Composite root-resistant waterproofing membrane

Abstract

The present application relates to the technical field of building waterproof material, and discloses a composite layer root penetration resistant waterproof roll material.The present application adopts gradient layering function cooperative design logic, and splits two kinds of functions of root resistance, antibiosis and fire resistance and bonding into two independent modified asphalt layers, the upper layer takes 90# road asphalt and SBS thermoplastic elastomer as a matrix, matches root resistance agent and composite nano antibacterial agent, and specially undertakes root resistance and antibiosis functions, the lower layer takes 10# building asphalt and atactic polypropylene as a matrix, matches graphene loaded composite fire retardant and tackifying resin, and specially undertakes fire resistance and bonding functions.

Description

Technical Field

[0001] This invention relates to the field of building waterproofing materials technology, specifically a composite layer root-penetration resistant waterproof membrane. Background Technology

[0002] With the rapid promotion of sponge city construction and vertical greening projects in my country, the market demand for root-penetration resistant waterproof membranes, as core functional materials for green roofs, underground greening roofs, and ecological slope protection, is increasing year by year. Most existing root-penetration resistant waterproof membranes use modified bitumen as the matrix and add chemical root inhibitors to achieve the function of blocking plant roots from penetrating. However, they still have significant performance shortcomings in complex application scenarios: First, mold erosion is a prominent problem: In the long-term outdoor service environment of rainy and humid southern regions and corrosive de-icing agents in northern regions, ordinary root-penetration resistant waterproof membranes are prone to the growth of mold and algae on the surface, which not only accelerates the aging and cracking of the bitumen matrix, but also leads to the premature precipitation and loss of chemical root inhibitors and functional additives. Second, flame retardant performance is insufficient: The proportion of green roofs in high-rise and super high-rise buildings is increasing year by year, and B1 flame retardant performance has become a mandatory requirement for projects in many places. However, existing flame-retardant root-penetration resistant membranes mostly use small molecule flame retardants, which have poor compatibility with bitumen matrix and are prone to migration and precipitation during long-term use, resulting in the flame retardant rating decaying to below B2, which cannot meet the requirements of fire protection codes. Therefore, developing a root-penetration resistant waterproof membrane that combines long-lasting mildew resistance and high-stability flame retardancy is of great application value for supporting the large-scale promotion of vertical greening projects, improving the service life of waterproofing in municipal and civil buildings, and promoting the technological upgrading of the functional waterproof building materials industry. Summary of the Invention

[0003] To address the shortcomings of existing technologies, this invention provides a composite-layer root-penetration resistant waterproof membrane. The waterproof membrane prepared by this invention exhibits good resistance to mold and flame retardancy.

[0004] To achieve the above objectives, the present invention provides the following technical solution: a composite layer root-penetration resistant waterproof membrane, comprising, from top to bottom: a protective layer, a root-barrier and antibacterial layer, an intermediate reinforcing layer, a flame-retardant adhesive layer, and a release layer; the protective layer is basalt mineral granules; the intermediate reinforcing layer is a polyester base; the release layer is a PE release film; the root-barrier and antibacterial layer comprises the following weight components: 110-130 parts by weight of 90# asphalt, 15-19 parts by weight of SBS thermoplastic elastomer, and 0.5-0.8 parts by weight of 2- (4-Chloro-2-methylphenoxy)propionic acid polyethylene glycol root inhibitor, 2.2-3 parts by weight of composite nano antibacterial agent, 80-100 parts by weight of waste tire rubber powder, and 135-155 parts by weight of heavy calcium carbonate; the flame-retardant adhesive layer comprises the following weight components: 140-160 parts by weight of No. 10 asphalt, 14-16 parts by weight of atactic polypropylene, 9-11 parts by weight of graphene-supported composite flame retardant, 7-9 parts by weight of terpene resin tackifier, and 155-175 parts by weight of heavy calcium carbonate.

[0005] Preferably, the composite nano-antibacterial agent is prepared by the following steps: (1) Add 4.26-4.46 g of 1,1-dimethylguanidine to 20-30 mL of anhydrous ethanol solvent, stir to dissolve, melt 7.36-7.7 g of 6-chlorohexanoic acid in a water bath at 35-40 °C, and add it dropwise to the 1,1-dimethylguanidine solution. Keep the temperature at 30-40 °C during the dropwise addition. After the dropwise addition is complete, react at 20-30 °C for 0.5-1 h. After the reaction is complete, remove the solvent by rotary evaporation and dry under vacuum to obtain the guanidine salt intermediate. (2) Add 1.18-1.58 g of activated halloysite nanotubes to 80-100 mL of anhydrous ethanol solvent, disperse ultrasonically for 10-20 min, evacuate to -0.09--0.06 MPa and maintain for 10-15 min, restore normal pressure and stir for 2-4 min, add 2.2-2.56 g of guanidine salt intermediate, stir to dissolve, purge with nitrogen for protection, add 2.56-2.96 g of triphenylphosphine, stir to dissolve, heat to 82-88℃ and react for 3.5-5.5 h, after the reaction is completed, centrifuge to remove the supernatant, wash and vacuum dry to obtain composite nano antibacterial agent.

