FI126517B - Organic / inorganic composite and refractory board containing it - Google Patents

Description

Organic / inorganic composite and fire-resistant sheet containing it

BACKGROUND OF THE INVENTION Field of the Invention The invention relates to organic / inorganic composites having excellent fire resistance properties, and to an organic / inorganic composite fire retardant sheet.

Description of Related Art Fire resistant or flame retardant materials may be used as architectural or decorative materials. The architectural materials disclosed in Taiwanese Patent Nos. 583,078 and 397,885 consist essentially of a filler layer which functions as a fire resistant layer comprising inorganic materials such as perlite, MgCl 2, MgO, CaCO 3 or cement. In addition, a rigid, fire-resistant laminate can be obtained from flexible substrates of fibers or nonwovens mixed with flame retardants, blowing agents and 50-80% by weight of inorganic materials.

Flame retardant coatings, which act as decorative materials and are disclosed in Taiwanese Patent Nos. 442,549, 499,469, and 419,514, comprise a combination of foaming and expanding agents, carbonating agents, flame retardants, and adhesives that foam and expand when exposed. U.S. Patent No. 5,723,515 discloses a flame-retardant coating material comprising a fluid, expandable base material comprising blowing agents, a blowing agent, a carbonising agent, a binder, a solvent, and a pigment, which improves fracture and shrink resistance. The blend disclosed in U.S. Patent No. 5,218,027 is prepared from a composition of a copolymer or terpolymer, a low modulus polymer, and a synthetic hydrocarbon elastomer. The flame retardant additive comprises a Group I, Group II or Group III metal hydroxide, provided that at least 1% by weight of the composition is in the form of an organopolysiloxane. U.S. Patent No. 6,262,161 relates to filled copolymer compositions of ethylene and / or alpha-olefin / vinyl or vinylidene monomers having improved properties upon exposure to flame or ignition sources, and products made therefrom. Products can be in the form of film, sheet metal, multilayer structure, floor, wall or ceiling coverings, foams, fibers, electrical equipment or cable and cable installations. Conventional flame retardant polymer compositions are obtained by physical mixing of an organic polymer with an inorganic flame retardant, in which binders or surfactants are typically incorporated to improve dispersion of the inorganic flame retardant. However, since the organic polymer does not react with the inorganic component to form a well-structured composite by forming chemical bonds, conventional flame retardant compositions will readily melt, ignite, or produce flammable droplets when exposed to flame or ignition sources.

EP 1384752 discloses an insulated electric cable comprising a combination of a micro-mixture and a modified micro-mixture, wherein the micro-mixture comprises polypropylene and the modified micro-mixture is made by bonding an organic acid group to the micro-mixture; polypropylene; and an ionic cross-linking filler which is magnesium hydroxide.

US 4,246,146 discloses a fire retardant protective coating produced by dissolving a water soluble polyisocyanate prepolymer in an aqueous slurry or solution of either fire retardant materials or thickeners. Aluminum trihydrate, Al (OH) 3, is used as a flame retardant or thickener.

US 4066578 discloses a polyurethane composition, in particular a cross-linked hydrophilic polyurethane foam system.

In particular, as shown in Figures 1a to 1b, the heated region of a conventional fire-resistant material may rapidly char and expand by 8 to 10 times its original volume due to the blowing, swelling and carbonizing agents contained therein. However, as shown in Figures 1c-1d, after prolonged heating, the expanding carbonization layer (or heated portion) breaks slightly and peeles away so that flame and heat can be transferred directly to the interior materials and fire resistance is lost. Thus, improved fire-resistant material is desirable.

BRIEF SUMMARY OF THE INVENTION Due to the problems of conventional technology, the present invention employs a fire-resistant composite material comprising various inorganic particles dispersed completely in a polymer, copolymer or oligomer having reactive functional groups. The inorganic particles may also contain reactive functional groups, either initially or after surface modification, which may react with the corresponding reactive functional groups of the organic component to form organic / inorganic composite materials. The reaction between the organic and inorganic components strengthens and improves the mechanical and fire resistance properties of the organic polymer. The formation of chemical bonds provides a well-structured composite, the carbon layer formed on the surface being strong and capable of retaining its structural integrity without peeling or fracturing, effectively preventing heat transfer to the interior.

The organic / inorganic composite of the invention comprises a polymer, copolymer or oligomer having a first reactive functional group; and inorganic particles having a second reactive functional group; wherein the inorganic particles are chemically bonded to the polymer, copolymer or oligomer by reaction between the first and second reactive groups.

The invention further provides a fire-resistant panel comprising the disclosed composite.

The following embodiments will provide a detailed description with reference to the accompanying drawings.

Brief Description of the Drawings

The invention will be better understood by reading the following detailed description and examples, with reference to the accompanying drawings, in which: Figures 1a to 1d show conventional expandable flame-retardant materials which have been subjected to a flame test; Figure 2 shows a composite material of an organic polymer and inorganic particles according to the invention subjected to a flame test; Figure 3 is a flowchart illustrating a process for the synthesis of an organic polymer and composite material formed by inorganic particles; Fig. 4 is a schematic diagram showing a flame test performed on a sample of a composite material formed by an organic polymer and inorganic particles; Fig. 5 is a schematic diagram showing the temperature measurement of A4 paper in Example 10; and Fig. 6 is a graph showing the temperature at the back of A4 paper as a function of the heating time comparing the fire resistant sheet of Example 9 with a commercial flame retardant coating material.

