WO2018152869A1 - 一种防火胶液基质及其制备方法和防火胶液及其制备方法 - Google Patents

一种防火胶液基质及其制备方法和防火胶液及其制备方法 Download PDF

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WO2018152869A1
WO2018152869A1 PCT/CN2017/075918 CN2017075918W WO2018152869A1 WO 2018152869 A1 WO2018152869 A1 WO 2018152869A1 CN 2017075918 W CN2017075918 W CN 2017075918W WO 2018152869 A1 WO2018152869 A1 WO 2018152869A1
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fireproof glue
monomer
fireproof
mass ratio
soap
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PCT/CN2017/075918
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English (en)
French (fr)
Inventor
穆元春
杜大艳
徐志伟
李要辉
徐磊
付静
王晋珍
张凡
安远
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中国建筑材料科学研究总院
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Priority to US16/071,765 priority Critical patent/US20210002527A1/en
Publication of WO2018152869A1 publication Critical patent/WO2018152869A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/069—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of intumescent material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/10—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B32B2264/1021—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/213—SiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the invention relates to a fireproof glue liquid and a preparation method thereof, and belongs to the field of fire safety glass.
  • Fireproof glass is a kind of building exterior wall or door and window glass with fireproof function. It not only has the conventional performance of ordinary glass, but also has specific energy to control fire spread, smoke insulation and heat insulation.
  • fireproof glass is mainly divided into four types: composite fireproof glass, special fireproof glass, hollow fireproof glass and high strength single layer lanthanum potassium fireproof glass.
  • Laminated Fire-Resistant Glass has good light transmission properties, and is classified as Class A fireproof because of its excellent fire integrity (Integrity, E) and insulation (Isulation, I). Glass, in the fire, can protect escapers and rescuers from heat radiation and minimize the damage of fire.
  • the existing composite fireproof glass is composed of two or more layers of glass and a transparent fireproof glue layer sandwiched between the glass; when a fire is encountered, the fireproof glue layer will be quickly released.
  • the bubble expands to form an insulating refractory insulating foam layer that absorbs the heat generated by the fire, and the fireproof glue layer can also bond the broken glass piece to maintain the integrity of the glass as a whole.
  • the common fireproof glue for composite fireproof glass is a mixture of water and water glass.
  • the fireproof glue layer prepared by using the fireproof glue liquid has a large amount of microbubbles.
  • the main reason is: fireproof glue formed by mixing water and water glass.
  • the viscosity of the liquid is large, and it is easy to form a large amount of micro during the process of injecting the fireproof layer.
  • Foaming, and the above microbubbles are difficult to eliminate using an antifoaming agent.
  • the generation of microbubbles not only affects the light transmittance and aesthetics of the composite fireproof glass, but also reduces the hardness and fire and heat insulation of the fireproof glue layer, which seriously affects the use effect and service life of the fireproof glass.
  • Chinese patent document CN105131761A discloses a fireproof liquid for composite fireproof glass, which is prepared by mixing a polyol, a functional monomer, a heat resistant stabilizer, a curing agent, a carbon forming agent and deionized water.
  • the first mixed emulsion is prepared by stirring; the first mixed emulsion is mixed with the hydrophilic nano silica particles, and the nano silica particle dispersed emulsion is obtained by stirring; styrene, methyl methacrylate and butyl acrylate are prepared; Mixing and stirring to obtain a second mixed monomer emulsion; adding a second mixed monomer emulsion, an emulsifier, a crosslinking agent and deionized water to the nano silica particle dispersion emulsion, and heating to 60 ° C - 65 °C, then adding a redox initiator to the nano silica particle dispersion emulsion, so that the nano silica particles are externally wrapped with an inner shell layer to obtain a low soap seed emulsion; acrylic acid, styrene, methyl methacrylate And butyl acrylate are mixed and stirred to obtain a third mixed monomer emulsion; the third mixed monomer emulsion
  • the above technique performs primary shell-forming modification of the silica particles by using the first mixed emulsion and the second mixed emulsion, and further performs secondary shell-forming modification by using the third mixed emulsion, and when it forms a fireproof glue with potassium hydroxide.
  • the formation of silicon hydroxy groups is reduced, thereby reducing the partial viscosity of the fireproof glue, thereby reducing the amount of microbubbles formed by the fireproof glue during the process of injecting the fire barrier layer.
  • the light transmittance and fireproof performance of the fireproof glue are improved, and the hardness of the fireproof glue layer is also increased.
  • Ultra-thin composite fire-resistant glass refers to composite fire-resistant glass with a fire-proof layer thickness of less than 1mm. Because in the industry, it is necessary to use a height difference to inject the fire-proof glue into the cavity between the two glasses, so the thickness of the fire-proof glue layer is smaller.
  • the viscosity of the fireproof glue is required to be smaller, but the particles of the two-layer core-shell structure in the above fireproof glue are structurally belonging to the positive core-shell structure particles, and the structure does not have thixotropic properties, so that the fireproof glue system
  • the viscosity is still large enough to meet the requirements of ultra-thin composite fire-resistant glass, and it can only prepare composite fire-resistant glass with a fire-proof layer thickness of 1 mm or more.
  • the technical problem to be solved by the present invention is to overcome the problem that the viscosity of the fireproof glue in the prior art is too large to prepare an ultra-thin composite fireproof glass with a fireproof layer of less than 1 mm, thereby providing a fireproof glue liquid matrix and preparation thereof.
  • Method and fireproof glue and preparation method thereof is to overcome the problem that the viscosity of the fireproof glue in the prior art is too large to prepare an ultra-thin composite fireproof glass with a fireproof layer of less than 1 mm, thereby providing a fireproof glue liquid matrix and preparation thereof.
  • a fireproof glue matrix comprising silica and further comprising a lubricating material which is a copolymer of an aromatic olefin and/or an acrylate.
  • the aromatic olefin is styrene; and the acrylate is butyl acrylate.
  • the lubricating substance is particles.
  • the fireproof glue matrix is made of silica as a core, and has an inner shell layer coated on the outer layer of the silica, and is coated on the inner shell.
  • An outer layer of the outer layer, the lubricating material being present at least between the inner shell layer and the silicon dioxide.
  • the lubricating substance is also present in the inner shell layer.
  • the inner shell layer is a polymer formed by one or more of acrylic acid, methacrylic acid and polyacrylamide;
  • the outer shell layer is a polymer formed by the initiation of acrylic acid, styrene, and butyl acrylate.
  • the silica is of a nanometer scale, having a particle diameter of 60-150 nm and a specific surface area of 60-120 m 2 /g.
  • the fireproof glue matrix is spherical.
  • a method of preparing a fireproof glue matrix comprising the steps of:
  • the redox initiator is a mixture of ammonium persulfate and sodium hydrogen sulfite in a molar ratio of 1:1; the crosslinking agent is 1,2-two. Vinyl benzene.
  • the aromatic olefin is styrene; and the acrylate is butyl acrylate.
  • the mass ratio of glycerin, polymerized monomer and water in the mixture of inner shell material is 15-20:2-25:35-50;
  • the mass ratio of the inner shell material mixture, the nano silica particles, the redox initiator is 30-50:20-60:0.01-0.04;
  • the mass ratio of the soap-free seed emulsion, the lubricating monomer, the redox initiator and the water is 50-100:1-5:0.01-0.05:1-10;
  • the mass ratio of the soap-free single-shell emulsion, the crosslinking monomer, the crosslinking agent, the redox initiator and the water is 60-110:1-10:0.01-0.05:0.0125-0.05:1 -10.
  • the polymerization monomer is acrylic acid, methacrylic acid and polyacrylamide, and the mass ratio thereof is 2-10: 0.01-10: 0.01-5;
  • the lubricating monomer is styrene and butyl acrylate, the mass ratio of the styrene and butyl acrylate is 30-45: 30-40;
  • the crosslinking monomer is acrylic acid, styrene and butyl acrylate in a mass ratio of 15-20:50-70:10-15.
  • the step (1) further comprises the steps of adding a carbon forming agent, a polyol, a heat stabilizer, a curing agent and potassium hydroxide.
