) polymer, and the thicknesses of the grafted substances on the shell layer surface are both 40 nm to 120 nm. The two polyacrylamide-based organic / inorganic hybrid nanoparticles are narrow-distribution particles.

[0075] Further, in the above step S16), the stirring time is 20 to 60 min, preferably 40 min.

[0076] When preparing the fireproof pre-reaction solution in the embodiments of the present invention, first, tetraethyl orthosilicate, ammonia water with a concentration of 20%, and deionized water are mixed and left to stand for aging to obtain a silica seed solution; the silica seed solution, amino-silane coupling agent, and ethanol are subjected to high-pressure homogenization and dispersion, and then stirred and reacted at a stirring speed of less than 150 r / min to obtain a silica dispersion with amino groups on the surface; the silica seed solution, alkenyl-silane coupling agent, and ethanol are subjected to high-pressure homogenization and dispersion, and then stirred and reacted at a stirring speed of less than 150 r / min to obtain a silica dispersion with alkenyl groups on the surface; butyl acrylate, melamine, styrene, divinyl sulfone, ammonia water with a concentration of 20 wt%, 2,4-methyl-3-cyclohexene formaldehyde, and a reactive emulsifier are mixed to prepare a first mixed solution; by means of the starvation polymerization method, the first mixed solution, deionized water, and initiator are dropped into the polyacrylamide emulsion to obtain a first polymer template emulsion with a crosslinked core-shell structure; butyl acrylate, methyl methacrylate, methacrylic acid, and a reactive emulsifier are mixed to prepare a second mixed solution; by means of the starvation polymerization method, the second mixed solution, deionized water, the silica dispersion with amino groups on the surface, and the initiator are dropped into the first polymer template emulsion to obtain a second polymer template emulsion with a multi-layer core-shell structure; ammonium polyphosphate, ethanol, and deionized water are mixed to prepare a third mixed solution; by means of an ion exchange reaction, the third mixed solution is dropped into the second polymer template emulsion and refluxed and condensed to react to obtain a polymer emulsion containing a first polyacrylamide-based organic / inorganic multi-layer core-shell structure with a "rosa roxburghii tratt" shape, with linear ammonium polyphosphate as the outermost layer branches and capable of multiple crosslinking; the second mixed solution, ionized water, the silica dispersion with double bonds on the surface, and the initiator are dropped into the first polymer template emulsion to obtain a third polymer template emulsion with a multi-layer core-shell structure; glycidyl methacrylate, initiator, and deionized water are mixed to prepare a fourth mixed solution; the fourth mixed solution is dropped into the third polymer template emulsion at a constant speed and refluxed and condensed to react to obtain a polymer emulsion containing a second polyacrylamide-based organic / inorganic multi-layer core-shell structure with a "rosa roxburghii tratt" shape, with linear polyglycidyl methacrylate polymer as the outermost layer branches and capable of multiple crosslinking; the charring agent, rheological aid, and deionized water are mixed and stirred at a stirring speed of less than 100 r / min, and left to stand for aging to obtain a gelled material; the acrylamide-based organic / inorganic hybrid nanoparticles with a "rosa roxburghii tratt" shape multi-layer core-shell structure and capable of multiple crosslinking, cellulose solvent, catalyst, and deionized water are mixed and stirred at a stirring speed of less than 80 r / min, and then the gelled material is added thereto and stirred at a stirring speed of less than 80 r / min to obtain a pre-reaction solution;The catalyst and the defoamer are sequentially added to the pre-reaction solution, and stirred at a stirring speed lower than 80 r / min to obtain a fireproof pre-reaction solution on the surface of the transparent cellulose-modified soda-lime glass product. The fireproof pre-reaction solution is sprayed onto the surface of the transparent cellulose-modified soda-lime glass product. After the surface of the glass product is surface-dried, it is baked so that the cellulose on the glass surface and the fireproof pre-reaction solution covering it form a multiple cross-linking system to form an interpenetrating network structure, improving the flame retardant performance of the product.

[0077] The fireproof material formed after the reaction of the fireproof pre-reaction solution provided by the embodiment of the present invention is an intumescent flame retardant system. When encountering a fire, ammonium polyphosphate on the surface of glass cellulose decomposes by heating, generating phosphoric acid and pyrophosphoric acid with strong dehydration effects, esterifying the charring agent, and then dehydrating and carbonizing. The water vapor formed by the reaction and the ammonia gas decomposed from melamine formaldehyde resin can also cause the carbon layer to expand, and finally form a multi-porous carbon layer, thereby isolating air and heat conduction, protecting the glass product, and achieving the purpose of flame retardance. At the same time, the fireproof material formed after the reaction of the fireproof pre-reaction solution provided by the embodiment of the present invention has the following advantages: good thermal stability, and the multiple cross-linking system ensures that the coating can withstand high-temperature re-treatment above 150 °C after low-temperature baking; when suddenly encountering a fire, it can release a large amount of volatile substances, block oxygen, and at the same time expand and foam; this fireproof structure with a "rosa roxburghii tratt" - shaped multi-layer core-shell structure and capable of multiple cross-linking can be evenly distributed on the surface of wood fibers during the film-forming process, and can form an expanded carbonaceous layer completely covering the surface of the material in a fire, preventing it from dripping and spreading the fire.

[0078] As a preferred embodiment, the thickness of the fireproof layer is 0.02 - 0.3 mm.

[0079] The present invention can control the thickness of the fireproof layer formed by the fireproof pre-reaction solution on the glass surface to be 0.02 - 0.3 mm. On the premise of ensuring the fireproof performance, a fireproof layer with a relatively thin thickness is manufactured, reducing the production cost of the window and expanding the application range of the fireproof material. The fireproof material formed after the reaction of the fireproof pre-reaction solution in the embodiment of the present invention will expand to form a porous heat insulation layer when encountering fire, and the thickness of its expansion layer is about 15 - 20 times the original thickness of the fireproof layer, gradually forming a heat insulation layer of about 1 mm - 4 mm; if the thickness of the fireproof material is less than 0.02 mm, the fireproof layer is too thin, and the formed heat insulation layer cannot isolate the heat transfer within a certain period of time, resulting in the overall fireproof time being lower than the design value; if the thickness of the fireproof material is greater than 0.3 mm, the fireproof layer is too thick, which will cause the excess fireproof pre-reaction solution on the glass surface to not form an effective network entanglement with cellulose, and also block the volatilization of the solution inside the coating, greatly increasing the pre-baking time and cost, and reducing the fireproof efficiency.

