CN102587607A - Fireproof and flame-retarding type composite heat-insulation decorating plate for outer wall and preparation method of fireproof and flame-retarding type composite heat-insulation decorating plate - Google Patents
Fireproof and flame-retarding type composite heat-insulation decorating plate for outer wall and preparation method of fireproof and flame-retarding type composite heat-insulation decorating plate Download PDFInfo
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Abstract
The invention relates to a fireproof and flame-retarding type composite heat-insulation decorating plate for an outer wall. The fireproof and flame-retarding composite heat-insulation decorating plate comprises a water-soluble non-combustible ceramic protective layer, an organic-inorganic composite toughening layer and a flame-retarding heat-insulation layer, wherein the water-soluble non-combustible ceramic protective layer comprises the components of slag powder, an inorganic filler, re-dispersible latex powder, water glass, an auxiliary agent and a gas phase nano-silica; the organic-inorganic composite toughening layer is fireproof and flame-retarding type polymer mortar and comprises the components of a gel material S, a ceramic microbead, hydroxyethyl methylcellulose, re-dispersible latex powder, limestone powder and modified expandable graphite; and the flame-retarding heat-insulation layer comprises the components of modified expandable polystyrene and modified expandable graphite. The flame-retarding and heat-insulation plate is installed on a wall surface in a manner of adhesion and anchoring. The environment-friendly and energy-saving type flame-retarding and heat-insulation plate for the outer wall, provided by the invention, integrates various performances, such as controllable preforming quality, construction assembling, heat insulation, fire proofing, water proofing, light weight, sound insulation, crazing resistance, hollowing resistance, falling resistance and the like.
Description
Technical Field
The invention relates to an outer wall fireproof flame-retardant composite heat-insulation decorative plate, which is mainly used for fireproof heat insulation and heat preservation of an outer wall of a building enclosure structure wall, and is an environment-friendly energy-saving outer wall fireproof heat-insulation thermal-insulation plate integrating various performances of controllable prefabricating and forming quality, construction assembly, heat preservation, heat insulation, fire prevention, water resistance, light weight, sound insulation, cracking resistance, hollowing resistance, falling resistance and the like.
Background
At present, the building energy consumption of China accounts for 27% of the total national energy consumption, and with the continuous development of economy, the living standard of people is continuously improved, the proportion of the building energy consumption is further increased, and the building energy consumption of developed countries in Europe and America reaches 40% of the total social energy consumption. Therefore, the energy consumption of the building is saved, and the significance of popularization and implementation of the energy-saving work of the building is great and imperative.
However, most enterprises research the external wall heat insulation decoration system by directly prefabricating the external wall heat insulation system and then applying the prefabricated external wall heat insulation decoration system to engineering practice, so that a great number of technical problems occur, such as the quality problem of the prefabricated heat insulation decoration plate, the defects of the heat insulation decoration integrated multifunctional plate construction technology, the lack of corresponding research on the matching materials of the plate system, and the like. Moreover, under the large background of great promotion of building energy conservation in China, all buildings need to reach corresponding energy conservation standards, but in the currently adopted heat insulation materials, about 80 percent of the heat insulation materials are organic combustible materials, and an external wall external heat insulation system is mainly made of thin-plastered organic heat insulation system materials with poor fireproof performance. From the current state of fire protection technology of the existing external thermal insulation system for the external wall and the frequency of fire disasters, how to perform a fire protection safety test of the external thermal insulation system for the external wall and improve the fire protection safety of the external thermal insulation system for the external wall of various buildings is a major subject at present.
Under the current technical conditions of China, the flammable materials such as polystyrene foam, rigid foam polyurethane and the like are most widely used in the external thermal insulation system of the external wall of the building, which is the cause of the problem of fire safety of the external thermal insulation system of the external wall. With the gradual improvement of the energy-saving standard, the thickness of the flammable organic heat-insulating material is increased continuously, and the problems of fire of the outer wall of the building and the fire spread are more prominent.
The Ministry of public Security issues a-public expense No. 2011]65 red-headed document under 3, 14 months in 2011, which provides unprecedented highest requirements for the safety and fire resistance of national external wall insulation boards and strictly supervises under-construction and non-approval projects. Correspondingly, the building external wall heat insulation system with good fireproof performance and excellent heat insulation performance can meet the fireproof energy-saving requirement proposed by the state and gain the market recognition.
After the organic heat-insulating material meets the requirements of relevant standards or certain auxiliary measures are added, the overall fire safety of the system is emphasized. The evaluation of the fire rating of the thermal insulation material cannot represent the overall fire safety performance of the system or the real situation when a fire occurs, and even if some materials with flame-retardant rating can be burnt violently under the condition, the key point of the external thermal insulation fire protection problem should be grasped. Only if the overall fire reaction performance of the external thermal insulation system is good and the structural mode of the system is reasonable, the fire safety performance of the external thermal insulation system of the building can be ensured to meet the requirements, and the system has wide practical significance for engineering application.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel external thermal insulation board for an external wall, which is characterized by high efficiency, energy conservation, long service life, high safety and high construction speed. The invention combines the construction structure with energy conservation while fully utilizing the high-efficiency heat insulation material, thereby obtaining a higher-efficiency external heat insulation system.
