High-strength fire-resistant steel material for fire door and method for manufacturing the same

Abstract

The application discloses a kind of high-strength fire-resistant steel material for fire door and preparation method thereof, and relates to the technical field of fire-retardant coating, comprising steel material and fire-retardant coating arranged on the surface of steel material;The fire-retardant coating is formed after being coated and solidified by fire-retardant coating;The fire-retardant coating comprises the following components: 10-20 parts of fiber filler, 30-50 parts of particulate filler, 30-40 parts of resin material and 1-3 parts of auxiliary agent.The application can take into account fire resistance, mechanical strength and construction feasibility by compounding inorganic fiber and inorganic particles and introducing phosphorus compounds into the resin system to prepare fire-retardant coating.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fireproof coating, and particularly relates to high-strength fire-resistant steel material for fireproof door and a preparation method thereof. BACKGROUND

[0002] Preventing and blocking fire is very important, and the steel structure (steel material) is often contained in the structure of the fireproof door as a key component of the fireproof system. However, the fire resistance of the steel structure is poor. Although the steel material itself does not burn, the fire resistance limit of the steel material is very low. At high temperatures caused by fire, the strength and rigidity of the steel material will decrease significantly. When the temperature reaches about 540 DEG C, the strength of the steel material will decrease to 50%, so that the steel material is difficult to bear load. When the temperature exceeds 600 DEG C, the steel material basically loses the load bearing capacity. The temperature of fire can reach 800-1000 DEG C, which is enough to soften and collapse the steel material in a short time, thereby affecting the normal use of the fireproof door. In order to improve the fire resistance limit of the steel material, a conventional operation is to set a fireproof coating on the surface of the steel material by using a fireproof coating. Therefore, the present application provides a high-strength fire-resistant steel material for fireproof door and a preparation method thereof. SUMMARY

[0003] The present application aims to provide a high-strength fire-resistant steel material for fireproof door and a preparation method thereof, so as to solve the problems in the background.

[0004] In order to solve the above technical problems, the present application provides the following technical scheme: a high-strength fire-resistant steel material for fireproof door, comprising a steel material and a fireproof coating arranged on the surface of the steel material.

[0005] The fireproof coating is formed by coating and curing the fireproof coating.

[0006] Further, the fireproof coating comprises the following components: fiber filler, particle filler, resin material, additive and solvent.

[0007] Further, the fiber filler is one or more of glass fiber, ceramic fiber, basalt fiber, sepiolite fiber, aramid fiber, benzimidazole fiber, carbon fiber, mineral wool fiber and cellulose fiber.

[0008] Further, the particle filler is one or more of aluminum hydroxide, magnesium hydroxide, borate, phosphate, hollow microbead, montmorillonite, mica powder, expanded graphite, silicon dioxide, antimony oxide, titanium white powder and perlite.

[0009] Further, the resin material comprises one or more of epoxy resin, phenolic resin, polyacrylate resin and curing agent.

[0010] Further, the additive comprises leveling agent, dispersant, defoaming agent and surfactant.

[0011] Further, the fireproof coating comprises the following components: 10-20 parts of fiber fillers, 30-50 parts of particulate fillers, 30-40 parts of resin materials and 1-3 parts of auxiliary agents.

[0012] Further, the fiber fillers are a mixture of sepiolite fibers and glass fibers, with a mass ratio of (2-4):(6-8).

[0013] The length of the sepiolite fibers is 100-150 μm, and the length of the glass fibers is 100-300 μm.

[0014] Further, the particulate fillers are a mixture of aluminum hydroxide, magnesium hydroxide and zinc borate, with a mass ratio of (6-7):(2-3):1.

[0015] The particle size of the aluminum hydroxide is 5-20 μm, the particle size of the magnesium hydroxide is 1-10 μm, and the particle size of the zinc borate is 10-50 μm.

[0016] Further, the thickness of the fireproof coating is 1.8-5.5 mm.

[0017] Further, the steel material is one of 304, 316, 201 stainless steel and galvanized steel sheet.

[0018] In the above technical solution, the fillers are selected as a combination of fibrous fillers and particulate fillers. The fibers can form a stable three-dimensional skeleton structure at high temperatures, and the decomposition products of the particles effectively fill the skeleton pores, thereby constructing a multi-level three-dimensional heat barrier and achieving a synergistic fireproof and flame-retardant effect, which significantly improves the fireproof performance of the coating. Meanwhile, the macroscopic reinforcing effect of the fiber fillers and the microscopic reinforcing effect of the particulate fillers are mutually synergistic, which not only improves the mechanical strength of the coating, but also improves the surface hardness and the chemical stability of the coating.