[0080] The present invention will be further described below in conjunction with specific embodiments, but it is not a limitation to the present invention.

[0081] The reagents used in each embodiment of the present invention are all commercially available products.

[0082] Example 1

[0083] The fireproof pre-reaction solution in this embodiment is prepared through the following steps:

[0084] (1) Weigh the raw materials of the fireproof pre-reaction solution according to the following weights:

[0085] 4.6 kg of tetraethyl orthosilicate, 0.06 kg of concentrated ammonia water with a concentration of 25 wt%, 117.5 kg of deionized water, 0.3 kg of alkenyl silane coupling agent, 0.3 kg of amino silane coupling agent, 0.72 kg of ethanol, 80 kg of polyacrylamide solution, 14 kg of butyl acrylate, 4 kg of methyl methacrylate, 6 kg of melamine, 6 kg of styrene, 0.04 kg of divinyl sulfone, 0.2 kg of ammonia water with a concentration of 20 wt%, 8 kg of 2,4-methyl-3-cyclohexene carbaldehyde, 4 kg of methacrylic acid, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.38 kg of emulsifier, 0.65 kg of initiator, 3 kg of charring agent, 0.5 kg of rheology aid, 3 kg of cellulose solvent, 1.5 kg of catalyst, 0.02 kg of defoamer.

[0086] Since the particle size of the latex particles in the polyacrylamide emulsion has a narrow distribution, and the two polyacrylamide-based organic / inorganic hybrid nanoparticles also have a unimodal distribution. Similarly, the particle sizes of the flexible core layer particles and the two polyacrylamide-based organic / inorganic hybrid nanoparticles in the following examples also have a narrow distribution;

[0087] (2) Prepare the fireproof pre-reaction solution from the above raw materials according to the following steps:

[0088] Mix 2.3 kg of tetraethyl orthosilicate, 0.03 kg of concentrated ammonia water with a concentration of 25 wt%, and 15 kg of deionized water, and let it stand for aging for 36 h. After the alcoholysis of tetraethyl orthosilicate, a silica seed solution is formed, and the particle size of the silica particles is 20 nm to 30 nm;

[0089] Put 12.5 kg of the silica seed solution, 0.3 kg of amino silane coupling agent, and 0.01 kg of ethanol into a high-pressure homogenizer for cyclic dispersion for 10 min, then put it into a three-necked flask, and then put the three-necked flask into a water bath at 70 °C to 90 °C, and stir and disperse it at a stirring speed of 100 to 150 r / min for 30 min and then cool it to 20 °C to obtain a silica dispersion with amino groups on the surface;

[0090] Put 12.5 kg of silica seed solution, 0.3 kg of vinyl silane coupling agent, and 0.01 kg of ethanol into a high-pressure homogenizer and circulate and disperse for 10 min. Then put it into a three-necked flask, and then put the three-necked flask into a water bath at 70 °C to 90 °C. Stir and disperse at a stirring speed of 100 to 150 r / min for 30 min and then cool to 20 °C to obtain a silica dispersion with double bonds on the surface;

[0091] Mix 5 kg of butyl acrylate, 3 kg of melamine, 3 kg of styrene, 0.02 kg of divinyl sulfone, 0.1 kg of ammonia water with a concentration of 20 wt%, 4 kg of 2,4-methyl-3-cyclohexene carbaldehyde, and 0.04 kg of emulsifier to obtain a first mixed solution; By means of starvation polymerization, at a temperature of 60 to 65 °C, 15.16 kg of the first mixed solution, 7.5 kg of deionized water, and 0.05 kg of initiator are dropped into 40 kg of a polyacrylamide emulsion with a particle size of 40 nm to 200 nm and a solid content of 15 wt% to 55 wt% at a constant speed. After polymerization is completed, a layer of poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) material is coated on the surface of the polyacrylamide latex particles to obtain a first polymer template emulsion with a crosslinked core-shell structure;

[0092] Mix 2 kg of butyl acrylate, 2 kg of methyl methacrylate, 2 kg of methacrylic acid, and 0.015 kg of emulsifier to obtain a second mixed solution; By means of starvation polymerization, at a temperature of 60 to 65 °C, 6.015 kg of the second mixed solution, 20 kg of deionized water by weight, 12.81 kg of the silica dispersion with amino groups on the surface, and 0.02 kg of initiator are dropped into 62.71 kg of the first polymer template emulsion at a constant speed. After polymerization is completed, a layer of poly(butyl acrylate-methyl methacrylate-methacrylic acid) material embedded with silica particles with a particle size of 20 nm to 30 nm and amino groups is coated on the surface of the polyacrylamide latex particles to obtain a second polymer template emulsion with a bayberry-like multi-layer core-shell structure;

[0093] Mix 10 kg of ammonium polyphosphate, 0.7 kg of ethanol, and 5 kg of deionized water to obtain a third mixed solution; By means of ion exchange reaction, at a temperature of 30 to 40 °C, 15.7 kg of the third mixed solution is dropped into 101.555 kg of the second polymer template emulsion at a constant speed, stirred at a stirring speed of less than 80 r / min, and refluxed and condensed at this temperature for 4 h to form a first polymer emulsion with linear ammonium polyphosphate as the outermost branch chain on the surface of the latex particles; Obtain first polyacrylamide-based organic / inorganic hybrid nanoparticles with a "rosa roxburghii tratt"-like multi-layer core-shell structure and multiple crosslinking;

[0094] By means of starvation polymerization, 6.015 kg of the second mixed solution, 20 kg parts by weight of deionized water, 12.81 kg of a silica dispersion with double bonds on the surface, and 0.02 kg of an initiator were added dropwise to 62.71 kg of the first polymer template emulsion at a constant rate under the temperature condition of 60 - 65 °C. After the polymerization was completed, a poly(butyl acrylate-methyl methacrylate-methacrylic acid) material with silica particles having a particle size of 20 nm - 30 nm and double bonds was embedded on the surface of the polyacrylamide latex particles, and the third polymer template emulsion with a bayberry-like multi-layer core-shell structure was obtained;

[0095] 10 kg of glycidyl methacrylate, 0.15 kg of an initiator, and 7.5 kg of deionized water were used to prepare the fourth mixed solution. By means of starvation polymerization, 17.65 kg of the fourth mixed solution was added dropwise to 101.555 parts by weight of the third polymer template emulsion at a constant rate under the temperature condition of 60 - 65 °C, stirred at a stirring speed of less than 80 r / min, and refluxed and condensed for 4 h under this temperature condition to form a polymer emulsion with a linear polyglycidyl methacrylate polymer as the outermost branch on the surface of the latex particles; the second polyacrylamide-based organic / inorganic hybrid nanoparticles with a "prickly pear" - like multi-layer core-shell structure and capable of multiple crosslinking were obtained.