The invention adopts the following technical scheme for solving the technical problems: the fireproof and flame-retardant composite heat-insulating decorative plate for the outer wall is characterized by comprising a water-soluble non-combustible ceramic protective layer, an organic-inorganic composite toughening layer and a flame-retardant heat-insulating layer, wherein the thickness of the water-soluble non-combustible ceramic protective layer is 0.3-3 mm; the thickness of the organic-inorganic composite toughening layer is 1-5 mm; the thickness of the flame-retardant insulating layer is 30-50 mm; wherein,
the water-soluble non-combustible ceramic protective layer comprises the following components in percentage by mass: slag micro powder, inorganic filler, redispersible latex powder, water glass, auxiliary agent and gas phase nano-silica are 1-3: 0.2-1.2: 0.13-0.67: 1-2.3: 0.067-0.33: 0.067-0.13;
the organic-inorganic composite toughening layer is flame-retardant heat-preservation polymer mortar, and comprises the following components in percentage by mass: the binding material S, the ceramic microspheres, the hydroxyethyl methylcellulose, the redispersible latex powder, the limestone powder and the modified expandable graphite are 3-7: 1-2.3: 0-0.06: 0.2-0.8: 0-0.7: 0.5-2.5;
the flame-retardant heat-insulating layer comprises the following components in percentage by mass: the ratio of the modified expandable polystyrene to the modified expandable graphite is 1: 0.08-0.25.
According to the scheme, the preparation method of the cementing material S is that P.O42.5R cement, 42.5 sulphoaluminate cement and anhydrite are fully and uniformly mixed according to the mass ratio of P.O42.5R cement to 42.5 sulphoaluminate cement to anhydrite of 4.6 to 1.9 to 1.
According to the scheme, the preparation method of the modified expandable polystyrene comprises the steps of mixing water, polystyrene master batch, sodium butylnaphthalene sulfonate, polyvinyl alcohol, butane, dicumyl peroxide, bromoalkane and an antioxidant according to the mass ratio of 1.6: 1: 0.03: 0.002: 0.1: 0.008: 0.01-0.02: 0.003, and carrying out impregnation reaction at the temperature of 72 +/-2 ℃, the pressure of 0.9 +/-0.1 MPa and the rotating speed of 95-100r/min for 10-12 hours to obtain the modified expandable polystyrene.
According to the scheme, the bromoalkane is tetrabromoethane, tetrabromobutane or hexabromocyclododecane.
According to the scheme, the modulus n of the water glass is 2.2-2.5.
According to the scheme, the inorganic filler is any one or mixture of more of talcum powder, mica powder and pigment, wherein the pigment is any one or mixture of more of titanium dioxide, lithopone, chromate series or iron oxide series pigment.
According to the scheme, the auxiliary agent is formed by mixing silok7110 water-based wetting dispersant of silok company and dicyclopentenyloxyethyl acrylate film-forming auxiliary agent according to the mass ratio of 2: 1.3.
The preparation method of the fireproof flame-retardant composite heat-insulation decorative plate for the outer wall is characterized by comprising the following steps of:
A) preparing a flame-retardant heat-insulating layer:
1) the weight ratio is as follows: taking the modified expandable polystyrene and the modified expandable graphite for later use, wherein the ratio of the modified expandable polystyrene to the modified expandable graphite is 1: 0.08-0.25;
2) feeding modified expandable polystyrene into a prefoamer with steam pressure of 0.2MPa and preheated to 70 ℃ for prefoaming, curing for 10h, uniformly mixing with modified expandable graphite, filling into a preheated plate forming machine, introducing steam with the temperature of 95-110 ℃ into a mold for heating, keeping the pressure at 0.08-0.15 MPa, cooling and demolding after ventilation is finished, cutting to obtain a flame-retardant modified heat-insulating layer, and carrying out organic silicon coupling treatment on the surface of the flame-retardant modified heat-insulating layer;
B) preparation of organic-inorganic composite toughening layer
1) P.O42.5R cement, 42.5 sulphoaluminate cement and anhydrite are fully and uniformly mixed according to the mass ratio of P.O42.5R cement to 42.5 sulphoaluminate cement to anhydrite of 4.6: 1.9: 1 to obtain a cementing material S, and then the cementing material S, ceramic microspheres, hydroxyethyl methylcellulose, redispersible emulsion powder, limestone powder and modified expandable graphite are weighed according to the mass ratio of 3-7: 1-2.3: 0-0.06: 0.2-0.8: 0-0.7: 0.5-2.5;
2) mixing the cementing material S, the ceramic microspheres, the hydroxyethyl methyl cellulose, the redispersible latex powder, the limestone powder and the modified expandable graphite with water and mixing; the dosage of the mixing water is determined according to the fluidity GB2419-81 of the fresh mixed mortar, and the fluidity is controlled to be 165 +/-5 mm; coating the obtained flame-retardant heat-preservation polymer mortar on the surface of the flame-retardant heat-preservation layer for molding;
C) preparation of water-soluble non-combustible ceramic protective layer
The slag micro powder, the inorganic filler, the redispersible latex powder, the water glass, the assistant and the gas phase nano-silica are fully and uniformly mixed according to the mass ratio of 1-3: 0.2-1.2: 0.13-0.67: 1-2.3: 0.067-0.33: 0.067-0.13, and then the mixture is brushed or sprayed on the organic-inorganic composite toughening layer.
