CN113480273A - Composite flame-retardant building material and preparation method thereof - Google Patents
Composite flame-retardant building material and preparation method thereof Download PDFInfo
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- CN113480273A CN113480273A CN202110945086.5A CN202110945086A CN113480273A CN 113480273 A CN113480273 A CN 113480273A CN 202110945086 A CN202110945086 A CN 202110945086A CN 113480273 A CN113480273 A CN 113480273A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/024—Steam hardening, e.g. in an autoclave
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0277—Hardening promoted by using additional water, e.g. by spraying water on the green concrete element
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0277—Hardening promoted by using additional water, e.g. by spraying water on the green concrete element
- C04B40/029—Hardening promoted by using additional water, e.g. by spraying water on the green concrete element using an aqueous solution or dispersion
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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Abstract
The invention discloses a composite flame-retardant building material and a preparation method thereof, belonging to the technical field of flame-retardant building materials. The composite flame-retardant building material comprises the following raw materials: portland cement, quartz sand, bentonite, diatomite, modified polyurethane, carbon fiber and a composite flame retardant. In the invention, the P-O-Si bond is formed by the reaction of the Si-OH group generated after the siloxane in the disiloxane-terminated POSS is hydrolyzed and the P-OH group on the surface of the ammonium polyphosphate powder, so that the POSS is modified on the surface of the ammonium polyphosphate powder, the water solubility of the ammonium polyphosphate powder is further reduced, the compatibility of the ammonium polyphosphate powder and the modified polyurethane is increased, the similarity exists between the structure of the Si-O bond in the structure of the POSS and the structure of the silicate cement, and the ammonium polyphosphate powder modified with the POSS on the surface is uniformly filled in the silicate cement and modified polyurethane composite material, thereby improving the flame retardant property of the composite material.
Description
Technical Field
The invention belongs to the technical field of flame-retardant building materials, and particularly relates to a composite flame-retardant building material and a preparation method thereof.
Background
Building materials can be divided into structural materials, decorative materials and certain specialized materials. The structural materials comprise wood, bamboo, stone, cement, concrete, metal, tiles, ceramics, glass, engineering plastics, composite materials and the like; the decorative material comprises various coatings, paints, plating layers, veneers, ceramic tiles with various colors, glass with special effects and the like; the special material is used for water proofing, moisture proofing, corrosion prevention, fire prevention, flame retardance, sound insulation, heat preservation, sealing and the like. Among them, the building materials having flame retardant properties have been rapidly developed in recent years because they can effectively reduce the damage of fire to buildings and prevent the further deterioration of the fire disaster when a fire breaks out.
For example, chinese patent CN104961431B discloses a composite flame-retardant building material and a preparation method thereof, wherein the building material comprises 17-22 parts of aluminum phosphate, 5-10 parts of aluminum borate, 4-9 parts of zirconium dioxide, 5-11 parts of antimony trioxide, 6-12 parts of diatomite, 12-15 parts of magnesium chloride, 10-12 parts of boron carbide, 13-17 parts of isoprene rubber and 5-10 parts of chlorosulfonated polyethylene, and the preparation method comprises the following steps: (1) taking aluminum phosphate, aluminum borate, zirconium dioxide, antimony trioxide, diatomite, magnesium chloride and boron carbide for mechanical crushing; (2) taking the above materials according to weight, and uniformly stirring; (3) and (3) pressing and forming the mixed material obtained in the step (2), and cooling to obtain the composite flame-retardant building material. The building material obtained by the invention has good compressive strength, breaking strength and flame retardant effect. However, the composite flame-retardant building material is heavy in weight, and limits the application range, and the composite material is prepared by mixing inorganic materials and organic materials, the flame retardant property, the flexural strength and the compressive strength of the composite material are enhanced by boron carbide and the introduction of isoprene rubber, so that the following defects exist: firstly, the dispersion uniformity of boron carbide can not be ensured, thereby affecting the flame retardant property of the composite material; and secondly, the isoprene rubber is a high polymer material and has low flame retardant property, so that the flame retardant property of the composite material is influenced.
Therefore, the invention provides a composite flame-retardant building material and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a composite flame-retardant building material and a preparation method thereof.
The technical problems to be solved by the invention are as follows: how to provide a composite flame-retardant building material with light weight and high flame-retardant performance.
