Lightweight high-strength fireproof decorative material as well as preparation method and application thereof

Abstract

The invention discloses a light high-strength fireproof decorative material as well as a preparation method and application thereof, belongs to the technical field of fireproof decorative materials, and aims at solving the technical problem that the fire resistance rating, the water absorption performance and the mechanical strength of a light fireproof material in the prior art need to be further improved. The lightweight concrete is specifically prepared from the following components in parts by weight: 80-100 parts of a silicon-calcium material, 8-10 parts of modified triphosphoric acid, 10-14 parts of a modified fiber reinforcement, 15-18 parts of modified lightweight aggregate, 5-8 parts of an adhesive and 2-3 parts of an additive, the modified triphosphoric acid is used as a flame retardant, the lightweight aggregate is pretreated, the fiber reinforcement is improved, and the lightweight high-strength fireproof decorative material is prepared through mutual cooperation with the additive, so that the fireproof performance and compressive strength of the material are improved, and the volume density of the material is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of fireproof decorative material processing, and in particular to a light and high-strength fireproof decorative material and a preparation method and application thereof. Background Art

[0002] In recent years, multiphase structural materials represented by fiber-reinforced composites and ceramic-based composites have achieved synergistic improvements in mechanical properties and thermal stability through microstructure optimization. Among them, the pore control technology of aerogel composites has significantly improved the thermal insulation efficiency of the material. At the application level, integrated panels with both decorative functions and fire-resistant properties have gradually replaced traditional stone and metal panels, forming a large-scale application trend in fields such as high-rise building curtain walls and rail transit interiors.

[0003] However, existing technologies still face deep contradictions between the basic material system and functional requirements: the lightweight goal leads to insufficient material density, which restricts structural integrity at high temperatures. There is an adaptability conflict between high-strength requirements and flexible processing technology. Although some systems achieve performance balance through multi-layer composites, it is difficult to balance manufacturing costs and environmental protection, which restricts market penetration.

[0004] Currently, the performance degradation of existing materials at extreme temperatures stems from the cumulative effect of multi-scale structural defects. In inorganic-organic hybrid systems, high-temperature-induced molecular chain desorption and lattice reorganization can lead to a significant decrease in interfacial binding energy. For example, the free radicals formed after the rupture of silicon-oxygen bonds can induce a chain reaction of degradation. For fiber-reinforced systems, thermal oxidative aging of the matrix resin can weaken the shear strength of the fiber / matrix interface, resulting in an exponential decay in stress transfer efficiency.

[0005] In porous structural materials, excessively high closed porosity will reduce the thermal convection barrier performance, while increased open porosity will weaken the structural bearing capacity. This mutually exclusive relationship between pore structure and mechanical properties has not yet formed an effective regulation method. In addition, the molecular-level compatibility between flame retardants and matrix materials is insufficient, resulting in the flame retardant components easily migrating and precipitating at high temperatures, making it impossible to continuously play a thermal insulation role.

[0006] Based on existing technologies, the industry is turning to composite modified materials to break through technical bottlenecks and solve problems such as insufficient fire resistance, low water absorption and poor mechanical properties of lightweight and high-strength fire-proof decorative materials. Summary of the Invention

[0007] The purpose of the present invention is to provide a lightweight and high-strength fireproof decorative material and its preparation method and application, which are used to solve the technical problem in the prior art that the fire resistance grade, water absorption performance and mechanical strength of lightweight fireproof materials need to be further improved.

[0008] The object of the present invention can be achieved by the following technical solution: a lightweight and high-strength fireproof decorative material, comprising the following components in parts by weight: 80-100 parts of a silicon-calcium material, 8-10 parts of a modified triphosphate, 10-14 parts of a modified fiber reinforcement, 15-18 parts of a modified lightweight aggregate, 5-8 parts of a binder, and 2-3 parts of an additive;

[0009] The preparation method of the modified triphosphoric acid comprises the following steps: adding melamine, vanillin and DMF into a three-necked flask, raising the temperature to 60-80°C, stirring and reacting for 2-3 hours, and post-treating to obtain a flame retardant powder; adding the flame retardant powder and DMF into a three-necked flask, raising the temperature to 100-120°C, adding triphosphoric acid, and reacting for 1-2 hours to obtain the modified triphosphoric acid;

[0010] The synthetic reaction formula of modified triphosphoric acid is:

[0011]

[0012]

[0013] Where: The asterisk indicates the connection point between R and the hydroxyl group.

[0014] The synthetic mechanism of modified triphosphoric acid is:

[0015] The aldehyde group of vanillin undergoes nucleophilic addition reaction with the amino group of melamine to generate imine, which is then dehydrated. The phenolic hydroxyl group of vanillin further condenses with the remaining amino group or imine group of melamine to form a cross-linked phenol-aldehyde amine polymer. Multiple condensations form a three-dimensional network structure to obtain a flame retardant. The hydroxyl group in the flame retardant undergoes an esterification reaction with the phosphate group of the modified triphosphoric acid to form a phosphate ester bond to obtain the modified triphosphoric acid.

[0016] The modified lightweight aggregate consists of hollow glass microspheres, pretreated expanded perlite and pretreated polystyrene particles in a weight ratio of 3:2:5.