  • the inner shell material mixture contains glycerin, a polymerizable monomer, a carbon forming agent, a polyol, a heat stabilizer, a curing agent, potassium hydroxide and water.
  • the mass ratio is 15-20:2-25:0.01-3:0.02-4:0.01-0.6:0.01-0.1:0.01-0.2:35-50;
  • the char forming agent is one or more of sucrose, fructose, glucose and granulated sugar;
  • the heat stabilizer is borax and/or boric acid
  • the curing agent is one or more of sodium fluorosilicate, potassium fluorosilicate and aluminum fluoride;
  • the polyol is xylitol and/or pentaerythritol.
  • the method further comprises the step of mixing the crosslinking monomers in advance;
  • step (4) the step of swelling the soap-free core-shell emulsion with a crosslinking monomer, water and a crosslinking agent is further included.
  • a fireproof glue comprising the fireproof glue matrix of the present invention.
  • the fireproof glue further comprises potassium hydroxide.
  • the mass ratio of the fireproof glue matrix to the potassium hydroxide is 70-75:2-15.
  • the fireproof glue further comprises a char forming aid, an ion fixing agent, an antifoaming agent and a curing agent.
  • the mass ratio of the fireproof glue matrix, the potassium hydroxide, the char forming aid, the ion fixing agent, the defoaming agent and the curing agent is 70-75:2-15:0.01- 0.2: 0.01-0.1: 0.01-0.05: 0.01-0.2.
  • a method for preparing a fireproof glue comprising the steps of preparing the fireproof glue matrix, and further comprising the steps of:
  • the fireproof glue matrix is mixed with potassium hydroxide to obtain the fireproof glue.
  • the method further comprises adding a carbonization aid, leaving a step of a sub-fixing agent, an antifoaming agent and a curing agent;
  • the char forming aid is one or more of potassium dihydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate and sodium hydrogen phosphate;
  • the ion fixing agent is one or more of zinc oxide, aluminum oxide and starch;
  • the antifoaming agent is a polyether modified silicone or polyurethane auxiliary
  • the curing agent is one or more of sodium fluorosilicate, potassium fluorosilicate, and aluminum fluoride.
  • the method for preparing the fireproof glue further comprises the step of stirring and defoaming at a vacuum of 10-40 mbar.
  • the fireproof glue matrix of the present invention focusing on the modification of the nano silica particles by using a lubricating material formed of a copolymer of an aromatic olefin and/or an acrylate, which has high elasticity due to the lubricating property.
  • a lubricating material formed of a copolymer of an aromatic olefin and/or an acrylate, which has high elasticity due to the lubricating property.
  • the fireproof glue matrix of the present invention which has silica as a core and externally modified two shell layers, on the basis of which an aromatic olefin is disposed between the silica and the inner shell layer.
  • a lubricating oil formed by a copolymer of acrylate having a higher elasticity which increases the relative deformation of the silica particles and the inner shell layer, thereby increasing the thixotropy of the entire fireproof glue matrix. Therefore, the fireproof glue formed by the combination of potassium hydroxide or sodium hydroxide has a very good thixotropy, so that the viscosity of the fireproof glue is very low.
  • the method for preparing a fireproof glue matrix according to the present invention after the nano-silica forms an inner shell layer, a lubricating monomer is added, and the amphiphilicity of the lubricating monomer is utilized to make it enter the nano-oxidation. A droplet-like morphology is formed between the silicon and the inner shell layer, and then formed in the subsequent polymerization.
  • the granular lubricity avoids the encapsulation of the lubricity sheet outside the nano-silica, ensuring the formation of a fire-resistant glue matrix with high thixotropic properties.
  • a fireproof glue according to the present invention which is characterized in that the fireproof glue matrix of the present invention is mixed with potassium hydroxide to form a low-viscosity fireproof glue, and the viscosity of the fireproof glue prepared by the above method is only 50-1000cp, can be used to prepare composite fireproof glass with fireproof layer thickness less than 1mm, and the fireproof layer prepared by the above fireproof glue has the advantages of good fireproof and heat insulation performance, high hardness, high transmittance and good UV resistance. .
  • Figure 1 is a schematic view showing the structure of a fireproof glue matrix prepared in Examples 4 and 8 of the present invention
  • Figure 2 is an electron micrograph of the fireproof glue prepared in Examples 4 and 8 of the present invention.
  • redox initiator Preparation of redox initiator: mixing ammonium persulfate with sodium bisulfite in a molar ratio of 1:1 The mixture was stirred well to obtain a redox type initiator.
  • This embodiment provides a method for preparing a fireproof glue matrix, comprising the following steps:
  • the polymerization monomer includes a mass ratio of 2:0.01. : 0.01% acrylic acid, methacrylic acid and polyacrylamide;
  • the soap-free seed emulsion, deionized water and lubricating monomer heating to 65 ° C, introducing nitrogen gas, adding a redox initiator at a speed of 250 rpm, lubricating the monomer to penetrate and pass through the inner shell layer, The lubricant is polymerized for 30 minutes under the action of a redox initiator to form a lubricity, and a soap-free single-shell emulsion is obtained.
  • the lubricating monomer is prepared by mixing styrene and butyl acrylate at a mass ratio of 30:30, soap-free seed emulsion, and lubrication.
  • the mass ratio of the monomer, the redox initiator and the deionized water is 50:1:0.01:5;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and The mass ratio of ionized water is 60:1:0.01:0.05:10.
  • This embodiment provides a method for preparing a fireproof glue matrix, comprising the following steps:
  • the polymerization monomer comprises a mass ratio of 10:10. : 5 acrylic acid, methacrylic acid and polyacrylamide;
  • the lubricating monomer is prepared by mixing styrene and butyl acrylate at a mass ratio of 45:40, a soap-free seed emulsion, a lubricating monomer, a redox initiator and The mass ratio of deionized water is 100:1:0.05:5;
  • the cross-linking monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 20:70:15,
  • the mass ratio of the soap single-shell emulsion, the crosslinking monomer, the 1,2-divinylbenzene, the redox initiator and the deionized water is 110:10:0.01:0.0125:10.
  • This embodiment provides a method for preparing a fireproof glue matrix, comprising the following steps:
  • the mass ratio of glycerin, polymer monomer, sucrose, polyol, heat stabilizer, sodium fluorosilicate, potassium hydroxide and deionized water is 15:25:2:2:0.3:0.05:0.1: 40 mixing, stirring evenly, preparing a mixture of inner shell material, in this step, the polymerized monomer comprises acrylic acid, methacrylic acid and polyacrylamide in a mass ratio of 10:0.01:5, and the polyol comprises a mass ratio of 1:1.
  • Xylitol and pentaerythritol, heat stabilizers include borax and boric acid in a mass ratio of 1:1;
  • silica particles with a particle size of 60 nm with the inner shell material mixture after ultrasonic dispersion, standing for 24 h, heating to 65 ° C, and adding a redox initiator after being purged with nitrogen at a rotation speed of 250 rpm.
  • polymerization for 30min the polymerization monomer is polymerized by the action of redox initiator, and polymerized outside the nano silica particles to form an inner shell layer to obtain a soap-free seed emulsion.
  • the mass ratio of the silica particles to the redox initiator is 50:60:0.01;
  • the soap-free seed emulsion, deionized water and lubricating monomer heating to 65 ° C, introducing nitrogen gas, adding a redox initiator at a speed of 250 rpm, lubricating the monomer to penetrate and pass through the inner shell layer, The lubricant is polymerized for 30 min under the action of a redox initiator to form a lubricity, and a soap-free single-shell emulsion is obtained.
  • the lubricating monomer is composed of styrene and butyl acrylate at a mass ratio of 30:40. Mixed, the mass ratio of soap-free seed emulsion, lubricating monomer, redox initiator and deionized water is 50:1:0.05:5;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 20:70:15, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the water mass ratio is 110:1:0.01:0.0125:1.
