CN112159631A - Expandable fireproof armor and application thereof - Google Patents
Expandable fireproof armor and application thereof Download PDFInfo
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- CN112159631A CN112159631A CN202011045347.XA CN202011045347A CN112159631A CN 112159631 A CN112159631 A CN 112159631A CN 202011045347 A CN202011045347 A CN 202011045347A CN 112159631 A CN112159631 A CN 112159631A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/92—Protection against other undesired influences or dangers
- E04B1/94—Protection against other undesired influences or dangers against fire
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/26—Presence of textile or fabric
- C09J2400/263—Presence of textile or fabric in the substrate
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Abstract
The invention provides an expandable fireproof armor and application, wherein the fireproof armor comprises a fireproof coating, a non-woven fabric layer and an adhesive layer, the non-woven fabric layer I and the non-woven fabric layer II are respectively covered on two surfaces of the fireproof coating, the adhesive layer is positioned on the other surface of the non-woven fabric layer I relative to the fireproof coating, the fireproof coating contains hydroxypropyl methyl cellulose and a flame-retardant fireproof expansion type coating, the fireproof coating expands by more than 5 times after being combusted and does not fall off from a protected part, and cracks can not occur when the fireproof coating is bent by more than 60 degrees, so that the construction is convenient, namely the fireproof armor is used after being bonded, the fireproof effect is excellent, and the fireproof armor can resist the combustion at more; the outer layer is coated with the non-woven fabric layer to replace the traditional glass fiber layer, so that the phenomenon that the fireproof armor is itchy when contacting the skin of a human body is avoided.
Description
Technical Field
The invention relates to the field of fire protection, in particular to an expandable fire-proof armor.
Background
For buildings, steel structure fire protection, wall fire protection, wire and cable fire protection and door and window fire protection are all very important. The common fire protection method comprises the following steps: spraying fireproof paint and coating fireproof plate. However, the fireproof coating usually cannot reach the same age as a building, the expansibility is insufficient, the fire danger is difficult to be effectively isolated, the construction is time-consuming and labor-consuming, the heat insulation effect is poor while the fire is retarded, and the coating is easy to fall off when the fire is ignited and combusted.
CN108018997A discloses a fire-proof and decoration integrated prefabricated column, which comprises H-shaped steel, wherein the H-shaped steel comprises a web plate and flanges which are arranged at two ends of the web plate and are vertical to the web plate; steel bars are welded between the flanges; a metal net is fixed on the outer side of the steel bar; concrete is poured between the flanges and on two sides of the web; the outer surface of the flange is wrapped with an ALC air-entrapping sheet; the mortar surface course coats on the four corners of H shaped steel and the concrete surface, mortar surface course surface can set up the decorative surface layer, and this decorative surface layer plays the effect of decorating and fire prevention simultaneously. No specific fire-resistant decorative layer composition is disclosed, nor is there any mention of specific fire-resistant effects.
CN107882263A discloses an assembled heat preservation, fire prevention, veneer integration prefabricated wallboard, it includes a reinforced concrete wallboard, the upper surface of reinforced concrete wallboard is coated with a layer of 4-6mm thick polymer dry-mixed bonding mortar layer, the upper surface of dry-mixed bonding mortar layer is evenly distributed with fire prevention heat preservation strip, a layer of facing EPS board is adhered on the dry-mixed mortar at the two sides of fire prevention heat preservation strip, a layer of alkali-resistant mesh cloth is arranged on the facing EPS board, polymer facing mortar with thickness of 2-4mm is filled between the mesh cloth and the facing EPS board and the fire prevention heat preservation strip, a layer of back cover putty is coated on the facing mortar, a layer of color layer is sprayed on the back cover putty, and a finishing agent layer is evenly distributed on the color layer. The reinforced concrete wall board is a shear wall board or a common external hanging board. There is no disclosure of specific fire-resistant insulating strip compositions nor mention of specific fire-resistant effects.