[0017] Furthermore, the calcium silicate material is composed of silicon dioxide, calcium oxide and glass fiber in a weight ratio of 50-70:20-30:5-10; the adhesive is silica sol, and the chemical additives are composed of polycarboxylic acid, alkyl sulfonate and bentonite in a weight ratio of 0.5-1.5:0.1-0.3:0.2-0.5.

[0018] Furthermore, the preparation method of the pretreated expanded perlite is as follows: soaking the perlite particles in a silica sol with a pH of 3-4 and a solid content of 30%, stirring for 10-15 minutes, then transferring to an 80-100°C oven and drying to constant weight, then spraying a 0.5-1wt% KH-560 solution on the surface of the particles, transferring to a 60°C oven for curing for 30 minutes, and cooling at room temperature to obtain the pretreated expanded perlite, wherein the amount ratio of the perlite particles to the silica sol is 100g:1.03L.

[0019] Furthermore, the preparation method of the pretreated polystyrene particles is as follows: polystyrene particles and red phosphorus masterbatch are added into a high-speed mixer at a weight ratio of 20:1 and mixed for 10-15 minutes to obtain pretreated polystyrene particles.

[0020] Furthermore, the usage ratio of melamine, vanillin, DMF solvent and triphosphoric acid is 0.7 g:1.8 g:10 mL:2.5 g; and the post-treatment method is: after the reaction is completed, low-boiling substances are evaporated under reduced pressure, the product is washed alternately with deionized water and ethanol, and then transferred to a 60° C. vacuum drying oven and dried to constant weight.

[0021] Furthermore, the preparation method of the modified fiber reinforcement is:

[0022] A1. Immerse the pretreated mixed fiber in KH-570 ethanol solution, raise the temperature to 60-80°C, react for 4-6 hours, remove the fiber, and dry it in a 60-80°C oven to constant weight to obtain a fiber bundle;

[0023] A2. Add the fiber bundle, azobisisobutyronitrile and methyl methacrylate into a reactor filled with nitrogen, raise the temperature to 55-65° C. and react for 6 hours, and then post-treat to obtain a modified fiber reinforcement.

[0024] The synthesis mechanism of modified fiber reinforcement is:

[0025] γ-Methacryloxypropyltrimethoxysilane undergoes a hydrolysis reaction with a trace amount of water in ethanol to generate reactive silanol groups, which condense with hydroxyl groups on the fiber surface to form stable Si-O-Si covalent bonds, thereby achieving chemical modification of the fiber surface. Vacuuming to negative pressure removes bubbles inside the fiber bundle, promoting the full infiltration of methyl methacrylate monomer into the fiber surface and pores. Azobisisobutyronitrile decomposes upon heating to generate active free radicals, which attack the methyl groups of methyl methacrylate to generate growing chain free radicals. The free radicals continuously initiate the polymerization of methyl methacrylate monomer to form polymethyl methacrylate. The two free radicals combine or disproportionately terminate to form a highly cross-linked polymethyl methacrylate coating, thereby obtaining a modified fiber reinforcement.

[0026] Furthermore, in step A1, the mixed fiber, KH-570 ethanol solution, azobisisobutyronitrile and methyl methacrylate are used in a ratio of 5g:25mL:0.1g:50-100mL, the mixed fiber is composed of carbon fiber and basalt fiber in a weight ratio of 1:1, and the KH-570 ethanol solution is composed of γ-glycidyloxypropyltrimethoxysilane, ethanol and purified water in a ratio of 3g:90mL:10mL; in step A2, the post-treatment method includes: after the reaction is completed, laying the fiber bundle, pressurizing to 10MPa at 150-160°C and curing for 30-40min, then heat treating at 200°C for 1h, and ultrasonically cleaning with acetone for 10min to obtain a modified fiber reinforcement;

[0027] Furthermore, the pretreatment method of the mixed fiber is: the carbon fiber and basalt fiber are chopped and mixed, and the mixture is immersed in 10wt% nitric acid solution and 5wt% KH-550 ethanol solution in sequence, the temperature is raised to 60°C and reacted for 2-3h. After the reaction is completed, it is ultrasonically cleaned with deionized water, dehydrated with ethanol, and then placed in a vacuum drying oven at 60-80°C to constant weight to obtain pretreated mixed fibers, wherein the KH-550 ethanol solution is composed of γ-aminopropyltriethoxysilane, ethanol and purified water in a ratio of 5g:90mL:10mL, and the amount ratio of carbon fiber, basalt fiber, nitric acid solution and KH-550 ethanol solution is 1g:1g:16mL:12mL.

[0028] The present invention also proposes a method for preparing a lightweight and high-strength fireproof decorative material: adding a silicon-calcium material, an additive, a modified fiber reinforcement and a modified lightweight aggregate into a forced mixer, dry-mixing for 5 minutes, adding modified triphosphoric acid and a binder, mixing for 10 minutes, injecting the slurry into a mold and vibrating it; then performing pre-curing at 60-80°C for 2-4 hours and autoclaving curing at 180-200°C, 1.0-1.5MPa, for 8-12 hours, naturally cooling and demolding, cutting into boards and polishing the surface to obtain a lightweight and high-strength fireproof material.

