Flame-retardant exposed liquid coiled material as well as preparation method and application thereof

Abstract

The invention discloses a flame-retardant exposed liquid coiled material and a preparation method and application thereof, and belongs to the technical field of liquid coiled materials, ZIF-8 grows on ammonium polyphosphate in situ, anchoring is achieved through the ion exchange effect of zinc ions and NH4 < + > in an ammonium polyphosphate molecular chain, then coordination reaction with 2-methylimidazole is carried out, and the flame-retardant exposed liquid coiled material is obtained. Ammonium polyphosphate is added into ZIF-8 to form molecular-level coating of the ZIF-8 on the ammonium polyphosphate, so that the hydrophilicity of the ammonium polyphosphate is reduced, the precipitation risk in a humid and hot environment is reduced, the compatibility of the ammonium polyphosphate and a polymer matrix is improved, agglomeration is avoided, the ammonium polyphosphate and a charring agent melamine-formaldehyde resin form a synergistic flame-retardant system, and through the phosphorus-nitrogen synergistic effect, the flame-retardant property of the ammonium polyphosphate is improved. The flame retardant can be used for promoting the formation of a compact expanded carbon layer during combustion, so that the dual effects of gas-phase flame retardance and condensed-phase flame retardance are realized, the problem that the flame-retardant structure of a traditional product is damaged due to a humid and hot environment is effectively solved, and the flame-retardant grade and the long-term effect are remarkably improved.

Description

Technical Field

[0001] This invention belongs to the field of liquid roll material technology, and relates to a flame-retardant exposed liquid roll material, its preparation method and application. Background Technology

[0002] In the field of building waterproofing engineering, liquid roofing membranes are widely used in roofs, basements, kitchens and bathrooms, exterior walls, as well as in building-integrated photovoltaic roofs and industrial plants due to their outstanding advantages such as convenient construction, strong adaptability to complex and irregular substrates, and good overall waterproofing and sealing performance. With the continuous upgrading of modern buildings' requirements for fire safety and green energy conservation, liquid roofing membranes that combine exposed use with high-efficiency flame retardant properties are gradually becoming the core direction of industry research and development and market application.

[0003] Traditional liquid roll materials are mostly based on bitumen-based materials or ordinary acrylic or styrene-acrylic emulsions. When exposed to the elements, these products are susceptible to natural factors such as ultraviolet radiation, high and low temperature cycles, and rain and snow erosion, resulting in durability problems such as surface powdering, cracking, and reduced adhesion. They usually require additional protective layers such as cement mortar or colored sand, which not only increases the construction process and cost, but may also lead to secondary leakage risks due to poor adhesion between the protective layer and the roll material layer.

[0004] Chinese invention patent application CN119286399A discloses an exposed modified bitumen waterproof coating and its preparation method and application. The raw materials used in the modified bitumen waterproof coating include compound functional emulsion, defoamer, dispersant, multifunctional additive, heavy calcium carbonate, glass microspheres, silane coupling agent, ultraviolet absorber and light stabilizer. This solution only adds filler to the coating and does not require an additional protective layer, making it convenient to use.

[0005] However, under humid and hot conditions with high humidity or large temperature fluctuations, moisture can still easily penetrate into the interior of the asphalt waterproof coating. On the one hand, moisture will form a water film at the interface between the coating and the building surface, weakening the physical adsorption and chemical bonding between the coating and the substrate, resulting in a decrease in the interfacial bonding strength. At the same time, the penetration of moisture will cause micropores and stress cracks to form inside the coating. On the other hand, repeated temperature fluctuations will intensify the circulation of moisture in the pores, further expanding the pore size and destroying the dense structure inside the coating. Heat and oxygen can be freely transferred through the pores, ultimately causing a significant decrease in flame retardant efficiency. Summary of the Invention

[0006] The purpose of this invention is to provide a flame-retardant exposed liquid roll material, its preparation method and application. By combining flame-retardant composite materials with emulsified asphalt, and then compounding it with fluorocarbon modified acrylic emulsion and functional additives, the invention achieves the effects of high flame retardancy, long-lasting weather resistance and good compatibility of each component.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A flame-retardant, exposed liquid roll material is prepared by the following steps:

[0009] Step 1: Mix and knead ammonium polyphosphate loaded with ZIF-8, melamine-formaldehyde resin and vinyl acetate-ethylene copolymer to obtain flame-retardant composite material.

[0010] Step 2: Pre-emulsify and disperse the flame-retardant composite material, then combine and shear it with emulsified asphalt to obtain modified emulsified asphalt.

[0011] Step 3: After dispersing and mixing the fluorocarbon modified acrylic emulsion, functional additives and mixed fillers, add the modified emulsified asphalt with premixed emulsifier, then add rheology thickener, bactericide and pH adjuster and stir evenly to obtain flame-retardant exposed liquid roll material.