CN105040848A discloses a fire-proof plate, includes precoat, glass fiber net cloth, fire-proof plate core, glass fiber net cloth and bed charge layer in proper order. However, the main components of both the primer layer and the facing layer are cement and inorganic salt, and the main components of the core body of the fire retardant panel are silica and inorganic salt, which makes the weight of the fire retardant panel large.
The fire-retardant coating, also called flame-retardant coating, is a generic name of coatings which are coated on flammable building materials such as timber, textile fiber, polymer products and the like or coated on the surfaces of objects such as cables, steel structure building materials and the like. The fireproof coating can block flame to prevent the flame from directly contacting with a substrate, so that the burning time of the substrate is delayed, the propagation speed of the flame on the surface of the substrate can be delayed, the expansion of a fire disaster is prevented, the burning resistance time of the substrate can be prolonged, the time of structural damage is delayed, and the like, and the fireproof coating plays a plurality of roles of fireproof protection, corrosion prevention, rust prevention, acid and alkali resistance, smoke prevention and the like. The intumescent fire-retardant coating is the most widely used fire-retardant coating at home and abroad at present based on the excellent fire-retardant property and environmental protection property.
So far, a plurality of patents in China disclose the preparation and application of the fireproof flame-retardant coating. For example:
CN107903746A discloses a water-based acrylate composite heat-insulating fireproof coating, which comprises the following components in parts by weight: 20-40 parts of acrylate emulsion, 2-5 parts of glass hollow microspheres, 8-15 parts of diatomite, 5-10 parts of nano titanium dioxide, 6-10 parts of ceramic hollow microspheres, 3-6 parts of nano far infrared ceramic powder, 10-20 parts of pentaerythritol, 15-25 parts of melamine, 10-15 parts of ammonium polyphosphate, 5-10 parts of nano aluminum hydroxide, 2-5 parts of zinc borate, 0.3-0.9 part of pH regulator, 0.5-1.0 part of dispersant, 0.2-0.5 part of defoamer, 1.0-2.5 parts of film-forming assistant, 0.5-0.8 part of thickener, 0.1-0.3 part of wetting agent and 30-50 parts of distilled water. According to the invention, acrylate emulsion is used as a film forming material, an expansion fire retardant composed of pentaerythritol, melamine and ammonium polyphosphate is added, nano aluminum hydroxide and zinc borate are added as fire retardants, reflective heat-insulating pigment fillers such as glass hollow microspheres, diatomite, nano titanium dioxide, ceramic hollow microspheres and nano far infrared ceramic powder are added, and a part of additives are added, so that the water-based acrylate composite heat-insulating fireproof coating is prepared. The nanometer aluminum hydroxide and zinc borate flame-retardant filler has a synergistic flame-retardant effect on the intumescent fire retardant, can absorb a large amount of heat at the initial combustion stage, reduces the generation of a large amount of smoke when organic matters are combusted, and simultaneously can ensure that expanded foam is compact and uniform and is not easy to fall off. The nano titanium dioxide and the nano far infrared ceramic powder have good reflection effect on solar radiation, the heat accumulation is reduced, the hollow ceramic microspheres and the hollow glass microspheres have lower heat conductivity coefficients, and the materials are added into the coating to play a role in heat insulation, heat preservation and fire prevention;
CN107858056A discloses a fireproof and waterproof coating for basements, kitchens and toilets, which comprises the following raw materials in parts by weight: 80-120 parts of acrylate emulsion, 25-35 parts of aluminum hydroxide, 8-1 part of zinc borate, 3-6 parts of dispersing agent, 5-8 parts of plasticizer, 2-5 parts of pigment and filler, 1-2 parts of titanium dioxide, 0.1-0.3 part of initiator, 5-8 parts of film forming additive, 0.1-0.5 part of mildew-proof bactericide, 0.1-0.3 part of defoaming agent, 1-1.5 parts of thickening agent and 30-50 parts of deionized water, and the coating has the advantages of good antibacterial and mildew-proof effects, artificial weather aging resistance, scouring resistance, firmness, no deformation, strong decorative effect, no toxicity and no harm to human bodies, environmental protection and attractive decorative effect, ultraviolet irradiation resistance, high adhesion, good waterproof and shock-resistant effects, good fireproof performance and the like;
CN105542587A discloses a steel structure fireproof paint, which is prepared from the following main raw materials in parts by weight: 19-23 parts of ammonium polyphosphate, 9-17 parts of melamine, 7-14 parts of pentaerythritol, 4-9 parts of silica sol, 8-11 parts of vinyl acetate-acrylic emulsion, 5-11 parts of high chlorinated polyethylene resin, 3-6 parts of glass fiber powder, 20-24 parts of deionized water, 1.2-2.2 parts of thickening agent, 2-4 parts of dispersing agent and 0.2-0.3 part of defoaming agent.
