Flame-retardant modified emulsified asphalt and preparation method thereof

Abstract

The invention relates to flame-retardant modified emulsified asphalt and a preparation method thereof, and relates to the technical field of asphalt, and the flame-retardant modified emulsified asphalt comprises the following components in parts by mass: 100-120 parts of matrix asphalt, 10-15 parts of an organic-inorganic synergistic flame retardant, 20-30 parts of high-weather-resistance flame-retardant epoxy resin, 3-5 parts of an emulsifier, 1-3 parts of an auxiliary agent and 40-50 parts of water. The flame-retardant modified emulsified asphalt is prepared by the following steps: heating matrix asphalt until the matrix asphalt is molten to obtain molten asphalt; the preparation method comprises the following steps: mixing high-weather-resistance flame-retardant epoxy resin and an emulsifier into water, and stirring to obtain an emulsion; adding the emulsified liquid and an auxiliary agent into the molten asphalt, and stirring to obtain asphalt emulsified liquid; and adding an organic-inorganic synergistic flame retardant into the asphalt emulsion, and heating and stirring to obtain the flame-retardant modified emulsified asphalt. The method has the effect of improving the flame retardant property and weather resistance of the asphalt.

Description

Technical Field

[0001] The present application relates to the field of asphalt technology, and in particular to a flame retardant modified emulsified asphalt and a preparation method thereof. Background Art

[0002] As the pace of highway construction in my country accelerates, large-scale tunnel projects are increasing. Asphalt is flammable to a certain extent, and there are certain fire safety hazards when used in tunnels, especially large highway tunnels. Once a traffic accident occurs in a tunnel, it is easy to cause a fire due to a car collision. The temperature after a fire in the tunnel will far exceed the flash point and ignition point of asphalt. Once the asphalt starts to burn, it will not only contribute to the development and spread of the fire, but also produce a large amount of toxic gases and thick smoke, causing serious safety problems and economic losses, leading to serious casualties, serious damage to tunnel facilities and structures, and long-term road traffic interruption.

[0003] Modified emulsified asphalt is a kind of water-in-oil or oil-in-water emulsion liquid asphalt processed by mechanical stirring and chemically stable emulsification process from asphalt, modifier and emulsifier. It is a road construction material with low viscosity and good fluidity at room temperature. Modified emulsified asphalt has been widely used in roads of all grades due to its convenient use, cold mixing and cold laying, wider construction season, and good coating with aggregates. At present, the fire retardant performance of emulsified asphalt is limited, and there is a safety hazard of easy combustion, so it needs to be improved. Summary of the invention

[0004] In order to improve the flame retardant properties of emulsified asphalt, the present application provides a flame retardant modified emulsified asphalt and a preparation method thereof.

[0005] The present application provides a flame retardant modified emulsified asphalt and a preparation method thereof using the following technical scheme: In the first aspect, the present application provides a flame retardant modified emulsified asphalt, which adopts the following technical solution: A flame retardant modified emulsified asphalt and a preparation method thereof, comprising the following components in parts by weight: Base asphalt 100-120 parts 10-15 parts of organic-inorganic synergistic flame retardant 20-30 parts of high weather-resistant flame-retardant epoxy resin Emulsifier 3-5 parts 1-3 parts of additives 40-50 parts of water.

[0006] Organic-inorganic synergistic flame retardants combine organic phase flame retardant components with inorganic phase components, and comprehensively utilize the two mechanisms of condensed phase flame retardancy and gas phase flame retardancy to interrupt the combustion process, effectively improving the flame retardant properties of flame retardant modified emulsified asphalt; high weather resistant flame retardant epoxy resin is modified to improve the weather resistance and flame retardant properties of epoxy resin. High weather resistant flame retardant epoxy resin can improve the water resistance of emulsified asphalt, reduce the impact of moisture erosion on asphalt materials, and improve the adhesion and durability of asphalt.

[0007] Preferably, the raw materials for preparing the organic-inorganic synergistic flame retardant include nitrogen-phosphorus-boron modified cage-type silsesquioxane and modified titanium hybrid graphene.

[0008] By introducing nitrogen, phosphorus and boron elements into cage silsesquioxane, the organic phase nitrogen, phosphorus and boron modified cage silsesquioxane forms a nitrogen, phosphorus, boron and silicon synergistic flame retardant system, generating gas and active free radicals to block the combustion reaction; cage silsesquioxane has a cage structure, which can improve the thermal insulation performance, thereby further improving the flame retardant properties of the organic-inorganic synergistic flame retardant; modified titanium hybrid graphene forms a good carbon layer barrier through titanium element and graphene, and through modification, the modified titanium hybrid graphene has good reaction performance and can be connected to nitrogen, phosphorus and boron modified cage silsesquioxane. The combination of the two can better exert a synergistic effect and improve flame retardant properties.

[0009] Nitrogen, phosphorus and boron modified cage-type silsesquioxane can effectively absorb and scatter ultraviolet rays and reduce the generation of free radicals. The cage-type structure provides good rigidity and stability, which can improve the stability and durability of emulsified asphalt. Modified titanium hybrid graphene can absorb ultraviolet light, quench free radicals, has good anti-ultraviolet properties, and as an inorganic phase can effectively reinforce and toughen asphalt materials, improve their strength and stability, and synergize with nitrogen, phosphorus and boron modified cage-type silsesquioxane to improve the weather resistance and durability of flame-retardant modified emulsified asphalt.

[0010] Preferably, the raw materials for preparing the nitrogen, phosphorus and boron modified cage-type silsesquioxane include hexachlorocyclotriphosphazene, aminopropyltriethoxysilane and boric acid.