[0029] The present invention also proposes an application of a lightweight and high-strength fireproof decorative material, and the lightweight and high-strength fireproof decorative material prepared by the above-mentioned method for preparing a lightweight and high-strength fireproof decorative material is applied to interior decoration.

[0030] The present invention has the following beneficial effects:

[0031] 1. The present invention uses modified triphosphoric acid as a flame retardant, pre-treats lightweight aggregates, improves the performance of perlite and polystyrene particles, and improves fiber reinforcement. Then, through the interaction between the additives, a lightweight, high-strength fireproof decorative material is prepared. This not only improves the fireproof performance and compressive strength of the material, but also reduces the water absorption rate and bulk density of the fireproof material.

[0032] Perlite reacts with silica sol and silane, and silica sol penetrates the microporous structure of perlite particles. After drying, it forms a dense three-dimensional network structure of inorganic coating, reducing porosity. It also hydrolyzes with silane to form a chemically bonded organic-inorganic hybrid layer, which improves the adhesion between perlite and the substrate, reduces interfacial debonding, and retains the porous structure of perlite while reducing water adsorption, lowering water absorption and bulk density.

[0033] The red phosphorus masterbatch is evenly dispersed on the surface of polystyrene particles through mixing. During high-temperature processing, it partially melts with the polystyrene matrix to form a physical barrier. Red phosphorus is oxidized to generate phosphoric acid at high temperature, which catalyzes the dehydrogenation and carbonization of polystyrene, forming a dense carbon layer to isolate oxygen, inhibit the combustion chain reaction, and improve the flame retardant properties of the material.

[0034] 2. The present invention also modifies triphosphoric acid. The amino group of melamine and the aldehyde group of vanillin are condensed to form an imine structure to form a cross-linked copolymer network, thereby enhancing impact resistance. The large amount of nitrogen introduced cooperates with the phosphoric acid group to form a synergistic flame retardant in the material, further improving the flame retardant properties of the material. The copolymer forms nanoparticles through hydrogen bonding and π-π stacking to improve dispersibility. The basic amino group of the flame retardant reacts with the phosphoric acid group of triphosphoric acid to form a phosphate bond. The polyphosphate cross-linked structure enhances the intermolecular chain interaction through the POC bond, thereby improving thermal stability. The phenolic hydroxyl hydrophobic group of the vanillin in the copolymer cooperates with the silane coupling agent to reduce the surface energy and reduce the water absorption rate of the material.

[0035] 3. The present invention also modifies the fiber reinforcement by pre-treating the fiber to remove surface impurities and forming micro-etching pits on the surface to increase roughness, improve the fiber surface energy, and enhance the chemical bonding between the subsequent coupling agent and the fiber. γ-aminopropyltriethoxysilane is hydrolyzed to generate silanol, which then condenses with the hydroxyl or carboxyl groups on the fiber surface to form a chemical bond, thereby improving the interfacial bonding between the fiber and the matrix and reducing debonding.

[0036] The methacryloyloxy group of γ-methacryloxypropyltrimethoxysilane provides active sites for subsequent polymerization with methyl methacrylate. Furthermore, under the action of an initiator, free radical polymerization of methyl methacrylate is initiated to form a polymethyl methacrylate coating, which prevents fiber oxidation and wear. It also cross-links and cures at high temperatures to form a three-dimensional network structure, thereby improving the mechanical strength and heat resistance of the coating. With the mutual cooperation of double silane modification and elastic coating of polymethyl methacrylate, the interfacial bonding strength, impact resistance and heat resistance of the material are greatly improved. DETAILED DESCRIPTION

[0037] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0038] In the present invention, melamine is from Guangzhou Haoyu International Trade Co., Ltd., with CAS number 108-78-1 and purity of 99.5%;

[0039] In the present invention, vanillin is from Shanghai Titan Technology Co., Ltd., with a CAS number of 121-33-5 and a density of 1.056 g / cm3;

[0040] In the present invention, the polystyrene particles are from Shanghai Jizhi Biochemical Technology Co., Ltd., with a CAS number of 9003-53-6 and a melting point of 212°C;

[0041] In the present invention, KH-560 is γ-glycidyloxypropyltrimethoxysilane, which is from Shanghai Xinyu Biotechnology Co., Ltd., with a CAS number of 2530-83-8 and a boiling point of 290°C;

[0042] In the present invention, KH-550 is γ-aminopropyltriethoxysilane, which is from Danyang Organic Silicon Materials Industrial Company, with a CAS number of 919-30-2 and a boiling point of 217°C;

[0043] In the present invention, KH-570 is γ-methacryloxypropyltrimethoxysilane, which is from Hangzhou Jessica Chemical Co., Ltd. and has a CAS number of 2530-85-0;

[0044] In the present invention, the pH of the silica sol is 3 and the solid content is 30%.