[0096] 3 kg of a charring agent, 0.5 kg of a rheology aid, and 20 kg of deionized water were mixed and stirred at a stirring speed of less than 100 r / min for 40 minutes to form a uniform suspension, and a transparent and dynamically reversible gelation material was obtained after standing and aging for 12 h;

[0097] 117.255 kg of the first polyacrylamide-based organic / inorganic hybrid nanoparticles, 119.205 kg of the second polyacrylamide-based organic / inorganic hybrid nanoparticles, and 3 kg of a cellulose solvent were stirred at a stirring speed of less than 80 r / min for 40 minutes at room temperature to form a uniform suspension; then 23.5 kg of the transparent and dynamically reversible gelation material was added thereto, and stirred at a stirring speed of less than 100 r / min for 60 minutes at room temperature to obtain a clear or slightly turbid pre-reaction solution; then 1.5 kg of a catalyst and 0.02 kg of an antifoaming agent were successively added to the pre-reaction solution, and stirred at a stirring speed of less than 80 r / min for 40 minutes at room temperature to obtain a fire-proof pre-reaction solution for the surface of wooden products for railway vehicles, and it was left standing for use;

[0098] According to the standard requirements of XF 159-2011 "Water-based Flame Retardant", the fire prevention pre-reaction liquid is sprayed on the surface of the transparent cellulose-modified soda-lime glass product, and left standing for 50 minutes. After the surface of the glass product is surface-dried, it is placed in an oven at 50°C and baked for 4 hours, and then the temperature is raised to 80°C and baked for 3 hours, so that the cellulose on the glass surface and the fire prevention pre-reaction liquid covering it form a multi-crosslinked system to form an interpenetrating network structure, improving the flame retardant performance of the product.

[0099] Example 2

[0100] The fire prevention pre-reaction liquid in this example is prepared through the following steps:

[0101] (1) Weigh the raw materials of the fire prevention pre-reaction liquid according to the following weights:

[0102] 4.6 kg of tetraethyl orthosilicate, 0.06 kg of concentrated ammonia water with a concentration of 25 wt%, 117.5 kg of deionized water, 0.3 kg of alkenyl silane coupling agent, 0.3 kg of amino silane coupling agent, 0.72 kg of ethanol, 80 kg of polyacrylamide solution, 14 kg of butyl acrylate, 4 kg of methyl methacrylate, 5.5 kg of melamine, 6 kg of styrene, 0.04 kg of divinyl sulfone, 0.2 kg of ammonia water with a concentration of 20 wt%, 7.5 kg of 2,4-methyl-3-cyclohexene formaldehyde, 4 kg of methacrylic acid, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.38 kg of emulsifier, 0.65 kg of initiator, 3 kg of charring agent, 0.5 kg of rheology aid, 3 kg of cellulose solvent, 1.5 kg of catalyst, 0.02 kg of defoamer.

[0103] (2) Prepare the fire prevention pre-reaction liquid from the above raw materials according to the same preparation method as in Example 1.

[0104] The preparation method of the fire prevention pre-reaction liquid in this example is the same as that of the fire prevention pre-reaction liquid in Example 1, except that the composition of the fire prevention pre-reaction liquid is different.

[0105] Example 3

[0106] The fire prevention pre-reaction liquid in this example is prepared through the following steps:

[0107] (1) Weigh the raw materials of the fire prevention pre-reaction liquid according to the following weights:

[0108] 4.6 kg tetraethyl orthosilicate, 0.06 kg concentrated ammonia water with a concentration of 25 wt%, 117.5 kg deionized water, 0.3 kg alkenyl silane coupling agent, 0.3 kg amino silane coupling agent, 0.72 kg ethanol, 80 kg polyacrylamide solution, 14 kg butyl acrylate, 4 kg methyl methacrylate, 5 kg melamine, 6 kg styrene, 0.04 kg divinyl sulfone, 0.2 kg ammonia water with a concentration of 20 wt%, 7 kg 2,4-methyl-3-cyclohexene carbaldehyde, 4 kg methacrylic acid, 10 kg ammonium polyphosphate, 10 kg glycidyl methacrylate, 0.38 kg emulsifier, 0.65 kg initiator, 3 kg charring agent, 0.5 kg rheology aid, 3 kg cellulose solvent, 1.5 kg catalyst, 0.02 kg defoamer.

[0109] (2) Prepare the fireproof pre-reaction solution from the above raw materials according to the same preparation method as in Example 1.

[0110] The preparation method of the fireproof pre-reaction solution in this example is the same as that in Example 1, except for the different composition of the fireproof pre-reaction solution.

[0111] Example 4

[0112] The fireproof pre-reaction solution in this example is prepared through the following steps:

[0113] (1) Weigh the raw materials of the fireproof pre-reaction solution according to the following weights:

[0114] 4.6 kg tetraethyl orthosilicate, 0.06 kg concentrated ammonia water with a concentration of 25 wt%, 117.5 kg deionized water, 0.3 kg alkenyl silane coupling agent, 0.3 kg amino silane coupling agent, 0.72 kg ethanol, 80 kg polyacrylamide solution, 14 kg butyl acrylate, 4 kg methyl methacrylate, 4.5 kg melamine, 6 kg styrene, 0.04 kg divinyl sulfone, 0.2 kg ammonia water with a concentration of 20 wt%, 6.5 kg 2,4-methyl-3-cyclohexene carbaldehyde, 4 kg methacrylic acid, 10 kg ammonium polyphosphate, 10 kg glycidyl methacrylate, 0.38 kg emulsifier, 0.65 kg initiator, 3 kg charring agent, 0.5 kg rheology aid, 3 kg cellulose solvent, 1.5 kg catalyst, 0.02 kg defoamer.