[0011] The nitrogen-phosphorus-boron modified cage-type silsesquioxane obtained by the reaction of hexachlorocyclotriphosphazene, aminopropyltriethoxysilane and boric acid is rich in nitrogen, phosphorus, boron and silicon elements and has a cage structure. It has good thermal insulation and flame retardant properties, and at the same time has rigidity, which can greatly improve the stability, flame retardant properties and durability of flame retardant modified emulsified asphalt.

[0012] Preferably, the mass ratio of the hexachlorocyclotriphosphazene, aminopropyltriethoxysilane and boric acid is 1:(3.8-4.6):1.07.

[0013] The nitrogen, phosphorus and boron modified cage-type silsesquioxane prepared according to the above mass ratio can effectively improve the flame retardant properties and weather resistance.

[0014] Preferably, the raw materials for preparing the modified titanium hybrid graphene include graphene oxide, ammonium fluorotitanate and an amino titanate coupling agent.

[0015] Preferably, the modified titanium hybrid graphene is prepared by the following steps: The graphene oxide is dispersed in deionized water, and a graphene dispersion is obtained after ultrasonic treatment; ammonium fluorotitanate is added to the graphene dispersion, and the pH is adjusted to acidic using hydrochloric acid to obtain a mixed reaction liquid, and the mixed reaction liquid is reacted under stirring in a water bath, and the mixed reaction liquid after the reaction is centrifuged to obtain a solid, and the solid is dried, and the dried solid is calcined and ground to obtain titanium hybrid graphene; the titanium hybrid graphene prepared above and the amino titanate coupling agent are dispersed in an ethanol aqueous solution to obtain a modified suspension, and the modified suspension is stirred in a water bath for reaction, and filtered and dried to obtain the modified titanium hybrid graphene.

[0016] Titanium dioxide is loaded onto the surface of graphene oxide by ammonium fluorotitanate under hydrothermal and calcination conditions, so that titanium dioxide and graphene oxide can better synergize and improve weather resistance and flame retardancy; amino titanate coupling agent is used to modify titanium hybrid graphene to increase the reactive groups on the surface of titanium hybrid graphene, so that the inorganic phase modified titanium hybrid graphene can be connected to the organic phase nitrogen, phosphorus and boron modified cage-type silsesquioxane, and the two can synergize to better improve weather resistance and flame retardancy.

[0017] Preferably, the raw materials for preparing the highly weather-resistant flame-retardant epoxy resin include diallyl chlorophosphite, 11-aminoundecyltriethoxysilane and modified epoxy resin.

[0018] Diallyl chlorophosphite has good reactivity and can react with 11-aminoundecyltriethoxysilane to obtain silane containing phosphite groups. The occurrence of combustion can be effectively reduced through chemical reaction and physical isolation. The epoxy resin can be further silanized and modified by silane containing phosphite groups to further improve the flame retardant properties of the epoxy resin. Phosphite also has good antioxidant properties, which can slow down the aging of asphalt materials and improve weather resistance.

[0019] Preferably, the raw materials for preparing the modified epoxy resin include 3-methoxy-4-hydroxybenzaldehyde, epichlorohydrin and 2-furylamine.

[0020] 3-methoxy-4-hydroxybenzaldehyde can absorb ultraviolet rays, capture and neutralize free radicals, reduce the occurrence of oxidation reactions, and improve the thermal stability and weather resistance of epoxy resins; 2-furanmethylamine reacts with epoxy groups to form a cross-linked structure, thereby improving the thermal stability and weather resistance of epoxy resins. The epoxy resin obtained by the reaction of 3-methoxy-4-hydroxybenzaldehyde, epichlorohydrin and 2-furanmethylamine has good ultraviolet resistance and antioxidant properties, and can improve the weather resistance of flame-retardant modified emulsified asphalt.

[0021] Preferably, the mass ratio of diallyl chlorophosphite, 11-aminoundecyltriethoxysilane and modified epoxy resin is 1:1.85:(5-6).

[0022] The highly weather-resistant flame-retardant epoxy resin prepared according to the above mass ratio has good flame-retardant properties and weather resistance.

[0023] In a second aspect, the present application provides a method for preparing a flame retardant modified emulsified asphalt, using the following technical solution: A method for preparing flame retardant modified emulsified asphalt, comprising the following steps: The base asphalt is heated until it is melted to obtain melted asphalt; a highly weather-resistant flame-retardant epoxy resin and an emulsifier are mixed into water, and an emulsion is obtained after stirring; the emulsion and an auxiliary agent are added to the melted asphalt and stirred to obtain an asphalt emulsion; an organic-inorganic synergistic flame retardant is added to the asphalt emulsion, and the temperature is increased and stirred to obtain a flame-retardant modified emulsified asphalt.

[0024] The emulsified asphalt prepared according to the above steps has good flame retardant and weather resistance.

[0025] In summary, the present application includes at least one of the following beneficial technical effects: 1. Organic-inorganic synergistic flame retardants combine organic phase flame retardant components with inorganic phase components, and comprehensively utilize the two mechanisms of condensed phase flame retardancy and gas phase flame retardancy to interrupt the combustion process, effectively improving the flame retardant properties of flame retardant modified emulsified asphalt; high weather resistant flame retardant epoxy resin is modified to improve the weather resistance and flame retardant properties of epoxy resin. High weather resistant flame retardant epoxy resin can improve the water resistance of emulsified asphalt, reduce the impact of moisture erosion on asphalt materials, and improve the adhesion and durability of asphalt.

[0026] 2. By introducing nitrogen, phosphorus and boron elements into cage silsesquioxane, the organic phase nitrogen, phosphorus and boron modified cage silsesquioxane forms a nitrogen, phosphorus, boron and silicon synergistic flame retardant system, generating gas and active free radicals to block the combustion reaction; cage silsesquioxane has a cage structure, which can improve the thermal insulation performance, thereby further improving the flame retardant properties of the organic-inorganic synergistic flame retardant; modified titanium hybrid graphene forms a good carbon layer barrier through titanium element and graphene, and through modification, the modified titanium hybrid graphene has good reaction performance and can be connected to nitrogen, phosphorus and boron modified cage silsesquioxane. The combination of the two can better play a synergistic role and improve flame retardant properties.