[0012] Furthermore, the mass ratio of ZIF-8-loaded ammonium polyphosphate, melamine-formaldehyde resin, and vinyl acetate-ethylene copolymer is 4.5-6.5: 21.5-27.5: 74-84.

[0013] This formulation achieves synergistic compatibility between the flame retardant, the char-forming agent melamine-formaldehyde resin, and the polymer matrix, ensuring both flame retardant efficiency and avoiding damage to the mechanical properties of the material.

[0014] Furthermore, the preparation process of ZIF-8-loaded ammonium polyphosphate is as follows:

[0015] Ammonium polyphosphate and anhydrous methanol were added to a reaction vessel and ultrasonically dispersed. Zinc nitrate hexahydrate was then added and stirred at 50-55°C for 12-14 hours. 2-methylimidazole and anhydrous methanol were mixed evenly and then added dropwise to the reaction vessel. The mixture was stirred for 30-40 minutes and allowed to stand for 24-26 hours. The mixture was then filtered, washed, and dried to obtain ZIF-8-loaded ammonium polyphosphate.

[0016] Furthermore, the ratio of ammonium polyphosphate, anhydrous methanol, zinc nitrate hexahydrate, and 2-methylimidazole is 20-25g: 200-300mL: 2.22-4.22g: 2.46-4.46g.

[0017] This ensures that zinc ions are fully anchored on the surface of ammonium polyphosphate through ion exchange, providing sufficient active sites for the in-situ growth of ZIF-8.

[0018] Furthermore, the preparation process of modified emulsified asphalt is as follows:

[0019] Add water to the reactor and heat to 60°C. While stirring, add sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, and cellulose ether. Adjust the pH to 11-13. Add an organosilicon defoamer and stir until homogeneous to obtain a soap solution. Pour the soap solution into a colloid mill and shear for 2-4 minutes. Then add 90# base asphalt at 130-140°C and run for 2-4 minutes to obtain emulsified asphalt. Shear the flame-retardant composite material, sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, and water at 1500-2000 r / min for 10-15 minutes. Then add the emulsified asphalt and shear for 5-10 minutes to obtain modified emulsified asphalt.

[0020] A stable soap solution system was constructed using sodium alkyl sulfonate, sodium dioctyl sulfosuccinate, and cellulose ether. The asphalt was then uniformly emulsified by combining this system with the high shear effect of a colloid mill. Flame-retardant composite materials were then added to achieve flame-retardant modification.

[0021] Furthermore, the mass ratio of water, sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, cellulose ether, and organosilicon defoamer is 400-500:10-15:2-3:1-2:0.3-0.4.

[0022] Cellulose ethers construct a complex and stable system, enhancing the interfacial and storage stability of the soap solution; the dosages of sodium secondary alkyl sulfonate and sodium dioctyl sulfosuccinate are precisely matched to the emulsification requirements of asphalt, avoiding demulsification problems caused by insufficient or excessive emulsification; the dosage of organosilicon defoamers can effectively eliminate bubbles generated during stirring, ensuring the uniformity of emulsified asphalt.

[0023] Furthermore, the mass ratio of soap solution to 90# base asphalt is 400-500:500-600.

[0024] Ensure that asphalt droplets are evenly dispersed in the aqueous phase to form a stable emulsified asphalt system and avoid stratification or sedimentation.

[0025] Furthermore, the mass ratio of flame-retardant composite material, sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, water, and emulsified asphalt is 50-100:3-4:1-3:50-60:700-900.

[0026] Pre-emulsifying flame-retardant composite materials with a small amount of sodium secondary alkyl sulfonate and sodium dioctyl sulfosuccinate can form a charge protection layer on the material surface, allowing it to be uniformly dispersed in the emulsified asphalt, thereby achieving a synergistic improvement in flame-retardant performance and asphalt waterproofing performance.

[0027] Furthermore, the functional additives consist of rheology modifiers, ultraviolet absorbers, light stabilizers, hydrophobic dispersants, and defoamers.

[0028] Rheology modifiers can enhance the anti-slip properties and product stability of coatings; UV absorbers and light stabilizers work synergistically to improve anti-aging performance in exposed environments; hydrophobic dispersants ensure uniform dispersion of fillers and functional additives and reduce water absorption; defoamers eliminate bubbles in the system and ensure a smooth coating surface.

[0029] Furthermore, the mass ratio of fluorocarbon modified acrylic emulsion, rheology modifier, ultraviolet absorber, light stabilizer, hydrophobic dispersant, defoamer and mixed filler is 400-500: 50-60: 10-15: 8-10: 3-5: 3-5: 200-280.