[0115] (2) Prepare the fireproof pre-reaction solution from the above raw materials according to the same preparation method as in Example 1.

[0116] The preparation method of the fireproof pre-reaction solution in this example is the same as that in Example 1, except for the different composition of the fireproof pre-reaction solution.

[0117] Example 5

[0118] The fire prevention pre-reaction liquid in this embodiment is prepared through the following steps:

[0119] (1) Weigh the raw materials of the fire prevention pre-reaction liquid according to the following weights:

[0120] 4.6 kg of tetraethyl orthosilicate, 0.06 kg of concentrated ammonia water with a concentration of 25 wt%, 117.5 kg of deionized water, 0.3 kg of alkenyl silane coupling agent, 0.3 kg of amino silane coupling agent, 0.72 kg of ethanol, 80 kg of polyacrylamide solution, 14 kg of butyl acrylate, 4 kg of methyl methacrylate, 4 kg of melamine, 6 kg of styrene, 0.04 kg of divinyl sulfone, 0.2 kg of ammonia water with a concentration of 20 wt%, 6 kg of 2,4-methyl-3-cyclohexene carbaldehyde, 4 kg of methacrylic acid, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.38 kg of emulsifier, 0.65 kg of initiator, 3 kg of charring agent, 0.5 kg of rheology aid, 3 kg of cellulose solvent, 1.5 kg of catalyst, 0.02 kg of defoamer.

[0121] (2) Prepare the fire prevention pre-reaction liquid from the above raw materials according to the same preparation method as in Example 1.

[0122] The preparation method of the fire prevention pre-reaction liquid in this embodiment is the same as that of the fire prevention pre-reaction liquid in Example 1, except for the different composition of the fire prevention pre-reaction liquid.

[0123] Example 6

[0124] The fire prevention pre-reaction liquid in this embodiment is prepared through the following steps:

[0125] (1) Weigh the raw materials of the fire prevention pre-reaction liquid according to the following weights:

[0126] 4.6 kg of tetraethyl orthosilicate, 0.06 kg of concentrated ammonia water with a concentration of 25 wt%, 117.5 kg of deionized water, 0.3 kg of alkenyl silane coupling agent, 0.3 kg of amino silane coupling agent, 0.72 kg of ethanol, 80 kg of polyacrylamide solution, 14 kg of butyl acrylate, 4 kg of methyl methacrylate, 6.5 kg of melamine, 6 kg of styrene, 0.04 kg of divinyl sulfone, 0.2 kg of ammonia water with a concentration of 20 wt%, 8.5 kg of 2,4-methyl-3-cyclohexene carbaldehyde, 4 kg of methacrylic acid, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.38 kg of emulsifier, 0.65 kg of initiator, 3 kg of charring agent, 0.5 kg of rheology aid, 3 kg of cellulose solvent, 1.5 kg of catalyst, 0.02 kg of defoamer.

[0127] (2) Prepare the fireproof pre-reaction liquid from the above raw materials according to the same preparation method as in Example 1.

[0128] The preparation method of the fireproof pre-reaction liquid in this example is the same as that in Example 1, except that the composition of the fireproof pre-reaction liquid is different.

[0129] Example 7

[0130] The fireproof pre-reaction liquid in this example is prepared through the following steps:

[0131] (1) Weigh the raw materials of the fireproof pre-reaction liquid according to the following weights:

[0132] 4.6 kg of tetraethyl orthosilicate, 0.06 kg of concentrated ammonia water with a concentration of 25 wt%, 117.5 kg of deionized water, 0.3 kg of alkenyl silane coupling agent, 0.3 kg of amino silane coupling agent, 0.72 kg of ethanol, 80 kg of polyacrylamide solution, 14 kg of butyl acrylate, 4 kg of methyl methacrylate, 6 kg of melamine, 6 kg of styrene, 0.04 kg of divinyl sulfone, 0.2 kg of ammonia water with a concentration of 20 wt%, 8 kg of 2,4-methyl-3-cyclohexene carbaldehyde, 4 kg of methacrylic acid, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.38 kg of emulsifier, 0.65 kg of initiator, 3 kg of charring agent, 0.5 kg of rheology aid, 2.5 kg of cellulose solvent, 1.5 kg of catalyst, 0.02 kg of defoamer.

[0133] (2) Prepare the fireproof pre-reaction liquid from the above raw materials according to the same preparation method as in Example 1.

[0134] The preparation method of the fireproof pre-reaction liquid in this example is the same as that in Example 1, except that the composition of the fireproof pre-reaction liquid is different.

[0135] Example 8

[0136] The fireproof pre-reaction liquid in this example is prepared through the following steps:

[0137] (1) Weigh the raw materials of the fireproof pre-reaction liquid according to the following weights:

[0138] 4.6 kg tetraethyl orthosilicate, 0.06 kg concentrated ammonia water with a concentration of 25 wt%, 117.5 kg deionized water, 0.3 kg alkenyl silane coupling agent, 0.3 kg amino silane coupling agent, 0.72 kg ethanol, 80 kg polyacrylamide solution, 14 kg butyl acrylate, 4 kg methyl methacrylate, 6 kg melamine, 6 kg styrene, 0.04 kg divinyl sulfone, 0.2 kg ammonia water with a concentration of 20 wt%, 8 kg 2,4-methyl-3-cyclohexene carbaldehyde, 4 kg methacrylic acid, 10 kg ammonium polyphosphate, 10 kg glycidyl methacrylate, 0.38 kg emulsifier, 0.65 kg initiator, 3 kg charring agent, 0.5 kg rheology aid, 3.5 kg cellulose solvent, 1.5 kg catalyst, 0.02 kg defoamer.

[0139] (2) Prepare the fireproof pre-reaction liquid from the above raw materials according to the same preparation method as in Example 1.

[0140] The preparation method of the fireproof pre-reaction liquid in this example is the same as that in Example 1, except that the composition of the fireproof pre-reaction liquid is different.