DETAILED DESCRIPTION OF THE INVENTION The following description is the preferred embodiment for carrying out the invention. This description is made for the purpose of illustrating the general principles of the invention and is not to be construed as limiting. The scope of the invention is best defined by reference to the appended claims.

The invention relates to an organic / inorganic composite comprising: an organic component comprising from 30 to 70% by weight of a polymer, copolymer or oligomer comprising polyurethane, or a polyolefin copolymer having a first reactive, functional isocyanate group; and 70 to 30% by weight of inorganic particles comprising metal hydroxide Al (OH) 3 or Mg (OH) 2 having another reactive, hydroxyl functional group; wherein the inorganic particles are chemically bonded to the polymer, copolymer or oligomer by reaction between the first and second reactive functional groups, wherein the inorganic and organic components are sufficiently bonded to provide a fire-resistant coating material capable of withstanding 1000-1200 ° C: flame temperatures for more than 3 minutes.

The invention further relates to a flame-retardant sheet comprising: an organic / inorganic composite comprising: 30 to 70% by weight of an organic component comprising polylic acid, polyurethane, epoxy resin, polyolefin, or polyamine having a first reactive, isocyanate functional group; and 70 to 30% by weight of inorganic particles comprising a metal hydroxide, nitride, oxide, carbide, metal salt or inorganic layered material having another reactive, hydroxyl functional group; wherein the inorganic particles are chemically bonded to the polylic acid, polyurethane, epoxy resin, polyolefin or polyamine by reaction between the first and second reactive functional groups; wherein the inorganic and organic components are sufficiently bonded to provide a flame-retardant coating material capable of withstanding flame temperatures from 1000 to 1200 ° C for more than 3 minutes.

When the organic / inorganic composite material is burned or subjected to combustion, the organic component forms a carbon layer and the inorganic particles radiate the absorbed heat. The inorganic particles also reinforce the mechanical properties of the structure by reaction between the inorganic and organic materials so that the carbon layer formed on the surface is strong and able to retain its structural integrity without peeling or fracturing, effectively preventing direct heat transfer to the interior. The fire-resistant material is not only flame retardant, but also protects the materials of the interior. As a result, the fire resistance time is significantly increased.

Inorganic particles having reactive, functional groups initially or after surface modification are well dispersed and allowed to react with an organic component such as a polymer, monomer, oligomer, prepolymer or copolymer to improve their flame-retardant and mechanical properties. Generally, the organic / inorganic composite may comprise 10 to 90% by weight of the organic component and 90 to 10% by weight of the inorganic particle. According to the invention, the organic / inorganic composite comprises 30-70% by weight of the organic component and 70-30% by weight of the inorganic particle, and more preferably 40-60% by weight of the organic component and 60-40% by weight of the inorganic particle.

The organic component in the resulting composite may comprise a polymer, copolymer or oligomer. For purposes of the invention, the term "polymer" or "copolymer" refers to compounds having a number average molecular weight of 1500 to 100,000 daltons, while "oligomer" refers to compounds having a number average molecular weight of 200-1499 daltons.

In the organic / inorganic composite, the organic component and the inorganic particles are chemically bonded together by the reaction of the respective reactive functional groups. Reactive functional groups of the organic component and the inorganic particles may include, but are not limited to, -OH, -COOH, -NOO, -NH3, -NH2, -NH and epoxy groups. For example, an organic component having -COOH or -NCO groups (e.g., organic acid or reactive polyurethane) may be used to react with inorganic acids having -OH groups (e.g., metal hydroxide). In addition, the organic component containing the epoxy groups can be used to react with inorganic particles having -NH 2 groups. Alternatively, the organic component having -OH groups (e.g., polyvinyl alcohol) may react with the inorganic particles having -COOH or -NCO groups, and the organic component having NH2 groups may react with the inorganic particles having epoxy groups.

Suitable organic components include any monomers, oligomers, monopolymers, copolymers or prepolymers containing the aforementioned reactive functional groups. Reactive functional groups may be located on the backbone or side chain of the polymer. Preferred organic components are polyorganic acid, polyurethane, epoxy compound, polyolefin and polyamine. Polyorganic acid includes homopolymers or copolymers containing carboxylic or sulfonic acids such as poly (ethylene-coacrylic acid) and poly (acrylic acid-co-maleic acid). Representative examples of epoxy compounds include bis (3,4-epoxy-6-methylcyclohexylmethyl) diphenyl, vinylcyclohexene dioxide, diglycidyl-tetrahydrophthalate, poly-glycidyl hexamide, bis (2,3-epoxycyclopentyl ether resin, polyphenol-ethylethyl), and polyphenol-epinyl. (NH (CH 2) 5 CO) n), nylon 66 ((NH (CH 2) 6 -NH-CO (CH 2) 4 CO) n) and nylon 12 ((NH (CH 2) n CO) n). The polyimide contains a diamine such as 4,4-oxydianiline, 1,4-bis (4-aminophenoxy) benzene or 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and also includes a polyimide synthesized by diamine and dianhydride such as Polyolefins suitable for use include olefinic monomer and the aforementioned reactive functional groups containing anhydrous phthalic anhydride, pyromellitic acid dianhydride or benzophenone tetracarboxylic acid dianhydride. It should be noted that the organic component also includes the monomer, oligomer, copolymer and prepolymer of the typical polymers described above. Further, the organic components may be used singly or in a mixture of two or more.