The purpose of the invention can be realized by the following technical scheme:
a composite flame-retardant building material comprises the following raw materials in parts by weight: 15-30 parts of Portland cement, 4-12 parts of quartz sand, 3-6 parts of bentonite, 3-6 parts of kieselguhr, 6-22 parts of modified polyurethane, 4-7 parts of carbon fiber and 2.5-8 parts of a composite flame retardant.
The preparation method of the composite flame-retardant building material comprises the following steps:
crushing, grinding and sieving bentonite and diatomite, uniformly mixing the bentonite and the diatomite with Portland cement, quartz sand, organosilicon modified polyurethane, carbon fiber and a composite flame retardant, adding water in the same weight part as the Portland cement, and stirring for 2 hours at 30-50 ℃ and under the condition of 200 plus materials/min to obtain a mixed material;
step two, casting and molding the mixed material, wherein the casting temperature is 90-110 ℃, the casting vibration frequency is 30-50Hz, after standing for 12h, the temperature is reduced to 5-9 ℃ at the speed of 3-5 ℃/min, quenching is prevented, stress cracks in the material are avoided, steam at the temperature of 5-9 ℃ is introduced for 30-60min, and demolding is carried out to obtain the initial composite flame-retardant building material;
covering the surface of the initial composite flame-retardant building material by using a straw plait, spraying water, heating to 80 ℃ at a speed of 3-5 ℃/min, keeping the temperature for 60-100min to ensure that the interior of the initial composite flame-retardant building material is completely adaptive to high temperature, lifting the straw plait, reducing the temperature to 50-60 ℃ at a speed of 3-5 ℃/min, introducing 50-60 ℃ steam for 60-100min, stopping introducing the steam, spraying a curing agent on the surface of the initial composite flame-retardant building material, spraying the curing agent until the surface of the initial composite flame-retardant building material is completely covered, keeping the temperature for 60-100min at 50-60 ℃, and naturally cooling to obtain the composite flame-retardant building material.
Further, the curing agent in the third step is sodium silicate.
Further, the modified polyurethane is prepared by the following steps:
firstly, mixing dihydric alcohol, diisocyanate, dioctyltin dilaurate and toluene, stirring at 76 ℃ for reaction for 8 hours, stopping the reaction, and removing the solvent by rotary evaporation to obtain a polyurethane oligomer; dissolving a polyurethane oligomer in toluene, adding hydroxyl-terminated polydimethylsiloxane and dioctyltin dilaurate, and stirring at 81 ℃ for 12 hours to react to obtain the modified polyurethane, wherein the molar ratio of the dihydric alcohol to the diisocyanate is 1: 2.2 to 2.5, the added mass of dioctyltin dilaurate is 3 to 5% of the added mass of diol, and the amount of diisocyanate is controlled to be more than twice the mass of diol to form an isocyanate-terminated polyurethane oligomer, facilitating the reaction of the oligomer with a hydroxyl-terminated polydimethylsiloxane in a molar ratio of hydroxyl-terminated polydimethylsiloxane to polyurethane oligomer of 1.2 to 1.4: 1, the adding mass of the dioctyltin dilaurate is 1-3% of the adding mass of the hydroxyl-terminated polydimethylsiloxane.
Further, the dihydric alcohol is polyether dihydric alcohol, and the number average molecular mass of the polyether dihydric alcohol is 2000-3500.
Further, the diisocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate.
Further, the number average molecular mass of the hydroxyl-terminated polydimethylsiloxane was 2000-3500.