CN2292018Y discloses a flame-retardant decorative wall cloth comprising a substrate layer and a decorative layer, which is characterized in that a flame-retardant coating layer is coated on the surface of a cloth substrate layer of inorganic material glass fiber yarns, and decorative patterns with various colors are printed on the coating layer.
Currently available fire-retardant coatings are generally applied to fiberglass cloth and then the building structure is coated to improve the fire-retardant properties of the various related structures. The fire-retardant coating materials have advantages, but they are not mentioned in terms of the degree of swelling, the degree of flexibility and the retention of the form after combustion, or even in terms of the simultaneous optimization of various properties, in view of the specific construction and further applications to follow.
Therefore, it is highly desirable to develop an effective fire-proof armor material, which can rapidly expand during the fire, effectively inhibit the spread of the fire, and perform the functions of thermal insulation, and at the same time, the fire-proof layer can keep for at least three hours without falling off along with the duration of the fire, thereby improving the safety level of the building components. Furthermore, it is safer and more comfortable for the constructor and easier to handle.
Disclosure of Invention
In order to solve the problems, the application provides an expandable fireproof armor and a preparation method thereof, the expandable fireproof armor is a coating-shaped fireproof armor, and can be directly bonded to a protected structure through a binder layer in the using process, so that the construction is convenient, namely the expandable fireproof armor can be used after being bonded, and the waiting time for construction is not needed; the fireproof effect is excellent, and the fire-resistant fireproof paint can resist burning at the temperature of more than 1000 ℃ for half an hour; the outer layer is coated with the non-woven fabric layer to replace the traditional glass fiber layer, so that the phenomenon that the fireproof armor is itchy when contacting the skin of a human body is avoided; the smoke density generated by combustion is low, and the smoke is halogen-free white smoke. The expandable fireproof armor provided by the invention has high fireproof grade, can expand to a certain degree at high temperature, and can effectively prevent fire cross and smoke diffusion. The fireproof armor provided by the invention extends to be an isolation component with a fireproof effect, can be in various forms such as a plate shape, a strip shape, a block shape and even a granular shape, can freely select the shape according to different use occasions, and can be used in occasions such as buildings, nuclear power, shipbuilding, high-speed trains, offshore stone drilling platforms, furniture and the like, and particularly can be used in the aspects of steel structure protective layers, through-wall protection of cables, bridges, ship interlayers, fireproof door and window partition cores, partition walls, elevators, suspended ceilings, floors, pipelines and the like.
Specifically, the application firstly provides an expandable fireproof armor, which comprises a fireproof coating, a non-woven fabric layer and an adhesive layer, wherein the non-woven fabric layer I and the non-woven fabric layer II respectively cover two surfaces of the fireproof coating, and the adhesive layer is positioned on the other surface, opposite to the fireproof coating, of the non-woven fabric layer I.
A schematic diagram of the fire armor provided by the present invention is shown in fig. 1.
The thickness of each layer of the expandable fireproof armor accords with the common knowledge in the field, and is not particularly limited, generally speaking, the fireproof coating is 1-3mm, the non-woven fabric layers I and II are independently 0.5-1mm, and the adhesive layer is 0.2-0.5 mm.
Preferably, the fire-retardant coating is a mixture of hydroxypropyl methylcellulose and a flame-retardant fire-retardant intumescent coating. Further preferably, the hydroxypropyl methylcellulose is used in an amount of 3-8%, preferably 4-6% by weight of the total coating.