Suitable inorganic particles for use herein are those which, initially or after surface modification, have corresponding functional groups which are capable of reacting with the functional groups of the organic component. Preferred inorganic particles include hydroxides, nitrides, oxides, carbides, metal salts, and inorganic layered materials. Hydroxides include metal hydroxides such as Al (OH) 3 or Mg (OH) 2. Nitrides include, for example, BN and S13N4. Carbides include, for example, SiC. Metal salts include, for example, CaCO 3. Inorganic layered materials include, for example, clay, talc and layered double hydroxide (LDH), where the clay may be smectite clay, vermiculite, halloecite, sericite, saponite, monmorillonite, beidellite, nontronite, mica. The inorganic particles can also be used as a mixture of two or more. For example, clay containing reactive functional groups can be used in combination with metal hydroxide. Suitable inorganic particles include microparticulate particles and nanoparticulate particles. Nanoparticulate particles having diameters in the range of 1 to 100 nm are particularly preferred because the smaller the particle size, the larger the surface area per unit weight.

The organic component and the inorganic particles may be directly mixed for the reaction to form covalent or ionic bonds, or the reaction may be carried out in various solvents (e.g., water, ethanol or methyl ethyl ketone). The reaction temperature is usually from room temperature to about 150 ° C and the reaction time may vary from 10 minutes to a few days depending on the starting materials used. Figure 3 is a flowchart illustrating the processes of the organic polymer and composite material formed by inorganic particles. As shown in Figure 3, an organic polymer containing reactive functional groups (such as R-COOH where R represents carbon chains) in its backbone is mixed with solvents (such as water, alcohol or MEK). Thereafter, inorganic particles having corresponding reactive functional groups (such as M-OH where M represents metal) are added to the polymer solution and the mixture is stirred at 70-90 ° C for 20 minutes to several hours until the reaction is completed. The R-COO'M + slurry is formed by the reaction between the R-COOH groups of the polymer and the M-OH groups of the inorganic particles, where R represents carbon chains and M represents metal. The composite sample layer can be obtained by coating the Teflon film with slurry followed by drying and casting the slurry layer at elevated temperature. The sample layer may be rigid or flexible depending on the organic / inorganic system of the composite.

The organic / inorganic composite according to the invention can be molded into fire-resistant sheets, strips or films by various methods. It will be appreciated that although the term "fire-resistant plate" is used throughout the Explanatory Note for simplicity, it is to be understood to include films less than 0.5 mm thick, strips between 0.5 and 2 mm thick, or plates greater than 2 mm thick. mm. Suitable casting methods include conventional compression molding, injection molding, extrusion casting, calendering casting, etc. The sample may be oven-dried or kept at room temperature until casting.

The flame-retardant sheet of the invention can be mounted on the surface of flame-retardant or flammable products by means of adhesives or mechanical tools (e.g. screws, nails or fasteners) to improve fire resistance. In addition, a fire-resistant sheet can be made of a multilayer structure with or without other fire sheets or flammable sheets. When the organic / inorganic composite of the invention is burned or exposed to fire, the polymer forms a carbon layer and the inorganic particles radiate absorbed heat. The inorganic particles also reinforce the mechanical properties of the structure by reaction between the inorganic and organic materials so that the carbonization layer formed is strong and able to retain its structural integrity without peeling or fracturing, effectively preventing direct heat transfer to the interior. The flame-retardant plate is not only flame retardant, but also protects the inner materials. As a result, the fire resistance is significantly increased. In preferred embodiments, the flame-retardant sheet is capable of withstanding flame temperatures of 1000 to 1200 ° C for more than 3 minutes. Because the organic component and the inorganic particles are chemically bonded (as compared to conventional physically mixed products), the flame-retardant composite of the invention does not melt, ignite or produce flammable droplets when exposed to flame or ignition sources.

The fire-resistant panel of the invention has a wide range of applications. It is suitable, for example, as fire-resistant filler panels or as fire-resistant wallpaper. In addition, it can be used to make flexible fire-resistant boards. Thus, various additives may be incorporated by those of ordinary skill in the art depending upon the particular application. For example, a flame retardant such as melamine phosphates, red phosphorus, and a phosphorus based flame retardant may be present to improve fire protection. A silane (such as TEOS or TEVS) or siloxane may be present to enhance structural integrity and facilitate curing. Glass sand and fiberglass may be present to improve heat resistance and strengthen structural integrity. The amount of these additives is typically 0.1 to 20 parts by weight per 100 parts by weight of the organic / inorganic composite.

Examples of Fire Resistant Composites Example 1 Poly (ethylene-coacrylic acid) containing R-COOH groups was dissolved or dispersed in water. Thereafter, inorganic Al (OH) 3 particles having reactive M-OH functional groups were added to the polymer solution and the mixture was stirred at 70-90 ° C for 20 minutes. A 1 mm thick slurry was applied to the surface of a Teflon membrane and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 At 30 ° C for 30 minutes, at 160 ° C for 30 minutes, at 180 ° C for 30 minutes and finally cast at 200 ° C for 240 minutes.