[0019] The fiber fillers are selected as sepiolite and glass fibers. The sepiolite fibers have a nanopore structure, which can enhance the heat insulation capacity of the coating, and their excellent thixotropic properties can prevent the sagging phenomenon during construction. The glass fibers construct a three-dimensional reinforcing network to ensure the structural integrity of the coating at high temperatures and prevent the cracking of the carbon layer. The particulate fillers are selected as aluminum hydroxide, magnesium hydroxide and zinc borate. The aluminum hydroxide acts as the main flame retardant and plays a heat-absorbing and flame-retardant role in the medium and low temperature zones. The magnesium hydroxide supplements the flame-retardant requirements in the high temperature zone, thereby widening the effective flame-retardant temperature range of the coating. The zinc borate melts to form a dense glass barrier at high temperatures, effectively isolating oxygen. The synergistic effect of these multi-component particulate fillers achieves full-temperature coverage of the flame-retardant performance of the coating, ensuring the reliability and durability of the fireproof protection.

[0020] And the resin system provides adhesion and film-forming property for the coating, and the cured coating has good chemical stability.

[0021] A preparation method of high-strength fire-resistant steel material for fireproof door comprises the following process steps:

[0022] The fiber filler, the particle filler, the resin system, the additive and the solvent are mixed and stirred to disperse, to obtain the coating;

[0023] The coating is applied to the surface of the steel material, and is cured to form a fireproof coating, to obtain the fire-resistant steel material.

[0024] Further, the resin system comprises the following components: 60-70 parts by mass of water-based epoxy resin emulsion, 30-40 parts by mass of polyacrylate emulsion, 3-5 parts by mass of curing agent, and 0.5-2 parts by mass of accelerator.

[0025] Further, the resin system is prepared by the following process: the curing agent and the accelerator are dissolved in the polyacrylate emulsion by stirring; and the water-based epoxy resin emulsion is added to obtain the resin system.

[0026] Further, the curing agent is dicyandiamide curing agent, and the accelerator is organic urea.

[0027] The solid content of the water-based epoxy resin emulsion is 40-60 wt%.

[0028] Further, the curing process is as follows: 60°C for 1 h; 100°C for 1 h; and 125°C for 2 h.

[0029] Further, the polyacrylate emulsion is prepared by the following process:

[0030] The 1 / 2 emulsifier solution and the mixed monomers are mixed to obtain a pre-emulsion;

[0031] The 1 / 10 pre-emulsion and the remaining emulsifier solution are mixed, and sodium bicarbonate and 1 / 2 initiator solution are added, and the temperature is raised to 78-82°C, and the reaction is stirred until the blue phase appears, and after the blue phase is obvious, the temperature is maintained for 10-20 min; the remaining initiator and the remaining pre-emulsion are added, and the temperature is maintained for 90-120 min; the system is cooled, the pH is adjusted to 7-8, and the system is sieved to obtain the polyacrylate emulsion.

[0032] Further, the polyacrylate emulsion comprises the following components: 40-45 parts by mass of mixed monomers, 0.2-0.5 parts by mass of initiator, and 1.0-1.5 parts by mass of emulsifier.

[0033] Further, the emulsifier is a mixture of alkylphenol polyoxyethylene ether (OP-10) and sodium dodecyl sulfonate (SLS) with a mass ratio of 1:1.

[0034] The mass concentration of the emulsifier solution is 2% to 4%, and the mass concentration of the initiator solution is 1% to 5%.

[0035] The solid content of the polyacrylate emulsion is 45% to 55% by weight.

[0036] Further, the mixed monomers include the following components: 20 to 23 parts by mass of n-butyl acrylate, 11 to 13 parts by mass of methyl methacrylate, 5 to 7 parts by mass of styrene, 1.5 to 2.5 parts by mass of vinyl triethoxysilane, 1.5 to 2.5 parts by mass of octamethylcyclotetrasiloxane, 1 to 3 parts by mass of glycidyl methacrylate, and 1 to 10 parts by mass of a phosphorus-containing alkenyl compound.

[0037] Further, the phosphorus-containing alkenyl compound is prepared by the following process:

[0038] (1) trichlorophosphine, p-acetamidophenol, a catalyst are mixed in acetone, and heated to 60 to 80°C under nitrogen atmosphere protection, and kept at the temperature for 8 to 96 hours; after the reaction, filtration, washing, and vacuum drying are performed to obtain hexaacetyl cyclotriphosphazene;

[0039] (2) hexaacetyl cyclotriphosphazene, an alcohol aqueous solution, and sodium hydroxide are mixed, and refluxed at 70 to 75°C for 4 to 36 hours; after the reaction, cooling, filtration, washing, and vacuum drying are performed to obtain hexanilino cyclotriphosphazene;

[0040] (3) propenylbenzaldehyde and hexanilino cyclotriphosphazene are mixed in N,N-dimethylformamide, and reacted at 60 to 65°C under nitrogen atmosphere protection for 30 to 60 minutes; the temperature is lowered to 50±5°C, DOPO and triethylamine are added, and the temperature is raised to 80 to 85°C for further reaction for 1 to 3 hours; after the reaction, washing and vacuum drying are performed to obtain the phosphorus-containing alkenyl compound.