[0030] It can achieve synergistic compatibility of film-forming substances, functional additives and fillers, ensuring the flexibility and adhesion of the coating film, while giving full play to the role of each functional additive, thereby improving the overall performance of the product.

[0031] Furthermore, the mixed filler is composed of heavy calcium carbonate and titanium dioxide mixed in a mass ratio of 4:1.

[0032] Heavy calcium carbonate serves as a skeleton filler to enhance the strength and wear resistance of the coating film, while titanium dioxide contributes to its hiding power, weather resistance, and corrosion resistance. Together, they optimize the physical properties and leveling properties of the coating film.

[0033] Furthermore, the mass ratio of modified emulsified asphalt, rheology thickener, bactericide, and pH adjuster is 200-300:5-6:5-7:2-3:2-3.

[0034] Anionic emulsifiers can effectively improve the compatibility between anionic modified emulsified asphalt and anionic fluorocarbon modified acrylic emulsions, avoiding flocculation caused by charge conflict; the amount of rheology thickener can adjust the viscosity of the system to the appropriate range for construction, preventing sagging or difficulty in application; bactericides inhibit the growth of microorganisms, extending the product's shelf life and service life; pH adjusters match the optimal film-forming environment of fluorocarbon modified acrylic emulsions, ensuring stable coating performance.

[0035] This invention also provides a method for preparing a flame-retardant, exposed liquid roll material, comprising the following steps:

[0036] Fluorocarbon modified acrylic emulsion, rheology modifier, UV absorber, light stabilizer, hydrophobic dispersant, and defoamer are added to a high-speed disperser and stirred at 500-1000 rpm for 5-10 minutes. The above-mentioned mixed filler is slowly added and stirred for 10-15 minutes. The mixture is then allowed to stand for 2-5 minutes to defoam. The above-mentioned modified emulsified asphalt is added to the system and stirred at 400-500 rpm for 10-15 minutes. Finally, the rheology thickener, bactericide, and pH adjuster are slowly added and stirred for 10-15 minutes to obtain a flame-retardant, exposed liquid roll material.

[0037] This invention also provides an application of a flame-retardant, exposed liquid roll material for waterproofing and flame retardancy on exposed building surfaces.

[0038] The beneficial effects of this invention are:

[0039] 1. In this invention, ZIF-8 is first grown in situ on ammonium polyphosphate, and then the zinc ions react with the NH4+ in the ammonium polyphosphate molecular chain. + The ion exchange process achieves anchoring, followed by a coordination reaction with 2-methylimidazole to form ZIF-8, which encapsulates ammonium polyphosphate at the molecular level. This reduces the hydrophilicity of ammonium polyphosphate, decreasing the risk of precipitation in humid and hot environments, and improves the compatibility of ammonium polyphosphate with the polymer matrix, preventing agglomeration. It then forms a synergistic flame retardant system with the char-forming agent melamine-formaldehyde resin. Through the synergistic effect of phosphorus and nitrogen, it promotes the formation of a dense and expanded char layer during combustion, achieving both gas-phase and condensed-phase flame retardancy. This effectively compensates for the flame retardant structure damage caused by humid and hot environments in traditional products, significantly improving the flame retardant rating and longevity. It completely solves the problem of short-lasting flame retardant effect of traditional flame-retardant liquid rolls when used for a long time in humid and hot environments.

[0040] 2. This invention improves the weather resistance of flame-retardant exposed liquid rolls by combining fluorocarbon modified acrylic emulsion, ultraviolet absorber, light stabilizer and titanium dioxide. The ultraviolet absorber can efficiently absorb the 280-320nm ultraviolet band and block the direct corrosion of the roll matrix by ultraviolet rays. The light stabilizer captures the free radicals generated by photo-oxidation reaction and inhibits molecular chain degradation. The titanium dioxide builds a dense structure inside the coating and can effectively resist ultraviolet degradation. The three work together to improve the ultraviolet aging performance of the liquid rolls.

[0041] 3. This invention employs a pre-emulsified flame-retardant composite material scheme. Sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, and cellulose ether pre-emulsify the flame-retardant composite material, forming a charge-protective layer on its surface. This allows the material to be uniformly dispersed in the emulsified asphalt. Furthermore, an emulsifier improves the interfacial compatibility between the emulsified asphalt and the fluorocarbon-modified acrylic emulsion. A hydrophobic dispersant further promotes the uniform dispersion of the filler. By adjusting the charge, achieving interfacial compatibility, and enhancing dispersion, the stable compatibility of each component is achieved. This results in a uniform and dense coating film after construction, with low water absorption, excellent impermeability, and high bonding strength, ensuring both waterproof sealing and good leveling properties during construction.