According to the scheme, the preparation method of the modified expandable polystyrene comprises the steps of mixing water, polystyrene master batch, sodium butylnaphthalene sulfonate, polyvinyl alcohol, butane, dicumyl peroxide, bromoalkane and an antioxidant according to the mass ratio of 1.6: 1: 0.03: 0.002: 0.1: 0.008: 0.01-0.02: 0.003, and carrying out impregnation reaction at the temperature of 72 +/-2 ℃, the pressure of 0.9 +/-0.1 MPa and the rotating speed of 95-100r/min for 10-12 hours to obtain the modified expandable polystyrene.
According to the scheme, the preparation method of the modified expandable graphite comprises the steps of mixing the crystalline flake graphite, hydrogen peroxide and fuming nitric acid, rapidly stirring in an ice water bath, keeping the temperature of a reaction system at 25 ℃ after the reaction is gentle, washing, filtering, dropwise adding an acetic acid solution, continuously stirring, reacting for 60-120 min, washing with water, filtering, and drying to obtain the modified expandable graphite; or flake graphite and KMnO according to mass ratio4Adding KMnO into the crystalline flake graphite in a ratio of 1: 0.2-0.44All stirring is carried outHomogenizing, adding HClO3And (3) intermittently stirring and reacting the solution at 35 ℃ for 60-120 min, then washing with water, carrying out suction filtration, and drying to obtain the modified expandable graphite.
The main raw materials in the invention have the following functions:
the modified expandable polystyrene is a foamable high polymer material, is a main heat-insulating material after pre-foaming and secondary foaming molding, and has a lower heat conductivity coefficient; wherein bromoalkane is added as a halogenated alkane flame retardant and can react with active free radical OH & generated by combustion to generate H2O, OH groups and heat are greatly reduced, so that the high-efficiency flame retardant effect is achieved;
the modified expandable graphite is an intumescent flame retardant, and has the functions of generating large-volume and large-amplitude expansion or generating a foam substance to cover the surface at a higher temperature to form a stable heat insulation covering layer to play the roles of isolating air and efficiently insulating heat, thereby achieving the purpose of flame retardance2，NH3，H2O and other non-combustible gases, so that the combustible gas released by the thermal decomposition of the high molecular polymer is diluted to achieve the flame-retardant effect;
the gelling material S, which has the main gelling effect, reacts with water to form C-S-H, ettringite and Ca (OH)2Etc., to improve the strength of the system;
the redispersible latex powder has the functions of adjusting the adhesive property and the rheological property of the cementing material and improving the volume stability;
the water glass has the function of forming a stable and compact silica network layer and a calcium silicate hydrate protective layer with the active base material mineral powder;
the inorganic filler is filled in the cementing material to improve the strength;
the ceramic microsphere is a hollow inorganic lightweight aggregate, mainly contains silicon dioxide and aluminum oxide as chemical components, and has multiple functions of fine particles, hollowness, light weight, heat preservation, high strength, wear resistance, high temperature resistance, heat preservation, insulation, flame retardance and the like;
the water-based wetting dispersant is an inorganic coating additive, is suitable for wetting dispersion of an inorganic coating, keeps good dispersibility and fluidity of slurry, and can greatly improve the color development and luster of the coating;
dicyclopentenyloxyethyl acrylate, a film-forming assistant of inorganic coating, can reduce the glass transition temperature of the coating, carry on polymerization and cross-linking automatically under the environment of film-forming, become a constituent part of the membrane, can reach better hardness and gloss than original coating film-forming, do not cause the pollution to the environment by itself, non-volatile, and have long-term stability after compounding into coating;
the gas phase nanometer silicon dioxide has large specific surface area and great activity, can form a net structure when the paint is dried, simultaneously increases the strength and the smoothness of the paint, improves the suspension property of the pigment, can keep the paint not to fade or delaminate for a long time, has thixotropy, sagging prevention and good style application performance, particularly greatly improves the stain resistance, has excellent self-cleaning capability and adhesive force, has extremely strong ultraviolet absorption and infrared reflection characteristics, and increases the heat insulation property and the durability of the paint.
The flame-retardant heat-insulation board is arranged on the wall surface in a bonding and anchoring combined mode, and is an environment-friendly energy-saving type flame-retardant heat-insulation board for the outer wall, which integrates various performances of controllable prefabricated molding quality, construction assembly, heat insulation, fire prevention, water resistance, light weight, sound insulation, cracking resistance, hollowing resistance, falling resistance and the like; the fireproof flame-retardant composite heat-insulation decorative plate is a prefabricated plate with the integration of high-efficiency flame retardance, fire resistance, heat insulation, high durability, permeability resistance and water resistance.