[0141] Example 9

[0142] The fireproof pre-reaction liquid in this example is prepared through the following steps:

[0143] (1) Weigh the raw materials of the fireproof pre-reaction liquid according to the following weights:

[0144] 4.6 kg tetraethyl orthosilicate, 0.06 kg concentrated ammonia water with a concentration of 25 wt%, 117.5 kg deionized water, 0.3 kg alkenyl silane coupling agent, 0.3 kg amino silane coupling agent, 0.72 kg ethanol, 80 kg polyacrylamide solution, 14 kg butyl acrylate, 4 kg methyl methacrylate, 6 kg melamine, 6 kg styrene, 0.04 kg divinyl sulfone, 0.2 kg ammonia water with a concentration of 20 wt%, 8 kg 2,4-methyl-3-cyclohexene carbaldehyde, 4 kg methacrylic acid, 10 kg ammonium polyphosphate, 10 kg glycidyl methacrylate, 0.38 kg emulsifier, 0.65 kg initiator, 3 kg charring agent, 0.8 kg rheology aid, 3.5 kg cellulose solvent, 1.5 kg catalyst, 0.02 kg defoamer.

[0145] (2) Prepare the fireproof pre-reaction liquid from the above raw materials according to the same preparation method as in Example 1.

[0146] The preparation method of the fireproof pre-reaction liquid in this example is the same as that in Example 1, except that the composition of the fireproof pre-reaction liquid is different.

[0147] Example 10

[0148] The fire - prevention pre - reaction liquid in this embodiment is prepared through the following steps:

[0149] (1) Weigh the raw materials of the fire - prevention pre - reaction liquid according to the following weights:

[0150] 4.6 kg of tetraethyl orthosilicate, 0.06 kg of concentrated ammonia water with a concentration of 25 wt%, 117.5 kg of deionized water, 0.3 kg of alkenyl silane coupling agent, 0.3 kg of amino silane coupling agent, 0.72 kg of ethanol, 80 kg of polyacrylamide solution, 14 kg of butyl acrylate, 4 kg of methyl methacrylate, 6 kg of melamine, 6 kg of styrene, 0.05 kg of divinyl sulfone, 0.2 kg of ammonia water with a concentration of 20 wt%, 8 kg of 2,4 - methyl - 3 - cyclohexene formaldehyde, 4 kg of methacrylic acid, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.38 kg of emulsifier, 0.65 kg of initiator, 3 kg of char - forming agent, 0.8 kg of rheology aid, 3.5 kg of cellulose solvent, 1.5 kg of catalyst, 0.02 kg of defoamer.

[0151] (2) Prepare the fire - prevention pre - reaction liquid from the above - mentioned raw materials according to the same preparation method as in Example 1.

[0152] The preparation method of the fire - prevention pre - reaction liquid in this embodiment is the same as that of the fire - prevention pre - reaction liquid in Example 1, except for the different composition of the fire - prevention pre - reaction liquid.

[0153] Example 11

[0154] The fire - prevention pre - reaction liquid in this embodiment is prepared through the following steps:

[0155] (1) Weigh the raw materials of the fire - prevention pre - reaction liquid according to the following weights:

[0156] 4.6 kg of tetraethyl orthosilicate, 0.06 kg of concentrated ammonia water with a concentration of 25 wt%, 117.5 kg of deionized water, 0.3 kg of alkenyl silane coupling agent, 0.3 kg of amino silane coupling agent, 0.72 kg of ethanol, 80 kg of polyacrylamide solution, 14 kg of butyl acrylate, 4 kg of methyl methacrylate, 6 kg of melamine, 6 kg of styrene, 0.03 kg of divinyl sulfone, 0.2 kg of ammonia water with a concentration of 20 wt%, 8 kg of 2,4 - methyl - 3 - cyclohexene formaldehyde, 4 kg of methacrylic acid, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.38 kg of emulsifier, 0.65 kg of initiator, 3 kg of char - forming agent, 0.8 kg of rheology aid, 3.5 kg of cellulose solvent, 1.5 kg of catalyst, 0.02 kg of defoamer..

[0157] (2) Prepare the fireproof pre-reaction liquid from the above raw materials by the same preparation method as in Example 1.

[0158] The preparation method of the fireproof pre-reaction liquid in this example is the same as that in Example 1, except that the composition of the fireproof pre-reaction liquid is different.

[0159] Comparative Example 1

[0160] This comparative example provides a fireproof pre-reaction liquid, the raw materials of which are 55 kg of deionized water, 3 kg of melamine, 4 kg of 2,4-methyl-3-cyclohexene formaldehyde, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.05 kg of initiator, 3 kg of charring agent, 0.5 kg of rheology aid, 3 kg of cellulose solvent, 1.5 kg of catalyst, and 0.02 kg of defoamer. The preparation method of the fireproof pre-reaction liquid in this comparative example is the same as that in Example 1, except that the composition of the fireproof pre-reaction liquid is different.

[0161] Comparative Example 2

[0162] This comparative example provides a fireproof pre-reaction liquid, the raw materials of which are 55 kg of deionized water, 3 kg of melamine, 4 kg of 2,4-methyl-3-cyclohexene formaldehyde, 10 kg of ammonium polyphosphate, 10 kg of glycidyl methacrylate, 0.05 kg of initiator, 1.5 kg of catalyst, and 0.02 kg of defoamer.

[0163] The preparation method of the fireproof pre-reaction liquid in this comparative example is the same as that in Example 1, except that the composition of the fireproof pre-reaction liquid is different.

[0164] Comparative Example 3

[0165] This comparative example is a transparent cellulose-modified soda-lime glass product without flame retardant treatment.

[0166] Carry out a flame retardant performance experiment on the glass samples coated with the fireproof pre-reaction liquid provided in Examples 1 to 12 and Comparative Examples 1 to 3 according to the standard requirements of XF 159-2011 "Water-based Flame Retardants". Take 4 parallel specimens for the experiment, and take the average value of their data as the experimental result; detect the viscosity of the fireproof pre-reaction liquid according to the method for determining the viscosity of paints in GB / T 1723; and observe the apparent quality of each wooden product with the naked eye. The performance parameters of the fireproof pre-reaction liquid prepared in the examples and comparative examples of the present invention are shown in Table 1.