[0045] Example 1

[0046] This embodiment provides a method for preparing a lightweight and high-strength fireproof decorative material, comprising the following steps:

[0047] S1. Preparation of modified triphosphoric acid

[0048] Weigh: 7 g of melamine, 18 g of vanillin, and 100 mL of DMF were added to a three-necked flask, the temperature was raised to 60°C, and the mixture was stirred for reaction for 2 h. After the reaction was completed, the temperature of the three-necked flask was raised to 100°C, and low-boiling substances were evaporated under reduced pressure. 50 mL of deionized water was added to the three-necked flask, and the mixture was stirred until the temperature of the three-necked flask dropped to room temperature. The mixture was filtered; the mixture was washed three times with deionized water and anhydrous ethanol, and then dried. The filter cake was transferred to a 60°C vacuum drying oven and dried to constant weight to obtain a flame retardant powder.

[0049] 25 g of flame retardant powder and 100 mL of DMF were added to a three-necked flask, the temperature was raised to 60°C, 25 g of triphosphoric acid was added, and the reaction was carried out for 1 h. The temperature of the three-necked flask was raised to 100°C, and low-boiling substances were evaporated under reduced pressure. 50 mL of deionized water was added to the three-necked flask, and the mixture was stirred until the temperature of the three-necked flask dropped to room temperature. The mixture was filtered; the mixture was washed three times with deionized water and anhydrous ethanol in sequence, and then dried. The filter cake was transferred to a vacuum drying oven at 60°C and dried to constant weight to obtain modified triphosphoric acid.

[0050] S2. Preparation of pretreated expanded perlite

[0051] Weigh 300 g of perlite particles, soak them in 3.1 L of silica sol, stir for 10 minutes, transfer to an 80°C oven and dry to constant weight, then spray the particles with a 0.5 wt% KH-560 solution, transfer to a 60°C oven and cure for 30 minutes, then cool to room temperature to obtain pretreated expanded perlite.

[0052] S3. Preparation of pretreated polystyrene particles

[0053] 500 g of polystyrene particles and 25 g of red phosphorus masterbatch were added to a high-speed mixer and mixed for 10 minutes to obtain pretreated polystyrene particles.

[0054] S4. Preparation of modified fiber reinforcement

[0055] Mix 30 g of γ-methacryloxypropyltrimethoxysilane, 900 mL of ethanol, and 100 mL of purified water to obtain a KH-570 ethanol solution;

[0056] Mix 25 g of γ-aminopropyltriethoxysilane, 450 mL of ethanol, and 50 mL of purified water to obtain a KH-550 ethanol solution;

[0057] Measure 400 mL of deionized water and slowly add 40 mL of concentrated nitric acid to obtain a nitric acid solution for later use;

[0058] Weigh: 25g carbon fiber and 25g basalt fiber chopped short mix, add the mixed fiber and 400mL nitric acid solution into a beaker, heat to 60℃, keep warm for 2h, after the reaction is complete, transfer the fiber to a beaker, rinse with deionized water, and then ultrasonically clean for 10min, then soak the fiber in anhydrous ethanol for 5min, centrifuge to obtain a pretreated fiber precursor;

[0059] 50 g of pretreated fiber precursor fiber and 300 mL of KH-550 ethanol solution were added to a beaker, and the temperature was raised to 60 ° C for reaction for 2 h. After the reaction was completed, it was ultrasonically cleaned with deionized water, dehydrated with ethanol, and then placed in a vacuum drying oven at 60 ° C to constant weight to obtain pretreated mixed fibers;

[0060] 50 g of pretreated mixed fibers were immersed in 250 mL of KH-570 ethanol solution, the temperature was raised to 60 ° C, the reaction was continued for 4 h, the fibers were taken out, and dried in a 60 ° C oven to constant weight to obtain a fiber bundle;

[0061] 50 g of fiber bundle, 0.1 g of azobisisobutyronitrile and 80 mL of methyl methacrylate were added to a reactor filled with nitrogen, the temperature was raised to 55 ° C and the reaction was carried out for 6 hours. After the reaction was completed, the fiber bundle was evenly spread in a stainless steel flat mold with a layer thickness of about 6 mm. It was transferred to a hot press, the temperature was raised to 150 ° C, the pressure was 10 MPa, and it was cured for 30 minutes, then heat treated at 200 ° C for 1 hour, and ultrasonically cleaned with acetone for 10 minutes to obtain a modified fiber reinforcement.

[0062] S5. Preparation of lightweight and high-strength fireproof materials

[0063] The polycarboxylic acid, alkyl sulfonate and bentonite are mixed in a weight ratio of 1.5:0.3:0.5 to obtain an additive;

[0064] Weigh by weight: 80 parts of silicon calcium material, 10 parts of modified fiber reinforcement, and 2 parts of additives, add them to a mixer, dry mix for 5 minutes, add 8-10 parts of modified triphosphate, 15 parts of modified lightweight aggregate and 5 parts of silica sol to the mixer, mix for 10 minutes, inject the slurry into the mold and vibrate to expel bubbles, then put the green body into a curing room with a normal pressure temperature of 60°C and a humidity of 60% for 2 hours, and then transfer it to an autoclave, increase the temperature to 180°C at 2°C / min, introduce saturated steam, increase the pressure to 1.0 MPa, maintain constant temperature and pressure for 8 hours, naturally cool and demold, cut into plates, and polish the surface to obtain a lightweight and high-strength fireproof material.