Compared with the prior art, the invention has the following main advantages:
1) high-efficiency energy conservation and durability: the temperature system and the pressure system are controlled in the preparation process of the flame-retardant heat-insulating layer, so that the improvement on the flame-retardant heat-insulating layerThe packing compactness of the polymer foam particles has higher tensile strength and lower thermal seepage coefficient compared with the common XPS plate and EPS plate, and the density of the polymer insulation plate is controlled to be 22 +/-2 kg/m3. The thermal conductivity coefficient can be controlled to be 0.030-0.038W/(m.K), which is better than that of the common EPS board and XPS extruded sheet (the thermal conductivity coefficient of the EPS board is 0.042W/m.K, and the thermal conductivity coefficient of the XPS board is 0.038W/m.K); the ceramic microspheres added into the organic-inorganic composite toughening layer and the gas-phase nano silicon dioxide added into the water-soluble non-combustible ceramic protective layer can effectively play the functions of composite heat preservation and insulation, radiation protection, ageing resistance and the like;
2) high-grade flame retardance: bromoalkane is added into the polymer foam master batch for flame retardant modification, modified expandable graphite is added into the flame-retardant heat-insulating layer and the organic-inorganic composite toughening layer, and a water-soluble non-combustible ceramic protective layer is designed, so that the fireproof and flame-retardant performance of the plate is further improved, the fireproof level of the flame-retardant heat-insulating layer is improved to B1 level from the traditional B2 level according to the GB8426-1996 standard, and the whole fireproof level of the plate reaches A level through the flame-retardant design of the organic-inorganic composite toughening layer and the water-soluble non-combustible ceramic protective layer;
3) organic-inorganic unity: an organic-inorganic composite toughening layer is added between the flame-retardant insulating layer and the water-soluble non-combustible ceramic protective layer, so that the anti-cracking performance of the invention is improved by toughening modification; the upper interface and the lower interface of the organic-inorganic composite toughening layer are modified by organic silicon coupling, so that the bonding strength between the organic-inorganic composite toughening layer and the flame-retardant insulating layer and the bonding strength between the organic-inorganic composite toughening layer and the water-soluble non-combustible ceramic protective layer are enhanced, and the integrity of the plate is improved;
4) surface incombustibility: unlike most of the flammable Organic coatings such as polyacrylate, polyurethane, polyurea and the like adopted by the outer walls in China, the self-made water-soluble non-combustible ceramic protective layer with no toxicity and low pollution, a Volatile Organic Compound (VOC) value of 0 and A-level fireproof performance is applied to the outermost layer of the plate, and the coating has quick drying property, does not need post-baking treatment and can realize industrialized quick coating. The incombustible nature of the coating enables the overall fire-retardant rating of the plate to meet the A-level requirement.
Drawings
FIG. 1 is a structural diagram of the fireproof flame-retardant composite thermal insulation decorative plate for the exterior wall.
The specific implementation mode is as follows:
the present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
the preparation method of the fireproof flame-retardant composite heat-insulation decorative plate for the outer wall comprises the following steps:
1) preparing modified expandable graphite: rapidly stirring flake graphite, hydrogen peroxide and fuming nitric acid in an ice water bath, keeping the temperature of the reaction system at 25 ℃ after the reaction is gentle, washing, filtering, dropwise adding an acetic acid solution with the content of more than or equal to 99.5%, continuously stirring, reacting for 60min, washing, filtering, and drying to obtain sulfur-free ash-free modified expandable graphite with the expansion volume of 300-350ml/g, wherein the proportion of the flake graphite, the fuming nitric acid, the hydrogen peroxide and the acetic acid is 5(g) to 12(ml) to 1(ml) to 5 (ml);
2) preparation of modified expandable polystyrene: mixing water, polystyrene master batch, butyl naphthalene sodium sulfonate, polyvinyl alcohol, butane, dicumyl peroxide, tetrabromobutane and antioxidant BHT according to the mass ratio of 1.6: 1: 0.03: 0.002: 0.1: 0.008: 0.013: 0.003, and carrying out impregnation reaction for 12 hours at the temperature of 72 +/-2 ℃, the pressure of 0.9 +/-0.1 MPa and the rotating speed of 100r/min to obtain the product;
3) preparing a flame-retardant heat-insulating layer: feeding the modified expandable polystyrene obtained in the step 2) into a prefoamer with steam pressure of 0.2MPa and preheated to 70 ℃ for prefoaming, curing for 10 hours, mixing with modified expandable graphite according to the mass ratio of 5: 1, filling and placing into a preheated plate forming machine, introducing 105 ℃ steam into a die for heating, keeping the pressure at 0.13MPa for secondary foaming forming, cooling and demoulding after ventilation is finished, cutting to obtain a flame-retardant heat-insulating layer 3 with the thickness of 30mm, and spraying a silane coupling agent thin coating on the surface of the flame-retardant heat-insulating layer 3;
4) preparing an organic-inorganic composite toughening layer: P.O42.5R cement, 42.5 sulphoaluminate cement and anhydrite are fully and uniformly mixed according to the mass ratio of P.O42.5R cement to 42.5 sulphoaluminate cement to anhydrite of 4.6: 1.9: 1 to obtain a cementing material S, then the cementing material S, ceramic microspheres, hydroxyethyl methyl cellulose, redispersible latex powder, limestone powder and modified expandable graphite are mixed according to the mass ratio of 4.3: 1.5: 0.02: 0.6: 1.7, the mixture is uniformly coated on a flame-retardant heat-insulating layer after being mixed with water, the dosage of the mixed water is determined according to the fluidity GB2419-81 of the newly mixed mortar, the fluidity is controlled to be 165 +/-5 mm, the thickness is 3mm, and a thin coating of a silane coupling agent is sprayed on the surface of the mixture;
5) preparing a water-soluble non-combustible ceramic protective layer: slag micro powder, inorganic filler, redispersible latex powder, water glass (modulus n is 2.2), an auxiliary agent and gas phase nano-silica are fully and uniformly mixed according to the proportion of 1: 0.29: 0.16: 1.2: 0.068: 0.13, and 2mm is sprayed on the organic-inorganic composite toughening layer 2 to prepare a water-soluble non-combustible ceramic protective layer 1, wherein the inorganic filler is formed by mixing talcum powder and mica powder according to the mass proportion of 2: 1; the auxiliary agent is formed by mixing silok7110 aqueous wetting dispersant produced by silok company and dicyclopentenyloxyethyl acrylate film-forming auxiliary agent according to the mass ratio of 2: 1.3.