[0167] Table 1 Performance parameter table of the fireproof pre-reaction liquid

[0168]

[0169] As can be seen from Table 1, the fireproof pre-reaction liquid in the present invention forms a fireproof layer with a long fire resistance time and water erosion resistance after curing, while the fireproof layer formed after curing the fireproof pre-reaction liquid prepared in the comparative example does not have the characteristic of water erosion resistance; the fire resistance time of the fireproof pre-reaction liquid in the present invention after curing is 1.5 - 7 times that of the comparative example, and the hardness and ultraviolet irradiation resistance time are also significantly higher than those of the comparative example. The above shows that using only 2,4-methyl-3-cyclohexene melamine formaldehyde resin and ammonium polyphosphate as fireproof materials is easily washed away during the water flushing process, seriously affecting the use safety of glass window panes. By improving the formula of the fireproof pre-reaction liquid, the present invention mixes polyacrylamide-based organic / inorganic hybrid latex particles with a "prickly pear" - shaped multi-layer core-shell structure and capable of multiple cross-linking with additives, and a synergistic effect is generated among the components of the fireproof pre-reaction liquid, improving the flame retardant performance of the material. Especially after water flushing, the flame retardant performance of the glass product remains unaffected, and at the same time, the low-temperature resistance of the fireproof layer formed after curing the fireproof pre-reaction liquid is also improved, and it can be used in a low-temperature (-25°C ± 1°C) outdoor environment. The fireproof pre-reaction liquid prepared in the examples of the present invention has the advantages of low viscosity, high hardness, good adhesion, long flame retardant time, low-temperature resistance and ultraviolet irradiation resistance, and can form a transparent coating when coated on the surface of an object.

[0170] In the above embodiments, the descriptions of each embodiment have their own focuses. For the parts not detailed in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0171] The above is only a preferred embodiment of the present invention, and does not impose any form of limitation on the present invention. Any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. Organic / inorganic hybrid nanomaterials, characterized in that: The invention comprises a first polyacrylamide-based organic / inorganic hybrid nanoparticle and a second polyacrylamide-based organic / inorganic hybrid nanoparticle, wherein the first polyacrylamide-based organic / inorganic hybrid nanoparticle and the second polyacrylamide-based organic / inorganic hybrid nanoparticle both comprise a flexible core layer, a shell layer and a reinforcing transition layer, wherein the reinforcing transition layer is arranged between the flexible core layer and the shell layer; wherein the shell layer of the first polyacrylamide-based organic / inorganic hybrid nanoparticle is a poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer having a surface grafted with linear ammonium polyphosphate and inlaid with amine-containing silicon dioxide particles having a particle size of 20nm to 30nm, and the shell layer of the second polyacrylamide-based organic / inorganic hybrid nanoparticle is a surface grafted with linear poly(glycidyl methacrylate) and inlaid with amine-containing silicon dioxide particles having a particle size of 20nm to 30nm. 30nm, poly(butyl acrylate-methyl methacrylate-methacrylic acid) copolymer of silica particles with double bonds, the flexible core layer of the first polyacrylamide-based organic / inorganic hybrid nanoparticles and the flexible core layer of the second polyacrylamide-based organic / inorganic hybrid nanoparticles are both polyacrylamide latex particles, the reinforcing transition layer of the first polyacrylamide-based organic / inorganic hybrid nanoparticles and the reinforcing transition layer of the second polyacrylamide-based organic / inorganic hybrid nanoparticles are both polymer layers containing melamine formaldehyde material with a cross-linked network structure; the polymer in the shell layer of the first polyacrylamide-based organic / inorganic hybrid nanoparticles and the polymer in the shell layer of the second polyacrylamide-based organic / inorganic hybrid nanoparticles both contain at least one polymer that can form an interpenetrating network structure with cellulose; The material composed of the first polyacrylamide-based organic / inorganic hybrid nanoparticles is made of the following components: 7 to 26 parts by weight of the third mixed solution and 51 to 327 parts by weight of the second polymer template emulsion; the third mixed solution is made by mixing 5 to 15 parts by weight of ammonium polyphosphate, 0.1 to 1 parts by weight of ethanol and 2 to 10 parts by weight of deionized water; the second polymer template emulsion is made by mixing 0.1 to 18 parts by weight of the second mixed solution, 15 to 40 parts by weight of deionized water, 10 to 26 parts by weight of a silicon dioxide dispersion with amino groups on the surface, 0.003 to 0.03 parts by weight of an initiator and 26 to 243 parts by weight of the first polymer template emulsion; the second mixed solution is made by mixing 0.1 to 6 parts by weight of butyl acrylate, 0.1 to 6 parts by weight of methyl methacrylate, 0.1 to 6 parts by weight of methacrylic acid and 0.01 to 0.02 parts by weight of a reactive emulsifier; the first polymer template emulsion is made by mixing 0.5 to 80 parts by weight of the first mixed solution, 6 to 12 parts by weight of deionized water, 0 The first mixed solution is prepared by mixing 0.1-20 parts by weight of butyl acrylate, 0.1-20 parts by weight of melamine, 0.1-20 parts by weight of styrene, 0.01-0.03 parts by weight of divinyl sulfone, 0.05-0.2 parts by weight of 20wt% ammonia water, 0.1-20 parts by weight of 2,4 -methyl-3-cyclohexene formaldehyde and 0.002-0.08 parts by weight of a reactive emulsifier; a hydrophilic silica dispersion with amino groups on the surface is made of 10-25 parts by weight of a silica seed solution, 0.1-1 parts by weight of an amino silane coupling agent and 0.001-0.02 parts by weight of ethanol; a silica seed solution is made of 2-3 parts by weight of ethyl orthosilicate, 0.02-0.04 parts by weight of concentrated ammonia water with a concentration of 25wt% and 8-22 parts by weight of deionized water; The second polyacrylamide-based organic / inorganic hybrid nanoparticle material is made of the following components: The invention discloses a method for preparing a polymer template emulsion comprising: preparing a polymer template emulsion comprising: a first polymer template emulsion comprising: a first polymer template emulsion comprising: a first polymer template emulsion comprising: a second ... The first mixed solution is prepared by mixing 0.1-20 parts by weight of butyl acrylate, 0.1-20 parts by weight of melamine, 0.1-20 parts by weight of styrene, 0.01-0.03 parts by weight of divinyl sulfone, 0.05-0.2 parts by weight of 20wt% ammonia water, 0.1-20 parts by weight of 2,4-methyl-3- -cyclohexene formaldehyde and 0.002-0.08 parts by weight of a reactive emulsifier are mixed; a hydrophilic silica dispersion with double bonds on the surface is made of 10-25 parts by weight of a silica seed solution, 0.1-1 parts by weight of an alkenyl silane coupling agent and 0.001-0.02 parts by weight of ethanol; a silica seed solution is made of 2-3 parts by weight of tetraethyl orthosilicate, 0.02-0.04 parts by weight of 25wt% concentrated ammonia water and 8-22 parts by weight of deionized water.