The inventor finds that the hydroxypropyl methyl cellulose and the flame-retardant and fireproof intumescent coating generate a synergistic effect, so that the cracking resistance of the fireproof coating can be obviously improved, the fireproof coating expands more than 4 times after being combusted and does not fall off from a protected part, and cracking does not occur when the fireproof coating is bent by more than 60 degrees; in the preferred technical scheme of the invention, the fireproof coating expands more than 6 times and does not fall off from the protected component; no crack occurs when the glass is bent by more than 90 degrees.
The adhesive layer is a high-temperature-resistant adhesive, wherein the adhesive contains silica fume as a filler, and the silica fume accounts for 10-20 wt%.
The non-woven fabric is a terylene non-woven fabric with certain flame retardance, the thickness is 1-3mm, and the gram weight is 200-2。
The expandable fireproof armor preferably further comprises more than one (including one) glass fiber net reinforcing layer, and the glass fiber net reinforcing layer is buried in the paint layer.
The flame-retardant fireproof intumescent coating comprises: water, resin emulsion, modified expandable graphite, a fireproof flame retardant, a reinforcing agent, white carbon black treated by siloxane and other auxiliary agents.
The preparation raw materials of the modified expandable graphite comprise crystalline flake graphite, an oxidant, an anion intercalation agent and mixed acid, wherein the mixed acid comprises benzene trisulfonic acid; the anionic intercalation agent is an anionic surfactant with long-chain alkyl, such as sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium diisooctyl succinate sulfonate, sodium lauryl sulfate and sodium fatty alcohol ether sulfate.
Further, the modified expandable graphite comprises the following raw materials in parts by weight: 10-15 parts of natural crystalline flake graphite, 0.5-0.8 part of oxidant, 30-80 parts of mixed acid and 3-5 parts of anion intercalation agent.
The oxidant is KMnO4，KClO3，K2Cr2O7,(NH)4S2O8And (3) at least one of hydrogen peroxide (30-40%).
The mixed acid is concentrated sulfuric acid, concentrated nitric acid, oxalic acid and benzene trisulfonic acid according to the mass ratio of 4-6: 2-2.5: 1-2: 2-3.
The amount of the mixed acid is not particularly limited, and the natural crystalline flake graphite can be sufficiently soaked, and is generally more than 30 parts, but the excessive amount of the mixed acid causes waste of raw materials, and is generally controlled below 80 parts.
The inventor unexpectedly finds that when the expandable graphite is prepared, a certain amount of benzene trisulfonic acid is added into mixed acid to be matched with intercalation of an anionic surfactant, and the expansion rate of the prepared pit expandable graphite can reach a satisfactory degree at low temperature. Generally, the swelling rate is considerable at 200 ℃. Certain oxalic acid is added, namely the oxalic acid serves as an acid source and also serves as an organic intercalation agent, and the oxalic acid can be decomposed to generate carbon dioxide when being heated, so that the graphite is further expanded.
Preferably, the modified expandable graphite of the present invention is obtained by a preparation method comprising the following steps: dissolving an oxidant in mixed acid, adding natural crystalline flake graphite into the mixed acid solution, uniformly mixing, filtering, washing with hydrogen peroxide, washing with water to be neutral, and drying to obtain the modified expandable graphite.
The resin emulsion is selected from one or more of the group consisting of vinyl acetate-vinyl versatate polymerized emulsion, polyvinyl acetate emulsion, styrene-acrylate emulsion, organic silicon modified acrylate emulsion, polystyrene modified emulsion, acrylic emulsion, polyacrylate emulsion and water-soluble phenolic resin; the reinforcing agent is glass fiber, basalt reinforced fiber and the like.
The fireproof flame retardant is a mixture of pentaerythritol, ammonium polyphosphate and melamine, and the weight ratio of the pentaerythritol to the ammonium polyphosphate to the melamine is 2-4: 1-2: 1 to 2.