  • This embodiment provides a method for preparing a fireproof glue matrix, comprising the following steps:
  • the polymerization monomer comprises a mass ratio of 1:1. : 1 of acrylic acid, methacrylic acid and polyacrylamide;
  • the lubricating monomer is composed of styrene and The butyl acrylate is mixed at a mass ratio of 35:30, and the mass ratio of the soap-free seed emulsion, the lubricating monomer, the redox initiator and the deionized water is 100:2:0.01:5;
  • FIG. 1 is a schematic structural view of a fireproof glue matrix
  • FIG. 2 is an electron micrograph of the fireproof glue matrix, and the crosslinked single sheet in this step
  • the body is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionized water.
  • the mass ratio is 107:10:0.01:0.0125:10.
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, polymerized monomer, fructose, xylitol, borax, sodium fluorosilicate, potassium hydroxide and deionized water is 15:2:0.01:0.02:0.01:0.1:0.2:50 Mixing and stirring uniformly to obtain a mixture of inner shell material.
  • the polymerizable monomer comprises acrylic acid, methacrylic acid and polyacrylamide in a mass ratio of 2:0.01:0.01;
  • the soap-free seed emulsion, deionized water and lubricating monomer heating to 65 ° C, introducing nitrogen gas, adding a redox initiator at a speed of 250 rpm, lubricating the monomer to penetrate and pass through the inner shell layer, The lubricant is polymerized for 30 minutes under the action of a redox initiator to form a lubricity, and a soap-free single-shell emulsion is obtained.
  • the lubricating monomer is prepared by mixing styrene and butyl acrylate at a mass ratio of 30:30, soap-free seed emulsion, and lubrication.
  • the mass ratio of the monomer, the redox initiator and the deionized water is 50:1:0.01:5;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the water mass ratio is 60:1:0.01:0.05:10;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, polymerized monomer, fructose, xylitol, boric acid, sodium fluorosilicate, potassium hydroxide and deionized water is 20:25:3:4:0.6:0.01:0.01:35 Mixing and stirring uniformly to obtain a mixture of inner shell material.
  • the polymerized monomer comprises acrylic acid, methacrylic acid and polyacrylamide in a mass ratio of 10:10:5;
  • silica particles with a particle size of 80 nm with the inner shell material mixture after ultrasonic dispersion, standing for 24 h, heating to 65 ° C, and adding a redox initiator at a rotation speed of 250 rpm under nitrogen gas protection.
  • polymerization for 30min the polymerization monomer is polymerized by the action of redox initiator, and polymerized outside the nano silica particles to form an inner shell layer to obtain a soap-free seed emulsion.
  • the mass ratio of the silica particles to the redox initiator is 50:20:0.04;
  • the lubricating monomer is prepared by mixing styrene and butyl acrylate at a mass ratio of 45:40, a soap-free seed emulsion, a lubricating monomer, a redox initiator and The mass ratio of deionized water is 100:1:0.05:5;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the fireproof glue matrix prepared in Example 3 was mixed with potassium hydroxide, stirred for 20 min, and then potassium dihydrogen phosphate, starch, polyether modified silicone and sodium fluorosilicate were sequentially added, and stirred under a vacuum of 40 mbar for 30 min. Eliminate the bubbles in the liquid, keep the vacuum cooling to room temperature, then slowly increase the pressure to return to normal pressure, after standing and defoaming, filter with 100 mesh screen to obtain fireproof glue.
  • the fireproof glue matrix and hydrogen The mass ratio of potassium oxide, potassium dihydrogen phosphate, starch, polyether modified silicone and sodium fluorosilicate is 75:10:0.01:0.035:0.01:0.15.
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, polymer monomer, sucrose, polyol, heat stabilizer, sodium fluorosilicate, potassium hydroxide and deionized water is 15:6:1:2:0.6:0.05:0.15: 30 mixing, stirring evenly, to obtain a mixture of inner shell material, the polymerized monomer in this step comprises acrylic acid, methacrylic acid and polyacrylamide in a mass ratio of 1:1:1, and the polyol comprises a mass ratio of 1:1.
  • Xylitol and pentaerythritol, heat stabilizers include borax and boric acid in a mass ratio of 1:1;
  • the lubricating monomer is mass ratio of styrene and butyl acrylate. For mixing 35:30, the mass ratio of soap-free seed emulsion, lubricating monomer, redox initiator and deionized water is 100:2:0.01:5;
  • FIG. 1 is a schematic structural view of the fireproof glue matrix particles
  • FIG. 2 is an electron micrograph of the fireproof glue matrix, which is crosslinked in this step.
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the water mass ratio is 107:10:0.01:0.0125:10;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, polymer monomer, sucrose, polyol, heat stabilizer, sodium fluorosilicate, potassium hydroxide and deionized water is 15:6:1:2:0.6:0.05:0.15: 30 mixing, stirring evenly, to obtain a mixture of inner shell material, the polymerizable monomer in this step includes acrylic acid, methacrylic acid and polyacrylamide in a mass ratio of 2:10:0.1, and the polyol comprises a mass ratio of 1:1.
  • Xylitol and pentaerythritol, heat stabilizers include borax and boric acid in a mass ratio of 1:1;
  • the soap-free seed emulsion, deionized water and lubricating monomer heating to 65 ° C, introducing nitrogen gas, adding a redox initiator at a speed of 250 rpm, lubricating the monomer to penetrate and pass through the inner shell layer, Polymerization under the action of a redox initiator for 30 min to form a lubricating substance, resulting in no Soap single-shell emulsion, the lubricating monomer in this step is prepared by mixing styrene and butyl acrylate at a mass ratio of 30:40.
  • the mass ratio of soap-free seed emulsion, lubricating monomer, redox initiator and deionized water is 80:5:0.03:5;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 20:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the water mass ratio is 107:10:0.01:0.0125:10;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, polymer monomer, sucrose, polyol, heat stabilizer, sodium fluorosilicate, potassium hydroxide and deionized water is 15:6:1:2:0.6:0.05:0.15: 30 mixed, stirred evenly to obtain a mixture of inner shell material.
  • the polymerized monomer includes acrylic acid, methacrylic acid and polyacrylamide in a mass ratio of 2:10:5, and the polyol includes a mass ratio of 1:1.
  • Xylitol and pentaerythritol, heat stabilizers include borax and boric acid in a mass ratio of 1:1;
  • the soap-free seed emulsion, deionized water and lubricating monomer heating to 65 ° C, introducing nitrogen gas, adding a redox initiator at a speed of 250 rpm, lubricating the monomer to penetrate and pass through the inner shell layer, The lubricant is polymerized for 30 minutes under the action of a redox initiator to form a lubricity, and a soap-free single-shell emulsion is obtained.
  • the lubricating monomer is prepared by mixing styrene and butyl acrylate at a mass ratio of 30:40, soap-free seed emulsion, and lubrication.
  • the mass ratio of monomer, redox initiator and deionized water is 60:4:0.04:2;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 20:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the water mass ratio is 70:5:0.03:0.03:5;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the lubricating monomer is mass ratio of styrene and butyl acrylate. For mixing 35:30, the mass ratio of soap-free seed emulsion, lubricating monomer, redox initiator and deionized water is 70:2:0.01:5;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the water mass ratio is 80:10:0.01:0.0125:10;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, methacrylic acid, sucrose, polyol, heat stabilizer, sodium fluorosilicate, potassium hydroxide and deionized water is 15:6:1:2:0.6:0.05:0.15: 30 mixing, stirring evenly, to obtain a mixture of inner shell material, the polyol in this step comprises xylitol and pentaerythritol in a mass ratio of 1:1, and the heat stabilizer comprises borax and boric acid in a mass ratio of 1:1;
  • the lubricating monomer is mass ratio of styrene and butyl acrylate.
  • the mass ratio of soap-free seed emulsion, lubricating monomer, redox initiator and deionized water is 75:2:0.01:5;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the mass ratio of water is 100:10:0.01:0.0125:10;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, polyacrylamide, sucrose, polyol, heat stabilizer, sodium fluorosilicate, potassium hydroxide and deionized water is 15:6:1:2:0.6:0.05:0.15: 30 mixing, stirring evenly, to obtain a mixture of inner shell material, the polyol in this step comprises xylitol and pentaerythritol in a mass ratio of 1:1, and the heat stabilizer comprises borax and boric acid in a mass ratio of 1:1;
  • the lubricating monomer is mass ratio of styrene and butyl acrylate.