Further, the composite flame retardant is prepared by the following steps:
s1, adding isopropanol into a flask with a condenser pipe and magnetic stirring, sequentially adding phenyltrimethoxysilane, deionized water and flaky sodium hydroxide under stirring, heating a reaction system to 72 ℃ by using an oil bath pot after uniformly stirring, reacting for 6 hours under the nitrogen atmosphere, stirring and reacting for 18 hours at normal temperature, removing the isopropanol from the obtained mixed solution through rotary evaporation, and drying for 12 hours under vacuum at 65 ℃ to obtain octaphenylPOSS sodium salt, wherein the dosage ratio of the isopropanol, the phenyltrimethoxysilane, the deionized water and the flaky sodium hydroxide is 120-mL and 200 mL: 0.13-0.14 mol: 2-4 mg: 0.1 mol; adding octaphenyl POSS sodium salt into a three-neck flask, adding anhydrous tetrahydrofuran under the protection of nitrogen, stirring uniformly, adding triethylamine, reacting for 1h in ice bath at 0 ℃, slowly dropwise adding a tetrahydrofuran solution of methyl dichlorosilane by using a constant-pressure funnel at a dropwise speed of 2-4 drops/second for 4h, then raising the temperature to room temperature for 16h, filtering after the reaction is finished, performing column separation after the filtrate is dried in a spinning mode (the volume ratio of dichloromethane to petroleum ether is 1: 2), and performing vacuum drying to constant weight to obtain hydrogen-containing POSS, wherein the molar ratio of octaphenyl POSS to triethylamine to dimethylchlorosilane is 1: 2-2.5: 2.3-3; mixing hydrogen-containing POSS, vinyl trimethoxy siloxane and anhydrous tetrahydrofuran, adding chloroplatinic acid, reacting at 70 ℃ for 24 hours, carrying out rotary evaporation, and drying in vacuum to constant weight to obtain disiloxane-terminated POSS, wherein the molar ratio of the hydrogen-containing POSS to the vinyl trimethoxy siloxane is 1: 4.1-4.5, wherein the mass of the chloroplatinic acid is 7-12% of that of the hydrogen-containing POSS;
the bis-siloxane terminated POSS has the following structural formula:
in the reaction process of the first step, phenyl trimethoxy silane is hydrolyzed under the conditions of deionized water and sodium hydroxide to form octaphenyl POSS sodium salt, hydrolysis of the octaphenyl POSS sodium salt and methyl dichlorosilane is utilized to obtain hydrogen-containing POSS, and finally addition reaction of the hydrogen-containing POSS and vinyl trimethoxy siloxane under the catalysis of chloroplatinic acid is utilized to obtain disiloxane-terminated POSS;
s2, firstly, dissolving disiloxane-terminated POSS into an ethanol solution, adjusting the pH value of the solution to be between 5 and 6 by using hydrochloric acid, and heating to 77 ℃ for 1h at the speed of 150-300r/min to obtain a solution a; dispersing the ammonium polyphosphate powder in absolute ethyl alcohol, and stirring at the speed of 150-; and (3) adding the solution b into the solution a at the temperature of 55 ℃ under the condition of 150-300r/min, and reacting for 2-4h to obtain the composite flame retardant, wherein the mass ratio of the disiloxane terminated POSS to the ammonium polyphosphate is 12-23: 60-70.
The invention has the beneficial effects that:
the polyurethane oligomer with isocyanate group end capping is synthesized by dihydric alcohol and diisocyanate, and then the polydimethylsiloxane with hydroxyl end capping is reacted with the oligomer to form the modified polyurethane with the outer layer having a silica-oxygen chain, the silica chain enables the modified polyurethane to be better mixed with silicate cement, quartz sand, bentonite, diatomite and carbon fiber, so that a composite material system is more uniform, and the quality of the composite material can be reduced by adding the modified polyurethane material;
the invention utilizes Si-OH groups generated after siloxane in the disiloxane-terminated POSS is hydrolyzed to react with P-OH groups on the surface of the ammonium polyphosphate powder to form P-O-Si bonds, so that the surface of the ammonium polyphosphate powder is modified with the POSS, further reducing the water solubility of the ammonium polyphosphate powder, increasing the compatibility of the ammonium polyphosphate powder with modified polyurethane, leading the POSS to have a closed cage-shaped structure consisting of inorganic Si-O-Si chain links, the molecular is mainly provided with Si-O bonds with high bond energy, and the material is modified with ammonium polyphosphate powder compared with typical nano-sized materials, so that the flame retardant property of the ammonium polyphosphate powder is improved, the structure of the Si-O bond has similarity with the structure of the portland cement, the compatibility is better, and the ammonium polyphosphate powder modified with POSS on the surface is uniformly filled in the portland cement and modified polyurethane composite material, so that the flame retardant property of the composite material is improved;
in conclusion, the composite flame-retardant building material provided by the invention has excellent flame-retardant performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the modified polyurethane is prepared by the following steps:
firstly, 0.1mol of dihydric alcohol, 0.22mol of diisocyanate, 3% by mass of dioctyltin dilaurate added to the dihydric alcohol and 100mL of toluene are mixed, stirred at 76 ℃ for reaction for 8 hours, the reaction is stopped, and the solvent is removed by rotary evaporation to obtain a polyurethane oligomer; dissolving 0.1mol of polyurethane oligomer in 100mL of toluene, adding 0.12mol of hydroxyl-terminated polydimethylsiloxane and 1% of dioctyltin dilaurate by mass of the hydroxyl-terminated polydimethylsiloxane, and stirring at 81 ℃ to react for 12h to obtain the modified polyurethane, wherein the diol is polyether diol, the number average molecular mass of the diol is 2000, the diisocyanate is isophorone diisocyanate, and the number average molecular mass of the hydroxyl-terminated polydimethylsiloxane is 2000.