[0027] 3. Nitrogen, phosphorus and boron modified cage-type silsesquioxane can effectively absorb and scatter ultraviolet rays, reduce the generation of free radicals, and the cage-type structure provides good rigidity and stability, which can improve the stability and durability of emulsified asphalt; modified titanium hybrid graphene can absorb ultraviolet light, quench free radicals, has good anti-ultraviolet properties, and as an inorganic phase can effectively reinforce and toughen asphalt materials, improve their strength and stability, and synergize with nitrogen, phosphorus and boron modified cage-type silsesquioxane to improve the weather resistance and durability of flame-retardant modified emulsified asphalt. DETAILED DESCRIPTION

[0028] The present application discloses a flame retardant modified emulsified asphalt and a preparation method thereof. The raw materials used in the present application can be obtained through commercial channels unless otherwise specified. The present application is further described in detail in conjunction with the embodiments below: Raw materials description: Hexachlorocyclotriphosphazene (CAS No.: 940-71-6), boric acid (CAS No.: 10043-35-3), aminopropyltriethoxysilane (CAS No.: 919-30-2), triethylamine (CAS No.: 121-44-8), graphene oxide purchased from Zhejiang Zhiti Nano Micro New Materials, ammonium fluorotitanate (CAS No.: 16962-40-6), aminotitanate coupling agent is TCA-K44 (CAS No.: 65380-84-9), 3-methoxy-4-hydroxybenzaldehyde (CAS No.: 121-33-5), epichlorohydrin (CAS No.: 106-89-8), tetrabutylammonium bromide (CAS No.: 1643-19-2), 2-furylamine (CAS No.: 617-89-0), diallylphosphite chloride Acid ester (CAS No.: 41662-46-8), 11-aminoundecyltriethoxysilane (CAS No.: 116821-45-5), emulsifier model is OP-10 (CAS No.: 9041-29-6), auxiliary model is Span-80 (CAS No.: 1338-43-8), tetramethylsilane (CAS No.: 75-76-3), nano titanium dioxide was purchased from Ningbo Jiwei Nano New Material Technology Co., Ltd., tris (nonylphenol) phosphite (CAS No.: 26523-78-4), methyltriethoxysilane (CAS No.: 2031-67-6), bisphenol A (CAS No.: 80-05-7), flame retardant LY-1 was purchased from Changzhou Luyou Traffic Facilities Co., Ltd., and epoxy resin E44 was purchased from Jiangyin Wanqian Chemicals Co., Ltd.

[0029] Example 1 Preparation of organic-inorganic synergistic flame retardants Dissolve 5.11 kg of hexachlorocyclotriphosphazene in 25 L of acetone to obtain a phosphazene solution, dissolve 5.47 kg of boric acid in 25 L of water to obtain a boric acid aqueous solution, add the boric acid aqueous solution to the phosphazene solution under nitrogen protection, and add the boric acid aqueous solution within 1 hour to obtain a reaction solution, react the reaction solution at 60° C. for 3 hours, and rotary evaporate the reaction solution to obtain hexaboron phosphazene. 19.42kg aminopropyltriethoxysilane, 100L acetone and 10kg triethylamine were mixed and dispersed, stirred at a speed of 200rpm until the mixture was uniformly mixed, and the silane dispersion was heated to 60°C under the protection of chlorine gas to obtain a silane dispersion; the hexaboron phosphazene prepared above was dispersed in 100L acetone, stirred at a speed of 200rpm until fully dissolved to obtain a hexaboron phosphazene solution, and the hexaboron phosphazene solution was added to the silane dispersion, and the addition was completed within 1h. After the dropwise addition was completed, the temperature was raised to 70°C and reacted for 2h to obtain a preliminary product solution, and the preliminary product was filtered and then rotary evaporated to obtain a preliminary product. The preliminary product, 200L acetone, 50L of 98% concentrated hydrochloric acid and 50L deionized water were mixed and dispersed to obtain a preliminary product reaction solution, and the reaction was stirred at a speed of 200rpm in a 40°C water bath for 4h to obtain a crude product, and the crude product was washed three times with acetone, filtered and dried at 60°C for 2h to obtain nitrogen-phosphorus-boron modified cage-type silsesquioxane.

[0030] 0.5 kg of graphene oxide was dispersed in 100 L of deionized water, and a graphene dispersion was obtained after ultrasonic treatment for 30 min; 5 kg of ammonium fluorotitanate was added to the graphene dispersion, and the pH was adjusted to 3 with hydrochloric acid to obtain a mixed reaction solution, the mixed reaction solution was stirred in a water bath at 80 ° C and reacted at a speed of 200 rpm for 4 h, the mixed reaction solution after the reaction was centrifuged to obtain a solid, the solid was dried in an oven at 60 ° C, the dried solid was calcined at 200 ° C for 2 h, and titanium hybrid graphene was obtained after grinding; the titanium hybrid graphene prepared above and 0.1 kg of amino titanate coupling agent were dispersed in an ethanol aqueous solution with a volume content of 70% to obtain a modified suspension, the modified suspension was stirred in a water bath at 60 ° C and reacted at a speed of 200 rpm for 2 h, filtered and dried in an oven at 80 ° C to obtain modified titanium hybrid graphene.