  • the mass ratio of soap-free seed emulsion, lubricating monomer, redox initiator and deionized water is 90:2:0.01:5;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and The mass ratio of ionized water is 100:10:0.01:0.0125:10;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, polymer monomer, sucrose, polyol, heat stabilizer, sodium fluorosilicate, potassium hydroxide and deionized water is 15:6:1:2:0.6:0.05:0.15: 30 mixing, stirring evenly, to obtain a mixture of inner shell material, the polymerized monomer in this step includes acrylic acid and methacrylic acid with a mass ratio of 1:1, and the polyol includes xylitol and pentaerythritol with a mass ratio of 1:1, heat The stabilizer includes borax and boric acid in a mass ratio of 1:1;
  • the lubricating monomer is mass ratio of styrene and butyl acrylate.
  • the mass ratio of soap-free seed emulsion, lubricating monomer, redox initiator and deionized water is 95:2:0.01:5;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the water mass ratio is 110:10:0.01:0.0125:10;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the polymerization monomer includes a mass ratio of 1 : 1 of acrylic acid and polyacrylamide
  • the polyol comprises xylitol and pentaerythritol in a mass ratio of 1:1
  • the heat stabilizer comprises borax and boric acid in a mass ratio of 1:1;
  • the lubricating monomer is mass ratio of styrene and butyl acrylate.
  • the mass ratio of soap-free seed emulsion, lubricating monomer, redox initiator and deionized water is 100:2:0.02:3;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization. Water The mass ratio is 95:8:0.04:0.04:4;
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the fireproof glue liquid base prepared in Example 1 was mixed with potassium hydroxide, stirred for 20 minutes, and then potassium dihydrogen phosphate, starch, polyether modified silicone and sodium fluorosilicate were sequentially added, and stirred under a vacuum of 20 mbar for 30 minutes. Eliminate the bubbles in the liquid, keep the vacuum cooling to room temperature, then slowly increase the pressure to return to normal pressure, after standing and defoaming, filter with 100 mesh screen to obtain fireproof glue.
  • the fireproof glue matrix and hydrogen The mass ratio of potassium oxide, potassium dihydrogen phosphate, starch, polyether modified silicone and sodium fluorosilicate is 70:10:0.1:0.05:0.02:0.02.
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the fireproof glue matrix prepared in Example 2 was mixed with potassium hydroxide, stirred for 20 min, and then potassium dihydrogen phosphate, starch, polyether modified silicone and sodium fluorosilicate were sequentially added, and stirred under a vacuum of 20 mbar for 30 min. Eliminate the bubbles in the liquid, keep the vacuum cooling to room temperature, then slowly increase the pressure to return to normal pressure, after standing and defoaming, filter with 100 mesh screen to obtain fireproof glue.
  • the fireproof glue matrix and hydrogen Potassium oxide, potassium dihydrogen phosphate, starch, polyether modification The mass ratio of silicone to sodium fluorosilicate is 70:10:0.1:0.05:0.02:0.02.
  • This embodiment provides a method for preparing a fireproof glue, comprising the following steps:
  • the fireproof glue liquid base prepared in Example 4 was mixed with potassium hydroxide, stirred for 20 minutes, and then potassium dihydrogen phosphate, starch, polyether modified silicone and sodium fluorosilicate were sequentially added, and stirred under a vacuum of 20 mbar for 30 minutes. Eliminate the bubbles in the liquid, keep the vacuum cooling to room temperature, then slowly increase the pressure to return to normal pressure, after standing and defoaming, filter with 100 mesh screen to obtain fireproof glue.
  • the fireproof glue matrix and hydrogen The mass ratio of potassium oxide, potassium dihydrogen phosphate, starch, polyether modified silicone and sodium fluorosilicate is 70:10:0.1:0.05:0.02:0.02.
  • This comparative example provides a method for preparing a fireproof glue, comprising the following steps:
  • the mass ratio of glycerin, polymer monomer, sucrose, polyol, heat stabilizer, sodium fluorosilicate, potassium hydroxide and deionized water is 15:6:1:2:0.6:0.05:0.15: 30 mixing, stirring evenly, the polymerization monomer in this step includes acrylic acid, methacrylic acid and polyacrylamide in a mass ratio of 1:1:1, and the polyol includes xylitol and pentaerythritol in a mass ratio of 1:1, heat stabilizer Including borax and boric acid with a mass ratio of 1:1;
  • the monomer is formed by mixing acrylic acid, styrene and butyl acrylate at a mass ratio of 15:50:10, soap-free single-shell emulsion, crosslinking monomer, 1,2-divinylbenzene, redox initiator and deionization.
  • the water mass ratio is 107:10:0.01:0.0125:10;
  • the fireproof glue prepared by the embodiment 5 is poured into each cavity layer by layer, and is allowed to stand, defoam and seal;
  • the above-mentioned perfused glass is placed in an autoclave and pressurized to 0.5 MPa, and simultaneously heated to about 80 ° C for 120 min, cooled to room temperature, and taken out to obtain a composite fireproofing with 5 layers of glass and 4 layers of fireproof layer.
  • Glass, the composite fireproof glass number is 1, wherein each layer of fireproof layer has a thickness of 0.75 mm;
  • the fireproof layer is prepared as a composite fireproof glass which is prepared by the fireproof glue prepared in Examples 5-18, and the corresponding composite fireproof glass has the corresponding number 2-14.
  • the fireproof performance test of the composite fireproof glass with the number 1-14 is tested.
  • the test results are shown in Table 2; according to the Chinese national standard "GB15763.1-2009 safety glass for construction part 1" : Fireproof Glass: The UV-resistant irradiation time of the composite fireproof glass with the number 1-14 is tested.
  • the test results are shown in Table 2; according to the Chinese national standard "GB 15763.1-2009 Building Safety Glass Part 1: Fireproof Glass”
  • the transmittance of the composite fireproof glass with the number 1-14 is tested.
  • the test results are shown in Table 2.
  • the apparent quality of the composite fireproof glass with the number 1-14 is obtained by visual observation. The results are shown in Table 2;
  • the UV-resistant time of composite fire-resistant glass No. 1-14 is longer than the UV-resistant time specified in the national standard GB15763.1-2009 Building Safety Glass Part 1: Fire-resistant Glass.