2. The organic / inorganic hybrid nanomaterial according to claim 1, characterized in that: The polymerization degree of the polyacrylamide particles in the polyacrylamide emulsion is 10000-100000, the particle size is 40nm-200nm, and the particle size distribution is a single peak narrow distribution.

3. The organic / inorganic hybrid nanomaterial according to claim 1, characterized in that: The alkenyl silane coupling agent is one or more of vinyl tert-butyl triperoxide silane, vinyl triethoxy silane, butadienyl triethoxy silane, vinyl trimethoxy silane, isobutylenyl triethoxy silane and vinyl tri(β-methoxyethoxy) silane.

4. The organic / inorganic hybrid nanomaterial according to claim 1, characterized in that: The aminosilane coupling agent is one or more of one or more of the group consisting of anilinomethyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane.

5. The organic / inorganic hybrid nanomaterial according to claim 1, characterized in that: The initiator is one or both of a thermal initiator and a redox initiator.

6. The method for preparing the organic / inorganic hybrid nanomaterial according to claim 1, characterized in that: The steps include: S11) preparing a silicon dioxide seed solution: mixing tetraethyl orthosilicate, concentrated ammonia water with a concentration of 25 wt % and deionized water in a weight ratio of 2-3: 0.02-0.04: 8-22, standing and aging for 36 hours, and generating a silicon dioxide seed solution after alcoholysis of tetraethyl orthosilicate, wherein the particle size of the silicon dioxide particles is 20 nm to 30 nm; S12-1) preparing a silica dispersion with amine groups on the surface: placing a silica seed solution, an amino-silane coupling agent and ethanol in a weight ratio of 10 to 25: 0.1 to 1: 0.001 to 0.02 in a high-pressure homogenizer for circulation and dispersion for 10 minutes to obtain a first primary dispersion, placing the first primary dispersion in a three-necked flask, and then placing the three-necked flask in a water bath at 70°C to 90°C, stirring and dispersing at a stirring speed of 100 to 150 r / min for 30 minutes, and then cooling to 20°C to obtain a silica dispersion with amine groups on the surface; wherein the silica seed solution is the silica seed solution obtained in step S11); S12-2) preparing a silica dispersion with double bonds on the surface: placing a silica seed solution, an alkenyl silane coupling agent and ethanol in a weight ratio of 10 to 25: 0.1 to 1: 0.001 to 0.02 in a high-pressure homogenizer for circulation dispersion for 10 minutes to obtain a second primary dispersion, placing the second primary dispersion in a three-necked flask, and then placing the three-necked flask in a water bath at 70°C to 90°C, stirring and dispersing at a stirring speed of 100 to 150 r / min for 30 minutes, and then cooling to 20°C to obtain a silica dispersion with double bonds on the surface; wherein the silica seed solution is the silica seed solution obtained in step S11); S13) preparing a first polymer template emulsion, the specific steps are as follows: S13-1) mixing butyl acrylate, melamine, styrene, divinyl sulfone, 20 wt% ammonia water, 2,4-methyl-3-cyclohexene carboxaldehyde and a reactive emulsifier in a weight ratio of 0.1-20: 0.1-20: 0.1-20: 0.01-0.03: 0.05-0.2: 0.1-20: 0.002-0.08 to prepare a first mixed solution; S13-2) By means of starvation polymerization, 0.5 to 80 parts by weight of the first mixed solution, 6 to 12 parts by weight of deionized water and 0.005 to 1 part by weight of an initiator are added dropwise to 20 to 150 parts by weight of a polyacrylamide emulsion having a particle size of 40 nm to 200 nm and a solid content of 15 wt% to 55 wt% at a constant speed under a temperature condition of 60 to 65° C. After the polymerization is completed, a layer of poly(butyl acrylate-styrene-divinyl sulfone-2,4-methyl-3-cyclohexene melamine formaldehyde) material is coated on the surface of the polyacrylamide latex particles to obtain a first polymer template emulsion having a cross-linked core-shell structure; S14) preparing an emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles, the specific steps are as follows: S14-1) mixing butyl acrylate, methyl methacrylate, methacrylic acid and a reactive emulsifier in a weight ratio of 0.1-6: 0.1-6: 0.1-6: 0.01-0.02 parts to prepare a second mixed solution; S14-2) preparing a second polymer template emulsion: by means of starvation polymerization, at a temperature of 60 to 65° C., 0.1 to 18 parts by weight of a second mixed solution, 15 to 40 parts by weight of deionized water, 10 to 26 parts by weight of a silica dispersion with amino groups on the surface, and 0.003 to 0.03 parts by weight of an initiator are added dropwise to 26 to 243 parts by weight of a first polymer template emulsion at a constant speed. After the polymerization is completed, a layer of poly(butyl acrylate-methyl methacrylate-methacrylic acid) material inlaid with silica particles with an amino group and a particle size of 20 nm to 30 nm is coated on the surface of the polyacrylamide latex particles, thereby obtaining a second polymer template emulsion having a bayberry-like multilayer core-shell structure; S14-3) preparing a third mixed solution: mixing ammonium polyphosphate, ethanol and deionized water in a weight ratio of 5-15: 0.5-1: 2-10 to prepare a third mixed solution; S14-4) preparing an emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles: by means of an ion exchange reaction, 7 to 26 parts by weight of the third mixed solution are added dropwise to 51 to 327 parts by weight of the second polymer template emulsion at a constant speed at a temperature of 30 to 40° C., stirred at a stirring speed of less than 80 r / min, and refluxed and condensed under this temperature for 4 hours to form a polymer with linear ammonium polyphosphate as the outermost branch chain on the surface of the latex particles, thereby obtaining an emulsion containing first polyacrylamide-based organic / inorganic hybrid nanoparticles; S15) preparing an emulsion containing a second polyacrylamide-based organic / inorganic hybrid nanoparticle, the specific steps are as follows: S15-1) preparing a third polymer template emulsion: by means of a starvation polymerization method, at a temperature of 60 to 65° C., 0.1 to 18 parts by weight of the second mixed solution, 15 to 40 parts by weight of deionized water, 10 to 26 parts by weight of a silica dispersion having double bonds on the surface, and 0.003 to 0.03 parts by weight of an initiator are added dropwise to 26 to 242 parts by weight of the first polymer template emulsion at a constant speed. After the polymerization is completed, a layer of poly(butyl acrylate-methyl methacrylate-methacrylic acid) material embedded with silica particles having double bonds and a particle size of 20 nm to 30 nm is coated on the surface of the polyacrylamide latex particles, thereby obtaining a third polymer template emulsion having a multilayer core-shell structure; S15-2) preparing a fourth mixed solution: preparing a fourth mixed solution by mixing glycidyl methacrylate, an initiator and deionized water in a weight ratio of 5-15: 0.01-0.2: 5-10; S15-3) preparing an emulsion containing second polyacrylamide-based organic / inorganic hybrid nanoparticles: adding 10 to 25 parts by weight of the fourth mixed solution to 51 to 327 parts by weight of the third polymer template emulsion at a constant speed at a temperature of 60 to 65°C, stirring at a stirring speed of less than 80 r / min, and reflux condensing for 3 hours at this temperature to form a second polymer with linear polymethacrylate glycidyl ester as a branch on the surface of the latex particles, thereby obtaining an emulsion containing second polyacrylamide-based organic / inorganic hybrid nanoparticles; S16) Compounding the emulsion containing the first polyacrylamide-based organic / inorganic hybrid nanoparticles and the emulsion containing the second polyacrylamide-based organic / inorganic hybrid nanoparticles to obtain an organic / inorganic hybrid nanomaterial.