[0031] Preparation of highly weather-resistant flame-retardant epoxy resin 15 kg of 3-methoxy-4-hydroxybenzaldehyde, 36.45 kg of epichlorohydrin and 0.75 kg of tetrabutylammonium bromide were mixed and dispersed to obtain a monomer reaction liquid, stirred at a speed of 200 rpm for 2 h in a water bath at 80 ° C, and then cooled to 20 ° C. A 50% sodium hydroxide aqueous solution containing 9.9 kg of sodium hydroxide was added to the cooled monomer reaction liquid, and the reaction was continued for 3 h to obtain a monomer product solution. The monomer product solution was extracted with dichloromethane, anhydrous magnesium sulfate was added to the organic phase obtained by extraction, and water was removed by stirring at a speed of 200 rpm for 6 h. After filtering, an anhydrous organic phase was obtained, and the anhydrous organic phase was poured into petroleum ether for precipitation. The precipitate was filtered and washed with anhydrous ethanol, and the washed precipitate was dried in a vacuum oven at 70 ° C for 12 h to obtain a modified epoxy monomer. 25 kg of modified epoxy monomer and 4.375 kg of 2-furanmethylamine were mixed, and heated at 100 ° C for 3 min to obtain a modified epoxy resin.

[0032] 6.37 kg of diallyl chlorophosphite and 11.78 kg of 11-aminoundecyltriethoxysilane were mixed and dispersed in 100 L of a mixed solvent of triethylamine and toluene in a volume ratio of 1:4 to obtain a condensation reaction solution, the condensation reaction solution was heated to 115°C, refluxed for 5 hours, the mixed reaction solution after the reaction was filtered to obtain a product, the product was washed three times with toluene and deionized water respectively, and the washed product was dried in a vacuum oven at 115°C to obtain a condensation product. 31.85 kg of modified epoxy resin was dissolved in ethyl acetate to obtain an epoxy resin solution, the above-prepared condensation product and 0.2 kg of dibutyltin dilaurate were added to the epoxy resin solution, stirred at a speed of 500 rpm for 2 hours to obtain a product solution, the product solution was washed with deionized water and then distilled under reduced pressure to obtain a highly weather-resistant flame-retardant epoxy resin.

[0033] Preparation of flame retardant modified emulsified asphalt Heat 100 kg of base asphalt to 140°C to melt and obtain melted asphalt; mix 20 kg of high weather-resistant flame-retardant epoxy resin and 3 kg of emulsifier into 40 L of water, and stir at 200 rpm for 10 min to obtain an emulsion; add the emulsion and 1 kg of auxiliary agent to the melted asphalt within 30 min, and stir at 2000 rpm for 30 min to obtain an asphalt emulsion; add 10 kg of organic-inorganic synergistic flame retardant to the asphalt emulsion within 15 min, heat to 150°C, and stir for 30 min to obtain a flame-retardant modified emulsified asphalt.

[0034] Example 2 Preparation of organic-inorganic synergistic flame retardants Dissolve 4.5 kg of hexachlorocyclotriphosphazene in 25 L of acetone to obtain a phosphazene solution, dissolve 4.81 kg of boric acid in 25 L of water to obtain a boric acid aqueous solution, add the boric acid aqueous solution to the phosphazene solution under nitrogen protection, and add the boric acid aqueous solution within 1 hour to obtain a reaction solution, react the reaction solution at 60° C. for 3 hours, and rotary evaporate the reaction solution to obtain hexaboron phosphazene. 20.69kg aminopropyltriethoxysilane, 100L acetone and 10kg triethylamine were mixed and dispersed, stirred at a speed of 200rpm until the mixture was uniformly mixed, and the silane dispersion was heated to 60°C under the protection of chlorine gas to obtain a silane dispersion; the hexaboron phosphazene prepared above was dispersed in 100L acetone, stirred at a speed of 200rpm until fully dissolved to obtain a hexaboron phosphazene solution, and the hexaboron phosphazene solution was added to the silane dispersion, and the addition was completed within 1h. After the dropwise addition was completed, the temperature was raised to 70°C and reacted for 2h to obtain a preliminary product solution, and the preliminary product was filtered and then rotary evaporated to obtain a preliminary product. The preliminary product, 200L acetone, 50L of 98% concentrated hydrochloric acid and 50L deionized water were mixed and dispersed to obtain a preliminary product reaction solution, and the reaction was stirred at a speed of 200rpm in a 40°C water bath for 4h to obtain a crude product, and the crude product was washed three times with acetone, filtered and dried at 60°C for 2h to obtain nitrogen-phosphorus-boron modified cage-type silsesquioxane.

[0035] 0.5 kg of graphene oxide was dispersed in 100 L of deionized water, and a graphene dispersion was obtained after ultrasonic treatment for 30 min; 5 kg of ammonium fluorotitanate was added to the graphene dispersion, and the pH was adjusted to 3 with hydrochloric acid to obtain a mixed reaction solution, the mixed reaction solution was stirred in a water bath at 80 ° C and reacted at a speed of 200 rpm for 4 h, the mixed reaction solution after the reaction was centrifuged to obtain a solid, the solid was dried in an oven at 60 ° C, the dried solid was calcined at 200 ° C for 2 h, and titanium hybrid graphene was obtained after grinding; the titanium hybrid graphene prepared above and 0.1 kg of amino titanate coupling agent were dispersed in an ethanol aqueous solution with a volume content of 70% to obtain a modified suspension, the modified suspension was stirred in a water bath at 60 ° C and reacted at a speed of 200 rpm for 2 h, filtered and dried in an oven at 80 ° C to obtain modified titanium hybrid graphene.