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Abstract

一种防火胶液基质，含二氧化硅，还包含有润滑质，所述润滑质为芳香族烯烃和/或丙烯酸脂类的共聚物。还涉及一种防火胶液，包括所述的防火胶液基质。还涉及一种防火胶液基质制备方法和防火胶液制备方法。本发明制备的防火胶液的粘度仅为50-1000cp，可以用于制备防火层厚度为小于1mm的复合防火玻璃，且由上述防火胶液制备的防火层具有防火隔热性能好、硬度大、透过率高和耐紫外性能好的优点。

Description

一种防火胶液基质及其制备方法和防火胶液及其制备方法 技术领域
本发明涉及防火胶液及其制备方法，属于防火安全玻璃领域。
背景技术
防火玻璃是一种具有防火功能的建筑外墙或门窗用玻璃，其不仅具有普通玻璃的常规性能，而且还具有控制火势蔓延、隔烟和隔热等特异性能。目前，防火玻璃主要分为四种：复合防火玻璃、特种防火玻璃、中空防火玻璃和高强度单层铯钾防火玻璃。其中，复合防火玻璃(Laminated Fire-Resistant Glass)具有良好的透光性能，同时因其具有优异的耐火完整性(Integrity，E)和隔热性(Insulation，I)而被归类为A类防火玻璃，在火灾中可以使逃生人员和救援人员免遭热辐射伤害，并能将火灾的破坏力降低到最小程度。
从结构上来讲，现有的复合式防火玻璃是由两层或两层以上的玻璃、以及夹在玻璃之间的透明防火胶液层组成；当遇到火灾时，防火胶液层会迅速发泡膨胀，形成绝热的耐火隔热泡沫层，吸收火灾产生的热量，同时防火胶液层还可以粘结破碎的玻璃片，以保持玻璃整体的完整性。
目前，常用的复合防火玻璃专用防火胶液为水和水玻璃的混合物，采用该防火胶液所制备的防火胶液层存在大量微泡，主要原因是：水和水玻璃混合后形成的防火胶液粘度大，在灌注防火层过程中容易形成大量的微 泡，且上述微泡难于使用消泡剂消除。然而微泡的产生不仅会影响复合防火玻璃的透光率和美观性，而且会降低防火胶液层的硬度和耐火隔热性，严重影响防火玻璃的使用效果和使用寿命。
为此，中国专利文献CN105131761A公开了一种复合防火玻璃的防火液，其制备方法为，将多元醇、功能单体、耐热稳定剂、固化剂、成碳剂及去离子水进行混合，经搅拌制得第一混合乳液；将第一混合乳液与亲水性纳米二氧化硅颗粒进行混合，经搅拌制得纳米二氧化硅颗粒分散乳液；将苯乙烯、甲基丙烯酸甲酯及丙烯酸丁酯进行混合，经搅拌制得第二混合单体乳液；将第二混合单体乳液、乳化剂、交联剂及去离子水加入到纳米二氧化硅颗粒分散乳液中，并加热至60℃-65℃，再向纳米二氧化硅颗粒分散乳液中加入氧化还原型引发剂，使纳米二氧化硅颗粒外部包裹一层内壳层，得到低皂种子乳液；将丙烯酸、苯乙烯、甲基丙烯酸甲酯及丙烯酸丁酯进行混合，经搅拌制得第三混合单体乳液；将第三混合单体乳液、乳化剂、去离子水、氧化还原型引发剂及交联剂加入到低皂种子乳液中，在60℃-65℃反应3-5小时，使内壳层的外部包裹外壳层，从而形成两层核壳结构，得到低皂核壳乳液；将低皂核壳乳液和氢氧化钾水溶液进行混合，再加入成碳助剂、离子固定剂、消泡剂、流平剂及固化剂，经搅拌，静置，再过滤，所得滤液为复合防火玻璃的防火液。
上述技术通过使用第一混合乳液、第二混合乳液对二氧化硅颗粒进行一级成壳修饰，并进一步利用第三混合乳液进行二级成壳修饰，当其与氢氧化钾生成防火胶液的过程中，减少了硅羟基的形成，进而降低了防火胶液的部分粘度，从而减少了防火胶液在灌注防火层过程中形成的微泡的量， 提高了防火胶液的透光率和防火隔热性能，同时也增加了防火胶液层的硬度。
超薄型复合防火玻璃是指防火层厚度小于1mm的复合防火玻璃，因为工业中，需要采用高度差将防火胶液灌注到两块玻璃之间的空腔中，所以防火胶液层厚度越小，就要求防火胶液粘度越小，但是，上述防火胶液中的两层核壳结构的粒子，从结构上属于正向核壳结构粒子，这种结构不具有触变性，使得防火胶液体系粘度任然较大，无法满足超薄型复合防火玻璃的要求，其仅能制备防火层厚度在1mm以上的复合防火玻璃。
发明内容
因此，本发明所要解决的技术问题在于克服现有技术中的防火胶液粘度过大，无法制备防火层小于1mm的超薄复合防火玻璃的问题，从而提供了一种防火胶液基质及其制备方法和防火胶液及其制备方法。
一种防火胶液基质，含二氧化硅，还包含有润滑质，所述润滑质为芳香族烯烃和/或丙烯酸脂类的共聚物。
优选的是，所述的防火胶液基质中，所述芳香族烯烃为苯乙烯；所述丙烯酸脂类为丙烯酸丁酯。
优选的是，所述的防火胶液基质中，所述润滑质为颗粒。
优选的是，所述的防火胶液基质中，所述防火胶液基质以二氧化硅为核心，成型有包覆于所述二氧化硅外的内壳层，以及包覆在所述内壳层外的外壳层，所述润滑质至少存在于内壳层和二氧化硅之间。
优选的是，所述的防火胶液基质中，所述润滑质还存在于所述内壳层。
优选的是，所述的防火胶液基质中，所述内壳层是由丙烯酸、甲基丙烯酸和聚丙烯酰胺中的一种或几种引发形成的聚合物；
所述外壳层是由丙烯酸、苯乙烯和丙烯酸丁酯引发形成的聚合物。
优选的是，所述的防火胶液基质中，所述二氧化硅为纳米级别，其粒径为60-150nm，比表面积为60-120m2/g。
优选的是，所述的防火胶液基质中，所述的防火胶液基质为球形。
一种制备防火胶液基质的方法，其包括如下步骤：
(1)将甘油、聚合单体和水混合，制得内壳层材料混合液，其中，所述聚合单体为丙烯酸、甲基丙烯酸和聚丙烯酰胺中的一种或几种；
(2)在惰性气体保护下，向内壳层材料混合液中加入纳米二氧化硅颗粒和氧化还原引发剂，所述聚合单体在所述氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液；
(3)向所述无皂种子乳液中加入润滑单体、水和氧化还原引发剂，所述润滑单体，在所述氧化还原引发剂的作用下聚合形成润滑质，得到无皂单壳乳液，其中，所述润滑单体为芳香族烯烃和/或丙烯酸脂类；
(4)向所述无皂单壳乳液中加入交联单体、水、交联剂混合，再加入氧化还原引发剂，所述交联单体在所述交联剂和氧化还原引发剂的作用下交联，在所述内壳层的外部形成外壳层，得到防火胶液基质；其中所述交联单体为丙烯酸、苯乙烯和丙烯酸丁酯。
优选的是，所述的防火胶液基质制备方法中，所述氧化还原引发剂为摩尔比1:1的过硫酸铵与亚硫酸氢钠的混合物；所述交联剂为1,2-二乙烯基苯。
优选的是，所述的防火胶液基质制备方法中，所述步骤(3)中，所述芳香族烯烃为苯乙烯；所述丙烯酸脂类为丙烯酸丁酯。
优选的是，所述的防火胶液基质制备方法中，
所述步骤(1)中，所述内壳层材料混合液中甘油、聚合单体和水的质量比为15-20：2-25：35-50；
所述步骤(2)中，内壳层材料混合液、纳米二氧化硅颗粒、氧化还原引发剂的质量比30-50:20-60:0.01-0.04；
所述步骤(3)中，无皂种子乳液、润滑单体、氧化还原引发剂与水的质量比50-100:1-5:0.01-0.05:1-10；
所述步骤(4)中，无皂单壳乳液、交联单体、交联剂、氧化还原引发剂与水的质量比为60-110：1-10：0.01-0.05：0.0125-0.05：1-10。
优选的是，所述的防火胶液基质制备方法中，
所述聚合单体为丙烯酸、甲基丙烯酸和聚丙烯酰胺，其质量比为2-10:0.01-10:0.01-5；
所述润滑单体为苯乙烯和丙烯酸丁酯，所述苯乙烯和丙烯酸丁酯的质量比为30-45:30-40；
所述交联单体为丙烯酸、苯乙烯和丙烯酸丁酯，其质量比为15-20:50-70:10-15。
优选的是，所述的防火胶液基质制备方法中，所述步骤(1)中还包括加入成炭剂、多元醇、热稳定剂、固化剂和氢氧化钾的步骤。
优选的是，所述的防火胶液基质制备方法中，所述内壳层材料混合液中甘油、聚合单体、成炭剂、多元醇、热稳定剂、固化剂、氢氧化钾和水 的质量比为15-20：2-25：0.01-3：0.02-4：0.01-0.6：0.01-0.1：0.01-0.2：35-50；
其中，所述成炭剂为蔗糖、果糖、葡萄糖和砂糖中的一种或几种；
所述热稳定剂为硼砂和/或硼酸；
所述固化剂为氟硅酸钠、氟硅酸钾和氟化铝中的一种或几种；
所述多元醇为木糖醇和/或季戊四醇。
优选的是，所述的防火胶液基质制备方法中，
所述步骤(4)中，还包括将所述交联单体提前混合的步骤；
所述步骤(4)中，还包括将所述无皂核壳乳液与交联单体、水和交联剂混合后，进行溶胀的步骤。
一种防火胶液，包括本发明所述的防火胶液基质。
优选的是，所述的防火胶液中，还包括氢氧化钾。
优选的是，所述的防火胶液中，防火胶液基质与氢氧化钾的质量比为70-75：2-15。
优选的是，所述的防火胶液中，所述防火胶液还包括成炭助剂、离子固定剂、消泡剂和固化剂。
优选的是，所述的防火胶液中，防火胶液基质、氢氧化钾、成炭助剂、离子固定剂、消泡剂和固化剂的质量比为70-75：2-15：0.01-0.2：0.01-0.1：0.01-0.05：0.01-0.2。
一种制备防火胶液的方法，其包括上述制备防火胶液基质的步骤，还包括如下步骤：
将所述防火胶液基质与氢氧化钾混合，得到所述防火胶液。
优选的是，所述的防火胶液的制备方法中，还包括加入成炭助剂、离 子固定剂、消泡剂和固化剂的步骤；
其中，所述成炭助剂为磷酸二氢钾、磷酸氢钾、磷酸二氢钠及磷酸氢钠中一种或几种；
所述离子固定剂为氧化锌、氧化铝及淀粉中的一种或几种；
所述消泡剂为聚醚改性有机硅或聚氨酯类助剂；
所述固化剂为氟硅酸钠、氟硅酸钾和氟化铝中的一种或几种。
优选的是，所述的防火胶液的制备方法中，还包括在真空度为10-40mbar下搅拌消泡的步骤。
本发明技术方案，具有如下优点：
1.本发明所述的防火胶液基质，重点在采用由芳香族烯烃和/或丙烯酸脂类的共聚物形成的润滑质对纳米二氧化硅颗粒的修饰，由于润滑质具有较高的弹性，当其与氢氧化钾混合形成防火胶液，增加了防火胶液的触变性，进而大大的降低了防火胶液的粘度。
2.本发明所述的防火胶液基质，其以二氧化硅为核，在其外部修饰两层壳层，在此基础上，在二氧化硅和内壳层之间设置了由芳香族烯烃和/或丙烯酸脂类的共聚物形成的润滑质，该润滑质具有较高的弹性，增加了二氧化硅颗粒与内壳层的相对形变，进而增大了整个防火胶液基质的触变性，所以其与氢氧化钾或氢氧化钠形成的防火胶液触变性非常好，使得防火胶液的粘度非常低。
3.本发明所述的一种防火胶液基质的制备方法，在纳米二氧化硅形成内壳层后，添加了润滑单体，利用润滑单体的双亲性，使其在进入到纳米二氧化硅与内壳层之间形成液滴状的形态，进而在后续的聚合时，形成颗 粒状的润滑质，避免了润滑质成片的包裹在纳米二氧化硅外部，保证了形成的防火胶液基质具有高触变性。
4.本发明所述的一种防火胶液，重点在使用本发明所述防火胶液基质与氢氧化钾混合，生成低粘度的防火胶液，上述方法制备出的防火胶液的粘度仅为50-1000cp，可以用于制备防火层厚度为小于1mm的复合防火玻璃，且由上述防火胶液制备的防火层具有防火隔热性能好、硬度大、透过率高和耐紫外性能好的优点。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例4和8中制备的防火胶液基质的结构示意图；
图2是本发明实施例4和8中制备的防火胶液的电镜图。
具体实施方式
下面将对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结。
配制氧化还原型引发剂：将过硫酸铵与亚硫酸氢钠以摩尔比1:1混 合，搅拌均匀，得到氧化还原型引发剂。
实施例1
本实施例提供了一种防火胶液基质的制备方法，包括如下步骤：