[0065] Example 2

[0066] This embodiment provides a method for preparing a lightweight and high-strength fireproof decorative material, comprising the following steps:

[0067] S1. Preparation of modified triphosphoric acid

[0068] Weigh: 7 g of melamine, 18 g of vanillin, and 100 mL of DMF were added to a three-necked flask, the temperature was raised to 70°C, and the mixture was stirred for reaction for 2.5 hours. After the reaction was completed, the temperature of the three-necked flask was raised to 100°C, and low-boiling substances were evaporated under reduced pressure. 50 mL of deionized water was added to the three-necked flask, and the mixture was stirred until the temperature of the three-necked flask dropped to room temperature. The mixture was filtered; the mixture was washed three times with deionized water and anhydrous ethanol, and then dried. The filter cake was transferred to a vacuum drying oven at 70°C and dried to constant weight to obtain a flame retardant powder.

[0069] 25 g of flame retardant powder and 100 mL of DMF were added to a three-necked flask, the temperature was raised to 60°C, 25 g of triphosphoric acid was added, and the reaction was carried out for 1.5 h. The temperature of the three-necked flask was raised to 100°C, and low-boiling substances were evaporated under reduced pressure. 50 mL of deionized water was added to the three-necked flask, and the mixture was stirred until the temperature of the three-necked flask dropped to room temperature. The mixture was filtered; the mixture was washed three times with deionized water and anhydrous ethanol in sequence, and then dried. The filter cake was transferred to a 60°C vacuum drying oven and dried to constant weight to obtain modified triphosphoric acid.

[0070] S2. Preparation of pretreated expanded perlite

[0071] Weigh 300 g of perlite particles, soak them in 3.1 L of silica sol, stir for 10 minutes, transfer to a 90°C oven and dry to constant weight, then spray the particles with a 0.5 wt% KH-560 solution, transfer to a 60°C oven and cure for 30 minutes, then cool to room temperature to obtain pretreated expanded perlite.

[0072] S3. Preparation of polystyrene particles

[0073] 500 g of polystyrene particles and 25 g of red phosphorus masterbatch were added to a high-speed mixer and mixed for 10 minutes to obtain pretreated polystyrene particles.

[0074] S4. Preparation of modified fiber reinforcement

[0075] Mix 30 g of γ-methacryloxypropyltrimethoxysilane, 900 mL of ethanol, and 100 mL of purified water to obtain a KH-570 ethanol solution;

[0076] Mix 25 g of γ-aminopropyltriethoxysilane, 450 mL of ethanol, and 50 mL of purified water to obtain a KH-550 ethanol solution;

[0077] Measure 400 mL of deionized water and slowly add 40 mL of concentrated nitric acid to obtain a nitric acid solution for later use;

[0078] Weigh: 25g carbon fiber and 25g basalt fiber chopped short mix, add the mixed fiber and 400mL nitric acid solution into a beaker, heat to 60℃, keep warm for 2h, after the reaction is complete, transfer the fiber to a beaker, rinse with deionized water, and then ultrasonically clean for 10min, then soak the fiber in anhydrous ethanol for 5min, centrifuge to obtain a pretreated fiber precursor;

[0079] 50 g of pretreated fiber precursor and 300 mL of KH-550 ethanol solution were added to a beaker, and the temperature was raised to 60 ° C for reaction for 2.5 h. After the reaction was completed, the pretreated fiber was ultrasonically cleaned with deionized water, dehydrated with ethanol, and then placed in a vacuum drying oven at 70 ° C to constant weight to obtain a pretreated mixed fiber;

[0080] 50 g of pretreated mixed fiber was immersed in 250 mL of KH-570 ethanol solution, the temperature was raised to 60°C, the reaction was continued for 4 h, the fiber was taken out, and dried in a 60°C oven to constant weight to obtain a fiber bundle;

[0081] 50 g of fiber bundle, 0.1 g of azobisisobutyronitrile and 80 mL of methyl methacrylate were added to a reactor filled with nitrogen, the temperature was raised to 60 ° C and the reaction was carried out for 6 hours. After the reaction was completed, the fiber bundle was evenly spread in a stainless steel flat mold with a layer thickness of about 6 mm. It was transferred to a hot press, the temperature was raised to 155 ° C, the pressure was 10 MPa, and it was cured for 35 minutes, then heat treated at 200 ° C for 1 hour, and ultrasonically cleaned with acetone for 10 minutes to obtain a modified fiber reinforcement.

[0082] S5. Preparation of lightweight and high-strength fireproof materials

[0083] The polycarboxylic acid, alkyl sulfonate and bentonite are mixed in a weight ratio of 1.5:0.3:0.5 to obtain an additive;

[0084] Weigh by weight: 90 parts of silicon calcium material, 12 parts of modified fiber reinforcement, and 3 parts of additives, add them to a mixer, dry mix for 5 minutes, add 8-10 parts of modified triphosphate, 16 parts of modified lightweight aggregate and 7 parts of silica sol to the mixer, mix for 10 minutes, inject the slurry into the mold and vibrate to expel bubbles, then put the blank into a curing room with a normal pressure temperature of 60°C and a humidity of 60% for 2 hours, and then transfer it to an autoclave, increase the temperature to 180°C at 2°C / min, introduce saturated steam, increase the pressure to 1.0 MPa, maintain constant temperature and pressure for 8 hours, naturally cool and demold, cut into plates, and polish the surface to obtain a lightweight and high-strength fireproof material.