Example 2:
the modified polyurethane is prepared by the following steps:
firstly, 0.1mol of dihydric alcohol, 0.25mol of diisocyanate, 5% by mass of dioctyltin dilaurate added into the mixture of the dihydric alcohol and 100mL of toluene are mixed, the mixture is stirred at 76 ℃ for 8 hours of reaction, the reaction is stopped, and the solvent is removed by rotary evaporation to obtain a polyurethane oligomer; dissolving 0.1mol of polyurethane oligomer in 100mL of toluene, adding 0.14mol of hydroxyl-terminated polydimethylsiloxane and 3% of dioctyltin dilaurate in the mass of the hydroxyl-terminated polydimethylsiloxane, and stirring at 81 ℃ to react for 12h to obtain the modified polyurethane, wherein the dihydric alcohol is polyether dihydric alcohol, the mass of the number average molecular weight of the dihydric alcohol is 3500, the diisocyanate is diphenylmethane diisocyanate, and the mass of the number average molecular weight of the hydroxyl-terminated polydimethylsiloxane is 3500.
Example 3:
the modified polyurethane is prepared by the following steps:
firstly, 0.1mol of dihydric alcohol, 0.23mol of diisocyanate, 3% by mass of dioctyltin dilaurate added to the dihydric alcohol and 100mL of toluene are mixed, stirred at 76 ℃ for reaction for 8 hours, the reaction is stopped, and the solvent is removed by rotary evaporation to obtain a polyurethane oligomer; dissolving 0.1mol of polyurethane oligomer in 100mL of toluene, adding 0.13mol of hydroxyl-terminated polydimethylsiloxane and 2% of dioctyltin dilaurate by mass of the hydroxyl-terminated polydimethylsiloxane, and stirring at 81 ℃ to react for 12h to obtain the modified polyurethane, wherein the dihydric alcohol is polyether dihydric alcohol, the number average molecular mass of the dihydric alcohol is 3000, the diisocyanate is dicyclohexylmethane diisocyanate, and the number average molecular mass of the hydroxyl-terminated polydimethylsiloxane is 3000.
Example 4:
the composite flame retardant is prepared by the following steps:
s1, adding 120mL of isopropanol into a flask with a condenser pipe and magnetic stirring, sequentially adding 0.13mol of phenyltrimethoxysilane, 2mg of deionized water and 0.1mol of flaky sodium hydroxide while stirring, heating a reaction system to 72 ℃ by using an oil bath pot after uniformly stirring, reacting for 6 hours under a nitrogen atmosphere, stirring and reacting for 18 hours at normal temperature, removing the isopropanol from the obtained mixed solution through rotary evaporation, and performing vacuum drying for 12 hours at 65 ℃ to obtain octaphenyl POSS sodium salt; adding 0.1mol of octaphenyl POSS sodium salt into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran under the protection of nitrogen, stirring uniformly, adding 0.2mol of triethylamine, reacting for 1h at 0 ℃ in an ice bath, slowly dropwise adding 50mL of tetrahydrofuran solution containing 0.23mol of methyl dichlorosilane by using a constant-pressure funnel at the dropping speed of 2 drops/second, reacting for 4h, then raising the temperature to room temperature, reacting for 16h, filtering after the reaction is finished, spin-drying the filtrate, performing column separation (the volume ratio of dichloromethane to petroleum ether is 1: 2), and performing vacuum drying to constant weight to obtain hydrogen-containing POSS; mixing 0.1mol of hydrogen-containing POSS, 0.41mol of vinyl trimethoxy siloxane and 100mL of anhydrous tetrahydrofuran, adding chloroplatinic acid with the mass being 7% of that of the hydrogen-containing POSS, reacting at 70 ℃ for 24h, performing rotary evaporation, and performing vacuum drying to constant weight to obtain disiloxane-terminated POSS;
s2, firstly, dissolving 1.2g of disiloxane-terminated POSS into 30mL of ethanol solution (the volume ratio of water to ethanol is 1: 2), adjusting the pH value of the solution to be between 5 and 6 by using 0.1M hydrochloric acid, and heating to 77 ℃ at 150r/min for 1h to obtain solution a; dispersing 6g of ammonium polyphosphate powder in 50mL of absolute ethyl alcohol, and stirring at the speed of 150r/min for 20min to uniformly disperse the ammonium polyphosphate powder to obtain a solution b; and (3) adding the solution b into the solution a at the speed of 150r/min, keeping the temperature at 55 ℃, and reacting for 2h to obtain the composite flame retardant.