[0006] Preferably, the preparation method of activated halloysite nanotubes in step (2) is as follows: 5.8-6g of halloysite nanotubes are added to 40-60mL of 0.8-1.2mol / L hydrochloric acid solution, stirred evenly, ultrasonically dispersed at 30-40℃ for 30-40min, and activated by stirring at 55-65℃ for 2-4h. After activation, the supernatant is centrifuged and washed until the pH value reaches 6.5-7.0, vacuum dried, and ground into powder to obtain activated halloysite nanotubes.

[0007] Preferably, the graphene-supported composite flame retardant is prepared through the following steps: S1. Add 2.1-3.1 g of 3,5-dicarboxyphenylboronic acid pinacol ester and 2.6-3.16 g of 7-aminoquinoline to 30-60 mL of anhydrous ethanol solvent, stir and mix, add 0.1-0.14 g of acetic acid catalyst, heat to 70-80℃ and react for 3-4 h. After the reaction is completed, extract with dichloromethane solvent, combine and wash the organic phases, remove the solvent by rotary evaporation, recrystallize with anhydrous ethanol solvent, filter and vacuum dry to obtain bisquinoline borate intermediate; S2. Add 3.34-4.02 g of bisquinoline borate intermediate and 4.66-4.86 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 40-60 mL of 1,4-dioxane solvent, stir and mix, add 0.01-0.02 g of acid-binding agent, heat to 75-80℃ and react for 5.5-6.5 h. After the reaction is completed, remove the solvent by rotary evaporation, recrystallize with dichloromethane-anhydrous ethanol mixed solvent, filter and vacuum dry to obtain the composite flame retardant; S3. Add 0.5-0.6g of reduced graphene oxide to 80-90mL of N-methylpyrrolidone solvent, ultrasonically disperse for 30-50min, add 5.2-6g of composite flame retardant, stir for 10-20min, purge with nitrogen for protection, heat to 90-100℃, continue stirring for 2-3h, centrifuge to collect the precipitate, wash and vacuum dry to obtain graphene-supported composite flame retardant.

[0008] Preferably, the acid-binding agent in S2 is triethylamine.

[0009] Preferably, the preparation method of the composite layer root-penetration resistant waterproof membrane includes the following steps: Step 1: Add 90# asphalt to the reactor and heat it to 130-140℃ to melt it. Add SBS thermoplastic elastomer, raise the temperature to 175-185℃, shear it at 2500-3500r / min for 25-35min, cool it down to 170-180℃, add 2-(4-chloro-2-methylphenoxy)propionic acid polyethylene glycol root inhibitor, composite nano antibacterial agent, waste tire rubber powder, and heavy calcium carbonate, stir at 400-600r / min for 15-20min, and let it stand at 160-170℃ for 10-15min to degas, to obtain the root-inhibiting and antibacterial layer molten asphalt. Step 2: Add No. 10 asphalt to the reactor and heat it to 140-160℃ to melt it. Add atactic polypropylene and heat it to 185-190℃. Shear it at 2500-3500 r / min for 20-30 min. Cool it down to 175-180℃ and add graphene-supported composite flame retardant, terpene resin tackifier, and heavy calcium carbonate. Stir it at 400-600 r / min for 25-30 min and let it stand at 180-185℃ for 10-15 min to degas it, thus obtaining the flame-retardant adhesive layer molten asphalt. Step 3: The polyester base is placed in a drying oven and dried at 105-110℃. First, a flame-retardant adhesive layer of molten asphalt is applied to the lower surface of the base at 180-190℃, with the thickness controlled to 1.6-2mm by a scraper roller. The base is then cooled to 55-65℃. Next, a root-resistant and antibacterial layer of molten asphalt is applied to the upper surface of the base at 165-175℃, with the thickness controlled to 1.6-2mm by a scraper roller. The upper layer is covered with basalt mineral granules, and the lower layer is covered with PE release film. The base is then sent to a cooling roller group for air cooling to room temperature, with the cooling rate controlled at 4-6℃ / min. This yields a composite layer root-penetration resistant waterproof membrane.

[0010] In summary, this application includes at least one of the following beneficial technical effects: This invention employs a gradient layered functional synergistic design logic, separating the two functions of root-barrier antibacterial and flame-retardant bonding into two independent modified asphalt layers. The upper layer uses 90# road asphalt and SBS thermoplastic elastomer as the matrix, and is matched with root-barrier agents and composite nano antibacterial agents, specifically undertaking the functions of root-barrier and antibacterial. The lower layer uses 10# building asphalt and atactic polypropylene as the matrix, and is matched with graphene-loaded composite flame retardants and tackifying resins, specifically undertaking the functions of flame retardant and bonding.