[0085] Example 3

[0086] This embodiment provides a method for preparing a lightweight and high-strength fireproof decorative material, comprising the following steps:

[0087] S1. Preparation of modified triphosphoric acid

[0088] Weigh: 7 g of melamine, 18 g of vanillin and 100 mL of DMF were added to a three-necked flask, the temperature was raised to 60°C and stirred for reaction for 2 h. After the reaction was completed, the temperature of the three-necked flask was raised to 100°C, low-boiling substances were evaporated under reduced pressure, 50 mL of deionized water was added to the three-necked flask, and the temperature was stirred until the temperature of the three-necked flask dropped to room temperature. The flask was filtered; the flask was washed three times with deionized water and anhydrous ethanol in sequence and then dried. The filter cake was transferred to a vacuum drying oven at 80°C and dried to constant weight to obtain a flame retardant powder.

[0089] 25 g of flame retardant powder and 100 mL of DMF were added to a three-necked flask, the temperature was raised to 60° C., 25 g of triphosphoric acid was added, and the reaction was carried out for 1 hour. After the reaction was completed, the temperature of the three-necked flask was raised to 100° C., low-boiling substances were evaporated under reduced pressure, 50 mL of deionized water was added to the three-necked flask, and the mixture was stirred until the temperature of the three-necked flask dropped to room temperature. The mixture was filtered; the mixture was washed three times with deionized water and anhydrous ethanol in sequence and then dried. The filter cake was transferred to a 60° C. vacuum drying oven and dried to constant weight to obtain modified triphosphoric acid.

[0090] S2. Preparation of pretreated expanded perlite

[0091] Weigh 300 g of perlite particles and soak them in 3.1 L of silica sol. Stir for 10 minutes, then transfer to a 100°C oven and dry to constant weight. Then, spray the particles with a 0.5 wt% KH-560 solution, transfer to a 60°C oven and cure for 30 minutes. Cool to room temperature to obtain pretreated expanded perlite.

[0092] S3. Preparation of pretreated polystyrene particles

[0093] 500 g of polystyrene particles and 25 g of red phosphorus masterbatch were added to a high-speed mixer and mixed for 10 minutes to obtain pretreated polystyrene particles.

[0094] S4. Preparation of modified fiber reinforcement

[0095] Mix 30 g of γ-methacryloxypropyltrimethoxysilane, 900 mL of ethanol, and 100 mL of purified water to obtain a KH-570 ethanol solution;

[0096] Mix 25 g of γ-aminopropyltriethoxysilane, 450 mL of ethanol, and 50 mL of purified water to obtain a KH-550 ethanol solution;

[0097] Measure 400 mL of deionized water and slowly add 40 mL of concentrated nitric acid to obtain a nitric acid solution for later use;

[0098] Weigh: 25g carbon fiber and 25g basalt fiber chopped short mix, add the mixed fiber and 400mL nitric acid solution into a beaker, heat to 60℃, keep warm for 2h, after the reaction is complete, transfer the fiber to a beaker, rinse with deionized water, and then ultrasonically clean for 10min, then soak the fiber in anhydrous ethanol for 5min, centrifuge to obtain a pretreated fiber precursor;

[0099] 50g of pretreated fiber precursor and 300mL of KH-550 ethanol solution were added to a beaker, and the temperature was raised to 60℃ for reaction for 3h. After the reaction was completed, it was ultrasonically cleaned with deionized water, dehydrated with ethanol, and then placed in a vacuum drying oven at 70℃ to dry to constant weight to obtain pretreated mixed fiber.

[0100] 50 g of pretreated mixed fibers were immersed in 250 mL of KH-570 ethanol solution, the temperature was raised to 60 °C, the reaction was continued for 4 h, the fibers were taken out, and dried in an oven at 60 °C to constant weight to obtain fiber bundles;

[0101] 50 g of fiber bundle, 0.1 g of azobisisobutyronitrile and 80 mL of methyl methacrylate were added to a reactor filled with nitrogen, and the temperature was raised to 65 ° C for 6 hours. After the reaction, the fiber bundle was evenly spread in a stainless steel flat mold with a layer thickness of about 6 mm. It was transferred to a hot press and pressurized to 10 MPa at 160 ° C for 40 minutes, then heat treated at 200 ° C for 1 hour, and ultrasonically cleaned with acetone for 10 minutes to obtain a modified fiber reinforcement.