The chemical components and physical properties of the other main raw materials of the invention are respectively shown in tables 1-12.
The implementation process of the fireproof flame-retardant composite heat-insulation decorative plate for the outer wall comprises the steps of wall surface base layer treatment → local smearing of special polymer bonding mortar on the flame-retardant composite heat-insulation plate → pasting of the flame-retardant composite heat-insulation plate → anchoring of a special anchor piece → pointing treatment, wherein the bonding mortar is located at the position 1-3 cm away from the edge of the flame-retardant composite heat-insulation plate and at the geometric center of the plate; the anchoring piece is a metal or high-strength plastic anchoring piece, and the tensile strength is more than or equal to 0.98 KN; the heat conductivity coefficient is 0.030-0.038W/(m.k), the combustion grade of the heat-insulating layer material reaches B1 grade, and the overall combustion grade of the plate reaches A grade.
The physical properties of the fireproof flame-retardant composite heat-insulation decorative plate for the outer wall are applied, and the experimental results are shown in a table 13.
Example 2:
1) preparing modified expandable graphite: flake graphite and KMnO according to mass ratio4KMnO was added to the flake graphite at a ratio of 1: 0.34Stirring, adding 70% HClO3The solution and the solution are kept at 35 ℃ in a ratio of 1: 4, the mixture is intermittently stirred and reacted for 90min, and then the mixture is washed, filtered and dried to obtain the modified expandable expanded graphite with the expansion volume of 550 ml/g;
2) preparation of modified expandable polystyrene: mixing water, polystyrene master batch, butyl naphthalene sodium sulfonate, polyvinyl alcohol, butane, dicumyl peroxide, hexabromocyclododecane and antioxidant BHT according to the mass ratio of 1.6: 1: 0.03: 0.002: 0.1: 0.008: 0.02: 0.003, and carrying out impregnation reaction at the temperature of 72 +/-2 ℃, the pressure of 0.9 +/-0.1 MPa and the rotating speed of 100r/min for 10 hours to obtain the product;
3) preparing a flame-retardant heat-insulating layer: feeding the modified expandable polystyrene obtained in the step 2) into a prefoamer with steam pressure of 0.2MPa and preheated to 70 ℃ for prefoaming, curing for 10 hours, mixing with modified expandable graphite according to the mass ratio of 4.5: 1, filling and placing into a preheated plate forming machine, introducing steam with the temperature of 105 ℃ into a mold for heating, keeping the pressure at 0.12MPa for secondary foaming forming, cooling and demolding after ventilation is finished, cutting to obtain a flame-retardant heat-insulating layer with the thickness of 40mm, and spraying a silane coupling agent thin coating on the surface of the flame-retardant heat-insulating layer;
4) preparing an organic-inorganic composite toughening layer: P.O42.5R cement, 42.5 sulphoaluminate cement and anhydrite are taken according to the mass ratio of 4.6: 1.9: 1, the P.O42.5R cement, the 42.5 sulphoaluminate cement and the finely ground anhydrite are fully and uniformly mixed to obtain a gelled material S, then the gelled material S, ceramic microspheres, hydroxyethyl methyl cellulose, redispersible latex powder, limestone powder and modified expandable graphite are mixed according to the proportion of 3.7: 1.8: 0.03: 0.5: 0.6: 2, the mixture is uniformly coated on a flame-retardant heat-insulating layer after being mixed with water, the dosage of the mixed water is determined according to the fluidity 241GB 9-81 of the newly mixed mortar, the fluidity is controlled to be 165 +/-5 mm, the thickness is 3mm, and a silane coupling agent thin coating is sprayed on the surface of the mixed water;
5) preparing a water-soluble non-combustible ceramic protective layer: fully and uniformly mixing slag micro powder, inorganic filler, redispersible latex powder, water glass (the modulus n is 2.2), an auxiliary agent and gas-phase nano-silica according to the proportion of 2: 0.75: 0.35: 1.75: 0.15: 0.075, and spraying 2mm on the organic-inorganic composite toughening layer to prepare a water-soluble non-combustible ceramic protective layer, wherein the inorganic filler is formed by mixing talcum powder, mica powder and titanium dioxide according to the mass proportion of 3: 1; the auxiliary agent is formed by mixing silok7110 aqueous wetting dispersant produced by silok company and dicyclopentenyloxyethyl acrylate film-forming auxiliary agent according to the mass ratio of 2: 1.3.