[0011] Activated halloysite has a hollow, porous tubular structure. Guanidoyl and quaternary phosphonium salt active ingredients are anchored on its surface and within its internal pores through in-situ synthesis. On one hand, it can form a good inorganic-organic interface with the asphalt matrix, preventing the active ingredients from migrating and precipitating onto the membrane surface. On the other hand, halloysite's strong adsorption properties can actively capture bacterial and fungal spores from the surrounding environment, enriching them on the antibacterial agent surface and improving inactivation efficiency. Guanidoyl groups carry a strong positive charge, while the phospholipids and proteins on the cell membranes of bacteria and fungi carry a negative charge. After rapid adsorption through electrostatic interaction, the guanidoyl group can directly insert into the phospholipid bilayer structure of the cell membrane, disrupting cell membrane permeability and causing bacterial death. After the guanidoyl group disrupts the cell membrane integrity, the quaternary phosphonium salt can quickly penetrate the cell membrane and enter the cell, binding to active proteins such as proteases and ATPases, inhibiting normal bacterial metabolism and thus improving the mildew resistance of the waterproof membrane. The organic flame retardant in the composite flame retardant... The unit is non-covalently loaded onto the surface of the reduced graphene oxide two-dimensional sheet through π-π stacking and hydrogen bonding. This not only avoids destroying the active flame-retardant sites of the two materials themselves, but also prevents the reduced graphene oxide from agglomerating in the asphalt matrix, improving compatibility with asphalt and reducing the release rate of flame retardants. During combustion, the phosphoranthrophenone group of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide decomposes first upon heating, releasing phosphorus-oxygen free radicals, which can quickly capture free radicals in the combustion gas phase region and directly interrupt the energy transfer path of the flame. At the same time, the decomposition of the nitrogen-containing heterocyclic structure of the quinoline group releases inert gases such as nitrogen and ammonia, diluting the concentration of oxygen in the gas phase region and flammable hydrocarbons released by the thermal decomposition of asphalt, thus inhibiting the spread of flame. The boron trioxide glassy molten layer generated by the decomposition of boron esters is embedded in the polypyrophosphate carbon layer generated by the phosphorus component, filling the pores and cracks in the carbon layer, forming a double-layer dense barrier structure of boron-phosphorus composite glass phase-carbon layer, which improves the flame retardant performance of the waterproof membrane. Attached Figure Description

[0012] Figure 1 It is the synthesis reaction formula for guanidine salt intermediates.

[0013] Figure 2 This is a schematic diagram of the preparation process of composite nano-antibacterial agents.

[0014] Figure 3 It is the synthesis reaction formula for composite flame retardants. Detailed Implementation

[0015] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0016] To better understand the above technical solutions, the following will provide a detailed description of the technical solutions in conjunction with the accompanying drawings and specific embodiments.

[0017] Example 1: (1) Add 4.26 g of 1,1-dimethylguanidine to 20 mL of anhydrous ethanol solvent and stir to dissolve. Melt 7.36 g of 6-chlorohexanoic acid in a 35 °C water bath and add it dropwise to the 1,1-dimethylguanidine solution. Maintain the temperature at 30 °C during the dropwise addition. After the dropwise addition is complete, react at 20 °C for 0.5 h. After the reaction is complete, remove the solvent by rotary evaporation and dry under vacuum to obtain the guanidine salt intermediate. The synthesis reaction formula is as follows: Figure 1 As shown; (2) Add 5.8 g of halloysite nanotubes to 40 mL of 0.8 mol / L hydrochloric acid solution, stir evenly, ultrasonically disperse at 30 °C for 30 min, and activate by stirring at 55 °C for 2 h. After activation, centrifuge and wash with deionized water until the pH of the supernatant reaches 6.5, vacuum dry, grind into powder to obtain activated halloysite nanotubes. Add 1.18 g of activated halloysite nanotubes to 80 mL of anhydrous ethanol solvent, ultrasonically disperse for 10 min, evacuate to -0.09 MPa and maintain for 10 min, restore normal pressure and stir for 2 min, add 2.2 g of guanidine salt intermediate, stir to dissolve, purge with nitrogen gas for protection, add 2.56 g of triphenylphosphine, stir to dissolve, heat to 82 °C and react for 3.5 h. After the reaction, centrifuge to remove the supernatant, wash and vacuum dry to obtain composite nano antibacterial agent; the preparation process diagram is shown below. Figure 2 As shown; (3) Add 2.1 g of 3,5-dicarboxyphenylboronic acid pinacol ester and 2.6 g of 7-aminoquinoline to 30 mL of anhydrous ethanol solvent, stir and mix, add 0.1 g of acetic acid catalyst, heat to 70 °C and react for 3 h. After the reaction is completed, extract with dichloromethane solvent, combine and wash the organic phases, remove the solvent by rotary evaporation, recrystallize with anhydrous ethanol solvent, filter and vacuum dry to obtain bisquinoline borate intermediate; (4) Add 3.34 g of bisquinoline borate intermediate and 4.66 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 40 mL of 1,4-dioxane solvent, stir and mix, add 0.01 g of triethylamine acid-binding agent, heat to 75 °C and react for 5.5 h. After the reaction is complete, remove the solvent by rotary evaporation, recrystallize with a dichloromethane-anhydrous ethanol mixed solvent, filter and vacuum dry to obtain the composite flame retardant; the synthesis reaction formula is as follows Figure 3 As shown; (5) Add 0.5g of reduced graphene oxide to 80mL of N-methylpyrrolidone solvent, sonicate for 30min, add 5.2g of composite flame retardant, stir for 10min, purge with nitrogen for protection, heat to 90℃, continue stirring for 2h, centrifuge to collect the precipitate, wash and vacuum dry to obtain graphene-supported composite flame retardant. (6) 110 parts by weight of 90# asphalt was put into the reactor and heated to 130°C to melt. 15 parts by weight of SBS thermoplastic elastomer were added to it. The temperature was raised to 175°C and sheared at 2500 r / min for 25 min. The temperature was lowered to 170°C and 0.5 parts by weight of 2-(4-chloro-2-methylphenoxy)propionic acid polyethylene glycol root inhibitor, 2.2 parts by weight of composite nano antibacterial agent, 80 parts by weight of waste tire rubber powder, and 135 parts by weight of heavy calcium carbonate were added. The mixture was stirred at 400 r / min for 15 min and allowed to stand at 160°C for 10 min to degas, so as to obtain the root-inhibiting and antibacterial layer melted asphalt. (7) 140 parts by weight of No. 10 asphalt was put into the reactor and heated to 140°C to melt. 14 parts by weight of random polypropylene were added to it. The temperature was raised to 185°C and sheared at 2500 r / min for 20 min. The temperature was lowered to 175°C and 9 parts by weight of graphene-supported composite flame retardant, 7 parts by weight of terpene resin tackifier, and 155 parts by weight of heavy calcium carbonate were added. The mixture was stirred at 400 r / min for 25 min and allowed to stand at 180°C for 10 min to degas, so as to obtain the flame-retardant adhesive layer melted asphalt. (8) The polyester base is sent into the drying oven and dried at 105°C. First, the flame-retardant adhesive layer molten asphalt is dipped and coated on the lower surface of the base at 180°C. The thickness is controlled to be 1.6 mm by the scraper roller. It is cooled to 55°C. Then, the root-resistant and antibacterial layer molten asphalt is dipped and coated on the upper surface of the base at 165°C. The thickness is controlled to be 1.6 mm by the scraper roller. The upper layer is covered with basalt mineral granules, and the lower layer is covered with PE release film. It is sent into the cooling roller group for air cooling to room temperature. The cooling rate is controlled to be 4°C / min to obtain the composite layer root-penetration resistant waterproof membrane.