(1)将甘油、聚合单体和去离子水的按质量比为15：2：50混合，搅拌均匀，制备得到内壳层材料混合液，本步骤中聚合单体包括质量比为2:0.01:0.01的丙烯酸、甲基丙烯酸和聚丙烯酰胺；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至60℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为30:60:0.01；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为30:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为50:1:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交 联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为60:1:0.01:0.05:10。
实施例2
本实施例提供了一种防火胶液基质的制备方法，包括如下步骤：
(1)将甘油、聚合单体和去离子水的按质量比为20：25：35混合，搅拌均匀，制备得到内壳层材料混合液，本步骤中聚合单体包括质量比为10:10:5的丙烯酸、甲基丙烯酸和聚丙烯酰胺；
(2)将粒径为100nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为50:20:0.04；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至60℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体在氧化还原引发剂的作用下聚合30min形成润滑质，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为45:40混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为100：1:0.05:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作 用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为20:70:15混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为110：10:0.01:0.0125:10。
实施例3
本实施例提供了一种防火胶液基质的制备方法，包括如下步骤：
(1)将甘油、聚合单体、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：25：2：2：0.3：0.05：0.1：40混合，搅拌均匀，制备得到内壳层材料混合液，本步骤中聚合单体包括质量比为10:0.01:5的丙烯酸、甲基丙烯酸和聚丙烯酰胺，多元醇包括质量比为1:1的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为50:60:0.01；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为30:40 混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为50:1:0.05:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为20:70:15混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为110：1:0.01:0.0125:1。
实施例4
本实施例提供了一种防火胶液基质的制备方法，包括如下步骤：
(1)将甘油、聚合单体和去离子水的按质量比为15：6：30混合，搅拌均匀，制备得到内壳层材料混合液，本步骤中聚合单体包括质量比为1:1:1的丙烯酸、甲基丙烯酸和聚丙烯酰胺；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为40:60:0.01；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿 过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，分布在纳米二氧化硅颗粒与内壳层之间，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为35:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为100:2:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，即含有防火胶液基质的乳液，其中所述防火胶液基质的结构如图1和2所示，图1中为防火胶液基质的结构示意图，图2为防火胶液基质的电镜图，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为107:10:0.01:0.0125:10。
实施例5
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚合单体、果糖、木糖醇、硼砂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：2：0.01：0.02：0.01：0.1：0.2：50混合，搅拌均匀，得到内壳层材料混合液，本步骤中聚合单体包括质量比为2:0.01:0.01的丙烯酸、甲基丙烯酸和聚丙烯酰胺；
(2)将粒径为150nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至60℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的 作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为30:60:0.01；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为30:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为50:1:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为60:1:0.01:0.05:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、氧化锌、聚氨类助剂和氟硅酸钾，在真空度为25mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、氧化锌、聚氨类助剂和氟硅酸钾的质量比为70:2:0.2:0.1:0.05:0.01。
实施例6
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚合单体、果糖、木糖醇、硼酸、氟硅酸钠、氢氧化钾和去离子水的按质量比为20：25：3：4：0.6：0.01：0.01：35混合，搅拌均匀，得到内壳层材料混合液，本步骤中聚合单体包括质量比为10:10:5的丙烯酸、甲基丙烯酸和聚丙烯酰胺；
(2)将粒径为80nm的二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为50:20:0.04；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至60℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体在氧化还原引发剂的作用下聚合30min形成润滑质，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为45:40混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为100：1:0.05:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为20:70:15混合形成， 无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为110：10:0.01:0.0125:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为10mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
实施例7
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
将实施例3制备的防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为40mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为75:10:0.01:0.035:0.01:0.15。
实施例8
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚合单体、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，得到内壳层材料混合液，本步骤中聚合单体包括质量比为1:1:1的丙烯酸、甲基丙烯酸和聚丙烯酰胺，多元醇包括质量比为1:1的 木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为40:60:0.01；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，分布在纳米二氧化硅颗粒与内壳层之间，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为35:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为100:2:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，即含有防火胶液基质的乳液，其中所述防火胶液基质的结构如图1和2所示，图1中为防火胶液基质颗粒的结构示意图，图2为防火胶液基质的电镜图，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为107:10:0.01:0.0125:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
实施例9