Example 3:
1) preparing modified expandable graphite: flake graphite and KMnO according to mass ratio4KMnO was added to the flake graphite at a ratio of 1: 0.34Stirring, adding 70% HClO3The solution and the solution are kept at 35 ℃ in a ratio of 1: 4, the mixture is intermittently stirred and reacted for 90min, and then the mixture is washed, filtered and dried to obtain the modified expandable expanded graphite with the expansion volume of 550 ml/g;
2) preparation of modified expandable polystyrene: mixing water, polystyrene master batch, sodium butylnaphthalene sulfonate, polyvinyl alcohol, butane, dicumyl peroxide, tetrabromobutane and antioxidant BHT according to the mass ratio of 1.6: 1: 0.03: 0.002: 0.1: 0.008: 0.017: 0.003, and carrying out impregnation reaction for 12 hours at the rotating speed of 100r/min at the temperature of 72 +/-2 ℃, the pressure of 0.9 +/-0.1 MPa and the pressure of 0.9 +/-2 ℃ to obtain the product;
3) preparing a flame-retardant heat-insulating layer: feeding the modified expandable polystyrene obtained in the step 2) into a prefoamer with steam pressure of 0.2MPa and preheated to 70 ℃ for prefoaming, curing for 10 hours, mixing with modified expandable graphite according to the mass ratio of 5: 1, filling and placing into a preheated plate forming machine, introducing 105 ℃ steam into a die for heating, keeping the pressure at 0.13MPa for secondary foaming forming, cooling and demoulding after ventilation is finished, cutting to obtain a flame-retardant heat-insulating layer with the thickness of 30mm, and spraying a silane coupling agent thin coating on the surface of the flame-retardant heat-insulating layer;
4) preparing an organic-inorganic composite toughening layer: P.O42.5R cement, 42.5 sulphoaluminate cement and anhydrite are fully and uniformly mixed according to the mass ratio of P.O42.5R cement to 42.5 sulphoaluminate cement to anhydrite of 4.6: 1.9: 1 to obtain a gelled material S, then the gelled material S, ceramic microspheres, hydroxyethyl methyl cellulose, redispersible latex powder, limestone powder and modified expandable graphite are mixed according to the ratio of 4: 1.6: 0.04: 0.6: 2, the mixture is uniformly coated on a flame-retardant heat-insulating layer after being mixed with water, the using amount of mixing water is determined according to the fluidity GB2419-81 of the newly mixed mortar, the fluidity is controlled to be 165 +/-5 mm, the thickness is 3mm, and a silane coupling agent thin coating is sprayed on the surface of the mixture;
5) preparing a water-soluble non-combustible ceramic protective layer: slag micro powder, inorganic filler, redispersible latex powder, water glass (the modulus n is 2.2), an auxiliary agent and gas phase nano-silica are fully and uniformly mixed according to the proportion of 1: 0.26: 0.54: 1.4: 0.093: 0.13, and 2mm is sprayed on the organic-inorganic composite toughening layer to prepare the water-soluble non-combustible ceramic protective layer, wherein the inorganic filler is formed by mixing talcum powder, mica powder and iron oxide red pigment according to the mass proportion of 2: 1: 2; the auxiliary agent is formed by mixing silok7110 aqueous wetting dispersant produced by silok company and dicyclopentenyloxyethyl acrylate film-forming auxiliary agent according to the mass ratio of 2: 1.3.
Example 4:
1) preparing modified expandable graphite: rapidly stirring flake graphite, hydrogen peroxide and fuming nitric acid in an ice water bath, keeping the temperature of the reaction system at 25 ℃ after the reaction is gentle, washing, filtering, dropwise adding an acetic acid solution with the content of more than or equal to 99.5%, continuously stirring, reacting for 60min, washing, filtering, and drying to obtain sulfur-free ash-free modified expandable graphite with the expansion volume of 300-350ml/g, wherein the proportion of the flake graphite, the fuming nitric acid, the hydrogen peroxide and the acetic acid is 5(g) to 12(ml) to 1(ml) to 5 (ml);
2) preparation of modified expandable polystyrene: mixing water, polystyrene master batch, butyl naphthalene sodium sulfonate, polyvinyl alcohol, butane, dicumyl peroxide, hexabromocyclododecane and antioxidant BHT according to the proportion of 1.6: 1: 0.03: 0.002: 0.1: 0.008: 0.02: 0.003, and carrying out impregnation reaction for 12 hours at the temperature of 72 +/-2 ℃, the pressure of 0.9 +/-0.1 MPa and the rotating speed of 100r/min to obtain the product;
3) preparing a flame-retardant heat-insulating layer: feeding the modified expandable polystyrene obtained in the step 2) into a prefoamer with steam pressure of 0.2MPa and preheated to 70 ℃ for prefoaming, curing for 10 hours, mixing with modified expandable graphite according to the mass ratio of 4: 1, filling and placing into a preheated plate forming machine, introducing 105 ℃ steam into a die for heating, keeping the pressure at 0.12MPa for secondary foaming forming, cooling and demoulding after ventilation is finished, cutting to obtain a flame-retardant heat-insulating layer with the thickness of 35mm, and spraying a silane coupling agent thin coating on the surface of the flame-retardant heat-insulating layer;
4) preparing an organic-inorganic composite toughening layer: P.O42.5R cement, 42.5 sulphoaluminate cement and anhydrite are fully and uniformly mixed according to the mass ratio of P.O42.5R cement to 42.5 sulphoaluminate cement to anhydrite of 4.6: 1.9: 1 to obtain a cementing material S, then the cementing material S, ceramic microspheres, redispersible latex powder and modified expandable graphite are mixed according to the ratio of 4.2: 1.8: 0.5: 2, the mixture is uniformly coated on a flame-retardant heat-insulating layer after being mixed with water, the dosage of the mixing water is determined according to the fluidity GB2419-81 of the newly mixed mortar, the fluidity is controlled to be 165 +/-5 mm, the thickness is 2.5mm, and a thin coating of a silane coupling agent is sprayed on the surface of the mixing water;
5) preparing a water-soluble non-combustible ceramic protective layer: fully and uniformly mixing slag micro powder, inorganic filler, redispersible latex powder, water glass (the modulus n is 2.2), an auxiliary agent and gas-phase nano-silica according to the proportion of 2: 0.75: 0.35: 1.75: 0.15: 0.1, and spraying 2mm on the organic-inorganic composite toughening layer to prepare a water-soluble non-combustible ceramic protective layer, wherein the inorganic filler is formed by mixing talcum powder, lithopone and iron oxide yellow pigment according to the mass proportion of 3: 1; the auxiliary agent is formed by mixing silok7110 aqueous wetting dispersant produced by silok company and dicyclopentenyloxyethyl acrylate film-forming auxiliary agent according to the mass ratio of 2: 1.3.