As shown in Figure 4, the sample layer 20 was removed from the Teflon film (not shown) and placed on an A4 sheet of paper 10. The flame test was performed on the surface of the sample layer 20 on a butane gas burner 30 at a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of the burning of the A4 sheet of paper are summarized in Table 1. No carbonization was observed on the A4 sheet of paper after 30, 60 and 120 seconds of heating, while after 180 seconds of heating it became slightly charred.

According to this embodiment, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the R-COOH group of poly (ethylene-coacrylic acid) reacts with the M-OH group of Al (OH) 3 to form chemical bonds instead of physical mixing.

Example 2 Poly (ethylene-coacrylic acid) containing R-COOH groups was dissolved or dispersed in water. Thereafter, inorganic Mg (OH) 2 particles having reactive M-OH functional groups were added to the polymer solution and the mixture was stirred at 70-90 ° C for 20 minutes. A 1 mm thick slurry was applied to the surface of a Teflon membrane and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 At 30 ° C for 30 minutes, at 160 ° C for 30 minutes, at 180 ° C for 30 minutes and finally cast at 200 ° C for 240 minutes.

As shown in Figure 4, the sample layer 20 was removed from the Teflon film (not shown) and placed on an A4 sheet of paper 10. The flame test was performed on the surface of the sample layer 20 on a butane gas burner 30 at a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of the burning of the A4 sheet of paper are summarized in Table 1. No carbonization was observed on the A4 sheet of paper after 30, 60 and 120 seconds of heating, while after 180 seconds of heating it became slightly charred.

According to this embodiment, the fire resistance duration was more than 3 minutes due to the reinforced sample layer, i.e., the R-COOH group of poly (ethylene-coacrylic acid) reacts with the M-OH group of Mg (OH) 2 to form chemical bonds instead of physical mixing.

Example 3 Poly (acrylic acid-co-maleic acid) containing R-COOH groups was dissolved or dispersed in water. Thereafter, inorganic Al (OH) 3 particles having reactive M-OH functional groups were added to the polymer solution and the mixture was stirred at 70-90 ° C for 20 minutes. A 1 mm thick slurry was applied to the surface of a Teflon membrane and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 At 30 ° C for 30 minutes, at 160 ° C for 30 minutes, at 180 ° C for 30 minutes and finally cast at 200 ° C for 240 minutes.

As shown in Figure 4, the sample layer 20 was removed from the Teflon film (not shown) and placed on an A4 sheet of paper 10. The flame test was performed on the surface of the sample layer 20 on a butane gas burner 30 at a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of the burning of the A4 sheet of paper are summarized in Table 1. No carbonization was observed on the A4 sheet of paper after 30, 60 and 120 seconds of heating, while after 180 seconds of heating it became slightly charred.

According to this embodiment, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the R-COOH group of poly (acrylic acid-comelamic acid) reacts with the M-OH group of Al (OH) 3 to form chemical bonds instead of physical mixing.

Example 4 Polyurethane containing R-NCO groups was dissolved or dispersed in hexane. Thereafter, inorganic Al (OH) 3 particles having reactive M-OH functional groups were added to the polymer solution and the mixture was stirred at room temperature for 20 minutes. A 1 mm thick alloy slurry was applied to the surface of a Teflon film and then placed in an oven and cast at 60 ° C for 120 minutes.

As shown in Figure 4, the sample layer 20 was removed from the Teflon film (not shown) and placed on an A4 sheet of paper 10. The flame test was performed on the surface of the sample layer 20 on a butane gas burner 30 at a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of the burning of the A4 sheet of paper are summarized in Table 1. No carbonization was observed on the A4 sheet of paper after 30, 60 and 120 seconds of heating, while after 180 seconds of heating it became slightly charred.

According to this embodiment, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e. the R-NCO group of the polyurethane reacts with the M-OH group of Al (OH) 3 to form chemical bonds instead of physical mixing.

Comparative Example 1 Poly (ethylene-coacrylic acid) containing R-COOH groups was dissolved or dispersed in water. Subsequently, unmodified SiO 2 inorganic particles were added to the polymer solution and the mixture was stirred at 70 -90 ° C for 20 minutes. A 1 mm thick slurry was applied to the surface of a Teflon membrane and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 At 30 ° C for 30 minutes, at 160 ° C for 30 minutes, at 180 ° C for 30 minutes and finally cast at 200 ° C for 240 minutes.

As shown in Figure 4, the sample layer 20 was removed from the Teflon film (not shown) and placed on an A4 sheet of paper 10. The flame test was performed on the surface of the sample layer 20 on a butane gas burner 30 at a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of the burnout phenomenon on A4 sheet of paper are summarized in Table 1. When the flame touched the surface of the sample layer, the composite melted rapidly within seconds and then charred irregularly within 30 seconds. The non-uniform carbonation had lost its structural integrity due to the formation of fractures. The A4 sheet of paper turned slightly charred after 30 seconds of heating; it charred after 60 seconds of heating. Finally, the paper tray burned after 120 seconds of heating due to numerous cracks.

According to this comparative example, the fire resistance time was less than 2 minutes because the R-COOH groups of the poly (ethylene-coacrylic acid) did not react with unmodified SiO 2 and formed a well-structured composite by the formation of chemical bonds.