[0042] 4. This invention adjusts the viscosity of the system through a rheology thickener, making it suitable for high and low temperature construction environments. It can be directly brushed or sprayed onto complex irregular surfaces, and has strong adaptability to exposed surfaces such as building roofs, photovoltaic module mounting surfaces, and industrial plant exterior walls. The product uses a water-based system, with no large use of organic solvents throughout the process. The halogen-free flame-retardant formula avoids the generation of toxic and harmful gases during combustion, meeting the requirements of green building and environmental protection policies. Detailed Implementation

[0043] To further illustrate the technical means and effects of the present invention in achieving the intended purpose, the following detailed description of the specific implementation methods, features and effects of the present invention, in conjunction with preferred embodiments, is provided below.

[0044] Example 1: This example provides a flame-retardant, exposed liquid roll material, prepared through the following steps:

[0045] S1: Add 22.5g of ammonium polyphosphate and 250mL of anhydrous methanol to the reactor and sonicate for 12min. Then add 3.22g of zinc nitrate hexahydrate and sonicate for 12min. Stir for 13h at 52℃ and 400r / min. Mix 3.46g of 2-methylimidazole and 55mL of anhydrous methanol evenly and add it dropwise to the reactor. Stir at 52℃ for 35min after adding the mixture. Let stand at room temperature for 25h, filter, wash with methanol 4 times, and dry to constant weight at 85℃ to obtain ZIF-8-loaded ammonium polyphosphate.

[0046] Ammonium polyphosphate was dissolved in anhydrous methanol and ultrasonically dispersed to form a homogeneous suspension. Upon addition of zinc nitrate hexahydrate, zinc ions reacted with NH4+ in the ammonium polyphosphate molecular chain through ion exchange. + The 2-methylimidazole is anchored on the surface of ammonium polyphosphate, providing metal ion sites for the in-situ generation of ZIF-8. Under conditions of 50-55℃, 2-methylimidazole undergoes a coordination reaction with zinc ions, forming ZIF-8 nanoparticles in situ, which uniformly coat the surface of ammonium polyphosphate. This not only reduces the hydrophilicity of ammonium polyphosphate and reduces precipitation under humid and hot conditions, but also improves compatibility with the polymer matrix and avoids agglomeration.

[0047] S2: Mix 5.5g of melamine-formaldehyde resin, 24.5g of ammonium polyphosphate loaded with ZIF-8 and 79g of vinyl acetate-ethylene copolymer evenly, and knead at 175℃ for 9min to obtain flame-retardant composite material.

[0048] S3: Add 450g of water to the reactor and heat to 60℃. Add 1g of cellulose ether and stir at 500r / min until the cellulose ether is completely dissolved. Add 10g of sodium secondary alkyl sulfonate and 2g of sodium dioctyl sulfosuccinate and stir for 6min. Adjust the pH to 13 with a pH adjuster. Add 0.3g of organosilicon defoamer and stir evenly. Cool to 60℃ to obtain soap solution. Pour 450g of the soap solution at 60℃ into a colloid mill and shear for 3min. Then add 550g of 90# base asphalt (softening point ≥45℃) heated to 135℃ in three batches and run at 4000r / min for 3min to obtain emulsified asphalt. Shear 100g of flame retardant composite material, 4g of sodium secondary alkyl sulfonate, 2g of sodium dioctyl sulfosuccinate and 55g of water at 1750r / min for 12min. Then add 850g of emulsified asphalt and shear for 7min to obtain modified emulsified asphalt.

[0049] S4: Mix 220g of heavy calcium carbonate (800 mesh, calcium carbonate content 98%, whiteness 95%, purchased from Jiangxi Guangyuan Chemical Co., Ltd.) and 55g of titanium dioxide (purchased from Longbai Group Co., Ltd.) at a mass ratio of 4:1 and stir evenly to obtain a mixed filler.

[0050] S5: Add 50g water (i.e., rheology modifier), 500g fluorocarbon modified acrylic emulsion (50% solids content, pH 7-9, purchased from Shanghai Baolijia Chemical Co., Ltd.), 10g UV absorber (UV-1130), 10g light stabilizer (LQ-292), 3g hydrophobic dispersant, and 4g defoamer (metallic soap NOPCO NXZ and silicone BASF A10 in a 1:1 mass ratio) to a high-speed disperser and stir at 900r / min for 10min. Slowly add 220g mixed filler and stir for 15min. Let stand for 3min to defoam. Add 200g modified emulsified asphalt to the system and stir at 450r / min for 15min. Finally, slowly add 6g rheology thickener (HEUR-type and cellulose ether-type compound in a 3:4 ratio), 2g bactericide (isothiazoline-type), and 2.5g... pH adjuster (multifunctional additive AMP-95), stir for 12 minutes to obtain flame-retardant exposed liquid roll material.