Example 5:
except for the raw materials described in the example 4, 8% of alkali-resistant styrene-butadiene emulsion is doped in the organic-inorganic composite toughening layer, and the other raw materials are treated as in the example 4.
Example 6:
in addition to the raw materials described in example 4, 5% fly ash is added to the organic-inorganic composite toughening layer, and the mixture is ground to a specific surface area of 2500-3500 cm2Per g, other raw material treatments were the same as in example 4.
Example 7:
adding 3 percent of quicklime in addition to the raw materials in the embodiment 4, and grinding the mixture to the specific surface area of 3000-3500 cm2Per g, other raw material treatments were the same as in example 4.
Attached watch
TABLE 1 physical Properties of P.O42.5R Cement
TABLE 2 chemical analysis/Wt% of P.O42.5R Cement raw Material
TABLE 342.5 physical Properties of the sulphoaluminate cements
TABLE 442.5 chemical analysis of sulphoaluminate cement raw materials/Wt%
TABLE 5 chemical analysis/Wt% of Fine slag powder
TABLE 6 particle size distribution of limestone
TABLE 7 fumed nanosilica parameters
TABLE 8 redispersible emulsion powder physical Properties
TABLE 9 physical parameters and chemical analysis of ceramic Microbeads
Physical parameters of ceramic Microbeads
Chemical analysis of ceramic Microbeads/Wt%
TABLE 10silok7110 aqueous wetting dispersant parameters
TABLE 11 dicyclopentenyloxyethyl acrylate parameters
TABLE 12 antioxidant BHT parameters
TABLE 13 results of the experiment
*(volume weight of flame-retardant and heat-insulating base in brackets)
Claims (10)
1. The fireproof and flame-retardant composite heat-insulating decorative plate for the outer wall is characterized by comprising a water-soluble non-combustible ceramic protective layer, an organic-inorganic composite toughening layer and a flame-retardant heat-insulating layer, wherein the thickness of the water-soluble non-combustible ceramic protective layer is 0.3-3 mm; the thickness of the organic-inorganic composite toughening layer is 1-5 mm; the thickness of the flame-retardant insulating layer is 30-50 mm; wherein,
the water-soluble non-combustible ceramic protective layer comprises the following components in percentage by mass: slag micropowder: inorganic filler: redispersible latex powder: water glass: auxiliary agent: the gas-phase nano silicon dioxide = 1-3: 0.2-1.2: 0.13-0.67: 1-2.3: 0.067-0.33: 0.067-0.13;
the organic-inorganic composite toughening layer is flame-retardant heat-preservation polymer mortar, and comprises the following components in percentage by mass: and (3) a cementing material S: ceramic beads: hydroxyethyl methyl cellulose: redispersible latex powder: limestone powder: the modified expandable graphite = 3-7: 1-2.3: 0-0.06: 0.2-0.8: 0-0.7: 0.5 to 2.5;
the flame-retardant heat-insulating layer comprises the following components in percentage by mass: modified expandable polystyrene: modified expandable graphite = 1: 0.08 to 0.25.
2. The exterior wall fireproof flame-retardant composite heat-insulation decorative plate of claim 1, wherein the preparation method of the cementing material S is as follows according to the mass ratio of P.O42.5R cement: 42.5 sulphoaluminate cement: anhydrite = 4.6: 1.9: 1, taking P.O42.5R cement, 42.5 sulphoaluminate cement and anhydrite, and fully and uniformly mixing.
3. The exterior wall fireproof flame-retardant composite heat-insulation decorative plate of claim 1, wherein the preparation method of the modified expandable polystyrene comprises the following steps of mixing water, polystyrene master batch, butyl sodium naphthalene sulfonate, polyvinyl alcohol, butane, dicumyl peroxide, bromoalkane and an antioxidant according to a mass ratio of 1.6: 1: 0.03: 0.002: 0.1: 0.008: 0.01-0.02: 0.003 of mixture, and the impregnation reaction is carried out for 10 to 12 hours at the temperature of 72 plus or minus 2 ℃, the pressure of 0.9 plus or minus 0.1MPa and the rotating speed of 95 to 100r/min to obtain the modified expandable polystyrene.