[0102] S5. Preparation of lightweight and high-strength fireproof decorative materials

[0103] The polycarboxylic acid, alkyl sulfonate and bentonite are mixed in a weight ratio of 1.5:0.3:0.5 to obtain an additive;

[0104] Weigh by weight: 100 parts of silicon calcium material, 14 parts of modified fiber reinforcement, and 3 parts of additives, add them to a mixer, dry mix for 5 minutes, add 10 parts of modified triphosphate, 18 parts of modified lightweight aggregate and 8 parts of silica sol to the mixer, mix for 10 minutes, inject the slurry into the mold and vibrate to expel bubbles, then place the blank in a curing room with a normal pressure temperature of 60°C and a humidity of 60% for 2 hours, and then transfer it to an autoclave, raise the temperature to 180°C at a rate of 2°C / min, introduce saturated steam, raise the pressure to 1.0 MPa, maintain constant temperature and pressure for 8 hours, naturally cool and demold, cut into plates, and polish the surface to obtain a lightweight and high-strength fireproof material.

[0105] Comparative Example 1

[0106] The difference between this comparative example and Example 3 is that step S1 is eliminated and the modified triphosphoric acid is replaced by triphosphoric acid in step S1.

[0107] Comparative Example 2

[0108] The difference between this comparative example and Example 3 is that step S2 is omitted, and the pretreated expanded perlite is replaced by perlite particles in step S2.

[0109] Comparative Example 3

[0110] The difference between this comparative example and Example 3 is that step S3 is eliminated and the pretreated polystyrene particles are replaced by the polystyrene particles in step S3.

[0111] Comparative Example 4

[0112] The difference between this comparative example and Example 3 is that in step S4, carbon fiber is not added.

[0113] Performance testing:

[0114] The high-temperature flexural strength of the lightweight and high-strength fireproof materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was measured with reference to the standard GB / T 3002-2017 “Test method for high-temperature flexural strength of refractory materials”.

[0115] The wear resistance of the lightweight and high-strength fireproof materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was measured with reference to the standard GB / T 18301-2012 “Test method for wear resistance of refractory materials at room temperature”.

[0116] The impact resistance of the lightweight and high-strength fireproof materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was measured with reference to the standard JC / T 631-1996 "Test method for impact resistance of steel cement board".

[0117] The water absorption and bulk density of the lightweight and high-strength fireproof materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were measured with reference to the standard GB / T 2999-2016 “Test method for bulk density of refractory particles”.

[0118] The water absorption rates of the lightweight, high-strength fireproof materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were measured with reference to the standard GB 50016-2014 "Code for Fire Protection Design of Buildings (2018 Edition)". The specific test results are shown in Table 1 below:

[0119] Table 1-Performance test data of the sample

[0120]

[0121] Data Analysis:

[0122] A comparative analysis of the data in Table 1 above shows that the high-temperature flexural strength of the lightweight, high-strength fireproof decorative material prepared by the present invention reaches 4.6 MPa, the wear loss reaches 6.50 mg, the impact strength reaches 33 kJ m-2, the water absorption rate is reduced to 0.7%, and the fire resistance grade is level 1. All performance test data are better than those of the comparative example. The present invention uses modified triphosphoric acid as a flame retardant, pretreats the lightweight aggregate, improves the performance of perlite and polystyrene particles, and improves the fiber reinforcement. Then, through the mutual cooperation between the additives, a lightweight, high-strength fireproof decorative material is prepared, which not only improves the fire resistance and compressive strength of the material, but also reduces the water absorption and bulk density of the fireproof material.

[0123] Comparative Example 1 Compared with the Example, the amino groups of melamine and the aldehyde groups of vanillin condense to form an imine structure to form a cross-linked copolymer network, which enhances impact resistance and flame retardancy;

[0124] Comparative Example 2 Compared with the embodiment, the perlite is treated to form a chemically bonded organic-inorganic hybrid layer, which reduces interfacial debonding, retains the porous structure of the perlite, and reduces water adsorption, lowering water absorption and bulk density;

[0125] Comparative Example 3 Compared with the Example, the red phosphorus masterbatch is evenly dispersed on the surface of the polystyrene particles by mixing, and partially melts with the polystyrene matrix during high-temperature processing to form a physical barrier. The red phosphorus is oxidized at high temperature to generate phosphoric acid, which catalyzes the dehydrogenation and carbonization of the polystyrene, forming a dense carbon layer to isolate oxygen and inhibit the combustion chain reaction;

[0126] Comparative Example 4 Compared with the embodiment, the composite of carbon fiber and basalt fiber comprehensively improves the mechanical properties of the material through performance complementarity, interface synergy and functional integration.

[0127] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A light and high-strength fireproof decorative material, characterized in that: The lightweight and high-strength fireproof decorative material comprises the following components in parts by weight: 80-100 parts of silicon-calcium material, 8-10 parts of modified triphosphate, 10-14 parts of modified fiber reinforcement, 15-18 parts of modified lightweight aggregate, 5-8 parts of adhesive, and 2-3 parts of additives; The preparation method of the modified triphosphoric acid comprises: adding melamine, vanillin and DMF into a three-necked flask, raising the temperature to 60-80°C, stirring and reacting for 2-3 hours, and post-treating to obtain a flame retardant powder; adding the flame retardant powder and DMF into the three-necked flask, raising the temperature to 60-80°C, and then adding triphosphoric acid and reacting for 1-2 hours to obtain the modified triphosphoric acid; The modified lightweight aggregate consists of hollow glass microspheres, pretreated expanded perlite and pretreated polystyrene particles in a weight ratio of 3:2:

5.