[0041] Further, in step (1), the molar ratio of trichlorophosphine (CAS No. 940-71-6), p-acetamidophenol (CAS No. 103-90-2), and the catalyst is 1:(6.5 to 7.2):(0.1 to 7.2);

[0042] The catalyst is one of triethylamine, DBU (1,8-diazabicycloundec-7-ene), and tetrabutylammonium bromide;

[0043] The ratio of trichlorophosphine and acetone is (3 to 8) g / 100 mL.

[0044] Further, in step (2), the mass ratio of the amide group in hexaacetyl cyclotriphosphazene and sodium hydroxide is 1:(0.7 to 1.1);

[0045] The ratio of hexaacetyl cyclotriphosphazene and the alcohol aqueous solution is (10 to 15) g / 100 mL.

[0046] The alcohol aqueous solution is a mixture of ethanol and water in a volume ratio of 7:3;

[0047] The sodium hydroxide is added in the form of a 10-20 wt% aqueous solution.

[0048] Further, in step (3), the mass ratio of hexa-anilino-cyclotriphosphazene, propenylbenzaldehyde (CAS No. 77785-94-5), DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, CAS No. 35948-25-5), and triethylamine is 1:(1.1-1.2):(1.5-1.7):(0.8-1.2).

[0049] The ratio of hexa-anilino-cyclotriphosphazene and N,N-dimethylformamide is (10-12) g / 100 mL.

[0050] The propenylbenzaldehyde contains 0.1% of a polymerization inhibitor, hydroquinone, and 0.05% of tetramethylpiperidinooxy (TEMPO).

[0051] In the above technical solution, under the action of a catalyst, the chlorine group in trichlorophosphazene and the phenolic hydroxyl group in acetaminophen react to generate P-O-Ph, obtaining hexa-acetyl-cyclotriphosphazene; the hexa-acetyl-cyclotriphosphazene is hydrolyzed in a lye to generate an amino group, obtaining hexa-anilino-cyclotriphosphazene. Then, the hexa-anilino-cyclotriphosphazene reacts with propenylbenzaldehyde, the lone pair of electrons of the amino group in the system attacks the carbonyl carbon of the aldehyde group to form a hydroxylamine intermediate, and then dehydrates to generate an imine (C=N bond). The amino group preferentially undergoes nucleophilic addition-elimination reaction with the aldehyde group to generate an imine group, forming a hexa-aldehyde-cyclotriphosphazene compound, denoted as compound A; then, DOPO is added, the PH group of DOPO preferentially undergoes nucleophilic addition reaction with the imine (C=N) in compound A, the lone pair of electrons of the phosphorus atom in the P-H bond attacks the electron-deficient carbon of the C=N bond to form a P-C bond and an N-H bond, thereby obtaining a cyclotriphosphazene compound having polyalkenyl, DOPO, triazine, phenyl, and other structures, and nitrogen and phosphorus elements, denoted as a phosphorus-containing alkenyl compound.

[0052] It is introduced into the mixed monomer, participates in the preparation of the emulsion, polyacrylate emulsion is prepared, DOPO, triazine structure, phosphorus and nitrogen elements are embedded in the polymer main chain, can decompose to produce phosphoric acid and non-combustible gas at high temperature, promote carbon formation and release free radicals to interrupt combustion chain, dilute combustible gas and heat, cooperate with silicone to improve its gas phase and condensed phase flame retardant capacity, realize its intrinsic flame retardant. And the polyene group structure of the phosphorus-containing alkyl group compound helps to form the branched structure of the polyacrylate, increases the crosslinking point, so that the polyacrylate emulsion prepared by mixing with the epoxy resin can improve the crosslinking density after curing under the action of the curing agent and heat, which helps to improve the mechanical properties of the prepared coating. In addition, in the mixed monomer, octamethylcyclotetrasiloxane (D4) is ring-opening polymerized to form Si-O-Si segments, which react with Si-OH formed by hydrolysis of vinyltriethoxysilane (VTES) to generate flexible silicone, which is interpenetrated with the rigid network of epoxy resin, and the rotation freedom of Si-O bond endows the coating with toughness, offsetting the brittleness of the epoxy resin, which can effectively improve the impact resistance of the coating; and helps to improve the separation of epoxy / polyacrylate and improve the uniformity of the coating.