4. The fire-retardant composite heat-insulating decorative board of claim 3, wherein the bromoalkane is tetrabromoethane, tetrabromobutane or hexabromocyclododecane.
5. The fire-retardant composite heat-insulating decorative board for external walls according to claim 1, wherein the modulus n of the water glass is 2.2-2.5.
6. The fire-retardant composite heat-insulating decorative board for external walls according to claim 1, characterized in that the inorganic filler is any one or a mixture of more of talcum powder, mica powder and pigment, wherein the pigment is any one or a mixture of more of titanium dioxide, lithopone, chromate series or iron oxide series pigment.
7. The fire-retardant composite heat-insulating decorative board for external walls according to claim 1, characterized in that the auxiliary agent is silok7110 water-based wetting dispersant of silok company and dicyclopentenyloxyethyl acrylate film-forming auxiliary agent according to the mass ratio of 2: 1.3 mixing.
8. The preparation method of the exterior wall fireproof flame-retardant composite heat-insulation decorative plate of any one of claims 1 to 6 is characterized by comprising the following steps:
A) preparing a flame-retardant heat-insulating layer:
1) the weight ratio is as follows: modified expandable polystyrene: modified expandable graphite = 1: 0.08-0.25, taking the modified expandable polystyrene and the modified expandable graphite for later use;
2) feeding modified expandable polystyrene into a prefoamer with steam pressure of 0.2MPa and preheated to 70 ℃ for prefoaming, curing for 10h, uniformly mixing with modified expandable graphite, filling into a preheated plate forming machine, introducing steam with the temperature of 95-110 ℃ into a mold for heating, keeping the pressure at 0.08-0.15 MPa, cooling and demolding after ventilation is finished, cutting to obtain a flame-retardant modified heat-insulating layer, and carrying out organic silicon coupling treatment on the surface of the flame-retardant modified heat-insulating layer;
B) preparation of organic-inorganic composite toughening layer
1) The cement is prepared from the following components in percentage by mass: 42.5 sulphoaluminate cement: anhydrite = 4.6: 1.9: 1, sufficiently and uniformly mixing P.O42.5R cement, 42.5 sulphoaluminate cement and anhydrite to obtain a cementing material S, and then mixing the cementing material S, ceramic microspheres, hydroxyethyl methylcellulose, redispersible emulsion powder, limestone powder and modified expandable graphite according to the mass ratio of 3-7: 1-2.3: 0-0.06: 0.2-0.8: 0-0.7: weighing 0.5-2.5;
2) mixing the cementing material S, the ceramic microspheres, the hydroxyethyl methyl cellulose, the redispersible latex powder, the limestone powder and the modified expandable graphite with water and mixing; the dosage of the mixing water is determined according to the fluidity GB2419-81 of the fresh mixed mortar, and the fluidity is controlled to be 165 +/-5 mm; coating the obtained flame-retardant heat-preservation polymer mortar on the surface of the flame-retardant heat-preservation layer for molding;
C) preparation of water-soluble non-combustible ceramic protective layer
Slag micro powder, inorganic filler, redispersible latex powder, water glass, an auxiliary agent and gas-phase nano-silica are mixed according to a mass ratio of 1-3: 0.2-1.2: 0.13-0.67: 1-2.3: 0.067-0.33: 0.067-0.13, and then brushing or spraying the organic-inorganic composite toughening layer.
9. The preparation method of the external wall fireproof flame-retardant composite heat-insulation decorative plate according to claim 8, wherein the preparation method of the modified expandable polystyrene comprises the following steps of mixing water, polystyrene master batch, sodium butylnaphthalenesulfonate, polyvinyl alcohol, butane, dicumyl peroxide, bromoalkane and an antioxidant according to a mass ratio of 1.6: 1: 0.03: 0.002: 0.1: 0.008: 0.01-0.02: 0.003 of mixture, and the impregnation reaction is carried out for 10 to 12 hours at the temperature of 72 plus or minus 2 ℃, the pressure of 0.9 plus or minus 0.1MPa and the rotating speed of 95 to 100r/min to obtain the modified expandable polystyrene.
10. The preparation method of the fireproof flame-retardant composite heat-insulation decorative plate for the exterior wall according to claim 8 is characterized in that the preparation method of the modified expandable graphite is that the crystalline flake graphite, hydrogen peroxide and fuming nitric acid are mixed and rapidly stirred in an ice-water bath until the reaction is gentle, then the reaction system is kept at the constant temperature of 25 ℃, washed, filtered, dripped with an acetic acid solution and continuously stirred, reacted for 60-120 min, washed, filtered and dried to obtain the modified expandable graphite; or the flake graphite is prepared by the following steps: KMnO4= 1: 0.2-0.4 of KMnO is added into the crystalline flake graphite4Stirring, adding HClO3Solution andand (3) keeping the temperature of 35 ℃ and intermittently stirring for reaction for 60-120 min, then washing, carrying out suction filtration and drying to obtain the modified expandable graphite.
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