[0018] Example 2: (1) Add 4.46 g of 1,1-dimethylguanidine to 30 mL of anhydrous ethanol solvent and stir to dissolve. Melt 7.7 g of 6-chlorohexanoic acid in a 40 °C water bath and add it dropwise to the 1,1-dimethylguanidine solution. Maintain the temperature at 40 °C during the dropwise addition. After the dropwise addition is complete, react at 30 °C for 1 h. After the reaction is complete, remove the solvent by rotary evaporation and dry under vacuum to obtain the guanidine salt intermediate. The synthesis reaction formula is as follows: Figure 1 As shown; (2) Add 6g of halloysite nanotubes to 60mL of 1.2mol / L hydrochloric acid solution, stir evenly, ultrasonically disperse at 40℃ for 40min, and activate by stirring at 65℃ for 4h. After activation, centrifuge and wash with deionized water until the pH of the supernatant reaches 7.0, vacuum dry, grind into powder to obtain activated halloysite nanotubes. Add 1.58g of activated halloysite nanotubes to 100mL of anhydrous ethanol solvent, ultrasonically disperse for 20min, evacuate to -0.06MPa and maintain for 15min, restore normal pressure and stir for 4min, add 2.56g of guanidine salt intermediate, stir to dissolve, purge with nitrogen gas for protection, add 2.96g of triphenylphosphine, stir to dissolve, heat to 88℃ and react for 5.5h. After the reaction, centrifuge to remove the supernatant, wash and vacuum dry to obtain composite nano antibacterial agent; the preparation process diagram is shown below. Figure 2 As shown; (3) Add 3.1g of 3,5-dicarboxyphenylboronic acid pinacol ester and 3.16g of 7-aminoquinoline to 60mL of anhydrous ethanol solvent, stir and mix, add 0.14g of acetic acid catalyst, heat to 80℃ and react for 4h. After the reaction is completed, extract with dichloromethane solvent, combine and wash the organic phases, remove the solvent by rotary evaporation, recrystallize with anhydrous ethanol solvent, filter and vacuum dry to obtain bisquinoline borate intermediate; (4) Add 4.02 g of bisquinoline borate intermediate and 4.86 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 60 mL of 1,4-dioxane solvent, stir and mix, add 0.02 g of triethylamine acid-binding agent, heat to 80 °C and react for 6.5 h. After the reaction is complete, remove the solvent by rotary evaporation, recrystallize with a dichloromethane-anhydrous ethanol mixed solvent, filter and vacuum dry to obtain the composite flame retardant; the synthesis reaction formula is as follows Figure 3 As shown; (5) Add 0.6g of reduced graphene oxide to 90mL of N-methylpyrrolidone solvent, ultrasonically disperse for 50min, add 6g of composite flame retardant, stir for 20min, purge with nitrogen for protection, heat to 100℃, continue stirring for 3h, centrifuge to collect the precipitate, wash and vacuum dry to obtain graphene-supported composite flame retardant. (6) 130 parts by weight of 90# asphalt was put into the reactor and heated to 140°C to melt. 19 parts by weight of SBS thermoplastic elastomer were added to it. The temperature was raised to 185°C and sheared at 3500 r / min for 35 min. The temperature was lowered to 180°C and 0.8 parts by weight of 2-(4-chloro-2-methylphenoxy)propionic acid polyethylene glycol root inhibitor, 3 parts by weight of composite nano antibacterial agent, 100 parts by weight of waste tire rubber powder, and 155 parts by weight of heavy calcium carbonate were added. The mixture was stirred at 600 r / min for 20 min and allowed to stand at 170°C for 15 min to degas, so as to obtain the root-inhibiting and antibacterial layer melted asphalt. (7) 160 parts by weight of No. 10 asphalt was put into the reactor and heated to 160°C to melt. 16 parts by weight of random polypropylene were added to it. The temperature was raised to 190°C and sheared at 3500 r / min for 30 min. The temperature was lowered to 180°C and 11 parts by weight of graphene-supported composite flame retardant, 9 parts by weight of terpene resin tackifier, and 175 parts by weight of heavy calcium carbonate were added. The mixture was stirred at 600 r / min for 30 min and allowed to stand at 185°C for 15 min to degas, so as to obtain the flame-retardant adhesive layer melted asphalt. (8) The polyester base is sent into the drying oven and dried at 110°C. First, the flame-retardant adhesive layer molten asphalt is dipped and coated on the lower surface of the base at 190°C. The thickness is controlled to be 2mm by the scraper roller. It is cooled to 65°C. Then, the root-resistant and antibacterial layer molten asphalt is dipped and coated on the upper surface of the base at 175°C. The thickness is controlled to be 2mm by the scraper roller. The upper layer is covered with basalt mineral granules, and the lower layer is covered with PE release film. It is sent into the cooling roller group for air cooling to room temperature. The cooling rate is controlled to be 6°C / min to obtain the composite layer root-penetration resistant waterproof membrane.