[0053] Further, the fiber filler and the particle filler are modified by a coupling agent.

[0054] Compared with the prior art, the beneficial effects of the present application are as follows:

[0055] The high-strength fire-resistant steel material for fireproof doors of the present application can take into account fire resistance, mechanical strength and construction feasibility by compounding inorganic fibers and inorganic particles and introducing phosphorus-containing compounds into the resin system to prepare a fireproof coating. DETAILED DESCRIPTION

[0056] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0057] In the following specific embodiments, all are laboratory small tests, which can be scaled up proportionally.

[0058] The curing agent is dicyandiamide curing agent DYHARD-100S; the accelerator is organic urea 500SF;

[0059] The water-based epoxy resin emulsion is F0704, and the solid content is 53wt%;

[0060] The emulsifier is a mixture of alkylphenol polyoxyethylene ether (OP-10) and sodium dodecyl sulfonate (SLS) with a mass ratio of 1:1;

[0061] The propenylbenzaldehyde contains 0.1% of the polymerization inhibitor hydroquinone and 0.05% of tetramethylpiperidinium oxide; the 4-hydroxystyrene contains 0.1% of the polymerization inhibitor hydroquinone;

[0062] The average length of the sepiolite fibers is 120 μm, and the average length of the glass fibers is 200 μm;

[0063] The average particle size of the aluminum hydroxide is 15 μm, the average particle size of the magnesium hydroxide is 7.5 μm, and the average particle size of the zinc borate is 30 μm;

[0064] Both the fibrous filler and the particulate filler are modified by a coupling agent; the specific process is as follows: the coupling agent 1.5wt% KH-560 is mixed with an ethanol aqueous solution (V / V=9:1), the pH of the system is adjusted to 5, and hydrolysis is performed for 10 min; an equal volume of the filler is added and mixed for 20 min; and then drying is performed at 80°C for 30 min;

[0065] The propenylbenzaldehyde contains 0.1% of the polymerization inhibitor hydroquinone and 0.05% of tetramethylpiperidinium oxide;

[0066] The thickness of the fireproof coating is 2.0 mm; and the steel material is a galvanized steel plate;

[0067] The auxiliary agents include a leveling agent BYK-354, a dispersing agent EFKA-4010, an antifoaming agent TEGO Airex 902W, and a surfactant TEGO Wet 270, and the mass ratio is 3:7:1:2.

[0068] Embodiment 1: A preparation method of a high-strength fire-resistant steel material for a fireproof door, comprising the following process steps:

[0069] Step (1): 1.1. 3g of trichlorophosphazene, acetaminophen, and a catalyst DBU are mixed in 100mL of acetone, and under the protection of a nitrogen atmosphere, the temperature is raised to 60°C, and the reaction is kept for 16h; after the reaction, filtration, washing, and vacuum drying are performed to obtain hexaacetyl cyclotriphosphazene; the molar ratio of trichlorophosphazene, acetaminophen, and the catalyst is 1:6.5:0.1;

[0070] 10g of hexaacetyl cyclotriphosphazene, 100mL of an ethanol aqueous solution (v / v=7:3), and 10wt% of a sodium hydroxide aqueous solution are mixed, and reflux reaction is performed at 70°C for 36h; after the reaction, cooling, filtration, washing, and vacuum drying are performed to obtain hexanilaninyl cyclotriphosphazene; the mass ratio of the amide group in the hexaacetyl cyclotriphosphazene to the sodium hydroxide is 1:0.7;

[0071] Mixing 10 g of propenyl benzaldehyde, hexa-anilino cyclotriphosphazene in 100 mL of N,N-dimethylformamide, under the protection of nitrogen atmosphere, at 60℃ for 60 min; cooling to 50℃, adding DOPO, triethylamine, and continuing to react at 80℃ for 3 h; after the reaction, washing, and vacuum drying, a phosphorus-containing alkyl compound is obtained; the mass ratio of hexa-anilino cyclotriphosphazene, propenyl benzaldehyde, DOPO, and triethylamine is 1:1.1:1.5:0.8;

[0072] 1.2 Mix 1 / 2 emulsifier solution (4 wt%) and mixed monomers, stir for 30 min to obtain a pre-emulsion; mix 1 / 10 pre-emulsion and the remaining emulsifier solution, add sodium bicarbonate and 1 / 2 initiator solution (5 wt%), heat to 80℃, stir until blue phase appears, and then keep warm for 15 min; slowly add the remaining initiator and the remaining pre-emulsion, and the initiator is added completely in 90 min, and the pre-emulsion is added completely within 2 h; then keep warm for 90 min; cool the reaction to below 40℃, adjust the pH of the system to 7, pass through a 100-mesh sieve, and add water to obtain a polyacrylate emulsion with a solid content of 50 wt%; the polyacrylate emulsion comprises the following components: 40 parts of mixed monomers, 0.2 parts of initiator, and 1.0 parts of emulsifier; the mixed monomers comprise the following components: 20 parts of n-butyl acrylate, 11 parts of methyl methacrylate, 5 parts of styrene, 1.5 parts of vinyl triethoxysilane, 1.5 parts of octamethylcyclotetrasiloxane, 1 part of glycidyl methacrylate, and 1 part of phosphorus-containing alkyl compound;

