Root-puncture-resistant pre-laid waterproof coiled material coated with glue on back and preparation method of root-puncture-resistant pre-laid waterproof coiled material
By constructing a dual root barrier of chemical and physical components using improved biological root inhibitors, the problems of root penetration, chemical erosion, and physical damage in root-penetration resistant pre-laid waterproof membranes with adhesive backing were solved, resulting in a highly efficient, environmentally friendly, and durable waterproof membrane that improves the waterproof performance and service life of the material.
Patent Information
- Application Number
- CN202511712671.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-20
- Publication Date
- 2026-02-17
AI Technical Summary
Adhesive-backed, root-penetration-resistant pre-laid waterproof membranes face problems such as plant root penetration, chemical corrosion, physical damage, and poor waterproofing performance, leading to water penetration, structural damage, and increased maintenance costs.
A modified biological root barrier agent was used to construct a dual chemical and physical root barrier by combining a nano-copper-β-cyclodextrin complex with a bio-based polyurethane elastomer and a copper ion-diatomite complex. The antibacterial properties and root-repelling effect of the material were enhanced by combining nano-zinc oxide and azadirachtin extract. The properties of the complex were optimized by melt blending and heat treatment.
It achieves high-efficiency root barrier, environmental protection and durability, with excellent elastic recovery performance and biodegradability, reducing environmental impact, maintaining long-term stability and waterproof performance, and reducing harm to health and the environment.
Smart Images
Figure CN121536064A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of waterproof membrane production technology, specifically to a root-penetration resistant pre-laid waterproof membrane with adhesive backing and its preparation method. Background Technology
[0002] Adhesive-backed, root-penetration-resistant pre-laid waterproof membrane is a building material with dual functions of waterproofing and root-penetration prevention. It has an adhesive coating on the back to improve the adhesion between the membrane and the substrate, ensuring the stability of the membrane. Through special treatment, this membrane can effectively prevent plant roots from penetrating and is widely used in places such as roof greening and flower beds where root intrusion needs to be prevented.
[0003] Adhesive-backed, root-penetration-resistant pre-applied waterproof membranes face multiple challenges in green roof applications: plant roots may penetrate the membrane, causing water seepage; secondly, long-term exposure to harsh environments such as chemicals, acids, alkalis, salts, and moisture can easily lead to aging and failure of the membrane; external impacts or temperature changes can cause the membrane to stretch and shrink, exacerbating physical damage; at the same time, traditional waterproof membranes have poor waterproofing performance, leading to water seepage, structural damage, and increased maintenance costs, seriously affecting the safety and service life of buildings.
[0004] Therefore, the present invention provides a root-penetration resistant pre-laid waterproof membrane with backing and its preparation method to solve the aforementioned technical problems. Summary of the Invention
[0005] The purpose of this invention is to provide a root-penetration-resistant pre-laid waterproof membrane with adhesive backing and its preparation method. The root-penetration-resistant layer of the prepared adhesive-backed root-penetration-resistant pre-laid waterproof membrane integrates high-efficiency root inhibition and green environmental protection through a modified biological root inhibitor. It achieves precise root inhibition through a dual physical and chemical root inhibition synergistic mechanism. It has excellent durability, corrosion resistance, and elastic recovery performance, supports recycling, and has high biodegradability, complying with international environmental regulations. In addition, it has the effect of low toxicity residue and strong long-term stability, making it more environmentally friendly and safer, and can maintain good performance during long-term use, reducing the impact on the environment and health.
[0006] To achieve the above objectives, the present invention provides the following technical solution: A type of pre-laid waterproof membrane with adhesive backing and root penetration resistance includes a substrate layer and a root penetration resistance layer. A self-adhesive layer is fixedly connected to the top of the root penetration resistance layer, and a protective layer is provided on the top of the self-adhesive layer. Furthermore, the substrate layer is selected from either a polyester fiber layer or a glass fiber layer; the self-adhesive layer is selected from either a thermoplastic rubber layer, a polypropylene modified layer, or a synthetic rubber layer; and the protective layer is selected from either a polyethylene film layer, a polypropylene film layer, or a thin steel plate layer.
[0007] The thickness of the substrate layer is 0.8–1.5 mm, the thickness of the root penetration resistant layer is 0.3–1 mm, the thickness of the self-adhesive layer is 1–2 mm, and the thickness of the protective layer is 0.1–0.3 mm.