[0019] Example 3: (1) Add 4.36 g of 1,1-dimethylguanidine to 25 mL of anhydrous ethanol solvent and stir to dissolve. Melt 7.53 g of 6-chlorohexanoic acid in a 38 °C water bath and add it dropwise to the 1,1-dimethylguanidine solution. Maintain the temperature at 35 °C during the dropwise addition. After the dropwise addition is complete, react at 25 °C for 0.8 h. After the reaction is complete, remove the solvent by rotary evaporation and dry under vacuum to obtain the guanidine salt intermediate. The synthesis reaction formula is as follows: Figure 1 As shown; (2) Add 5.9 g of halloysite nanotubes to 50 mL of 1 mol / L hydrochloric acid solution, stir evenly, ultrasonically disperse at 35 °C for 35 min, and activate by stirring at 60 °C for 3 h. After activation, centrifuge and wash with deionized water until the pH of the supernatant reaches 6.8, vacuum dry, grind into powder to obtain activated halloysite nanotubes. Add 1.38 g of activated halloysite nanotubes to 90 mL of anhydrous ethanol solvent, ultrasonically disperse for 15 min, evacuate to -0.08 MPa and maintain for 12 min, restore normal pressure and stir for 3 min, add 2.38 g of guanidine salt intermediate, stir to dissolve, purge with nitrogen gas for protection, add 2.76 g of triphenylphosphine, stir to dissolve, heat to 85 °C and react for 4.5 h. After the reaction, centrifuge to remove the supernatant, wash and vacuum dry to obtain composite nano antibacterial agent; the preparation process diagram is shown below. Figure 2 As shown; (3) Add 2.6 g of 3,5-dicarboxyphenylboronic acid pinacol ester and 2.88 g of 7-aminoquinoline to 45 mL of anhydrous ethanol solvent, stir and mix, add 0.12 g of acetic acid catalyst, heat to 75 °C and react for 3.5 h. After the reaction is completed, extract with dichloromethane solvent, combine and wash the organic phases, remove the solvent by rotary evaporation, recrystallize with anhydrous ethanol solvent, filter and vacuum dry to obtain bisquinoline borate intermediate; (4) Add 3.68 g of bisquinoline borate intermediate and 4.76 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 50 mL of 1,4-dioxane solvent, stir and mix, add 0.015 g of triethylamine acid-binding agent, heat to 78 °C and react for 6 h. After the reaction is complete, remove the solvent by rotary evaporation, recrystallize with a dichloromethane-anhydrous ethanol mixed solvent, filter and vacuum dry to obtain the composite flame retardant; the synthesis reaction formula is as follows Figure 3 As shown; (5) Add 0.55g of reduced graphene oxide to 85mL of N-methylpyrrolidone solvent, ultrasonically disperse for 40min, add 5.6g of composite flame retardant, stir for 15min, purge with nitrogen for protection, heat to 95℃, continue stirring for 2.5h, centrifuge to collect the precipitate, wash and vacuum dry to obtain graphene-supported composite flame retardant; (6) 120 parts by weight of 90# asphalt was put into the reactor and heated to 135°C to melt. 17 parts by weight of SBS thermoplastic elastomer were added to it. The temperature was raised to 180°C and sheared at 3000 r / min for 30 min. The temperature was lowered to 175°C and 0.65 parts by weight of 2-(4-chloro-2-methylphenoxy)propionic acid polyethylene glycol root inhibitor, 2.6 parts by weight of composite nano antibacterial agent, 90 parts by weight of waste tire rubber powder, and 145 parts by weight of heavy calcium carbonate were added. The mixture was stirred at 500 r / min for 18 min and allowed to stand at 165°C for 12 min to degas, thus obtaining the root-inhibiting and antibacterial layer molten asphalt. (7) 150 parts by weight of No. 10 asphalt was put into the reactor and heated to 150°C to melt. 15 parts by weight of random polypropylene were added to it. The temperature was raised to 188°C and sheared at 3000 r / min for 25 min. The temperature was lowered to 178°C and 10 parts by weight of graphene-supported composite flame retardant, 8 parts by weight of terpene resin tackifier, and 165 parts by weight of heavy calcium carbonate were added. The mixture was stirred at 500 r / min for 28 min and allowed to stand at 182°C for 12 min to degas, so as to obtain the flame-retardant adhesive layer melted asphalt. (8) The polyester base is sent into the drying oven and dried at 108°C. First, the flame-retardant adhesive layer molten asphalt is dipped and coated on the lower surface of the base at 185°C. The thickness is controlled to be 1.8 mm by the scraper roller. It is cooled to 60°C. Then, the root-resistant and antibacterial layer molten asphalt is dipped and coated on the upper surface of the base at 170°C. The thickness is controlled to be 1.8 mm by the scraper roller. The upper layer is covered with basalt mineral granules, and the lower layer is covered with PE release film. It is sent into the cooling roller group for air cooling to room temperature. The cooling rate is controlled to be 5°C / min to obtain the composite layer root-penetration resistant waterproof membrane.