[0051] Example 2: This example provides a flame-retardant, exposed liquid roll material, prepared through the following steps:

[0052] S1: Add 20g of ammonium polyphosphate and 200mL of anhydrous methanol to the reactor and sonicate for 10min. Then add 2.22g of zinc nitrate hexahydrate and sonicate for 10min. Stir for 12h at 50℃ and 300r / min. Mix 2.46g of 2-methylimidazole and 50mL of anhydrous methanol evenly and add it dropwise to the reactor. Stir at 50℃ for 30min after adding the mixture. Let stand at room temperature for 24h. Filter the mixture, wash it three times with methanol, and dry it to constant weight at 80℃ to obtain ZIF-8-loaded ammonium polyphosphate.

[0053] S2: Mix 4.5g of melamine-formaldehyde resin, 21.5g of ammonium polyphosphate loaded with ZIF-8 and 74g of vinyl acetate-ethylene copolymer evenly, and knead at 170℃ for 8min to obtain flame-retardant composite material.

[0054] S3: Add 450g of water to the reactor and heat to 60℃. Add 2g of cellulose ether and stir at 500r / min until the cellulose ether is completely dissolved. Add 12g of sodium secondary alkyl sulfonate and 2g of sodium dioctyl sulfosuccinate and stir for 6min. Adjust the pH to 13 with a pH adjuster. Add 0.4g of organosilicon defoamer and stir evenly. Cool to 55℃ to obtain soap solution. Pour 450g of the soap solution at 55℃ into a colloid mill and shear for 3min. Then add 550g of 90# base asphalt (softening point ≥45℃) heated to 135℃ in three batches and run at 3000r / min for 3min to obtain emulsified asphalt. Shear 50g of flame retardant composite material, 4g of sodium secondary alkyl sulfonate, 2g of sodium dioctyl sulfosuccinate and 55g of water at 2000r / min for 12min. Then add 850g of emulsified asphalt and shear for 7min to obtain modified emulsified asphalt.

[0055] S4: Mix 200g of heavy calcium carbonate (800 mesh, calcium carbonate content 98%, whiteness 95%, purchased from Jiangxi Guangyuan Chemical Co., Ltd.) and 50g of titanium dioxide (purchased from Longbai Group Co., Ltd.) at a mass ratio of 4:1 and stir evenly to obtain a mixed filler.

[0056] S5: Add 50g water (i.e., rheology modifier), 450g fluorocarbon modified acrylic emulsion (50% solids content, pH 7-9, purchased from Shanghai Baolijia Chemical Co., Ltd.), 15g UV absorber (UV-1130), 10g light stabilizer (LQ-292), 4g hydrophobic dispersant, and 5g defoamer (metallic soap NOPCO NXZ and silicone BASF A10 in a 1:1 mass ratio) to a high-speed disperser and stir at 900 rpm for 10 min. Slowly add 250g mixed filler and stir for 15 min. Let stand for 3 min to defoam. Add 200g modified emulsified asphalt to the system and stir at 450 rpm for 15 min. Finally, slowly add 6g rheology thickener (HEUR-type and cellulose ether-type compound in a 3:4 ratio), 2g bactericide (isothiazoline-type), and 2.5g... pH adjuster (multifunctional additive AMP-95), stir for 12 minutes to obtain flame-retardant exposed liquid roll material.

[0057] Example 3: This example provides a flame-retardant, exposed liquid roll material, prepared through the following steps:

[0058] S1: Add 25g of ammonium polyphosphate and 300mL of anhydrous methanol to the reactor and sonicate for 15min. Then add 4.22g of zinc nitrate hexahydrate and sonicate for 15min. Stir at 55℃ and 500r / min for 14h. Mix 4.46g of 2-methylimidazole and 60mL of anhydrous methanol evenly and add it dropwise to the reactor. Stir at 55℃ for 40min after adding the mixture. Let stand at room temperature for 26h. Filter the mixture and wash it 5 times with methanol. Dry it at 90℃ to constant weight to obtain ZIF-8-loaded ammonium polyphosphate.

[0059] S2: Mix 6.5g of melamine-formaldehyde resin, 27.5g of ammonium polyphosphate loaded with ZIF-8 and 84g of vinyl acetate-ethylene copolymer evenly, and knead at 180℃ for 10min to obtain flame-retardant composite material.