Comparative Example 2 Poly (acrylic acid-co-maleic acid) containing R-COOH groups was dissolved or dispersed in water. Subsequently, unmodified Al 2 O 3 inorganic particles were added to the polymer solution and the mixture was stirred at 70 -90 ° C for 20 minutes. A 1 mm thick slurry was applied to the surface of a Teflon membrane and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 At 30 ° C for 30 minutes, at 160 ° C for 30 minutes, at 180 ° C for 30 minutes and finally cast at 200 ° C for 240 minutes.

As shown in Figure 4, the sample layer 20 was removed from the Teflon film (not shown) and placed on an A4 sheet of paper 10. The flame test was performed on the surface of the sample layer 20 on a butane gas burner 30 at a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of the burnout phenomenon on A4 sheet of paper are summarized in Table 1. When the flame touched the surface of the sample layer, the composite melted rapidly within seconds and then charred irregularly within 30 seconds. The non-uniform carbonation had lost its structural integrity due to the formation of fractures. The A4 sheet of paper turned slightly charred after 30 seconds of heating; it charred after 60 seconds of heating. Finally, the paper tray burned after 120 seconds of heating due to numerous cracks.

According to this comparative example, the fire resistance time was less than 2 minutes because the R-COOH groups of the poly (acrylic acid-maleic acid) did not react with unmodified Al 2 O 3 and formed a well-structured composite by the formation of chemical bonds.

Comparative Example 3 Polyurethane containing R-NCO groups was dissolved or dispersed in hexane. Unmodified inorganic SiO 2 particles were then added to the polymer solution and the mixture was stirred at room temperature for 20 minutes. A 1 mm thick alloy slurry was applied to the surface of a Teflon film and then placed in an oven and cast at 60 ° C for 120 minutes.

As shown in Figure 4, the sample layer 20 was removed from the Teflon film (not shown) and placed on an A4 sheet of paper 10. The flame test was performed on the surface of the sample layer 20 on a butane gas burner 30 at a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of the burnout phenomenon on A4 sheet of paper are summarized in Table 1. When the flame touched the surface of the sample layer, the composite melted rapidly within seconds and then charred irregularly within 30 seconds. The non-uniform carbonation had lost its structural integrity due to the formation of fractures. The A4 sheet of paper turned slightly charred after 30 to 60 seconds of heating; it charred after 120 seconds of heating. Finally, the paper tray burned after 180 seconds of heating due to numerous cracks.

According to this comparative example, the fire resistance time was less than 2 minutes because the R-NCO groups of the polyurethane did not react with the unmodified SiO 2 and formed a well-structured composite by the formation of chemical bonds.

Comparative Example 4 Poly (vinyl alcohol) containing R-OH groups was dissolved or dispersed in water. Thereafter, inorganic AbCl particles were added to the polymer solution and the mixture was stirred at 70-90 ° C for 20 minutes. A 1 mm thick slurry was applied to the surface of a Teflon membrane and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 At 30 ° C for 30 minutes, at 160 ° C for 30 minutes, at 180 ° C for 30 minutes and finally cast at 200 ° C for 240 minutes.

As shown in Figure 4, the sample layer 20 was removed from the Teflon film (not shown) and placed on an A4 sheet of paper 10. The flame test was performed on the surface of the sample layer 20 on a butane gas burner 30 at a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of the burnout phenomenon on A4 sheet of paper are summarized in Table 1. When the flame touched the surface of the sample layer, the composite melted rapidly within seconds and then charred irregularly within 30 seconds. The non-uniform carbonation had lost its structural integrity due to the formation of fractures. The A4 sheet of paper turned slightly charred after 30 seconds of heating; it charred after 60 seconds of heating. Finally, the paper tray burned after 120 seconds of heating due to numerous cracks.

According to this comparative example, the fire resistance time was less than 2 minutes because the R-OH groups of the poly (vinyl alcohol) did not react with the ΑΙ2θ3: η M-OH groups and formed a well-structured composite by the formation of chemical bonds.

Due to the chemical bonding between the organic polymer and the corresponding reactive functional groups of the inorganic particles, the carbon layer on the surface is strong, has excellent structural integrity and does not easily break or peel, which effectively prevents direct heat transfer to the interior. The fire-resistant material is not only flame retardant, but also protects the materials of the interior. As a result, the fire resistance is significantly increased.

[0051]

Table 1. Combustion test results for organic / inorganic composite materials

Examples of Fire Resistant Plates Example 5 10 g of poly (ethylene-coacrylic acid) was charged to the reactor, preheated to 80-120 ° C and then stirred at 300 rpm. 10.8 g deionized water and 10.8 g aqueous ammonia were added to the reactor to give a white emulsion after stirring for 10 minutes. Thereafter, 10 g of aluminum hydroxide powder was added to the reactor to give a white slurry after stirring for 10 minutes. The slurry was charged 100x 100x into a 2 mm Teflon mold and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 ° C. at 30 ° C, 30 minutes at 160 ° C, 30 minutes at 180 ° C, and finally cast at 200 ° C for 240 minutes.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was carried out on a flame-retardant plate surface with a butane gas burner at a flame temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the A4 paper sheet burn phenomenon are summarized in Table 2. No carbonization was observed on the A4 paper sheet after heating for 30, 60 and 120 seconds, while after 180 seconds it became slightly charred.