[0008] Furthermore, the substrate layer is preferably a polyester fiber layer with a thickness of 1 mm; the root penetration resistant layer has a thickness of 0.5 mm; the self-adhesive layer is preferably a thermoplastic rubber layer with a thickness of 1.5 mm; and the protective layer is preferably a polyethylene film layer with a thickness of 0.2 mm.
[0009] The root-penetration resistant layer is made of the following raw materials in parts by weight: 40-50 parts high-density polyethylene, 3-5 parts polyvinyl chloride, 10-20 parts maleic anhydride-grafted polyethylene, 5-15 parts bio-based polyurethane elastomer, 10-12 parts nano clay, 3-7 parts nano zinc oxide, 10-15 parts bio-root inhibitor and 3-9 parts chopped glass fiber. It should be noted that the high-density polyethylene is produced by Hebei Luxin Plastic Products Co., Ltd., the polyvinyl chloride can be sourced from Nanjing Milan New Materials Co., Ltd., the maleic anhydride-grafted polyethylene is purchased from Keais Chemical Co., Ltd., and the chopped glass fiber is produced by Cangzhou Zhongli New Materials Technology Co., Ltd. The method for preparing the root-penetration-resistant layer is as follows: High-density polyethylene and polyvinyl chloride are dry-mixed, and maleic anhydride-grafted polyethylene is added to obtain an adhesive. Bio-based polyurethane elastomer is added to the adhesive and mixed. After mixing, nano-adhesive and nano-zinc oxide are added to obtain a composite material. The composite raw material is fed into an extruder and melt-treated at a temperature of 180–220°C. Short glass fibers are added during the extrusion process to obtain the composite material, which is then made into a film using a blown film process. The bio-root barrier agent is coated onto the surface of the film using an impregnation process, and then dried and cured to obtain a root-penetration resistant layer.
[0010] Furthermore, the preparation method of the biological root inhibitor includes the following steps: A1: Copper chloride dihydrate, β-cyclodextrin, surfactant, and deionized water were mixed in a mass ratio of 0.15–0.20:0.5–0.9:0.03–0.05:8–10 and stirred in a water bath at 55–65°C. During stirring, 0.032–0.048 g / mL sodium hydroxide solution was added to adjust the pH to 8.0–8.5 to obtain a microemulsion. The microemulsion was then centrifuged for 10–20 min to collect the precipitate. The precipitate was washed 2–4 times with anhydrous ethanol and dried in a vacuum at 55–65°C for 10–14 h to obtain a nano-copper-β-cyclodextrin complex. A2: Add the nano-copper-β-cyclodextrin complex, bio-based polyurethane elastomer, and copper ion-diatomaceous earth complex to a high-speed mixer at a mass ratio of 2.1-2.3:1:1 and premix for 8-12 minutes. Add 15%-25% of the volume of the premixed mixture of nano-zinc oxide solution and continue mixing for 15-25 minutes. Finally, add 10%-20% of the mass of the premixed mixture of ethanol solution by spraying and stir at low speed for 12-18 minutes to obtain the complex. A3: The composite is fed into a twin-screw extruder and melt-blended at 180-200°C for 5-15 minutes. The melted composite is then cut into granules by water cooling and dried at 75-85°C for 7-9 hours to obtain a biological root inhibitor.
[0011] Furthermore, the surfactant in A1 is selected from any one of sodium dodecyl sulfate, sodium diisooctyl succinate sulfonate, hexadecyltrimethylammonium bromide, and polyoxyethylene ether.
[0012] Furthermore, the preparation method of the copper ion-diatomite composite in step A2 is as follows: Diatomaceous earth and copper salt solution were mixed at a mass ratio of 1:2.3 to 2.7 and ultrasonically vibrated at 55 to 65°C. After vibration, the mixture was dried at 100 to 120°C for 10 to 14 hours and calcined in a muffle furnace at 400 to 600°C for 1 to 3 hours. After cooling, it was ground through a 290 to 310 mesh sieve to obtain a copper ion-diatomaceous earth composite.