The other auxiliary agents comprise a dispersing agent, a film-forming auxiliary agent, an emulsifying agent, a pigment and filler, a defoaming agent, a bactericide and/or a stabilizing agent. The dispersant can be selected from sodium oleate, potassium carboxylate, sodium sulfonate, polyethylene glycol, stearic acid monoglyceride, oil ether type stearic acid soap, polyethylene wax, ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, etc.; the emulsifier may be selected from xanthan gum; the film forming auxiliary agent is selected from one or a mixture of more of alcohol ester twelve 2-amino-2-methyl-1-propanol, alcohol ester twelve, ethylene glycol butyl ether, propylene glycol butyl ether, benzyl alcohol and propylene glycol phenyl ether; the antifoaming agent is selected from emulsified silicone oil, higher alcohol fatty acid ester compound, polyoxyethylene polypropylene pentaerythritol, polyoxyethylene polyoxypropylene amine ether and polydimethylsiloxane, and the pigment and filler is superfine calcite powder, rutile type titanium dioxide and bentonite (titanium dioxide R930); the bactericide is selected from one or more of isothiazolinone, chloro methyl isothiazolinone, benzisothiazolinone, 1, 2' -dibromo-2, 4-dicyanobutane, 2-bromo-2-bromomethylglutaronitrile or 2-benzimidazolyl methyl carbamate.
The flame-retardant fireproof intumescent coating comprises the following raw materials in parts by mass: 180-230 parts of water, 180-230 parts of resin emulsion, 100-180 parts of fireproof flame retardant, 70-120 parts of expandable graphite, 14-20 parts of reinforcing agent and 75-90 parts of siloxane-treated white carbon black; preferably, the flame-retardant fireproof intumescent coating comprises the following raw materials in parts by mass: 200-210 parts of water, 200-210 parts of resin emulsion, 120-150 parts of fireproof flame retardant, 80-100 parts of expandable graphite, 15-17 parts of reinforcing agent and 80-85 parts of siloxane-treated white carbon black.
The dosage of the other auxiliary agents is flexibly adjusted according to the actual requirement in the field as long as the performance of the fireproof armor is not influenced.
For example, the dispersant is used in an amount of 2 to 5 parts, preferably 3 to 4 parts; the dosage of the film-forming additive is 7-11 parts, preferably 8-9 parts; the using amount of the defoaming agent is 3-7 parts, preferably 5-6 parts; the dosage of the pigment and the filler is 80-120 parts, preferably 90-100 parts; the amount of the bactericide is 0-3 parts, preferably 1-2 parts; the emulsifier is used in an amount of 1 to 4 parts, preferably 2 to 3 parts.
The hydroxypropyl methyl cellulose accounts for 3-8%, preferably 4-6% of the total weight of the coating.
In addition, the application also provides a preparation method of the expandable fireproof armor, which comprises the following steps:
(1) uniformly mixing all the raw materials of the fireproof intumescent coating;
(2) preparing a mixture A of the flame-retardant fireproof intumescent coating and hydroxypropyl methyl cellulose;
(3) enabling the mixture A to be located between two non-woven fabric layers, and enabling the mixture A to be solidified and formed into a fireproof coating; or the mixture A is applied on one non-woven fabric layer I to a determined thickness to form a fireproof coating, another non-woven fabric layer II is laid after the fireproof coating is cured to a certain degree, and an adhesive layer is added on the other side, opposite to the fireproof coating, of the non-woven fabric layer I after the mixture A is completely cured.
Preferably, the method further comprises the step of applying a fiberglass layer, wherein the fiberglass layer is located in the paint layer.
Preferably, the non-woven fabric layer I is provided with fine pores, and the adhesive layer is tightly adhered to the fireproof coating through the pores.
The invention also provides application of the expandable fireproof armor in the aspects of buildings, nuclear power, shipbuilding, high-speed trains, offshore stone drilling platforms and furniture, and particularly relates to application in the aspects of steel structure protective layers, through-wall protection of cables, bridges, ship interlayers, fireproof door and window partition cores, partition walls, elevators, suspended ceilings, floors, pipelines and the like.
Drawings
FIG. 1 is a schematic representation of fire protection armor provided by the present invention.