[0020] Example 4: (1) Add 4.26 g of 1,1-dimethylguanidine to 20 mL of anhydrous ethanol solvent and stir to dissolve. Melt 7.36 g of 6-chlorohexanoic acid in a 35 °C water bath and add it dropwise to the 1,1-dimethylguanidine solution. Maintain the temperature at 30 °C during the dropwise addition. After the dropwise addition is complete, react at 20 °C for 0.5 h. After the reaction is complete, remove the solvent by rotary evaporation and dry under vacuum to obtain the guanidine salt intermediate. The synthesis reaction formula is as follows: Figure 1 As shown; (2) Add 5.8 g of halloysite nanotubes to 40 mL of 0.8 mol / L hydrochloric acid solution, stir evenly, ultrasonically disperse at 30 °C for 30 min, and activate by stirring at 55 °C for 2 h. After activation, centrifuge and wash with deionized water until the pH of the supernatant reaches 6.5, vacuum dry, grind into powder to obtain activated halloysite nanotubes. Add 1.18 g of activated halloysite nanotubes to 80 mL of anhydrous ethanol solvent, ultrasonically disperse for 10 min, evacuate to -0.09 MPa and maintain for 10 min, restore normal pressure and stir for 2 min, add 2.2 g of guanidine salt intermediate, stir to dissolve, purge with nitrogen gas for protection, add 2.56 g of triphenylphosphine, stir to dissolve, heat to 82 °C and react for 3.5 h. After the reaction, centrifuge to remove the supernatant, wash and vacuum dry to obtain composite nano antibacterial agent; the preparation process diagram is shown below. Figure 2 As shown; (3) Add 3.1g of 3,5-dicarboxyphenylboronic acid pinacol ester and 3.16g of 7-aminoquinoline to 60mL of anhydrous ethanol solvent, stir and mix, add 0.14g of acetic acid catalyst, heat to 80℃ and react for 4h. After the reaction is completed, extract with dichloromethane solvent, combine and wash the organic phases, remove the solvent by rotary evaporation, recrystallize with anhydrous ethanol solvent, filter and vacuum dry to obtain bisquinoline borate intermediate; (4) Add 4.02 g of bisquinoline borate intermediate and 4.86 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 60 mL of 1,4-dioxane solvent, stir and mix, add 0.02 g of triethylamine acid-binding agent, heat to 80 °C and react for 6.5 h. After the reaction is complete, remove the solvent by rotary evaporation, recrystallize with a dichloromethane-anhydrous ethanol mixed solvent, filter and vacuum dry to obtain the composite flame retardant; the synthesis reaction formula is as follows Figure 3 As shown; (5) Add 0.6g of reduced graphene oxide to 90mL of N-methylpyrrolidone solvent, ultrasonically disperse for 50min, add 6g of composite flame retardant, stir for 20min, purge with nitrogen for protection, heat to 100℃, continue stirring for 3h, centrifuge to collect the precipitate, wash and vacuum dry to obtain graphene-supported composite flame retardant. (6) 120 parts by weight of 90# asphalt was put into the reactor and heated to 135°C to melt. 17 parts by weight of SBS thermoplastic elastomer were added to it. The temperature was raised to 180°C and sheared at 3000 r / min for 30 min. The temperature was lowered to 175°C and 0.65 parts by weight of 2-(4-chloro-2-methylphenoxy)propionic acid polyethylene glycol root inhibitor, 2.6 parts by weight of composite nano antibacterial agent, 90 parts by weight of waste tire rubber powder, and 145 parts by weight of heavy calcium carbonate were added. The mixture was stirred at 500 r / min for 18 min and allowed to stand at 165°C for 12 min to degas, thus obtaining the root-inhibiting and antibacterial layer molten asphalt. (7) 150 parts by weight of No. 10 asphalt was put into the reactor and heated to 150°C to melt. 15 parts by weight of random polypropylene were added to it. The temperature was raised to 188°C and sheared at 3000 r / min for 25 min. The temperature was lowered to 178°C and 10 parts by weight of graphene-supported composite flame retardant, 8 parts by weight of terpene resin tackifier, and 165 parts by weight of heavy calcium carbonate were added. The mixture was stirred at 500 r / min for 28 min and allowed to stand at 182°C for 12 min to degas, so as to obtain the flame-retardant adhesive layer melted asphalt. (8) The polyester base is sent into the drying oven and dried at 108°C. First, the flame-retardant adhesive layer molten asphalt is dipped and coated on the lower surface of the base at 185°C. The thickness is controlled to be 1.8 mm by the scraper roller. It is cooled to 60°C. Then, the root-resistant and antibacterial layer molten asphalt is dipped and coated on the upper surface of the base at 170°C. The thickness is controlled to be 1.8 mm by the scraper roller. The upper layer is covered with basalt mineral granules, and the lower layer is covered with PE release film. It is sent into the cooling roller group for air cooling to room temperature. The cooling rate is controlled to be 5°C / min to obtain the composite layer root-penetration resistant waterproof membrane.