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚合单体、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，得到内壳层材料混合液，本步骤中聚合单体包括质量比为2:10：0.1的丙烯酸、甲基丙烯酸和聚丙烯酰胺，多元醇包括质量比为1:1的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为40:50:0.03；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，得到无 皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为30:40混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为80:5:0.03:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为20:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为107：10:0.01:0.0125:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为72:6:0.1:0.1:0.03:0.08。
实施例10
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚合单体、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，得到内壳层材料混合液，本步骤中聚合单体包括质量比为2:10:5的丙烯酸、甲基丙烯酸和聚丙烯酰胺，多元醇包括质量比为1:1 的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至60℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为50:50:0.02；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为30:40混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为60:4:0.04:2；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至60℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为20:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为70:5:0.03:0.03:5；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅 拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为73:9:0.05:0.05:0.02:0.15。
实施例11
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、丙烯酸、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，得到内壳层材料混合液，多元醇包括质量比为1:1的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为40:60:0.01；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，分布在纳米二氧化硅颗粒与内壳层之间，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为35:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为70:2:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为80:10:0.01:0.0125:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
实施例12
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、甲基丙烯酸、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，得到内壳层材料混合液，本步骤中多元醇包括质量比为1:1的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的 作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为35:45:0.04；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，分布在纳米二氧化硅颗粒与内壳层之间，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为35:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为75:2:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为100:10:0.01:0.0125:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
实施例13
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚丙烯酰胺、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，得到内壳层材料混合液，本步骤中多元醇包括质量比为1:1的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为45:25:0.02；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，分布在纳米二氧化硅颗粒与内壳层之间，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为35:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为90:2:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交 联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为100：10:0.01:0.0125:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
实施例14
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚合单体、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，得到内壳层材料混合液，本步骤中聚合单体包括质量比为1:1的丙烯酸和甲基丙烯酸，多元醇包括质量比为1:1的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为40:60:0.01；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，分布在纳米二氧化硅颗粒与内壳层之间，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为35:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为95:2:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为110:10:0.01:0.0125:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02
实施例15
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚合单体、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢 氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，得到内壳层材料混合液，本步骤中聚合单体包括质量比为1:1的丙烯酸和聚丙烯酰胺，多元醇包括质量比为1:1的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的纳米二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，升温至65℃，在转速250rmp下，充氮气保护后，加入氧化还原引发剂，聚合30min，使聚合单体在氧化还原引发剂的作用下发生聚合反应，在纳米二氧化硅颗粒外部聚合形成内壳层，得到无皂种子乳液，本步骤中内壳层材料混合液、纳米二氧化硅颗粒与氧化还原引发剂的质量比为50:60:0.01；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，润滑单体渗透并穿过内壳层，在氧化还原引发剂的作用下聚合30min形成润滑质，分布在纳米二氧化硅颗粒与内壳层之间，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯和丙烯酸丁酯按质量比为35:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为100:2:0.02:3；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水 的质量比为95:8:0.04:0.04:4；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为75:15:0.15:0.1:0.04:0.2。
实施例16
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
将实施例1制备的防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
实施例17
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
将实施例2制备的防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性 有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
实施例18
本实施例提供了一种防火胶液的制备方法，包括如下步骤：
将实施例4制备的防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
对比例
本对比例提供了一种防火胶液的制备方法，包括如下步骤：
(1)将甘油、聚合单体、蔗糖、多元醇、热稳定剂、氟硅酸钠、氢氧化钾和去离子水的按质量比为15：6：1：2：0.6：0.05：0.15：30混合，搅拌均匀，本步骤中聚合单体包括质量比为1:1:1的丙烯酸、甲基丙烯酸和聚丙烯酰胺，多元醇包括质量比为1:1的木糖醇和季戊四醇，热稳定剂包括质量比为1:1的硼砂和硼酸；
(2)将粒径为60nm的二氧化硅颗粒与内壳层材料混合液混合，超声分散后，静置24h，得到无皂种子乳液，本步骤中内壳层材料混合液和纳米二氧化硅颗粒质量比为40:60；