[0036] Preparation of highly weather-resistant flame-retardant epoxy resin 15 kg of 3-methoxy-4-hydroxybenzaldehyde, 36.45 kg of epichlorohydrin and 0.75 kg of tetrabutylammonium bromide were mixed and dispersed to obtain a monomer reaction liquid, stirred at a speed of 200 rpm for 2 h in a water bath at 80 ° C, and then cooled to 20 ° C. A 50% sodium hydroxide aqueous solution containing 9.9 kg of sodium hydroxide was added to the cooled monomer reaction liquid, and the reaction was continued for 3 h to obtain a monomer product solution. The monomer product solution was extracted with dichloromethane, anhydrous magnesium sulfate was added to the organic phase obtained by extraction, and water was removed by stirring at a speed of 200 rpm for 6 h. After filtering, an anhydrous organic phase was obtained, and the anhydrous organic phase was poured into petroleum ether for precipitation. The precipitate was filtered and washed with anhydrous ethanol, and the washed precipitate was dried in a vacuum oven at 70 ° C for 12 h to obtain a modified epoxy monomer. 25 kg of modified epoxy monomer and 4.375 kg of 2-furanmethylamine were mixed, and heated at 100 ° C for 3 min to obtain a modified epoxy resin.

[0037] 5.65 kg of diallyl chlorophosphite and 10.45 kg of 11-aminoundecyltriethoxysilane were mixed and dispersed in 100 L of a mixed solvent of triethylamine and toluene in a volume ratio of 1:4 to obtain a condensation reaction solution, the condensation reaction solution was heated to 115°C, refluxed for 5 hours, the mixed reaction solution after the reaction was filtered to obtain a product, the product was washed three times with toluene and deionized water respectively, and the washed product was dried in a vacuum oven at 115°C to obtain a condensation product. 33.9 kg of modified epoxy resin was dissolved in ethyl acetate to obtain an epoxy resin solution, the above-prepared condensation product and 0.2 kg of dibutyltin dilaurate were added to the epoxy resin solution, stirred at a speed of 500 rpm for 2 hours to obtain a product solution, the product solution was washed with deionized water and then distilled under reduced pressure to obtain a highly weather-resistant flame-retardant epoxy resin.

[0038] Preparation of flame retardant modified emulsified asphalt Heat 120 kg of base asphalt to 140°C to melt and obtain melted asphalt; mix 30 kg of high weather-resistant flame-retardant epoxy resin and 5 kg of emulsifier into 50 L of water, and stir at 200 rpm for 10 min to obtain an emulsion; add the emulsion and 3 kg of additives to the melted asphalt within 30 min, and stir at 2000 rpm for 30 min to obtain an asphalt emulsion; add 15 kg of organic-inorganic synergistic flame retardant to the asphalt emulsion within 15 min, heat to 150°C, and stir for 30 min to obtain a flame-retardant modified emulsified asphalt.

[0039] Example 3 Preparation of organic-inorganic synergistic flame retardants Dissolve 4.78 kg of hexachlorocyclotriphosphazene in 25 L of acetone to obtain a phosphazene solution, dissolve 5.12 kg of boric acid in 25 L of water to obtain a boric acid aqueous solution, add the boric acid aqueous solution to the phosphazene solution under nitrogen protection, and add the boric acid aqueous solution within 1 hour to obtain a reaction solution, react the reaction solution at 60° C. for 3 hours, and rotary evaporate the reaction solution to obtain hexaboron phosphazene. 20.1kg aminopropyltriethoxysilane, 100L acetone and 10kg triethylamine were mixed and dispersed, stirred at a speed of 200rpm until the mixture was uniformly mixed, and the silane dispersion was heated to 60°C under the protection of chlorine gas to obtain a silane dispersion; the hexaboron phosphazene prepared above was dispersed in 100L acetone, stirred at a speed of 200rpm until fully dissolved to obtain a hexaboron phosphazene solution, and the hexaboron phosphazene solution was added to the silane dispersion, and the addition was completed within 1h. After the dropwise addition was completed, the temperature was raised to 70°C and reacted for 2h to obtain a preliminary product solution, and the preliminary product was filtered and then rotary evaporated to obtain a preliminary product. The preliminary product, 200L acetone, 50L of 98% concentrated hydrochloric acid and 50L deionized water were mixed and dispersed to obtain a preliminary product reaction solution, and the reaction was stirred at a speed of 200rpm in a 40°C water bath for 4h to obtain a crude product, and the crude product was washed three times with acetone, filtered and dried at 60°C for 2h to obtain nitrogen-phosphorus-boron modified cage-type silsesquioxane.

[0040] 0.5 kg of graphene oxide was dispersed in 100 L of deionized water, and a graphene dispersion was obtained after ultrasonic treatment for 30 min; 5 kg of ammonium fluorotitanate was added to the graphene dispersion, and the pH was adjusted to 3 with hydrochloric acid to obtain a mixed reaction solution, the mixed reaction solution was stirred in a water bath at 80 ° C and reacted at a speed of 200 rpm for 4 h, the mixed reaction solution after the reaction was centrifuged to obtain a solid, the solid was dried in an oven at 60 ° C, the dried solid was calcined at 200 ° C for 2 h, and titanium hybrid graphene was obtained after grinding; the titanium hybrid graphene prepared above and 0.1 kg of amino titanate coupling agent were dispersed in an ethanol aqueous solution with a volume content of 70% to obtain a modified suspension, the modified suspension was stirred in a water bath at 60 ° C and reacted at a speed of 200 rpm for 2 h, filtered and dried in an oven at 80 ° C to obtain modified titanium hybrid graphene.