Example 5:
the composite flame retardant is prepared by the following steps:
s1, adding 200mL of isopropanol into a flask with a condenser pipe and magnetic stirring, sequentially adding 0.14mol of phenyltrimethoxysilane, 4mg of deionized water and 0.1mol of flaky sodium hydroxide while stirring, heating a reaction system to 72 ℃ by using an oil bath pot after uniformly stirring, reacting for 6 hours under a nitrogen atmosphere, stirring and reacting for 18 hours at normal temperature, removing the isopropanol from the obtained mixed solution through rotary evaporation, and performing vacuum drying for 12 hours at 65 ℃ to obtain octaphenyl POSS sodium salt; adding 0.1mol of octaphenyl POSS sodium salt into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran under the protection of nitrogen, stirring uniformly, adding 0.25mol of triethylamine, reacting for 1h at 0 ℃ in an ice bath, slowly dropwise adding 50mL of tetrahydrofuran solution containing 0.3mol of methyl dichlorosilane by using a constant-pressure funnel at a dropwise adding speed of 4 drops/second, reacting for 4h, then raising the temperature to room temperature, reacting for 16h, filtering after the reaction is finished, spin-drying the filtrate, performing column separation (the volume ratio of dichloromethane to petroleum ether is 1: 2), and performing vacuum drying to constant weight to obtain hydrogen-containing POSS; mixing 0.1mol of hydrogen-containing POSS, 0.45mol of vinyl trimethoxy siloxane and 100mL of anhydrous tetrahydrofuran, adding chloroplatinic acid with the mass being 12% of that of the hydrogen-containing POSS, reacting at 70 ℃ for 24h, performing rotary evaporation, and performing vacuum drying to constant weight to obtain disiloxane-terminated POSS;
s2, firstly, dissolving 2.3g of disiloxane-terminated POSS into 30mL of ethanol solution (the volume ratio of water to ethanol is 1: 2), adjusting the pH value of the solution to be between 5 and 6 by using 0.1M hydrochloric acid, and heating to 77 ℃ at 300r/min for 1h to obtain solution a; dispersing 6-7g of ammonium polyphosphate powder in 50mL of absolute ethyl alcohol, and stirring at the speed of 300r/min for 20min to uniformly disperse the ammonium polyphosphate powder to obtain a solution b; and (3) adding the solution b into the solution a at 300r/min, keeping the temperature at 55 ℃, and reacting for 4 hours to obtain the composite flame retardant.
Example 6:
a composite flame-retardant building material comprises the following raw materials in parts by weight: 15 parts of Portland cement, 4 parts of quartz sand, 3 parts of bentonite, 3 parts of diatomite, 6 parts of modified polyurethane prepared in example 1, 4 parts of carbon fiber and 2.5 parts of composite flame retardant prepared in example 4.