[0073] 1.3 Dissolve the curing agent and the accelerator in the polyacrylate emulsion; add the water-based epoxy resin emulsion to obtain a resin system; the resin system comprises the following components: 70 parts of water-based epoxy resin emulsion, 30 parts of polyacrylate emulsion, 5 parts of curing agent, and 2 parts of accelerator;

[0074] Step (2) Mix the fiber filler, particulate filler, resin system, auxiliary agent, and solvent, stir and disperse to obtain a coating; apply the coating to the surface of the steel material, and cure to form a fireproof coating to obtain a fire-resistant steel material; the curing process is: 60℃ for 1 h; 100℃ for 1 h; and 125℃ for 2 h; the fireproof coating comprises the following components: 15 parts of fiber filler, 40 parts of particulate filler, 35 parts of resin material, and 2 parts of auxiliary agent; the fiber filler is a mixture of sepiolite fiber and glass fiber with a mass ratio of 4:6; the particulate filler is a mixture of aluminum hydroxide, magnesium hydroxide, and zinc borate with a mass ratio of 7:2:1.

[0075] Example 2: A method for preparing a high-strength fire-resistant steel material for fireproof doors, comprising the following process steps:

[0076] Step (1): 1.1. Mix 5 g of trichlorophosphine, p-acetylaminophenol, and catalyst DBU in 100 mL of acetone, and heat to 70°C under nitrogen atmosphere for 12 h. After the reaction, filter, wash, and dry under vacuum to obtain hexa-acetyl cyclotriphosphazene. The molar ratio of trichlorophosphine, p-acetylaminophenol, and catalyst is 1:6.9:0.2;

[0077] Mix 12 g of hexa-acetyl cyclotriphosphazene, 100 mL of ethanol aqueous solution (v / v=7:3), and 15 wt% sodium hydroxide aqueous solution, and reflux at 72°C for 30 h. After the reaction, cool, filter, wash, and dry under vacuum to obtain hexa-anilino cyclotriphosphazene. The mass ratio of amide group in hexa-acetyl cyclotriphosphazene and sodium hydroxide is 1:0.9;

[0078] Mix 11 g of propenylbenzaldehyde and hexa-anilino cyclotriphosphazene in 100 mL of N,N-dimethylformamide, and react at 62°C for 45 min under nitrogen atmosphere. Cool to 50°C, add DOPO and triethylamine, heat to 82°C, and continue to react for 2 h. After the reaction, wash, and dry under vacuum to obtain a phosphorus-containing alkenyl compound. The mass ratio of hexa-anilino cyclotriphosphazene, propenylbenzaldehyde, DOPO, and triethylamine is 1:1.15:1.6:1.0;

[0079] 1.2. Mix 1 / 2 emulsifier solution (3 wt%) and mixed monomers, and stir for 30 min to obtain a pre-emulsion. Mix 1 / 10 pre-emulsion and the remaining emulsifier solution, add sodium bicarbonate and 1 / 2 initiator solution (3 wt%), heat to 80°C, and stir until blue phase appears. After the blue phase is obvious, heat for 15 min. Slowly add the remaining initiator and the remaining pre-emulsion. The initiator is added completely in 90 min, and the pre-emulsion is added completely within 2 h. Then heat for 90 min. After the reaction, cool to below 40°C, adjust the pH of the system to 7.5, and pass through a 100-mesh sieve to obtain a polyacrylate emulsion with a solid content of 45 wt%. The polyacrylate emulsion comprises the following components: 42 parts of mixed monomers, 0.3 parts of initiator, and 1.2 parts of emulsifier, by mass. The mixed monomers comprise the following components: 21 parts of n-butyl acrylate, 12 parts of methyl methacrylate, 6 parts of styrene, 2 parts of vinyl triethoxysilane, 2 parts of octamethylcyclotetrasiloxane, 2 parts of glycidyl methacrylate, and 5 parts of a phosphorus-containing alkenyl compound, by mass.

[0080] 1.3. Dissolve the curing agent and the accelerator in the polyacrylate emulsion to obtain a resin system. The resin system comprises the following components: 65 parts of water-based epoxy resin emulsion, 35 parts of polyacrylate emulsion, 4 parts of curing agent, and 1.2 parts of accelerator, by mass.