Detailed Description
In the examples of the present invention, "part" means part by weight unless otherwise specified, and "%" means% by weight unless otherwise specified.
The concentration of concentrated sulfuric acid used in the embodiment of the invention is 98 wt%, the concentration of concentrated nitric acid is 66 wt%, and the natural crystalline flake graphite is purchased from Qingdao Tianyuan Daigao graphite Co Ltd, the granularity is 0.5mm-1 μm, and the carbon content is more than 98%. Hydroxypropyl methylcellulose is purchased from hong Hai cellulose, Inc., and has a hydroxypropoxy content of about 8 wt%, a particle size of 80 mesh, and an ash content of less than 3%.
The terylene non-woven fabric is purchased from Jintai felt factory in Nangong city, 400g/m2The thickness is 1.5 mm.
The adhesive is prepared by mixing and stirring a high-temperature-resistant adhesive (JL-528AB, which is purchased from a self-adhesive and has a temperature resistance range of-30 to 500 ℃) and silica fume, wherein the silica fume accounts for 13.2 wt% of the adhesive.
Preparation examplePreparation of modified expandable graphite
Preparation example 1
Dissolving 0.5 part of potassium permanganate and 3 parts of sodium dodecyl benzene sulfonate in 40 parts of mixed acid, wherein the mixed acid is concentrated sulfuric acid, concentrated nitric acid, oxalic acid and benzene trisulfonic acid according to a mass ratio of 5:2: 1: 3, stirring and mixing uniformly to obtain a mixed acid solution, adding 12 parts of natural crystalline flake graphite into the mixed acid solution, stirring and mixing uniformly, filtering after 6 hours, filtering a filter substance by using 20% hydrogen peroxide, washing the filter substance to be neutral by using pure water, and drying the filter substance overnight in an oven at 50 ℃ to obtain the modified expandable graphite, which is hereinafter referred to as expandable graphite 1.
Preparation example 2
Dissolving 0.5 part of potassium permanganate and 3 parts of sodium dodecyl sulfate in 40 parts of mixed acid, wherein the mixed acid is concentrated sulfuric acid, concentrated nitric acid, oxalic acid and benzene trisulfonic acid according to a mass ratio of 5:2: 1: 2, stirring and mixing uniformly to obtain a mixed acid solution, adding 12 parts of natural crystalline flake graphite into the mixed acid solution, stirring and mixing uniformly, filtering after 6 hours, filtering a filter substance by using 20% hydrogen peroxide, washing the filter substance to be neutral by using pure water, and drying the filter substance overnight in a 50 ℃ oven to obtain the modified expandable graphite, which is hereinafter referred to as expandable graphite 2.
Comparative preparation example 1
Dissolving 0.5 part of potassium permanganate and 3 parts of sodium dodecyl benzene sulfonate in 40 parts of mixed acid, wherein the mixed acid is prepared by compounding concentrated sulfuric acid, concentrated nitric acid and oxalic acid according to the mass ratio of 5:2:1, stirring and mixing uniformly to obtain a mixed acid solution, adding 12 parts of natural crystalline flake graphite into the mixed acid solution, stirring and mixing uniformly, filtering after 6 hours, filtering a filter substance by using 20% hydrogen peroxide, washing the filter substance to be neutral by using pure water, and drying the filter substance in an oven at 50 ℃ overnight to obtain modified expandable graphite, which is hereinafter referred to as expandable graphite 3.