[0013] Among them, the muffle furnace is an experimental device used for high-temperature heating and heat treatment. It is widely used in the sintering of materials, ash content determination, elemental analysis and chemical experiments. It provides a stable high-temperature environment through electric heating and can realize high-temperature calcination, drying, oxidation or other heat treatment processes of mixtures.
[0014] Furthermore, the copper salt solution is prepared by mixing and dissolving copper nitrate trihydrate and deionized water in a mass ratio of 0.8–1.2:15–18.
[0015] Furthermore, the ethanol solution is prepared by mixing azadirachtin extract with a purity ≥95% with anhydrous ethanol at a mass ratio of 0.4–0.6 g / mL; Among them, the azadirachtin extract can be purchased from the azadirachtin extract produced by Lanzhou Waterles Biotechnology Co., Ltd.
[0016] Furthermore, the nano zinc oxide solution in step A2 is prepared by mixing nano zinc oxide and anhydrous ethanol at a solid-liquid ratio of 0.4 to 0.6 g / mL, wherein the particle size of the nano zinc oxide is 5 to 60 nanometers.
[0017] Furthermore, the bio-based polyurethane elastomer comprises hard segments and soft segments, and the preparation method of the bio-based polyurethane elastomer includes the following steps: B1: Castor oil-based polyether polyol and polylactic acid polyol are mixed in a mass ratio of 2.8-3.2:1.5-2.5 to obtain a multi-component complex. The hydroxyl value of the multi-component complex is adjusted to 60-70 mgKOH / g to obtain a preliminary soft segment. B2: Mix the hard segment and the initial soft segment at a mass ratio of 2.5-3.5:9-11 and stir at 75-85℃ for 1.5-2.5 hours. During stirring, control the molar ratio of isocyanate groups to hydroxyl groups to be 1.1-1.3:0.9-1.1 to obtain the end-capped prepolymer. B3: After the end-capped prepolymer is cooled to 55-65℃, add 5%-10% by weight of nitrogen-coordinated boron-oxygen hexacyclic rings (hard segment) and 1%-3% by weight of nanofiller (end-capped prepolymer). Stir for 20-40 minutes to disperse. After dispersion, add 3%-8% by weight of 1,4-butanediol (end-capped prepolymer) and organotin catalyst and tertiary amine catalyst in a mass ratio of 0.8-1.2:1.7-2.3 to obtain the crosslinked compound. The organotin catalyst can be any one of tin tetrachloride, triphenyltin compound, diethyltin dichloride, dimethyltin dichloride, and tetraethyltin, while the tertiary amine catalyst can be any one of trimethylamine, triphenylamine, triisopropylamine, and tetramethylammonium chloride.
[0018] B4: Add 1.1% to 1.6% by mass of foaming agent and 0.2% to 0.4% by mass of dimethyl silicone oil to the crosslinking compound, stir at high speed for 50 to 70 seconds, pour into a mold and wait for curing for 23 to 25 hours to prepare a porous elastomer sponge. The foaming agent is prepared by mixing water and dichloromethane in a mass ratio of 1:1.5 to 2.5. B5: The porous elastomer sponge is dried in a vacuum environment at 75-85℃ for 10-14 hours. After drying, it is heat-treated at 110-130℃ for 1.5-2.5 hours and then ground through a 190-210 mesh sieve to obtain a bio-based polyurethane elastomer.
[0019] Furthermore, the nanofiller in step B3 is composed of nano-silica and polyurethane matrix mixed in a mass ratio of 0.8-1.2:38.5-39.6, and the particle size of the nano-silica is 10-40 nanometers.
[0020] Furthermore, the nano-clay is selected from any one of montmorillonite, kaolinite, bentonite, illite, and optically active clay.