[0060] S3: Add 500g of water to the reactor and heat to 60℃. Add 1g of cellulose ether and stir at 500r / min until the cellulose ether is completely dissolved. Add 15g of sodium secondary alkyl sulfonate and 2g of sodium dioctyl sulfosuccinate and stir for 6min. Adjust the pH to 13 with a pH adjuster. Add 0.3g of organosilicon defoamer and stir evenly. Cool to 55℃ to obtain soap solution. Pour 450g of the soap solution at 55℃ into a colloid mill and shear for 3min. Then add 550g of 90# base asphalt (softening point ≥45℃) heated to 135℃ in three batches and run at 3000r / min for 3min to obtain emulsified asphalt. Shear 80g of flame retardant composite material, 4g of sodium secondary alkyl sulfonate, 2g of sodium dioctyl sulfosuccinate and 55g of water at 2000r / min for 12min. Then add 850g of emulsified asphalt and shear for 7min to obtain modified emulsified asphalt.

[0061] S4: Mix 240g of heavy calcium carbonate (800 mesh, calcium carbonate content 98%, whiteness 95%, purchased from Jiangxi Guangyuan Chemical Co., Ltd.) and 60g of titanium dioxide (purchased from Longbai Group Co., Ltd.) at a mass ratio of 4:1 and stir evenly to obtain a mixed filler.

[0062] S5: Add 50g water (i.e., rheology modifier), 500g fluorocarbon modified acrylic emulsion (50% solids content, pH 7-9, purchased from Shanghai Baolijia Chemical Co., Ltd.), 15g UV absorber (UV-1130), 10g light stabilizer (LQ-292), 4g hydrophobic dispersant, and 5g defoamer (metallic soap NOPCO NXZ and silicone BASF A10 in a 1:1 mass ratio) to a high-speed disperser and stir at 900r / min for 10min. Slowly add 280g mixed filler and stir for 15min. Let stand for 3min to defoam. Add 200g modified emulsified asphalt to the system and stir at 450r / min for 15min. Finally, slowly add 6g rheology thickener (HEUR-type and cellulose ether-type compound in a 3:4 ratio), 2g bactericide (isothiazoline-type), and 2.5g... pH adjuster (multifunctional additive AMP-95), stir for 12 minutes to obtain flame-retardant exposed liquid roll material.

[0063] Example 4: This example provides a flame-retardant exposed liquid roll material. The difference from Example 1 is that UV-327 is used instead of UV-1130 as the ultraviolet absorber in step S5.

[0064] Example 5: This example provides a flame-retardant exposed liquid roll material. The difference from Example 1 is that in step S5, the light stabilizer is replaced by GW-540 instead of LQ-292.

[0065] Example 6: This example provides a flame-retardant exposed liquid roll material. The difference from Example 1 is that the ratio of rheology thickener HEUR type and cellulose ether type in step S5 is 4:3.

[0066] Comparative Example 1: This comparative example provides a flame-retardant exposed liquid roll material. The difference from Example 1 is that step S1 is omitted, and in step S2, ammonium polyphosphate is used instead of the ZIF-8-loaded ammonium polyphosphate.

[0067] Comparative Example 2: This comparative example provides a flame-retardant exposed liquid roll material, which differs from Example 1 in that ammonium polyphosphate is used instead of the flame-retardant composite material in step S3.

[0068] Comparative Example 3: This comparative example provides a flame-retardant exposed liquid roll material, which differs from Example 1 in that emulsified bitumen is used instead of modified emulsified bitumen in step S5.

[0069] The flame-retardant exposed liquid rolls prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to performance tests:

[0070] Bond strength: Referring to GB / T 16777-2008 "Test Methods for Waterproof Coatings for Buildings", a 70×70×20mm cement mortar block was prepared. Surface impurities and laitance were removed using sandpaper. The prepared flame-retardant, exposed liquid membrane was then applied in two coats to the cleaned surface of the block, with an interval of no more than 24 hours between coats. The final coating thickness was ensured to be 0.5-1.0mm. The specimen was cured under standard conditions for 5 days, followed by 2 days in a constant temperature drying oven at (40±2℃). A universal testing machine was used to test the maximum tensile load at a tensile speed of 5mm / min, and the maximum tensile force of the specimen was recorded. The test temperature was (23±2)℃.

[0071] Impermeability performance: Referring to GB / T 16777-2008 "Test Methods for Waterproof Coatings for Buildings", cut three 150mm×150mm specimens from the coating film cured to the specified age and place them for 2 hours under standard test conditions. Then place the coating film on a permeable tray conforming to the test standard of GB / T 16777-2008, cover the specimen with a metal mesh and a seven-hole disc, clamp the specimen tightly to the permeable tray, start the machine and slowly pressurize to the specified pressure, maintain the water pressure at 0.3MPa for 30±2min, and then carefully observe whether the non-water-facing side is permeable or whether the water pressure drops. If there is no permeability and no drop in water pressure, it is considered qualified.