According to this example, the fire resistance duration was more than 3 minutes due to the reinforced sample layer, i.e., the R-COOH groups of the poly (ethylene-coacrylic acid) react with the M-OH groups of Al (OH) 3 to form chemical bonds instead of physical mixing.

Example 6 10 g of poly (ethylene-coacrylic acid) was charged to the reactor, preheated to 80-120 ° C and then stirred at 300 rpm. Thereafter, 10 g of aluminum hydroxide powder was added to the reactor to give a white slurry after stirring for 10 minutes. The slurry was charged into a 100 x 100 x 2 mm Teflon mold and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 At 30 ° C, 30 minutes at 160 ° C, 30 minutes at 180 ° C and finally cast at 200 ° C for 240 minutes.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was carried out on a flame-retardant plate surface with a butane gas burner at a flame temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the A4 paper sheet burn phenomenon are summarized in Table 2. No carbonization was observed on the A4 paper sheet after heating for 30, 60 and 120 seconds, while after 180 seconds it became slightly charred.

According to this example, the fire resistance duration was more than 3 minutes due to the reinforced sample layer, i.e., the poly (ethylene-coacrylic acid) -COOH groups react with the Al (OH) 3 -OH groups to form chemical bonds instead of physical mixing.

Example 7 20 g of poly (acrylic acid-comalic acid) (solids content 50% by weight) was charged to the reactor, preheated to 80-90 ° C and then stirred at 300 rpm. 10 g of aqueous ammonia were added to the reactor and stirred for 10 minutes. Thereafter, 10 g of aluminum hydroxide powder was added to the reactor to give a yellow slurry after stirring for 10 minutes. The slurry was charged into a 100 x 100 x 2 mm Teflon mold and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 At 30 ° C, 30 minutes at 160 ° C, 30 minutes at 180 ° C and finally cast at 200 ° C for 240 minutes.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was carried out on a flame-retardant plate surface with a butane gas burner at a flame temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the A4 paper sheet burn phenomenon are summarized in Table 2. No carbonization was observed on the A4 paper sheet after heating for 30, 60 and 120 seconds, while after 180 seconds it became slightly charred.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the poly (acrylic acid-comic acid) -COOH groups react with Al (OH) 3 -OH groups to form chemical bonds instead of physical mixing.

Example 8 50 g of reactive polyurethane containing 8% of reactive isocyanate groups were charged into the reactor and stirred at 300 rpm. Thereafter, 50 g of aluminum hydroxide powder was added to the reactor to give a white slurry after 5 minutes of agitation. The slurry was charged into a 100 x 100 x 2 mm Teflon mold and then dried at room temperature for 24 hours.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was performed on a flame-retardant plate surface with a butane gas burner at a temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the A4 paper sheet burn phenomenon are summarized in Table 2. No carbonization was observed on the A4 paper sheet after heating for 30, 60 and 120 seconds, while after 180 seconds it became slightly charred.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the -NCO groups of the reactive polyurethane react with the -OH groups of Al (OH) 3 to form chemical bonds instead of physical mixing.

Example 9 50 g of reactive polyurethane containing 8% of reactive isocyanate groups were charged into the reactor and stirred at 300 rpm. Thereafter, 45 g of magnesium hydroxide powder and 5 g of modified nano-clay containing -OH groups (Cloidite 30B, ex. Southern Clay Product Corp.) were added to the reactor to give a white slurry after 5 minutes of stirring. The slurry was charged into a 100 x 100 x 2 mm Teflon mold and then dried at room temperature for 24 hours.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was carried out on a flame-retardant plate surface with a butane gas burner at 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the burning of the A4 sheet of paper are summarized in Table 2. No carbonization was observed on the surface of the A4 sheet of paper after 30, 60 and 120 seconds of heating, while after 180 seconds of heating, it became slightly charred.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e. the reactive polyurethane -NCO groups react with Mg (OH) 3 and nanosaven-OH groups to form chemical bonds instead of physical mixing.

Example 10 Referring to Figure 5, the fire-resistant plate 20 of Example 9 was placed on an A4 sheet of paper 10 and the flame test was performed on a surface of the fire-resistant plate with a butane gas burner at 1000-1200 ° C flame temperature (flame 40) for 180 seconds. in the experiment, the bottom surface of an A4 sheet was connected to a thermocouple thermocouple 60 to monitor the temperature rise. A commercial expandable flame-retardant plate (FM-900, ex. YUNG CHI PAINT & VARNISH MFG. CO., LTD) with a thickness of 2 mm was subjected to the same flame test. As shown in Figure 6, the temperature under the commercially expandable, flame-retardant plate rose rapidly to 200 ° C after 60 seconds of heating. By way of comparison, the temperature under the fire-resistant plate of Example 5 slowly rose to 200 ° C by heating for 100 seconds.

According to this example, the fire resistance time was significantly improved due to the reinforced sample layer, i.e., the -NCO groups of the reactive urethane react with the Mg (OH) 3 and nanosaven-OH groups to form chemical bonds instead of physical mixing.