The expandable graphite obtained in the above preparation example was subjected to an expansion test, and the results are shown in table 1 below:
TABLE 1
ExamplesPreparation of fire-proof armor
Example 1
(1) 2100g of resin emulsion EVA-1120 (with the solid content of 32 wt%) and 90g of alcohol ester dodecahydrate are poured into a stirrer, 2100g of pure water is added, 315g of ammonium polyphosphate, 315g of melamine, 630g of pentaerythritol, 1000g of titanium dioxide R930, 900g of expandable graphite 1 prepared in the preparation example, 800g of white carbon black treated by a silane coupling agent (KH-550), 30g of stearic acid monoglyceride, 50g of emulsified silicone oil, 170g of basalt fiber, 20g of xanthan gum and 10g of isothiazolinone are added, and the mixture is stirred (the stirring speed is 140R/min) for 20 minutes to prepare the coating; when the fireproof armor is used, 310g of hydroxypropyl methyl cellulose is added into the mixture, the mixture is uniformly stirred to prepare a mixture of the coating and the hydroxypropyl methyl cellulose, the mixture is firstly coated on a layer of non-woven fabric with the thickness of 1.2mm, then a layer of non-woven fabric is covered, finally a binding agent layer is coated on the outer layer of a certain non-woven fabric, and the thickness of the binding agent layer is about 0.2mm, so that the fireproof armor with the non-woven fabric sandwich coating layer is finally obtained. The resulting fire resistant armor was tested for fire performance and flexibility and the results are shown in table 2.
In the performance test, the shape (integrity) after combustion was observed with the naked eye; the fire-retardant rating is carried out according to the standard of the fire-retardant performance grades of building materials and products thereof (GB 8624-2006).
Example 2
The other conditions were the same as in example 1 except that the treated white carbon was replaced with white carbon which was not treated with the silane coupling agent.
Example 3
The other conditions were the same as in example 1 except that basalt fiber was not added.
Example 4
The other conditions were the same as in example 1 except that the amount of hydroxypropylmethylcellulose added was 250 g.
Example 5
The other conditions were the same as in example 1 except that the amount of hydroxypropylmethylcellulose added was 450 g.
Example 6
The other conditions were the same as in example 1 except that about half of the mixture of the coating material and hydroxypropyl methylcellulose was first coated on a layer of non-woven fabric with a thickness of about 0.6mm, then covered with a layer of glass fiber cloth, then the remaining mixture of the coating material and hydroxypropyl methylcellulose was coated with a thickness of about 0.6mm, and further covered with a layer of non-woven fabric to obtain a non-woven fabric sandwich coating layer, and the fire armor sandwiched with glass fiber cloth in the coating layer. The resulting fire resistant armor was tested for fire performance and flexibility and the results are shown in table 2.
Example 7
The other conditions were the same as in example 1 except that the expandable graphite 1 was replaced with an expandable graphite 2 of equal mass.
Comparative example 1
The other conditions were the same as in example 1 except that hydroxypropylmethylcellulose was not added.
Comparative example 2
The other conditions were the same as in example 1 except that the expandable graphite 1 was replaced with an expandable graphite 3 of equal mass.
TABLE 2 comparison of the properties of the examples and comparative examples
It will be understood that the embodiments described above are illustrative only and not restrictive, and that various obvious and equivalent modifications and substitutions for details described herein may be made by those skilled in the art without departing from the basic principles of the invention.
Claims (10)
1. The expandable fireproof armor comprises a fireproof coating, a non-woven fabric layer and an adhesive layer, wherein the non-woven fabric layer I and the non-woven fabric layer II cover two surfaces of the fireproof coating respectively, and the adhesive layer is positioned on the other surface, opposite to the fireproof coating, of the non-woven fabric layer I.
2. The fire protective armor of claim 1 wherein said fire protective coating is a mixture of hydroxypropyl methylcellulose and a fire retardant intumescent coating; preferably, the hydroxypropyl methylcellulose is used in an amount of 3 to 8%, preferably 4 to 6%, by weight of the total coating.
3. The fire armor of claim 1, wherein said adhesive layer is a high temperature resistant adhesive containing silica fume as a filler, the silica fume being 10-20 wt%;
the non-woven fabric is a terylene non-woven fabric with the thickness of 1-3mm and the gram weight of 200-1000g/m2。
4. The fire resistant armor of claim 1 further comprising more than one fiberglass web reinforcing layer embedded in said paint layer.