[0041] Preparation of highly weather-resistant flame-retardant epoxy resin 15 kg of 3-methoxy-4-hydroxybenzaldehyde, 36.45 kg of epichlorohydrin and 0.75 kg of tetrabutylammonium bromide were mixed and dispersed to obtain a monomer reaction liquid, stirred at a speed of 200 rpm for 2 hours in a water bath at 80°C, and then cooled to 20°C. A 50% sodium hydroxide aqueous solution containing 9.9 kg of sodium hydroxide was added to the cooled monomer reaction liquid, and the reaction was continued for 3 hours to obtain a monomer product solution. The monomer product solution was extracted with dichloromethane, anhydrous magnesium sulfate was added to the organic phase obtained by extraction, and water was removed by stirring at a speed of 200 rpm for 6 hours. After filtering, an anhydrous organic phase was obtained, and the anhydrous organic phase was poured into petroleum ether for precipitation. The precipitate was filtered and washed with anhydrous ethanol, and the washed precipitate was dried in a vacuum oven at 70°C for 12 hours to obtain a modified epoxy monomer. 25 kg of modified epoxy monomer and 4.375 kg of 2-furanmethylamine were mixed, and heated at 100°C for 3 minutes to obtain a modified epoxy resin.

[0042] 5.99 kg of diallyl chlorophosphite and 11.08 kg of 11-aminoundecyltriethoxysilane were mixed and dispersed in 100 L of a mixed solvent of triethylamine and toluene in a volume ratio of 1:4 to obtain a condensation reaction solution, the condensation reaction solution was heated to 115°C, refluxed for 5 hours, the mixed reaction solution after the reaction was filtered to obtain a product, the product was washed three times with toluene and deionized water respectively, and the washed product was dried in a vacuum oven at 115°C to obtain a condensation product. 32.93 kg of modified epoxy resin was dissolved in ethyl acetate to obtain an epoxy resin solution, the above-prepared condensation product and 0.2 kg of dibutyltin dilaurate were added to the epoxy resin solution, stirred at a speed of 500 rpm for 2 hours to obtain a product solution, the product solution was washed with deionized water and then distilled under reduced pressure to obtain a highly weather-resistant flame-retardant epoxy resin.

[0043] Preparation of flame retardant modified emulsified asphalt 110 kg of base asphalt was heated to 140°C to melt and obtain melted asphalt; 25 kg of highly weather-resistant flame-retardant epoxy resin and 4 kg of emulsifier were mixed into 45 L of water, and stirred at 200 rpm for 10 min to obtain an emulsion; the emulsion and 3 kg of additives were added to the melted asphalt within 30 min, and stirred at 2000 rpm for 30 min to obtain an asphalt emulsion; 12.5 kg of organic-inorganic synergistic flame retardant was added to the asphalt emulsion within 15 min, and the temperature was raised to 150°C and stirred for 30 min to obtain a flame-retardant modified emulsified asphalt.

[0044] Example 4 Example 4 is based on Example 3. The only difference between Example 4 and Example 3 is that in Example 4, the amount of hexachlorocyclotriphosphazene used is 5.92 kg, the amount of aminopropyltriethoxysilane used is 17.75 kg, and the amount of boric acid used is 6.33 kg.

[0045] Example 5 Example 5 is based on Example 3. The only difference between Example 5 and Example 3 is that in Example 5, the amount of hexachlorocyclotriphosphazene used is 4.24 kg, the amount of aminopropyltriethoxysilane used is 21.22 kg, and the amount of boric acid used is 4.54 kg.

[0046] Example 6 Example 6 is based on Example 3. The only difference between Example 6 and Example 3 is that in Example 6, no boric acid is added when preparing nitrogen, phosphorus and boron modified cage silsesquioxane.

[0047] Example 7 Example 7 is based on Example 3. The only difference between Example 7 and Example 3 is that in Example 7, aminopropyltriethoxysilane is replaced by tetramethylsilane when preparing nitrogen, phosphorus and boron modified cage-type silsesquioxane.

[0048] Example 8 Example 8 is based on Example 3. The only difference between Example 8 and Example 3 is that when preparing modified titanium hybrid graphene in Example 8, titanium hybrid graphene is replaced by a mixture of graphene oxide and nano-titanium dioxide, and the mass ratio of graphene oxide to nano-titanium dioxide is 1:1.

[0049] Example 9 Example 9 is based on Example 3. The only difference between Example 9 and Example 3 is that in Example 9, no amino titanate coupling agent is added when preparing the modified titanium hybrid graphene.

[0050] Example 10 Example 10 is based on Example 3. The only difference between Example 10 and Example 3 is that in Example 10, the amount of diallyl chlorophosphite used is 6.8 kg, the amount of 11-aminoundecyltriethoxysilane used is 12.59 kg, and the amount of modified epoxy resin used is 30.61 kg.

[0051] Embodiment 11 Example 11 is based on Example 3. The only difference between Example 11 and Example 3 is that in Example 11, the amount of diallyl chlorophosphite used is 5.35 kg, the amount of 11-aminoundecyltriethoxysilane used is 9.89 kg, and the amount of modified epoxy resin used is 34.76 kg.

[0052] Example 12 Example 12 is based on Example 3. The only difference between Example 12 and Example 3 is that in Example 12, diallyl chlorophosphite is replaced by tris(nonylphenol)phosphite when preparing the highly weather-resistant flame-retardant epoxy resin.

[0053] Example 13 Example 13 is based on Example 3. The only difference between Example 13 and Example 3 is that in Example 13, 11-aminoundecyltriethoxysilane is replaced with methyltriethoxysilane when preparing the highly weather-resistant flame-retardant epoxy resin.

[0054] Embodiment 14 Example 14 is based on Example 3. The only difference between Example 14 and Example 3 is that 3-methoxy-4-hydroxybenzaldehyde is not added when preparing the modified epoxy resin in Example 14.

[0055] Embodiment 15 Example 15 is based on Example 3. The only difference between Example 15 and Example 3 is that 2-furanmethylamine is replaced by bisphenol A when preparing the modified epoxy resin in Example 15.

[0056] Comparative Example 1 Comparative Example 1 is based on Example 3. The only difference between Comparative Example 1 and Example 3 is that in Comparative Example 1, the organic-inorganic synergistic flame retardant is replaced by flame retardant LY-1.