Example 11 50 g of reactive polyurethane containing 7.6% of reactive isocyanate groups were charged into the reactor and stirred at 300 rpm. Thereafter, 50 g of modified titanium dioxide powder with functional -OH groups on the surface was added to the reactor to give a white slurry after 5 minutes of agitation. The slurry was charged into a 100 x 100 x 2 mm Teflon mold, dried at room temperature for 24 hours, and finally cast in an oven at 80 ° C for 24 hours.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was carried out on the surface of a fire-resistant plate with a butane gas burner at a temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the burning of the A4 sheet of paper are summarized in Table 2. No carbonization was observed on the surface of the A4 sheet of paper after 30, 60 and 120 seconds of heating, while after 180 seconds of heating, it became slightly charred.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e. the reactive polyurethane -NCO groups react with the modified TiO 2 -OH groups to form chemical bonds instead of physical mixing.

Example 12 40 g of reactive polyurethane containing 7.6% of reactive isocyanate groups were charged into the reactor and stirred at 300 rpm. 50 g of modified titanium dioxide powder having -OH functional groups on the surface was added to the reactor and stirred for 3 minutes. Thereafter, 10 g of PPG 400 (polypropylene glycol; Mw 0 400) was added to the reactor to give a white slurry after 2 minutes of agitation. The slurry was charged into a 100 x 100 x 2 mm Teflon mold, dried at room temperature for 24 hours, and finally cast in an oven at 80 ° C for 24 hours.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The sheet had excellent flexibility with a bending radius of about 3 cm. The flame test was carried out on the surface of a fire-resistant plate with a butane gas burner at a temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the burning of the A4 sheet of paper are summarized in Table 2. No carbonization was observed on the surface of the A4 sheet of paper after 30, 60 and 120 seconds of heating, while after 180 seconds of heating, it became slightly charred.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the -NCO groups of the reactive polyurethane react with the -OH groups of the modified TiO 2 to form chemical bonds instead of physical mixing.

Example 13 40 g of reactive polyurethane containing 8% of reactive isocyanate groups were charged into the reactor and stirred at 300 rpm. Thereafter, 45 g of modified titanium dioxide powder with functional -OH groups on the surface and 5 g of modified nanoparticles containing -OH groups (Cloisite 30B, ex Southern Clay Product Corp.) were added to the reactor and stirred for 3 minutes. Next, 10 g of PPG 400 (polypropylene glycol; Mw = 400) was added to the reactor to give a pale yellow slurry after stirring for 2 minutes. The slurry was charged into a 100 x 100 x 2 mm Teflon mold, dried at room temperature for 24 hours, and finally cast in an oven at 80 ° C for 24 hours.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The sheet had excellent flexibility with a bending radius of about 3 cm. The flame test was carried out on the surface of a fire-resistant plate with a butane gas burner at a temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the burning of the A4 sheet of paper are summarized in Table 2. No carbonization was observed on the surface of the A4 sheet of paper after 30, 60 and 120 seconds of heating, while after 180 seconds of heating, it became slightly charred.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the -NCO groups of the reactive polyurethane react with the nanosized and modified TiO 2 -OH groups to form chemical bonds instead of physical mixing.

Example 14 20 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (E4221, epoxy resin, ex Union Carbide) was charged to the reactor and stirred at 300 rpm, followed by the addition of (8 g, equivalent ratio E4221 / MeHHPA = 1 / 1.14) MeHHPA (hexahydro-4-methylphthalic anhydride) as a curing agent and 0.1 g BDMA (N, N-dimethylbenzylamine) as a catalyst. After stirring for 5 minutes, 48.1 g of aluminum hydroxide powder was added to the reactor to give a white slurry after 10 minutes of stirring. The slurry was charged into a 100 x 100 x 2 mm and 100 x 100 x 4 mm Teflon mold and dried at 120 ° C for 1 hour.

Molded sheets of 2 mm and 4 mm thickness were removed from the Teflon mold and placed on a sheet of A4 paper. The flame test was carried out on the surface of fire-resistant plates with a butane gas burner at a temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the A4 paper sheet burn phenomenon are summarized in Table 2. For a 2 mm thick molded sheet, no carbonation was observed on the A4 paper sheet 30, and 60, while after 120 seconds it became slightly charred and charred after 180 seconds. For a 4 mm thick molded sheet, no carbonation was observed on the surface of an A4 sheet of paper after 30, 60, and 120 seconds of heating, while after 180 seconds of heating, it became slightly charred.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e. the anhydride groups of the epoxy resin (derived from excess MeHHPA) react with Al (OH) 3 -OH groups to form chemical bonds instead of physical mixing.

Comparative Example 5 50 g of reactive polyurethane containing 8% of reactive isocyanate groups were charged into the reactor and stirred at 300 rpm. Thereafter, 50 g of unmodified silica powder was added to the reactor to give a white slurry after 5 minutes of agitation. The slurry was charged into a 100 x 100 x 2 mm Teflon mold, then dried at room temperature for 24 hours and finally cast in an oven at 80 ° C for 24 hours.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was carried out on a flame-retardant plate surface with a butane gas burner at 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the burnout phenomenon on A4 paper are summarized in Table 2. When the flame touched the surface of the sample layer, the composite rapidly melted within seconds and then charred irregularly within 30 seconds. The non-uniform carbonation had lost its structural integrity due to the formation of fractures. The A4 sheet of paper turned slightly charred after 30 seconds of heating; it charred after 60 seconds of heating. Finally, the paper burned after 120 seconds of heating due to numerous cracks.

According to this comparative example, the board was not able to withstand a flame temperature of 1000-1200 ° C because unmodified SiCl 3 surfaces were unable to react with polyurethane -NCO groups and form a well-structured composite by chemical bond formation.