[0021] Comparative Example 1 The difference between this comparative example and Example 4 is that it does not include steps (1) and (2), and does not include the composite nano antibacterial agent in step (6).

[0022] Comparative Example 2 The difference between this comparative example and Example 4 is that it does not include steps (3), (4), and (5), and does not include graphene-supported composite flame retardant in step (7).

[0023] The flame retardancy rating of the composite root-penetration resistant waterproof membranes in Examples 1-4 and Comparative Examples 1-2 was tested according to GB8624-2012. The test results are shown in Table 1.

[0024] Table 1: Flame retardancy rating test.

[0025]

[0026] As shown in Table 1, the composite layer root-penetration resistant waterproof membranes in Examples 1-4 and Comparative Example 1 have better flame-retardant properties than the composite layer root-penetration resistant waterproof membrane in Comparative Example 2.

[0027] The root-penetration resistant waterproof membranes in Examples 1-4 and Comparative Examples 1-2 were tested for mildew resistance according to GB / T1741-2007. The test results are shown in Table 2.

[0028] Table 2: Mold Resistance Level Test.

[0029]

[0030] As shown in Table 2, the composite layer root-penetration resistant waterproof membranes in Examples 1-4 and Comparative Example 2 of the present invention have better anti-mildew properties compared with the composite layer root-penetration resistant waterproof membrane in Comparative Example 1.

[0031] It should be noted that, in this document, the terms "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. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0032] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0033] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. A composite layer root-penetration resistant waterproof membrane, characterized in that, From top to bottom, it comprises: a protective layer, a root-barrier and antibacterial layer, an intermediate reinforcing layer, a flame-retardant adhesive layer, and a release layer; the protective layer is basalt mineral granules, the intermediate reinforcing layer is polyester base, and the release layer is PE release film; the root-barrier and antibacterial layer comprises the following weight components: 110-130 parts by weight of 90# asphalt, 15-19 parts by weight of SBS thermoplastic elastomer, and 0.5-0.8 parts by weight of 2-(4-chloro-2-methylphenoxy)propionic acid polyethylene. The composition includes: glycol ester root inhibitor, 2.2-3 parts by weight of composite nano antibacterial agent, 80-100 parts by weight of waste tire rubber powder, and 135-155 parts by weight of heavy calcium carbonate; the flame-retardant adhesive layer comprises the following components by weight: 140-160 parts by weight of 10# asphalt, 14-16 parts by weight of atactic polypropylene, 9-11 parts by weight of graphene-supported composite flame retardant, 7-9 parts by weight of terpene resin tackifier, and 155-175 parts by weight of heavy calcium carbonate.