The preparation method of the composite flame-retardant building material comprises the following steps:
crushing, grinding and sieving bentonite and diatomite, uniformly mixing the bentonite and diatomite with portland cement, quartz sand, organosilicon modified polyurethane, carbon fiber and a composite flame retardant, adding water in the same weight part as the portland cement, and stirring for 2 hours at 30 ℃ and 200r/min to obtain a mixed material;
step two, casting and molding the mixed material, wherein the casting temperature is 90 ℃, the casting vibration frequency is 30Hz, after standing for 12 hours, the temperature is reduced to 5 ℃ at the speed of 3 ℃/min, then 5 ℃ steam is introduced for 30min, and demoulding is carried out to obtain the initial composite flame-retardant building material;
covering the surface of the initial composite flame-retardant building material by using a straw plait, spraying water, heating to 80 ℃ at the speed of 3 ℃/min, preserving the heat for 60min, lifting the straw plait, cooling to 50-60 ℃ at the speed of 3-5 ℃/min, introducing 50 ℃ steam for 60min, stopping introducing the steam, spraying sodium silicate on the surface of the initial composite flame-retardant building material, spraying the sodium silicate on the surface of the initial composite flame-retardant building material until the surface of the initial composite flame-retardant building material is completely covered, preserving the heat for 60min at the temperature of 50 ℃, and naturally cooling to obtain the composite flame-retardant building material.
Example 7:
a composite flame-retardant building material comprises the following raw materials in parts by weight: 20 parts of Portland cement, 8 parts of quartz sand, 4 parts of bentonite, 4 parts of diatomite, 13 parts of modified polyurethane prepared in example 2, 5 parts of carbon fiber and 5 parts of composite flame retardant prepared in example 5.
The preparation method of the composite flame-retardant building material comprises the following steps:
crushing, grinding and sieving bentonite and diatomite, uniformly mixing the bentonite and diatomite with portland cement, quartz sand, organosilicon modified polyurethane, carbon fiber and a composite flame retardant, adding water in the same weight part as the portland cement, and stirring for 2 hours at 50 ℃ and 300r/min to obtain a mixed material;
step two, casting and molding the mixed material, wherein the casting temperature is 110 ℃, the casting vibration frequency is 40Hz, after standing for 12 hours, the temperature is reduced to 9 ℃ at a speed of 4 ℃/min, quenching is prevented, stress cracks in the material are avoided, then 7 ℃ steam is introduced for 40min, and demolding is carried out to obtain the initial composite flame-retardant building material;
covering the surface of the initial composite flame-retardant building material by using a straw plaited fabric and spraying water, heating to 80 ℃ at a speed of 4 ℃/min, preserving the temperature for 90min to ensure that the interior of the initial composite flame-retardant building material is completely adaptive to high temperature, then lifting the straw plaited fabric, reducing the temperature to 55 ℃ at a speed of 4 ℃/min, introducing steam at a temperature of 55 ℃ for 90min, stopping introducing the steam, spraying sodium silicate on the surface of the initial composite flame-retardant building material, spraying the sodium silicate on the surface of the initial composite flame-retardant building material until the surface of the initial composite flame-retardant building material is completely covered, preserving the temperature for 80min at a temperature of 55 ℃, and naturally cooling to obtain the composite flame-retardant building material.
Example 8:
a composite flame-retardant building material comprises the following raw materials in parts by weight: 30 parts of Portland cement, 12 parts of quartz sand, 6 parts of bentonite, 6 parts of diatomite, 22 parts of modified polyurethane prepared in example 3, 7 parts of carbon fiber and 8 parts of composite flame retardant prepared in example 4.
The preparation method of the composite flame-retardant building material comprises the following steps:
crushing, grinding and sieving bentonite and diatomite, uniformly mixing the bentonite and diatomite with portland cement, quartz sand, organosilicon modified polyurethane, carbon fiber and a composite flame retardant, adding water in the same weight part as the portland cement, and stirring for 2 hours at 50 ℃ and 300r/min to obtain a mixed material;
step two, casting and molding the mixed material, wherein the casting temperature is 100 ℃, the casting vibration frequency is 50Hz, after standing for 12 hours, the temperature is reduced to 9 ℃ at the speed of 5 ℃/min, quenching is prevented, stress cracks in the material are avoided, 9 ℃ steam is introduced for 60min, and demolding is carried out to obtain the initial composite flame-retardant building material;
covering the surface of the initial composite flame-retardant building material by using a straw plaited fabric and spraying water, heating to 80 ℃ at a speed of 5 ℃/min, preserving the temperature for 100min to ensure that the interior of the initial composite flame-retardant building material is completely adaptive to high temperature, then lifting the straw plaited fabric, reducing the temperature to 60 ℃ at a speed of 5 ℃/min, introducing 60 ℃ steam for 100min, stopping introducing the steam, spraying sodium silicate on the surface of the initial composite flame-retardant building material, spraying the sodium silicate on the surface of the initial composite flame-retardant building material until the surface of the initial composite flame-retardant building material is completely covered, preserving the temperature for 100min at 60 ℃, and naturally cooling to obtain the composite flame-retardant building material.