Comparative Example 6 50 g of polyurethane without reactive isocyanate groups was charged into the reactor and stirred at 300 rpm. Thereafter, 50 g of aluminum hydroxide powder was added to the reactor to give a white slurry after 5 minutes of agitation. The slurry was charged into a 100 x 100 x 2 mm Teflon mold, then dried in an oven at 60 ° C for 120 minutes, 80 ° C for 120 minutes, 100 ° C for 120 minutes and finally poured at 120 ° C for 360 minutes. minutes.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was carried out on a flame-retardant plate surface with a butane gas burner at 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the burnout phenomenon on A4 paper are summarized in Table 2. When the flame touched the surface of the sample layer, the composite rapidly melted within seconds and then charred irregularly within 30 seconds. The non-uniform carbonation had lost its structural integrity due to the formation of fractures. A sheet of A4 paper turned charred after 30 seconds of heating. Finally, after 60 seconds of heating, the paper burned due to numerous cracks.

According to this comparative example, the board could not withstand a flame temperature of 1000-1200 ° C because the polyurethane had no functional groups that reacted with the aluminum hydroxide -OH groups and formed a well-structured composite by the formation of chemical bonds.

Comparative Example 7 50 g of poly (vinyl alcohol) containing -OH groups was dissolved in water and stirred at 300 rpm. 50 g of aluminum hydroxide powder was added to pol (vinyl alcohol) to give a white slurry after stirring for 20 minutes at 70 -90 ° C. The slurry was charged into a 100 x 100 x 2 mm Teflon mold and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C. minutes, 140 ° C for 30 minutes, 160 ° C for 30 minutes, 180 ° C for 3 minutes and finally cast at 200 ° C for 240 minutes.

A 2 mm thick molded sheet was removed from the Teflon mold and placed on an A4 sheet of paper. The flame test was carried out on a flame-retardant plate surface with a butane gas burner at a temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of the burnout phenomenon on A4 sheet of paper are summarized in Table 2. When the flame touched the surface of the sample layer, the composite rapidly melted within seconds and then charred irregularly within 30 seconds. The non-uniform carbonation had lost its structural integrity due to the formation of fractures. The A4 sheet of paper turned slightly charred after 30 seconds of heating; it charred after 60 seconds of heating. The paper eventually burned after 120 seconds of heating due to numerous cracks.

According to this comparative example, the sheet could not withstand the flame temperature of 1000-1200 ° C because the -OH groups of the aluminum hydroxide could not react with the poly (vinyl alcohol) -OH groups and form a well-structured composite by the formation of chemical bonds.

Table 2. Flame test results for fire resistant boards

Although the invention has been described by way of example and with respect to a preferred embodiment, it is to be understood that the invention is not limited thereto. On the contrary, it is intended to cover various modifications and similar arrangements (which would be apparent to those skilled in the art). Accordingly, the broad scope of the appended claims should be construed to include all such modifications and corresponding arrangements.

Claims (12)

An organic / inorganic composite comprising: an organic component comprising 30 to 70% by weight of a polymer, copolymer or oligomer comprising polyurethane, or a polyolefin copolymer having a first reactive, isocyanate functional group; and 70 to 30% by weight of inorganic particles comprising metal hydroxide Al (OH) 3 or Mg (OH) 2 having another reactive, hydroxyl functional group; wherein the inorganic particles are chemically bonded to the polymer, copolymer or oligomer by reaction between the first and second reactive functional groups, wherein the inorganic and organic components are sufficiently bonded to provide a fire-resistant coating material capable of withstanding 1000-1200 ° C: flame temperatures for more than 3 minutes. A flame-retardant sheet comprising: an organic / inorganic composite comprising: 30 to 70% by weight of an organic component comprising a polylic acid, a polyurethane, an epoxy resin, a polyolefin or a polyamine having a first reactive, isocyanate functional group; and 70 to 30% by weight of inorganic particles comprising a metal hydroxide, nitride, oxide, carbide, metal salt or inorganic layered material having another reactive, hydroxyl functional group; wherein the inorganic particles are chemically bonded to the polylic acid, polyurethane, epoxy resin, polyolefin or polyamine by reaction between the first and second reactive functional groups; wherein the inorganic and organic components are sufficiently bonded to provide a flame-retardant coating material capable of withstanding flame temperatures from 1000 to 1200 ° C for more than 3 minutes. The fire-resistant board of claim 2, wherein the metal hydroxide comprises Al (OH) 3 or Mg (OH) 2. The fire-resistant board of claim 2, further comprising an additive. The flame-retardant sheet of claim 4, wherein the additive comprises a flame retardant, silane, siloxane, glass sand, or fiberglass. A fire-resistant board according to claim 4 having a thickness of less than 0.5 mm. A fire-resistant board according to claim 2 having a thickness of less than 0.5 to 2 mm. A fire-resistant plate according to claim 2 having a thickness of more than 2 mm. The flame-retardant sheet of claim 2, further comprising a flammable or highly flammable sheet deposited on the surface of the organic / inorganic composite to form a multilayer structure. The fire resistant sheet of claim 2, which is used as a fire resistant fill sheet. A fire-resistant board according to claim 2 for use as a fire-resistant wallpaper. The fire-resistant board of claim 2, which is a flexible fire-resistant board. claim