2. The composite layer root-penetration resistant waterproof membrane according to claim 1, characterized in that, The composite nano-antibacterial agent is prepared through the following steps: (1) Add 4.26-4.46 g of 1,1-dimethylguanidine to 20-30 mL of anhydrous ethanol solvent, stir to dissolve, melt 7.36-7.7 g of 6-chlorohexanoic acid in a water bath at 35-40 °C, and add it dropwise to the 1,1-dimethylguanidine solution. Keep the temperature at 30-40 °C during the dropwise addition. After the dropwise addition is complete, react at 20-30 °C for 0.5-1 h. After the reaction is complete, remove the solvent by rotary evaporation and dry under vacuum to obtain the guanidine salt intermediate. (2) Add 1.18-1.58 g of activated halloysite nanotubes to 80-100 mL of anhydrous ethanol solvent, disperse ultrasonically for 10-20 min, evacuate to -0.09--0.06 MPa and maintain for 10-15 min, restore normal pressure and stir for 2-4 min, add 2.2-2.56 g of guanidine salt intermediate, stir to dissolve, purge with nitrogen for protection, add 2.56-2.96 g of triphenylphosphine, stir to dissolve, heat to 82-88℃ and react for 3.5-5.5 h, after the reaction is completed, centrifuge to remove the supernatant, wash and vacuum dry to obtain composite nano antibacterial agent.

3. The composite layer root-penetration resistant waterproof membrane according to claim 2, characterized in that, The preparation method of activated halloysite nanotubes in step (2) is as follows: 5.8-6g of halloysite nanotubes are added to 40-60mL of 0.8-1.2mol / L hydrochloric acid solution, stirred evenly, ultrasonically dispersed at 30-40℃ for 30-40min, and activated by stirring at 55-65℃ for 2-4h. After activation, the supernatant is centrifuged and washed until the pH value reaches 6.5-7.0, vacuum dried, and ground into powder to obtain activated halloysite nanotubes.

4. The composite layer root-penetration resistant waterproof membrane according to claim 1, characterized in that, The graphene-supported composite flame retardant is prepared through the following steps: S1. Add 2.1-3.1 g of 3,5-dicarboxyphenylboronic acid pinacol ester and 2.6-3.16 g of 7-aminoquinoline to 30-60 mL of anhydrous ethanol solvent, stir and mix, add 0.1-0.14 g of acetic acid catalyst, heat to 70-80℃ and react for 3-4 h. After the reaction is completed, extract with dichloromethane solvent, combine and wash the organic phases, remove the solvent by rotary evaporation, recrystallize with anhydrous ethanol solvent, filter and vacuum dry to obtain bisquinoline borate intermediate; S2. Add 3.34-4.02 g of bisquinoline borate intermediate and 4.66-4.86 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 40-60 mL of 1,4-dioxane solvent, stir and mix, add 0.01-0.02 g of acid-binding agent, heat to 75-80℃ and react for 5.5-6.5 h. After the reaction is completed, remove the solvent by rotary evaporation, recrystallize with dichloromethane-anhydrous ethanol mixed solvent, filter and vacuum dry to obtain the composite flame retardant; S3. Add 0.5-0.6g of reduced graphene oxide to 80-90mL of N-methylpyrrolidone solvent, ultrasonically disperse for 30-50min, add 5.2-6g of composite flame retardant, stir for 10-20min, purge with nitrogen for protection, heat to 90-100℃, continue stirring for 2-3h, centrifuge to collect the precipitate, wash and vacuum dry to obtain graphene-supported composite flame retardant.

5. The composite layer root-penetration resistant waterproof membrane according to claim 4, characterized in that, The acid-binding agent in S2 is triethylamine.

6. A method for preparing a composite layer root-penetration resistant waterproof membrane as described in any one of claims 1-5, characterized in that, Includes the following steps: Step 1: Add 90# asphalt to the reactor and heat it to 130-140℃ to melt it. Add SBS thermoplastic elastomer, raise the temperature to 175-185℃, shear it at 2500-3500r / min for 25-35min, cool it down to 170-180℃, add 2-(4-chloro-2-methylphenoxy)propionic acid polyethylene glycol root inhibitor, composite nano antibacterial agent, waste tire rubber powder, and heavy calcium carbonate, stir at 400-600r / min for 15-20min, and let it stand at 160-170℃ for 10-15min to degas, to obtain the root-inhibiting and antibacterial layer molten asphalt. Step 2: Add No. 10 asphalt to the reactor and heat it to 140-160℃ to melt it. Add atactic polypropylene and heat it to 185-190℃. Shear it at 2500-3500 r / min for 20-30 min. Cool it down to 175-180℃ and add graphene-supported composite flame retardant, terpene resin tackifier, and heavy calcium carbonate. Stir it at 400-600 r / min for 25-30 min and let it stand at 180-185℃ for 10-15 min to degas it, thus obtaining the flame-retardant adhesive layer molten asphalt. Step 3: The polyester base is placed in a drying oven and dried at 105-110℃. First, a flame-retardant adhesive layer of molten asphalt is applied to the lower surface of the base at 180-190℃, with the thickness controlled to 1.6-2mm by a scraper roller. The base is then cooled to 55-65℃. Next, a root-resistant and antibacterial layer of molten asphalt is applied to the upper surface of the base at 165-175℃, with the thickness controlled to 1.6-2mm by a scraper roller. The upper layer is covered with basalt mineral granules, and the lower layer is covered with PE release film. The base is then sent to a cooling roller group for air cooling to room temperature, with the cooling rate controlled at 4-6℃ / min. This yields a composite layer root-penetration resistant waterproof membrane.

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