[0081] Step (2) mixing the fiber filler, the particle filler, the resin system, the auxiliary agent and the solvent, stirring and dispersing to obtain a coating; coating the coating on the surface of the steel material, curing to form a fireproof coating, obtaining the fire-resistant steel material; the curing process is: 60℃ for 1h; 100℃ for 1h; 125℃ for 2h; the fireproof coating comprises the following components: 15 parts of fiber filler, 40 parts of particle filler, 35 parts of resin material and 2 parts of auxiliary agent; the fiber filler is a mixture of sepiolite fiber and glass fiber with a mass ratio of 3:7; the particle filler is a mixture of aluminum hydroxide, magnesium hydroxide and zinc borate with a mass ratio of 6.5:2.5:1.

[0082] Example 3: a preparation method of a high-strength fire-resistant steel material for a fireproof door, comprising the following process steps:

[0083] Step (1): 1.1. mixing 8g of trichlorophosphine, acetaminophen and catalyst DBU in 100mL of acetone, heating to 80℃ under nitrogen atmosphere, and keeping for 8h; after reaction, filtering, washing and vacuum drying to obtain hexa-acetyl cyclotriphosphazene; the molar ratio of trichlorophosphine, acetaminophen and catalyst is 1:7.2:0.2;

[0084] Mixing 15g of hexa-acetyl cyclotriphosphazene, 100mL of ethanol aqueous solution (v / v=7:3) and 20wt% sodium hydroxide aqueous solution, refluxing at 75℃ for 24h; after reaction, cooling, filtering, washing and vacuum drying to obtain hexa-anilino cyclotriphosphazene; the mass ratio of amide group in hexa-acetyl cyclotriphosphazene and sodium hydroxide is 1:1.1;

[0085] Mixing 12g of propenylbenzaldehyde and hexa-anilino cyclotriphosphazene in 100mL of N,N-dimethylformamide, reacting at 65℃ for 30min under nitrogen atmosphere; cooling to 50℃, adding DOPO and triethylamine, and continuing to react at 85℃ for 1h; after reaction, washing and vacuum drying to obtain a phosphorus-containing alkenyl compound; the mass ratio of hexa-anilino cyclotriphosphazene, propenylbenzaldehyde, DOPO and triethylamine is 1:1.2:1.7:1.2;

[0086] 1.2 Mix 1 / 2 emulsifier solution (4wt%), mixed monomers, stir for 30 min to obtain a pre-emulsion; mix 1 / 10 pre-emulsion, the rest of the emulsifier solution, add sodium bicarbonate, 1 / 2 initiator solution (5wt%), heat to 80℃, stir until blue phase appears, keep for 15 min after blue phase is obvious; slowly add the rest of the initiator and the rest of the pre-emulsion, the initiator is added for 90 min, and the pre-emulsion is added within 2 h; then keep for 90 min; cool the reaction to below 40℃, adjust the pH of the system to 8, pass through a 100 mesh sieve to obtain a polyacrylate emulsion with a solid content of 50wt%; the polyacrylate emulsion comprises the following components: 45 parts of mixed monomers, 0.5 parts of initiator, and 1.5 parts of emulsifier by mass; the mixed monomers comprise the following components: 23 parts of n-butyl acrylate, 13 parts of methyl methacrylate, 7 parts of styrene, 2.5 parts of vinyl triethoxysilane, 2.5 parts of octamethylcyclotetrasiloxane, 3 parts of glycidyl methacrylate, and 10 parts of phosphorus-containing alkyl compound by mass;

[0087] 1.3 Take the curing agent and the accelerator, dissolve them in the polyacrylate emulsion by stirring; add the water-based epoxy resin emulsion to obtain a resin system; the resin system comprises the following components: 60 parts of water-based epoxy resin emulsion, 40 parts of polyacrylate emulsion, 3 parts of curing agent, and 0.5 parts of accelerator by mass;

[0088] Step (2) Mix the fiber filler, the particulate filler, the resin system, the auxiliary agent, and the solvent by stirring and dispersing to obtain a coating; apply the coating to the surface of the steel material, and cure to form a fireproof coating layer to obtain a fire-resistant steel material; the curing process is as follows: 60℃ for 1 h; 100℃ for 1 h; 125℃ for 2 h; the fireproof coating comprises the following components: 15 parts of fiber filler, 40 parts of particulate filler, 35 parts of resin material, and 2 parts of auxiliary agent; the fiber filler is a mixture of sepiolite fiber and glass fiber with a mass ratio of 2:8; the particulate filler is a mixture of aluminum hydroxide, magnesium hydroxide, and zinc borate with a mass ratio of 6:3:1.