Comparative example 1:
a polyurethane oligomer: the polyurethane oligomer prepared in example 1.
Comparative example 2:
the flame retardant is prepared by the following steps:
s1, adding 120mL of isopropanol into a flask with a condenser pipe and magnetic stirring, sequentially adding 0.13mol of phenyltrimethoxysilane, 2mg of deionized water and 0.1mol of flaky sodium hydroxide while stirring, heating a reaction system to 72 ℃ by using an oil bath pot after uniformly stirring, reacting for 6 hours under a nitrogen atmosphere, stirring and reacting for 18 hours at normal temperature, removing the isopropanol from the obtained mixed solution through rotary evaporation, and performing vacuum drying for 12 hours at 65 ℃ to obtain octaphenyl POSS sodium salt;
s2, firstly, dissolving 1.2g octaphenyl POSS sodium salt into 30mL ethanol solution (the volume ratio of water to ethanol is 1: 2), adjusting the pH value of the solution to be between 5 and 6 by using 0.1M hydrochloric acid, and heating to 77 ℃ at 150r/min for 1h to obtain solution a; dispersing 6g of ammonium polyphosphate powder in 50mL of absolute ethyl alcohol, and stirring at the speed of 150r/min for 20min to uniformly disperse the ammonium polyphosphate powder to obtain a solution b; and (3) adding the solution b into the solution a at the speed of 150r/min, keeping the temperature at 55 ℃, and reacting for 2h to obtain the composite flame retardant.
Comparative example 3:
a composite flame-retardant building material comprises the following raw materials in parts by weight: 15 parts of Portland cement, 4 parts of quartz sand, 3 parts of bentonite, 3 parts of diatomite, 6 parts of polyurethane oligomer prepared in comparative example 1, 4 parts of carbon fiber and 2.5 parts of composite flame retardant prepared in example 4.
The preparation method of the composite flame-retardant building material comprises the following steps: refer to the procedure for preparation in example 6.
Comparative example 4:
a composite flame-retardant building material comprises the following raw materials in parts by weight: 20 parts of Portland cement, 8 parts of quartz sand, 4 parts of bentonite, 4 parts of diatomite, 13 parts of modified polyurethane prepared in example 2, 5 parts of carbon fiber and 5 parts of composite flame retardant prepared in comparative example 2.
The preparation method of the composite flame-retardant building material comprises the following steps: refer to the procedure for preparation in example 7.
Comparative example 5:
a composite flame-retardant building material comprises the following raw materials in parts by weight: 30 parts of Portland cement, 12 parts of quartz sand, 6 parts of bentonite, 6 parts of diatomite, 22 parts of the modified polyurethane prepared in example 3 and 7 parts of carbon fiber.
The preparation method of the composite flame-retardant building material comprises the following steps: refer to the steps in example 8.
Comparative example 6:
a composite flame-retardant building material comprises the following raw materials in parts by weight: 15 parts of Portland cement, 4 parts of quartz sand, 3 parts of bentonite, 3 parts of diatomite, 4 parts of carbon fiber and 2.5 parts of the composite flame retardant prepared in example 4.
The preparation method of the composite flame-retardant building material comprises the following steps: refer to the procedure for preparation in example 6.
Example 9:
the building materials obtained in examples 3 to 5 and comparative examples 3 to 6 were subjected to the following performance tests:
compressive strength and flexural strength: testing according to GB/T50081-2019 standard;
flame retardant rating: testing according to the GB/T16172 standard;
the data obtained are shown below.