5. The fire protective armor of claim 1 wherein said fire retardant intumescent coating comprises the following raw materials: water, resin emulsion, modified expandable graphite, a fireproof flame retardant, a reinforcing agent, white carbon black treated by siloxane and other auxiliary agents;
preferably, the resin emulsion is selected from one or more of the group consisting of vinyl acetate-vinyl versatate polymerized emulsion, polyvinyl acetate emulsion, styrene-acrylate emulsion, organosilicon modified acrylate emulsion, polystyrene modified emulsion, acrylic emulsion, polyacrylate emulsion and water-soluble phenolic resin; the solid content of the resin emulsion is 30-40 wt%; the reinforcing agent is glass fiber and basalt reinforcing fiber; the fireproof flame retardant is a mixture of pentaerythritol, ammonium polyphosphate and melamine, and the weight ratio of the pentaerythritol to the ammonium polyphosphate to the melamine is 2-4: 1-2: 1 to 2.
6. The fire resistant armor of claim 5 wherein said modified expandable graphite is prepared from starting materials including flake graphite, an oxidizing agent, an anionic intercalating agent, and a mixed acid, said mixed acid comprising trimellitic acid; the anionic intercalation agent is an anionic surfactant with long chain alkyl groups.
7. A fire resistant armor as claimed in claim 6, wherein said modified expandable graphite comprises the following raw materials in parts by weight: 10-15 parts of natural crystalline flake graphite, 0.5-0.8 part of oxidant, 30-80 parts of mixed acid and 3-5 parts of anion intercalation agent.
8. The fire-resistant armor of claim 7, wherein the mixed acid is concentrated sulfuric acid, concentrated nitric acid, oxalic acid and trimellitic acid in a mass ratio of 4-6: 2-2.5: 1-2: 2-3.
9. The fire resistant armor of claim 5 wherein said fire retardant intumescent coating comprises the following raw materials in parts by mass: 180-230 parts of water, 180-230 parts of resin emulsion, 100-180 parts of fireproof flame retardant, 70-120 parts of expandable graphite, 14-20 parts of reinforcing agent and 75-90 parts of siloxane-treated white carbon black; preferably, the flame-retardant fireproof intumescent coating comprises the following raw materials in parts by mass: 200-210 parts of water, 200-210 parts of resin emulsion, 120-150 parts of fireproof flame retardant, 80-100 parts of expandable graphite, 15-17 parts of reinforcing agent and 80-85 parts of siloxane-treated white carbon black.
10. Use of the fire protection armor according to any one of claims 1-9 in buildings, nuclear power, shipbuilding, high speed trains, offshore stone drilling platforms and furniture, in particular in steel structural sheathing, wall penetration protection of cables, bridges, marine mezzanines, fire protection door and window cores, partitions, elevators, suspended ceilings, floors, pipes, etc.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113733672A (en) * | 2021-09-07 | 2021-12-03 | 无锡海跃船舶新材料科技有限公司 | Anti-static explosion-proof heat-insulation material for deep sea platform |
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| CN101747817A (en) * | 2008-12-11 | 2010-06-23 | 同济大学 | Water-based halogen-free steel structure ultra-thin expansion fireproof coating and preparation method thereof |
| CN103663443A (en) * | 2013-12-17 | 2014-03-26 | 王伟 | Preparation method of expandable graphite |
| CN108999359A (en) * | 2017-06-07 | 2018-12-14 | 桂林市庆通有色金属工艺材料开发有限公司 | A kind of diatom ooze surface layer interior decoration panel |
| JP2019116551A (en) * | 2017-12-27 | 2019-07-18 | Ａｇｃ株式会社 | Expandable fireproof coating |
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| CN101747817A (en) * | 2008-12-11 | 2010-06-23 | 同济大学 | Water-based halogen-free steel structure ultra-thin expansion fireproof coating and preparation method thereof |
| CN103663443A (en) * | 2013-12-17 | 2014-03-26 | 王伟 | Preparation method of expandable graphite |
| CN108999359A (en) * | 2017-06-07 | 2018-12-14 | 桂林市庆通有色金属工艺材料开发有限公司 | A kind of diatom ooze surface layer interior decoration panel |
| JP2019116551A (en) * | 2017-12-27 | 2019-07-18 | Ａｇｃ株式会社 | Expandable fireproof coating |
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