7. Fire-proof pre-reaction liquid, characterized in that: The invention comprises at least the following components: 58 to 353 parts by weight of a first polyacrylamide-based organic / inorganic hybrid nanoparticle, 61 to 352 parts by weight of a second polyacrylamide-based organic / inorganic hybrid nanoparticle, 0.5 to 4 parts by weight of a cellulose solvent, 0.5 to 2.5 parts by weight of a catalyst and 10 to 30 parts by weight of deionized water; the first polyacrylamide-based organic / inorganic hybrid nanoparticle is the first polyacrylamide-based organic / inorganic hybrid nanoparticle in the organic / inorganic hybrid nanomaterial according to claim 1, and the second polyacrylamide-based organic / inorganic hybrid nanoparticle is the second polyacrylamide-based organic / inorganic hybrid nanoparticle in the organic / inorganic hybrid nanomaterial according to claim 1.

8. The fire-proof pre-reaction liquid according to claim 7, characterized in that: It also includes: 1 to 5 parts by weight of a carbonizing agent, 0.001 to 0.05 parts by weight of a defoaming agent and 0.1 to 1 parts by weight of a rheological additive; the carbonizing agent is a compound of pentaerythritol and one or more of sucrose, fructose, glucose and maltose; the rheological additive is one or more of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl cellulose; the antifreeze plasticizer is one or more of ethylene glycol, glycerol and 1,4-butanediol; the cellulose solvent is one or both of dipropylene glycol methyl ether and N-methylmorpholine oxide; the catalyst is a compound of a dilute hydrochloric acid solution with a mass concentration less than or equal to 20wt% and one or both of diethyl aluminum hypophosphite and inorganic aluminum hypophosphite; the defoaming agent is one or both of a polysiloxane defoaming agent and a polyether defoaming agent.

9. The method for preparing the fire-proof pre-reaction liquid according to claim 8, characterized in that: The steps include: Step S21), a carbonizing agent, a rheological additive, and deionized water are mixed in a weight ratio of 1-5: 0.1-1: 10-25, stirred at a stirring speed of less than 100 r / min for 40 minutes to form a uniform suspension, and allowed to stand for 12 hours to obtain a transparent and dynamically reversible gel material; Step S22) The first polyacrylamide-based organic / inorganic hybrid nanoparticles, the second polyacrylamide-based organic / inorganic hybrid nanoparticles, the cellulose solvent, the catalyst and deionized water are mixed in a weight ratio of 58-353:61-352:0.5-4:0.5-2.5:10-30 to obtain a first fireproof mixed solution. At room temperature, stir at a stirring speed of less than 80 r / min for 40 minutes to form a uniform suspension; then add 11 to 30 parts by weight of gelling material to the first fire-proof mixed liquid, and stir at room temperature at a stirring speed of less than 80 r / min for 80 minutes to obtain a clear or slightly turbid second fire-proof mixed liquid; then add 0.5 to 2.5 parts by weight of catalyst and 0.001 to 0.05 parts by weight of defoaming agent to the second fire-proof mixed liquid in sequence, and stir at room temperature at a stirring speed of less than 80 r / min for 40 minutes to obtain a fire-proof pre-reaction liquid, which is allowed to stand for use.

10. The use of the fire-proof pre-reaction liquid according to claim 8, characterized in that: It is used for flame retardant treatment of transparent cellulose modified soda-lime glass products and forms a fireproof layer with a thickness of 0.02-0.3mm on the surface of the glass products. The specific operation is: spray the fireproof pre-reaction liquid onto the surface of the transparent cellulose modified soda-lime glass product, let it stand for 50 minutes, and after the surface of the glass product is dry, put it into a 50℃ oven for baking for 4 hours, and then heat it to 80℃ and bake for 3 hours, so that the cellulose on the glass surface and the fireproof pre-reaction liquid covering it form a multiple cross-linking system to form an interpenetrating network structure.

Images