2. A light-weight and high-strength fireproof decorative material according to claim 1, characterized in that: The calcium silicate material is composed of silicon dioxide, calcium oxide and glass fiber in a weight ratio of 50-70:20-30:5-10; the adhesive is silica sol, and the chemical additives are composed of polycarboxylic acid, alkyl sulfonate and bentonite in a weight ratio of 0.5-1.5:0.1-0.3:0.2-0.

5.

3. The light-weight and high-strength fireproof decorative material according to claim 1, characterized in that: The preparation method of the pretreated expanded perlite comprises: soaking perlite particles in a silica sol with a pH of 3-4 and a solid content of 30%, stirring for 10-15 minutes, then transferring the particles to an 80-100° C. oven and drying to constant weight, then spraying a 0.5-1wt% KH-560 solution on the particle surface, transferring the particles to a 60° C. oven for curing for 30 minutes, and cooling at room temperature to obtain the pretreated expanded perlite, wherein the ratio of the perlite particles to the silica sol is 100 g:1.03 L.

4. The light-weight and high-strength fireproof decorative material according to claim 1, characterized in that: The preparation method of the pretreated polystyrene particles is as follows: polystyrene particles and red phosphorus masterbatch are added into a high-speed mixer at a weight ratio of 20:1 and mixed for 10-15 minutes to obtain the pretreated polystyrene particles.

5. The light-weight and high-strength fireproof decorative material according to claim 1, characterized in that: The usage ratio of melamine, vanillin, DMF and triphosphoric acid is 0.7 g:1.8 g:10 mL:2.5 g. The post-treatment method is as follows: after the reaction is completed, low-boiling substances are distilled off under reduced pressure, the product is washed alternately with deionized water and ethanol, and then transferred to a vacuum drying oven at 60° C. and dried to constant weight.

6. The light-weight and high-strength fireproof decorative material according to claim 1, characterized in that: The preparation method of the modified fiber reinforcement is: A1. Immerse the pretreated mixed fiber in KH-570 ethanol solution, raise the temperature to 60-80°C, react for 4-6 hours, remove the fiber, and dry it in a 60-80°C oven to constant weight to obtain a fiber bundle; A2. Add the fiber bundle, azobisisobutyronitrile and methyl methacrylate into a reactor filled with nitrogen, raise the temperature to 55-65° C. and react for 6 hours, and then post-treat to obtain a modified fiber reinforcement.

7. The light-weight and high-strength fireproof decorative material according to claim 1, characterized in that: In step A1, the mixed fiber, KH-570 ethanol solution, azobisisobutyronitrile and methyl methacrylate are used in a ratio of 5g:25mL:0.1g:50-100mL, the mixed fiber is composed of carbon fiber and basalt fiber in a weight ratio of 1:1, and the KH-570 ethanol solution is composed of γ-glycidyloxypropyltrimethoxysilane, ethanol and purified water in a ratio of 3g:90mL:10mL; in step A2, the post-treatment method includes: after the reaction is completed, laying the fiber bundle, pressurizing to 10MPa at 150-160°C and curing for 30-40min, then heat treating at 200°C for 1h, and ultrasonically cleaning with acetone for 10min to obtain a modified fiber reinforcement.

8. The light-weight and high-strength fireproof decorative material according to claim 1, characterized in that: The pretreatment method of the hybrid fiber is as follows: carbon fiber and basalt fiber are chopped and mixed, and the mixture is immersed in a 10wt% nitric acid solution and a 5wt% KH-550 ethanol solution in sequence, the temperature is raised to 60°C and reacted for 2-3h, and after the reaction is completed, ultrasonically cleaned with deionized water, dehydrated with ethanol, and then placed in a vacuum drying oven at 60-80°C and dried to constant weight to obtain pretreated hybrid fiber, wherein the γ-aminopropyltriethoxysilane ethanol solution is composed of γ-aminopropyltriethoxysilane, ethanol and purified water in a ratio of 5g:90mL:10mL; and the amount ratio of carbon fiber, basalt fiber, nitric acid solution and KH-550 ethanol solution is 1g:1g:16mL:12mL.

9. A method for preparing a lightweight and high-strength fireproof decorative material according to any one of claims 1 to 8, characterized in that: Calcium silicon material, additives, modified fiber reinforcement and modified lightweight aggregate are added to a forced mixer and dry-mixed for 5 minutes. Modified triphosphoric acid and adhesive are added and mixed for 10 minutes. The slurry is injected into a mold and vibrated. Subsequently, pre-curing at 60-80°C for 2-4 hours and autoclaving curing at 180-200°C, 1.0-1.5MPa for 8-12 hours are carried out in sequence. After natural cooling and demoulding, the material is cut into boards and the surface is polished to obtain a lightweight and high-strength fireproof material.

10. Application of a light and high-strength fireproof decorative material, characterized in that: The lightweight and high-strength fireproof decorative material prepared by the method for preparing a lightweight and high-strength fireproof decorative material as described in claim 9 is used for interior decoration.

Images