[0089] Comparative Example 1: A method for preparing a high-strength fire-resistant steel material for fireproof doors, comprising the following process steps:

[0090] Step (1): 1.1. Mix 3g of trichlorophosphazene, acetaminophen, and catalyst DBU in 100mL of acetone, heat to 60℃ under nitrogen atmosphere, and keep for 16h; after the reaction, filter, wash, and vacuum dry to obtain hexaacetyl cyclotriphosphazene; the molar ratio of trichlorophosphazene, acetaminophen, and catalyst is 1:6.5:0.1;

[0091] Mixing 10 g hexa-acetyl cyclotriphosphazene, 100 mL ethanol aqueous solution (v / v = 7:3), 10 wt% sodium hydroxide aqueous solution, refluxing at 70°C for 36 h; after reaction, cooling, filtering, washing, and vacuum drying, hexa-anilino cyclotriphosphazene is obtained; the mass ratio of amide group in hexa-acetyl cyclotriphosphazene to sodium hydroxide is 1:0.7;

[0092] Mixing 10 g propenylbenzaldehyde, hexa-anilino cyclotriphosphazene in 100 mL N,N-dimethylformamide, reacting at 60°C for 60 min under nitrogen atmosphere; after reaction, washing, and vacuum drying, the phosphorus-containing olefin compound is obtained; the mass ratio of hexa-anilino cyclotriphosphazene to propenylbenzaldehyde is 1:1.1;

[0093] Steps 1.2-1.3, (2) are the same as in Example 1, and the fire-resistant steel material is obtained.

[0094] Preparation method of a high-strength fire-resistant steel material for a fireproof door, comprising the following process steps:

[0095] Step (1): 1.1. Mixing 3 g trimeric phosphorus chloride, 4-hydroxy styrene, and catalyst DBU in 100 mL acetone, heating to 60°C, and reacting for 16 h under nitrogen atmosphere; after reaction, filtering, washing, and vacuum drying, the phosphorus-containing olefin compound is obtained; the molar ratio of trimeric phosphorus chloride, 4-hydroxy styrene, and catalyst is 1:6.5:0.1.

[0096] Steps 1.2-1.3, (2) are the same as in Example 1, and the fire-resistant steel material is obtained.

[0097] Preparation method of a high-strength fire-resistant steel material for a fireproof door, comprising the following process steps:

[0098] Step (1) polyacrylate emulsion comprises the following components: 40 parts by mass of mixed monomers, 0.2 parts by mass of initiator, and 1.0 parts by mass of emulsifier; the mixed monomers comprise the following components: 20 parts by mass of n-butyl acrylate, 11 parts by mass of methyl methacrylate, 5 parts by mass of styrene, 1.5 parts by mass of vinyl triethoxysilane, 1.5 parts by mass of octamethylcyclotetrasiloxane, and 1 part by mass of glycidyl methacrylate;

[0099] Other process steps are the same as in Example 1, and the fire-resistant steel material is obtained.

[0100] Preparation method of a high-strength fire-resistant steel material for a fireproof door, comprising the following process steps:

[0101] Step (1) the polyacrylate emulsion comprises the following components: 40 parts of mixed monomers, 0.2 parts of initiator, 1.0 parts of emulsifier by mass fraction; the mixed monomers comprise the following components: 20 parts of n-butyl acrylate, 11 parts of methyl methacrylate, 5 parts of styrene, 1 part of glycidyl methacrylate by mass fraction;

[0102] Other process steps are the same as those in Example 1, and a fire-resistant steel material is obtained.

[0103] Comparative Example 5: a method for preparing a high-strength fire-resistant steel material for a fireproof door, comprising the following process steps:

[0104] Step (1) the resin system comprises the following components: 100 parts of water-based epoxy resin emulsion, 5 parts of curing agent, 2 parts of accelerator by mass fraction;

[0105] Other process steps are the same as those in Example 1, and a fire-resistant steel material is obtained.

[0106] Experiment: take the fireproof coating and fire-resistant steel material obtained in Examples 1-3 and Comparative Examples 1-5, prepare samples, and detect the performance of the samples respectively and record the detection results:

[0107] According to GB / T 14907 as a reference standard, the fireproof performance of the sample is detected; according to GB / T 1732 as a reference standard, the impact resistance of the sample is detected; according to GB / T 1040 as a reference standard, the tensile strength of the sample is detected; and according to GB / T 9286 as a reference standard, the adhesion grade of the sample is detected.

[0108]

[0109] According to the data in the above table, the following conclusions can be clearly obtained:

[0110] The fireproof coating obtained in Examples 1-3 is compared with the fireproof coating obtained in Comparative Examples 1-5, and the detection results show that,

[0111] Compared with the comparative examples, the fireproof coating obtained in Examples 1-3 has better fire resistance time limit, impact resistance height, tensile strength, adhesion grade data. This fully shows that the present application realizes the improvement of the fireproof performance, strength, impact resistance and adhesion of the prepared fireproof coating.