[0072] Elongation at break: Refer to GB / T 16777-2008 "Test Methods for Waterproof Coatings for Buildings" and use a tensile testing machine for testing. The centerline of the specimen in the length direction should be aligned with the center of the tensile testing machine fixture. The tensile rate is 500 mm / min, and the spacing between the marks at the point of breakage is recorded.

[0073] Flame retardant performance test: The samples were cut into standard strips of 250mm×90mm×1.5mm according to GB / T 8626-2007 "Standard for Test Methods of Combustibility of Building Materials". Surface ignition positioning was used, and the strips were surface-ignited using a combustion tester (Songshu Instruments Co., Ltd.). The B2-E test (ignition for 15s, combustion for 20s, flame tip height F < 150mm, no burning drips igniting filter paper) was performed. Each experimental material was tested five times according to the above procedure, and its flame retardant rating was determined based on the obtained data.

[0074] UV aging test: The test was conducted using a UV aging tester in accordance with ASTM D4587 standard.

[0075] Damp heat aging test: The sample was placed in a hydrothermal aging chamber at a constant temperature (50±2℃) and high humidity (relative humidity 95±3%RH) for 168h (7 days) of accelerated aging. All the distilled water in the inner liner of the aging chamber was collected, transferred to a 1000mL volumetric flask, and brought to the mark. The mixture was shaken to obtain the mother liquor of the precipitate. The mother liquor was diluted to a certain factor. The absorbance of the diluted precipitate was measured at the characteristic absorption wavelength, with distilled water as a blank. The concentration of ammonium polyphosphate in the precipitate was calculated. The bonding strength of the sample was tested and the bonding strength retention rate after the damp heat aging test was calculated.

[0076] The test results are shown in the table below:

[0077] Table 1 Performance Test Overview

[0078]

[0079] As shown in Table 1, Examples 1-6 all achieved the B2-E flame retardant rating, LOI ≥ 30.2%, bond strength ≥ 0.92 MPa, elongation at break ≥ 985%, and qualified water impermeability, demonstrating the reliability of the process of this invention.

[0080] As shown in Table 1, the bonding strength and elongation at break of Examples 1-6 are greater than those of Comparative Examples 1-3. This may be because the use of ZIF-8 to molecularly encapsulate ammonium polyphosphate improves the compatibility between the flame retardant and the polymer matrix, avoids stress concentration caused by agglomeration, optimizes multiphase compatibility through emulsifier bridging, and makes the coating structure uniform and dense. In addition, the synergistic filling and reinforcing effect of heavy calcium carbonate and titanium dioxide enhances the cohesion and flexibility of the coating.

[0081] As shown in Table 1, the LOI values ​​of Examples 1-6 are all greater than those of Comparative Examples 1-3, and their flame retardant ratings are superior to those of Comparative Examples 1-3. This may be because the ammonium polyphosphate loaded with ZIF-8 and the melamine-formaldehyde resin form a phosphorus-nitrogen synergistic flame retardant system. The zinc oxide produced by the decomposition of ZIF-8 can be catalyzed into char, promoting the formation of a dense and expanded char layer, thus achieving dual flame retardancy in both the gas phase and the condensed phase. Furthermore, the flame retardant composite material is uniformly dispersed after pre-emulsification treatment, which can fully exert the synergistic flame retardant effect.

[0082] As shown in Table 1, the LOI retention rate of Examples 1-6 after 1000h of UV aging was higher than that of Comparative Examples 1-3, indicating good weather resistance. This may be because the UV absorber and light stabilizer form a composite weather-resistant system. The UV absorber efficiently absorbs the UV band, and the light stabilizer captures free radicals to inhibit photo-oxidation reaction. At the same time, the ZIF-8 modification reduces the precipitation of flame retardant and avoids damage to the coating structure.

[0083] As shown in Table 1, the flame retardant release rate of Examples 1-6 after 168 hours of hydrothermal aging was lower than that of Comparative Examples 1-3, while the bond strength retention rate was higher than that of Comparative Examples 1-3. This may be because ZIF-8 was used to perform molecular-level coating modification of ammonium polyphosphate. The hydrophobic framework structure of ZIF-8 can effectively block the penetration of water molecules, while zinc ions and NH4+ in the ammonium polyphosphate molecular chain... + The ion exchange effect and the interfacial bonding between ZIF-8 and ammonium polyphosphate enhance the bonding force between the flame retardant and the polymer matrix, inhibit the migration and precipitation of ammonium polyphosphate in a humid and hot environment, and avoid the formation of pores in the coating film due to the migration of flame retardant. In addition, after the flame retardant composite material is pre-emulsified, the charge protection layer formed on the surface further improves its dispersion stability in the system and reduces the risk of local precipitation caused by agglomeration. With the synergistic filling of heavy calcium carbonate and titanium dioxide, the titanium dioxide builds a dense structure in the coating film, which can effectively resist ultraviolet degradation. The three work together to improve the ultraviolet aging performance of liquid roll material.