[0057] Comparative Example 2 Comparative Example 2 is based on Example 3. The only difference between Comparative Example 2 and Example 3 is that the highly weather-resistant and flame-retardant epoxy resin is replaced by epoxy resin E44 in Comparative Example 2.

[0058] Performance testing (1) Selecting GB / T29051-2012 Flame-retardant asphalt concrete for roads as the standard, the flame-retardant modified emulsified asphalt was prepared into a 20g solid strip sample for limiting oxygen index test. Three samples were prepared for each sample, and the average value was taken after measurement. The results are recorded in Table 1.

[0059] (2) Selecting GB / T8627-2007 Test method for smoke density of burning or decomposition of building materials as the standard, the flame retardant modified emulsified asphalt was prepared into samples of 25.4mm*25.4mm*6.2mm, and the smoke density level was tested in a smoke box. Three samples were prepared for each test sample, and the average value was taken after measurement. The results are recorded in Table 1.

[0060] (3) Selecting "JTG E20-2011 Highway Engineering Asphalt and Asphalt Mixture Test Procedure" as the standard, flame retardant modified emulsified asphalt is mixed with aggregate, filler and water to obtain a mixture, which is cast into a plate-shaped specimen and cured. Then a dynamic stability test is carried out. The dynamic stability is expressed by the number of times the wheel rolls when the rutting depth decreases by 1 mm. The greater the number, the better the dynamic stability of the specimen. Three specimens are prepared for each sample, and the average value is taken after measurement. The results are recorded in Table 1. The specimens are aged in a UV aging box for 1000 hours, and the dynamic stability of the specimens is tested. The average value is taken after measurement, and the results are recorded in Table 1.

[0061] Table 1 Test results of flame retardant properties and weather resistance of flame retardant modified emulsified asphalt It can be seen from Table 1 that the limiting oxygen index of Examples 1-3 is greater than 32.5%, the smoke density level is less than 38, the dynamic stability before UV aging is greater than 5673 times / mm, and the dynamic stability after UV aging is greater than 4817 times / mm, which shows that the flame retardant modified emulsified asphalt prepared in this application has good flame retardant properties and weather resistance.

[0062] As can be seen from Table 1, the only difference between Examples 4 and 5 and Example 3 is that the mass ratio of hexachlorocyclotriphosphazene, aminopropyltriethoxysilane and boric acid in Example 4 is 1:3:1.07, and the mass ratio of hexachlorocyclotriphosphazene, aminopropyltriethoxysilane and boric acid in Example 5 is 1:5:1.07. Compared with Example 3, the flame retardant properties and weather resistance of Examples 4 and 5 are reduced. This is because the mass ratio of hexachlorocyclotriphosphazene, aminopropyltriethoxysilane and boric acid is not within the specified range. After the specified ratio is destroyed, the formation of cage-type silsesquioxane will be affected, thereby reducing the stability of the organic-inorganic synergistic flame retardant, and thus reducing the flame retardant properties and weather resistance.

[0063] As shown in Table 1, the only difference between Examples 6, 7, 8, and 9 and Example 3 is that: in Example 6, boric acid is not added when preparing nitrogen, phosphorus, and boron modified cage silsesquioxane, aminopropyltriethoxysilane is replaced with tetramethylsilane when preparing nitrogen, phosphorus, and boron modified cage silsesquioxane in Example 7, titanium hybrid graphene is replaced with a mixture of graphene oxide and nano-titanium dioxide when preparing modified titanium hybrid graphene in Example 8, and amino titanate coupling agent is not added when preparing modified titanium hybrid graphene in Example 9. Compared with Example 3, the flame retardant properties of Examples 6, 7, 8, and 9 are better than those of Example 3. The weather resistance is reduced because the nitrogen-phosphorus-boron-silicon synergistic flame retardant system will be affected if boric acid is not added; replacing aminopropyltriethoxysilane with tetramethylsilane will affect the formation of cage-type silsesquioxane and the connection of modified titanium hybrid graphene, and the stability of the organic-inorganic synergistic flame retardant will be reduced; replacing titanium hybrid graphene with graphene oxide and nano-titanium dioxide will weaken the synergistic effect of the two; if titanate coupling agent is not added, the reaction performance of the modified titanium hybrid graphene will be reduced, and the stability of the organic-inorganic synergistic flame retardant will be reduced, thereby reducing the flame retardant and weather resistance properties.

[0064] As can be seen from Table 1, the only difference between Examples 10 and 11 and Example 3 is that in Example 10, the mass ratio of diallyl chlorophosphite, 11-aminoundecyltriethoxysilane and modified epoxy resin is 1:1.85:4.5, and in Example 11, the mass ratio of diallyl chlorophosphite, 11-aminoundecyltriethoxysilane and modified epoxy resin is 1:1.85:6.5. Compared with Example 3, the flame retardant properties and weather resistance of Examples 10 and 11 are reduced. This is because the mass ratio of diallyl chlorophosphite, 11-aminoundecyltriethoxysilane and modified epoxy resin is not within the specified range. The stability and reactivity of the epoxy resin obtained after destroying the specified range are affected, and the synergistic effect with other components in the emulsified asphalt is reduced, thereby reducing the flame retardant properties and weather resistance.