[0112] Compared with the embodiment 1, in the phosphorus-containing alkyl compound in the comparative example 1, the DOPO does not participate in the reaction; the phosphorus-containing alkyl compound in the comparative example 2 is prepared from the trimeric phosphorus chloride and 4-hydroxy styrene; the phosphorus-containing alkyl compound is not set in the polyacrylate emulsion in the comparative example 3; the phosphorus-containing alkyl compound, the vinyl triethoxysilane and the octamethylcyclotetrasiloxane are not set in the polyacrylate emulsion in the comparative example 4; the polyacrylate emulsion is not set in the resin system in the comparative example 5. The fireproof coating obtained in the comparative examples 1-5 has the deteriorated fire resistance time, the impact resistance height, the tensile strength and the adhesion grade data. It can be known that the setting of the fireproof coating process and the components used in the process can promote the comprehensive improvement of the fireproof performance, the strength, the impact resistance and the adhesion.

[0113] It will be obvious to a person skilled in the art that, without departing from the spirit or essential characteristics of the application, the present application can be carried out in other specific forms than those described and exemplified hereinabove. Particularly, the present embodiments are to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the description given above, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

1. A high-strength fire-resistant steel material for a fire door, characterized by: The fireproof coating is formed by coating and curing the fireproof coating material on the surface of the steel material; The fireproof coating material comprises the following components: 10-20 parts of fiber filler, 30-50 parts of particle filler, 30-40 parts of resin material and 1-3 parts of additive; The fiber filler is a mixture of sepiolite fiber and glass fiber, with a mass ratio of (2-4):(6-8); The particle filler is a mixture of aluminum hydroxide, magnesium hydroxide and zinc borate, with a mass ratio of (6-7):(2-3):1; The resin material comprises the following components: 60-70 parts of water-based epoxy resin emulsion, 30-40 parts of polyacrylate emulsion, 3-5 parts of curing agent and 0.5-2 parts of accelerator; The polyacrylate emulsion is prepared by the following process: Mix 1 / 2 emulsifier solution and mixed monomers to obtain a pre-emulsion; Mix 1 / 10 pre-emulsion, the remaining emulsifier solution, add sodium bicarbonate and 1 / 2 initiator solution, heat to 78-82℃, stir until blue phase appears, keep warm for 10-20 min, then add the remaining initiator and the remaining pre-emulsion, keep warm for 90-120 min, cool, adjust the pH of the system to 7-8, sieve to obtain the polyacrylate emulsion; The polyacrylate emulsion comprises the following components: 40-45 parts of mixed monomers, 0.2-0.5 parts of initiator and 1.0-1.5 parts of emulsifier; The mixed monomers comprise the following components: 20-23 parts of n-butyl acrylate, 11-13 parts of methyl methacrylate, 5-7 parts of styrene, 1.5-2.5 parts of vinyl triethoxysilane, 1.5-2.5 parts of octamethylcyclotetrasiloxane, 1-3 parts of glycidyl methacrylate and 1-10 parts of phosphorus-containing alkyl compound; The phosphorus-containing alkyl compound is prepared by the following process: (1) Mix phosphorus trichloride, acetaminophen and catalyst in acetone, heat to 60-80℃ under nitrogen atmosphere, keep warm for 8-96 h to obtain hexaacetyl cyclotriphosphazene; (2) Mix hexaacetyl cyclotriphosphazene, alcohol aqueous solution and sodium hydroxide, reflux at 70-75℃ for 4-36 h to obtain hexanilino cyclotriphosphazene; (3) Mix propenyl benzaldehyde and hexanilino cyclotriphosphazene in N,N-dimethylformamide, react at 60-65℃ under nitrogen atmosphere for 30-60 min, cool to 50±5℃, add DOPO and triethylamine, heat to 80-85℃ and continue to react for 1-3 h to obtain the phosphorus-containing alkyl compound.

2. The high-strength fire-resisting steel material for a fire door according to claim 1, characterized by: The molar ratio of phosphorus trichloride to acetaminophen is 1:(6.5-7.2); The mass ratio of hexanilino cyclotriphosphazene, propenyl benzaldehyde and DOPO is 1:(1.1-1.2):(1.5-1.7).

3. A method of manufacturing a high-strength fire-resistant steel material for a fire door according to any one of claims 1 to 2, characterized in that: The process comprises the following steps: Mix the fiber filler, particle filler, resin material, additive and solvent, stir and disperse to obtain the coating material; Coat the coating material on the surface of the steel material, cure to form the fireproof coating and obtain the fireproof steel material.

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