| Flexural strength | Compressive strength | Flame retardant rating | |
| Example 3 | 11.9MPa | 18.5MPa | A1 |
| Example 4 | 12.3MPa | 18.7MPa | A1 |
| Example 5 | 13.5MPa | 17.8MPa | A1 |
| Comparative example 3 | 10.2MPa | 16.1MPa | B1 |
| Comparative example 4 | 10.9MPa | 16.0MPa | B2 |
| Comparative example 5 | 10.5MPa | 15.9MPa | B2 |
| Comparative example 6 | 10.3MPa | 17.6MPa | A1 |
As can be seen from the above data, the flexural strength and compressive strength of the building materials of examples 3-5 are higher than those of comparative examples 3-6, which indicates that the mechanical properties of the building materials of examples 3-5 are better than those of the building materials of comparative examples 3-6, and the flame retardant properties of the building materials of examples 3-5 reach A1 grade.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. A composite flame-retardant building material is characterized in that: comprises the following components: portland cement, quartz sand, bentonite, diatomite, modified polyurethane, carbon fiber and a composite flame retardant;
the composite flame retardant is prepared by the following steps:
dissolving disiloxane terminated POSS into an ethanol solution, adjusting the pH value of the solution to be between 5 and 6, and stirring at 77 ℃ for 1h to obtain a solution a; dispersing ammonium polyphosphate powder in absolute ethyl alcohol, and stirring for 20min to obtain a solution b; and adding the solution b into the solution a, keeping the temperature at 55 ℃, and reacting for 2-4h to obtain the composite flame retardant.
2. The composite flame-retardant building material according to claim 1, wherein: the bis-siloxane terminated POSS is made by the steps of:
after hydrogen-containing POSS, vinyl trimethoxy siloxane and anhydrous tetrahydrofuran are mixed, chloroplatinic acid is added, reaction is carried out for 24 hours at 70 ℃, rotary evaporation and vacuum drying are carried out, and the disiloxane-terminated POSS is obtained.
3. The composite flame-retardant building material according to claim 1, wherein: the composite flame-retardant building material comprises the following components in parts by weight: 15-30 parts of Portland cement, 4-12 parts of quartz sand, 3-6 parts of bentonite, 3-6 parts of kieselguhr, 6-22 parts of modified polyurethane, 4-7 parts of carbon fiber and 2.5-8 parts of a composite flame retardant.
4. The composite flame-retardant building material according to claim 1, wherein: the modified polyurethane is prepared by the following steps:
mixing dihydric alcohol, diisocyanate, dioctyltin dilaurate and toluene, stirring at 76 ℃ for 8 hours, stopping reaction, and performing rotary evaporation to obtain a polyurethane oligomer; and dissolving the polyurethane oligomer in toluene, adding hydroxyl-terminated polydimethylsiloxane and dioctyltin dilaurate, and stirring at 81 ℃ for reaction for 12 hours to obtain the modified polyurethane.
5. The composite flame-retardant building material according to claim 4, wherein: the dihydric alcohol is polyether dihydric alcohol, and the number average molecular mass of the dihydric alcohol is 2000-3500.
6. The composite flame-retardant building material according to claim 4, wherein: the diisocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate.
7. The composite flame-retardant building material according to claim 4, wherein: the number average molecular mass of the hydroxyl-terminated polydimethylsiloxane was 2000-3500.
8. The preparation method of the composite flame-retardant building material according to claim 1, characterized in that: the method comprises the following steps:
crushing, grinding and sieving bentonite and diatomite, uniformly mixing the bentonite and diatomite with portland cement, quartz sand, modified polyurethane, carbon fiber and a composite flame retardant, adding water in the same weight part as the portland cement, and stirring for 2 hours at 30-50 ℃ to obtain a mixed material;
step two, casting and molding the mixed material, cooling to 5-9 ℃ at the speed of 3-5 ℃/min after standing for 12h, introducing steam at the temperature of 5-9 ℃ for 30-60min, and demolding to obtain an initial composite flame-retardant building material;
covering the surface of the initial composite flame-retardant building material by using a straw plait, spraying water, heating to 80 ℃, keeping the temperature for 60-100min, lifting the straw plait, reducing the temperature to 50-60 ℃ at the speed of 3-5 ℃/min, introducing 50-60 ℃ steam for 60-100min, stopping introducing the steam, spraying a curing agent on the surface of the initial composite flame-retardant building material, keeping the temperature for 60-100min at the temperature of 50-60 ℃, and naturally cooling to obtain the composite flame-retardant building material.
9. The method for preparing the composite flame-retardant building material according to claim 8, wherein the method comprises the following steps: in the second step, the pouring temperature is 90-110 ℃, and the pouring vibration frequency is 30-50 Hz.
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