(3)将无皂种子乳液、去离子水和润滑单体混合，升温至65℃，通入氮气，在转速250rmp下，加入氧化还原引发剂，在氧化还原引发剂的作用下聚合30min，得到无皂单壳乳液，本步骤中润滑单体由苯乙烯 和丙烯酸丁酯按质量比为35:30混合而成，无皂种子乳液、润滑单体、氧化还原引发剂和去离子水的质量比为100:2:0.01:5；
(4)将无皂单壳乳液、去离子水、交联单体和1,2-二乙烯基苯混合，搅拌5h，静置溶胀24h以上，升温至65℃，在氮气保护下，加入氧化还原引发剂，再继续保温熟化2h，交联单体在交联剂和氧化还原引发剂的作用下交联，在内壳层的外部形成外壳层，得到防火胶液基质，本步骤中交联单体由丙烯酸、苯乙烯和丙烯酸丁酯按质量比为15:50:10混合形成，无皂单壳乳液、交联单体、1,2-二乙烯基苯、氧化还原引发剂和去离子水的质量比为107:10:0.01:0.0125:10；
(5)将防火胶液基质与氢氧化钾混合，搅拌20min，再依次加入磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠，在真空度为20mbar下搅拌30min，消除液体中气泡，保持该真空度冷却至室温后，再缓慢升压恢复到常压，静置消泡后，用100目筛网过滤后得到防火胶液，本步骤中防火胶液基质、氢氧化钾、磷酸二氢钾、淀粉、聚醚改性有机硅和氟硅酸钠的质量比为70:10:0.1:0.05:0.02:0.02。
效果例
1.粘度检测
采用粘度计对由实施例5-18制备的防火胶液和由对比例制备的防火胶液的粘度进行检测，粘度检测结果见表1。
表1
  粘度(cp)
实施例5 364.2
实施例6 394.6
实施例7 333.2
实施例8 243.4
实施例9 287.9
实施例10 299.7
实施例11 457.8
实施例12 490.1
实施例13 520.9
实施例14 545.3
实施例15 470.8
实施例16 374.2
实施例17 384.6
实施例18 265.4
对比例 2400.5
从表1中可以看出，由实施例5-18制备的防火胶液的粘度值明显低于由对比例制备的防火胶液的粘度值。
2.防火性能、耐紫外线辐照时间和透过率检测
测试玻璃的制备
a、选取5片厚度为4mm的面型为曲面异形结构的玻璃，且每层玻璃的曲面面型一致；
b、在对上述任意一片玻璃的凸起面涂布厚度为0.1mm的单层二氧化硅(SiO2)减反层；
c、利用宽度小于5mm、厚度为0.75mm的耐候性围边密封条将上述 5块玻璃逐一层合，形成四个0.75mm厚的封闭空腔体、每层腔体上方仅留一个宽度10mm左右的灌注口，且带有减反层的玻璃放置在最外层；
d、将由实施例5制备得到的防火胶液分别逐层灌注到每个空腔中，静置、消泡、封口；
e、向上述灌注好的的玻璃放入蒸压釜中加压到0.5Mpa，同时同步升温至80℃左右蒸压120min，冷却至室温后取出，得到具有5层玻璃4层防火层的复合防火玻璃，该复合防火玻璃编号为1，其中每层防火层厚度为0.75mm；
f、按照上述方法制备防火层分别为由实施例5-18制备的防火胶液浇灌而成的复合防火玻璃，制备的复合防火玻璃的相应编号为2-14。
检测编号为1-14的复合防火玻璃的防火性、耐紫外线时间和透过率，检测结果见表2。
根据中国国家标准《GB/T12513-2006》对测编号为1-14的复合防火玻璃进行耐火性能试验，测试结果见表2；根据中国国家标准《GB15763.1-2009建筑用安全玻璃第1部分：防火玻璃》对测编号为1-14的复合防火玻璃的耐紫外线辐照时间进行检测，检测结果见表2；根据中国国家标准《GB 15763.1-2009建筑用安全玻璃第1部分：防火玻璃》对测编号为1-14的复合防火玻璃的透过率进行检测，检测结果见表2；测编号为1-14的复合防火玻璃的表观质量通过肉眼观测形式获得，结果见表2；
表2
  透过率 耐紫外线辐射时间/h 防火时间/h 表观质量
1 80％ 1500 70 无微泡，减反层无腐蚀
2 83％ 1700 70 无微泡，减反层无腐蚀
3 85％ 1650 70 无微泡，减反层无腐蚀
4 87％ 2000 75 无微泡，减反层无腐蚀
5 84％ 1800 70 无微泡，减反层无腐蚀
6 83％ 1900 70 无微泡，减反层无腐蚀
7 83％ 1550 65 无微泡，减反层无腐蚀
8 82％ 1850 65 无微泡，减反层无腐蚀
9 81％ 1750 60 无微泡，减反层无腐蚀
10 80％ 1750 60 无微泡，减反层无腐蚀
11 80％ 1850 65 无微泡，减反层无腐蚀
12 81％ 1550 70 无微泡，减反层无腐蚀
13 81％ 1700 70 无微泡，减反层无腐蚀
14 85％ 1950 70 无微泡，减反层无腐蚀
从表2中可以看出，编号为1-14的复合防火玻璃的防火时间均长于60h，透过率均达到了80％以上。
编号为1-14的复合防火玻璃的耐紫外线时间均比国家标准《GB15763.1-2009建筑用安全玻璃第1部分：防火玻璃》规定的耐紫外线时间100h长。
举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (24)

  1. 一种防火胶液基质，含二氧化硅，其特征在于，还包含有润滑质，所述润滑质为芳香族烯烃和/或丙烯酸脂类的共聚物。
  2. 根据权利要求1所述的防火胶液基质，其特征在于，
    所述芳香族烯烃为苯乙烯；
    所述丙烯酸脂类为丙烯酸丁酯。
  3. 根据权利要求1或2所述的防火胶液基质，其特征在于，所述润滑质为颗粒。
  4. 根据权利要求1-3任一项所述的防火胶液基质，其特征在于，所述防火胶液基质以二氧化硅为核心，成型有包覆于所述二氧化硅外的内壳层，以及包覆在所述内壳层外的外壳层，所述润滑质至少存在于内壳层和二氧化硅之间。
  5. 根据权利要求1-4任一项所述的防火胶液基质，其特征在于，所述润滑质还存在于所述内壳层。
  6. 如权利要求3-5任一项所述的防火胶液基质，其特征在于，
    所述内壳层是由丙烯酸、甲基丙烯酸和聚丙烯酰胺中的一种或几种引发形成的聚合物；
    所述外壳层是由丙烯酸、苯乙烯和丙烯酸丁酯引发形成的聚合物。
  7. 如权利要求1-6任一项所述的防火胶液基质，其特征在于，所述二氧化硅为纳米级别，其粒径为60-150nm，比表面积为60-120m2/g。
  8. 如权利要求1-7任一项所述的防火胶液基质，其特征在于，所述的防火胶液基质为球形。
  9. 一种制备权利要求1-8任一项所述的防火胶液基质的方法，其包括如下步骤：
    (1)将甘油、聚合单体和水混合，制得内壳层材料混合液，其中，所述聚合单体为丙烯酸、甲基丙烯酸和聚丙烯酰胺中的一种或几种；
    (2)在惰性气体保护下，向内壳层材料混合液中加入纳米二氧化硅颗粒和氧化还原引发剂，得到无皂种子乳液；
    (3)向所述无皂种子乳液中加入润滑单体、水和氧化还原引发剂，得到无皂单壳乳液，其中所述润滑单体为芳香族烯烃和/或丙烯酸脂类；
    (4)向所述无皂单壳乳液中加入交联单体、水、交联剂混合，再加入氧化还原引发剂，得到防火胶液基质，其中所述交联单体为丙烯酸、苯乙烯和丙烯酸丁酯。
  10. 根据权利要求9所述的防火胶液基质制备方法，其特征在于，
    所述氧化还原引发剂为摩尔比1:1的过硫酸铵与亚硫酸氢钠的混合物；
    所述交联剂为1,2-二乙烯基苯。
  11. 根据权利要求9或10所述的防火胶液基质制备方法，其特征在于，
    所述步骤(3)中，所述芳香族烯烃为苯乙烯；所述丙烯酸脂类为丙烯酸丁酯。
  12. 根据权利要求9-11任一项所述的防火胶液基质制备方法，其特征在于，
    所述步骤(1)中，所述内壳层材料混合液中甘油、聚合单体和水的质量比为15-20：2-25：35-50；
    所述步骤(2)中，内壳层材料混合液、纳米二氧化硅颗粒、氧化还原引发剂的质量比30-50:20-60:0.01-0.04；
    所述步骤(3)中，无皂种子乳液、润滑单体、氧化还原引发剂与水的质量比50-100:1-5:0.01-0.05:1-10；
    所述步骤(4)中，无皂单壳乳液、交联单体、交联剂、氧化还原引发剂与水的质量比为60-110：1-10：0.01-0.05：0.0125-0.05：1-10。
  13. 根据权利要求9-12任一项所述的防火胶液基质制备方法，其特征在于，
    所述聚合单体为丙烯酸、甲基丙烯酸和聚丙烯酰胺，其质量比为2-10:0.01-10:0.01-5；
    所述润滑单体为苯乙烯和丙烯酸丁酯，所述苯乙烯和丙烯酸丁酯的质量比为30-45:30-40；
    所述交联单体为丙烯酸、苯乙烯和丙烯酸丁酯，其质量比为15-20:50-70:10-15。
  14. 根据权利要求9-13任一项所述的防火胶液基质制备方法，其特征在于，所述步骤(1)中还包括加入成炭剂、多元醇、热稳定剂、固化剂和氢氧化钾的步骤。
  15. 根据权利要求14所述的防火胶液基质制备方法，其特征在于，
    所述内壳层材料混合液中甘油、聚合单体、成炭剂、多元醇、热稳定剂、固化剂、氢氧化钾和水的质量比为15-20：2-25：0.01-3：0.02-4：0.01-0.6：0.01-0.1：0.01-0.2：35-50；
    其中，所述成炭剂为蔗糖、果糖、葡萄糖和砂糖中的一种或几种；
    所述热稳定剂为硼砂和/或硼酸；
    所述固化剂为氟硅酸钠、氟硅酸钾和氟化铝中的一种或几种；
    所述多元醇为木糖醇和/或季戊四醇。
  16. 根据权利要求9-15任一项所述的防火胶液基质制备方法，其特征在于，
    所述步骤(4)中，还包括将所述交联单体提前混合的步骤；
    所述步骤(4)中，还包括将所述无皂核壳乳液与交联单体、水和交联剂混合后，进行溶胀的步骤。
  17. 一种防火胶液，其特征在于，包括权利要求1-8任一所述的防火胶液基质。
  18. 根据权利要求17所述的防火胶液，其特征在于，还包括氢氧化钾。
  19. 根据权利要求17或18所述的防火胶液，其特征在于，防火胶液基质与氢氧化钾的质量比为70-75：2-15。
  20. 根据权利要求17-19任一项所述的防火胶液，其特征在于，所述防火胶液还包括成炭助剂、离子固定剂、消泡剂和固化剂。
  21. 根据权利要求17-20所述的防火胶液，其特征在于，
    防火胶液基质、氢氧化钾、成炭助剂、离子固定剂、消泡剂和固化剂的质量比为70-75：2-15：0.01-0.2：0.01-0.1：0.01-0.05：0.01-0.2。
  22. 一种制备权利要求17-21任一项所述的防火胶液的方法，其包括权利要求9-16任一项所述的步骤，还包括如下步骤：
    将所述防火胶液基质与氢氧化钾混合，得到所述防火胶液。
  23. 根据权利要求22所述的防火胶液的制备方法，其特征在于，
    还包括加入成炭助剂、离子固定剂、消泡剂和固化剂的步骤；
    其中，所述成炭助剂为磷酸二氢钾、磷酸氢钾、磷酸二氢钠及磷酸氢钠中一种或几种；
    所述离子固定剂为氧化锌、氧化铝及淀粉中的一种或几种；
    所述消泡剂为聚醚改性有机硅或聚氨酯类助剂；
    所述固化剂为氟硅酸钠、氟硅酸钾和氟化铝中的一种或几种。
  24. 根据权利要求21-23任一项所述的防火胶液的制备方法，其特征在于，
    还包括在真空度为10-40mbar下搅拌消泡的步骤。
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