[0065] As can be seen from Table 1, the only difference between Examples 12, 13, 14, and 15 and Example 3 is that: in Example 12, diallyl chlorophosphite is replaced with tris(nonylphenol)phosphite when preparing the highly weather-resistant flame-retardant epoxy resin, in Example 13, 11-aminoundecyltriethoxysilane is replaced with methyltriethoxysilane when preparing the highly weather-resistant flame-retardant epoxy resin, in Example 14, 3-methoxy-4-hydroxybenzaldehyde is not added when preparing the modified epoxy resin, and in Example 15, 2-furanmethylamine is replaced with bisphenol A when preparing the modified epoxy resin. Compared with Example 3, Examples 12, 13, 14, and 15 are Both the flame retardant properties and weather resistance are reduced. This is because if diallyl chlorophosphite is replaced with tris(nonylphenol) phosphite, the reactivity between tris(nonylphenol) phosphite and silane becomes worse, and the modification effect is reduced; if 11-aminoundecyltriethoxysilane is replaced with methyltriethoxysilane, the reaction performance is reduced, and the modification effect is also reduced; without adding 3-methoxy-4-hydroxybenzaldehyde, the thermal stability and weather resistance of the modified epoxy resin are reduced; if 2-furanmethylamine is replaced with bisphenol A, the thermal stability of bisphenol A is reduced, which in turn affects the stability of asphalt, and thus the flame retardant properties and weather resistance are reduced.

[0066] It can be seen from Table 1 that the only difference between Comparative Example 1 and Example 3 is that in Comparative Example 1, the organic-inorganic synergistic flame retardant is replaced by flame retardant LY-1. Compared with Example 3, the flame retardant performance and weather resistance of Comparative Example 1 are significantly reduced. This is because the organic-inorganic synergistic flame retardant is replaced by flame retardant LY-1, which lacks the synergistic flame retardant effect of the organic phase and the inorganic phase, and the flame retardant effect is greatly reduced, and the anti-ultraviolet performance and antioxidant performance are both reduced, so that the flame retardant performance and weather resistance are significantly reduced.

[0067] It can be seen from Table 1 that the only difference between Comparative Example 2 and Example 3 is that the high weather resistant flame retardant epoxy resin is replaced by epoxy resin E44 in Comparative Example 2. Compared with Example 3, the flame retardant performance and weather resistance of Comparative Example 2 are significantly reduced. This is because the high weather resistant flame retardant epoxy resin is replaced by epoxy resin E44, and there is a lack of modification treatment. There is no flame retardant group on E44, and the antioxidant performance, UV resistance and thermal stability are reduced, so that the flame retardant performance and weather resistance are significantly reduced.

[0068] This specific embodiment is only an explanation of the present application, and it is not a limitation of the present application. Through the above description, relevant staff can make various changes and modifications without deviating from the technical idea of ​​the present application. The technical scope of the present application is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A flame retardant modified emulsified asphalt, Features: The composition includes the following components in parts by weight: Base asphalt 100-120 parts 10-15 parts of organic-inorganic synergistic flame retardant 20-30 parts of high weather-resistant flame-retardant epoxy resin Emulsifier 3-5 parts 1-3 parts of additives 40-50 parts of water.

2. A flame retardant modified emulsified asphalt according to claim 1, Features: The raw materials for preparing the organic-inorganic synergistic flame retardant include nitrogen-phosphorus-boron modified cage-type silsesquioxane and modified titanium hybrid graphene.

3. A flame retardant modified emulsified asphalt according to claim 2, Features: The raw materials for preparing the nitrogen, phosphorus and boron modified cage-type silsesquioxane include hexachlorocyclotriphosphazene, aminopropyltriethoxysilane and boric acid.

4. A flame retardant modified emulsified asphalt according to claim 3, Features: The mass ratio of the hexachlorocyclotriphosphazene, aminopropyltriethoxysilane and boric acid is 1:(3.8-4.6):1.

07.

5. The flame retardant modified emulsified asphalt according to claim 2, Features: The raw materials for preparing the modified titanium hybrid graphene include graphene oxide, ammonium fluorotitanate and an amino titanate coupling agent.

6. The flame retardant modified emulsified asphalt according to claim 5, Features: The modified titanium hybrid graphene is prepared by the following steps: The graphene oxide is dispersed in deionized water, and a graphene dispersion is obtained after ultrasonic treatment; ammonium fluorotitanate is added to the graphene dispersion, and the pH is adjusted to acidic using hydrochloric acid to obtain a mixed reaction liquid, and the mixed reaction liquid is reacted under stirring in a water bath, and the mixed reaction liquid after the reaction is centrifuged to obtain a solid, and the solid is dried, and the dried solid is calcined and ground to obtain titanium hybrid graphene; the titanium hybrid graphene prepared above and the amino titanate coupling agent are dispersed in an ethanol aqueous solution to obtain a modified suspension, and the modified suspension is stirred in a water bath for reaction, and filtered and dried to obtain the modified titanium hybrid graphene.

7. The flame retardant modified emulsified asphalt according to claim 1, Features: The raw materials for preparing the highly weather-resistant flame-retardant epoxy resin include diallyl chlorophosphite, 11-aminoundecyltriethoxysilane and modified epoxy resin.

8. The flame retardant modified emulsified asphalt according to claim 7, Features: The raw materials for preparing the modified epoxy resin include 3-methoxy-4-hydroxybenzaldehyde, epichlorohydrin and 2-furylamine.

9. The flame retardant modified emulsified asphalt according to claim 8, Features: The mass ratio of diallyl chlorophosphite, 11-aminoundecyltriethoxysilane and modified epoxy resin is 1:1.85:(5-6).

10. A method for preparing the flame retardant modified emulsified asphalt as claimed in claim 1, Features: Prepared by the following steps: The base asphalt is heated until it is melted to obtain melted asphalt; a highly weather-resistant flame-retardant epoxy resin and an emulsifier are mixed into water, and an emulsion is obtained after stirring; the emulsion and an auxiliary agent are added to the melted asphalt and stirred to obtain an asphalt emulsion; an organic-inorganic synergistic flame retardant is added to the asphalt emulsion, and the temperature is increased and stirred to obtain a flame-retardant modified emulsified asphalt.

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