[0084] It should be noted that, in this document, terms such as “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

[0085] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. A method for preparing a flame-retardant, exposed liquid roll material, characterized in that, Includes the following steps: Step 1: Mix and knead the ZIF-8-loaded ammonium polyphosphate, melamine-formaldehyde resin and vinyl acetate-ethylene copolymer to obtain the flame-retardant composite material; Step 2: Pre-emulsify and disperse the flame-retardant composite material, then combine and shear it with emulsified asphalt to obtain modified emulsified asphalt; Step 3: After dispersing and mixing the fluorocarbon modified acrylic emulsion, functional additives and mixed fillers, add the modified emulsified asphalt with premixed emulsifier, then add rheology thickener, bactericide and pH adjuster and stir evenly to obtain flame-retardant exposed liquid roll material.

2. The method for preparing a flame-retardant exposed liquid roll material according to claim 1, characterized in that, In step one, the mass ratio of the ZIF-8-loaded ammonium polyphosphate, melamine-formaldehyde resin, and vinyl acetate-ethylene copolymer is 4.5-6.5: 21.5-27.5: 74-84.

3. The method for preparing a flame-retardant exposed liquid roll material according to claim 1, characterized in that, The preparation process of the ZIF-8-loaded ammonium polyphosphate is as follows: Ammonium polyphosphate and anhydrous methanol were added to a reaction vessel and ultrasonically dispersed. Zinc nitrate hexahydrate was then added and stirred at 50-55°C for 12-14 hours. 2-methylimidazole and anhydrous methanol were mixed evenly and then added dropwise to the reaction vessel. The mixture was stirred for 30-40 minutes and allowed to stand for 24-26 hours. The mixture was then filtered, washed, and dried to obtain ZIF-8-loaded ammonium polyphosphate.

4. The method for preparing a flame-retardant exposed liquid roll material according to claim 3, characterized in that, The ratio of the amount of ammonium polyphosphate, anhydrous methanol, zinc nitrate hexahydrate and 2-methylimidazole is 20-25g: 200-300mL: 2.22-4.22g: 2.46-4.46g.

5. The method for preparing a flame-retardant exposed liquid roll material according to claim 1, characterized in that, The preparation process of the modified emulsified asphalt in step two is as follows: Add water to the reactor and heat to 60°C. While stirring, add sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, and cellulose ether. Adjust the pH to 11-13. Add an organosilicon defoamer and stir until homogeneous to obtain a soap solution. Pour the soap solution into a colloid mill and shear for 2-4 minutes. Then add 90# base asphalt at 130-140°C and run for 2-4 minutes to obtain emulsified asphalt. Shear the flame-retardant composite material, sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, and water at 1500-2000 r / min for 10-15 minutes. Then add the emulsified asphalt and shear for 5-10 minutes to obtain modified emulsified asphalt.

6. The method for preparing a flame-retardant exposed liquid roll material according to claim 5, characterized in that, The mass ratio of water, sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, cellulose ether, and organosilicon defoamer is 400-500:10-15:2-3:1-2:0.3-0.

4. The mass ratio of the soap solution to 90# base asphalt is 400-500:500-600; The mass ratio of the flame-retardant composite material, sodium secondary alkyl sulfonate, sodium dioctyl sulfosuccinate, water, and emulsified asphalt is 50-100:3-4:1-3:50-60:700-900.

7. The method for preparing a flame-retardant exposed liquid roll material according to claim 1, characterized in that, The functional additives mentioned in step three consist of rheology modifiers, ultraviolet absorbers, light stabilizers, hydrophobic dispersants, and defoamers; The mass ratio of the fluorocarbon modified acrylic emulsion, rheology modifier, ultraviolet absorber, light stabilizer, hydrophobic dispersant, defoamer, and mixed filler is 400-500: 50-60: 10-15: 8-10: 3-5: 3-5: 200-280. The mixed filler is composed of heavy calcium carbonate and titanium dioxide mixed in a mass ratio of 4:

1.

8. The method for preparing a flame-retardant exposed liquid roll material according to claim 1, characterized in that, The mass ratio of the modified emulsified asphalt, rheology thickener, bactericide, and pH adjuster is 200-300:5-6:5-7:2-3:2-3.

9. A flame-retardant exposed liquid roll material, prepared by the preparation method of the flame-retardant exposed liquid roll material according to any one of claims 1-8.

10. The application of the flame-retardant exposed liquid roll material according to claim 9 in waterproofing and flame retardancy of exposed building surfaces.

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