[0021] Compared with the prior art, the beneficial effects of the present invention are: The preparation of the bio-root inhibitor in this invention includes multiple steps. First, the synthesis of a nano-copper-β-cyclodextrin complex is carried out. Microemulsion liquid and pH adjustment are used to promote the complexation of copper ions with cyclodextrin and ensure the sustained release effect of copper ions. Second, through multi-component blending modification, the nano-copper-β-cyclodextrin complex, bio-based polyurethane elastomer and copper ion-diatomite complex are combined to construct a dual chemical and physical root barrier. The addition of nano-zinc oxide and azadirachtin extract further enhances the antibacterial properties and root-expelling effect of the material. The melt blending and molding steps optimize the performance of the complex through a twin-screw extruder and heat treatment, thereby improving the tensile strength and compression resilience of the material. Meanwhile, the preparation of the copper ion-diatomite composite involves diatomite adsorbing copper ions, and the calcination process enhances thermal stability and extends service life. The optimization steps of the bio-based polyurethane elastomer enhance the biodegradability and self-healing ability of the material by controlling the ratio of soft and hard segments and the crosslinking density. Furthermore, the addition of nano-silica further improves tensile strength and waterproof performance. Attached Figure Description
[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0023] Figure 1 A comparison diagram of the flexibility of the root-penetration resistant layer of a pre-laid waterproof membrane with adhesive backing provided by this invention; Figure 2 A comparison diagram showing the soft water absorption of the root-penetration resistant layer of a pre-laid waterproof membrane with adhesive backing provided by this invention. Detailed Implementation
[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and 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.
[0025] Example 1 A type of pre-laid waterproof membrane with adhesive backing and root penetration resistance includes a substrate layer and a root penetration resistance layer. A self-adhesive layer is fixedly connected to the top of the root penetration resistance layer, and a protective layer is provided on the top of the self-adhesive layer. In one specific embodiment, the substrate layer is preferably a polyester fiber layer with a thickness of 1 mm; the root penetration resistant layer has a thickness of 0.5 mm; the self-adhesive layer is preferably a thermoplastic rubber layer with a thickness of 1.5 mm; and the protective layer is preferably a polyethylene film layer with a thickness of 0.2 mm.
[0026] The root-penetration resistant layer is made of the following raw materials in parts by weight: 40 parts high-density polyethylene, 3 parts polyvinyl chloride, 10 parts maleic anhydride-grafted polyethylene, 5 parts bio-based polyurethane elastomer, 10 parts montmorillonite, 3 parts nano zinc oxide, 10 parts bio-root inhibitor and 3 parts chopped glass fiber. It should be noted that the high-density polyethylene is produced by Hebei Luxin Plastic Products Co., Ltd., the polyvinyl chloride can be sourced from Nanjing Milan New Materials Co., Ltd., the maleic anhydride-grafted polyethylene is purchased from Keais Chemical Co., Ltd., the chopped glass fiber is produced by Cangzhou Zhongli New Materials Technology Co., Ltd., and the montmorillonite is sourced from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd., with the product number 105191.
[0027] The method for preparing the root-penetration-resistant layer is as follows: High-density polyethylene and polyvinyl chloride are dry-mixed, and maleic anhydride-grafted polyethylene is added to obtain an adhesive. Bio-based polyurethane elastomer is added to the adhesive and mixed. After mixing, nano-adhesive and nano-zinc oxide are added to obtain a composite material. The composite raw material is fed into an extruder and melted at a temperature of 200°C. Short glass fibers are added during the extrusion process to obtain a composite material, which is then made into a film using a blown film process. The biological root inhibitor is coated onto the surface of the film using an impregnation process, and then dried and cured to obtain a root-penetration-resistant layer. The preparation method of the biological root inhibitor includes the following steps: A1: Copper chloride dihydrate, β-cyclodextrin, sodium dodecyl sulfate, and deionized water were mixed in a mass ratio of 0.15:0.5:0.03:8 and stirred in a water bath at 55°C. During stirring, 0.032 g / mL sodium hydroxide solution was added to adjust the pH to 8.0 to obtain a microemulsion. The microemulsion was then centrifuged for 10 min to collect the precipitate. The precipitate was washed twice with anhydrous ethanol and dried in a vacuum at 55°C for 10 h to obtain a nano-copper-β-cyclodextrin complex. A2: The nano-copper-β-cyclodextrin complex, bio-based polyurethane elastomer and copper ion-diatomite complex were added to a high-speed mixer at a mass ratio of 2.1:1:1 and premixed for 8 min. Then, a nano-zinc oxide solution of 15% by volume of the premix was added and the mixture was continued for 15 min. Finally, an ethanol solution of 10% by mass of the premix was added by spraying and stirred at low speed for 12 min to obtain the complex. A3: The composite was fed into a twin-screw extruder and melt-blended at 180°C for 5 min. The melted composite was then cut into granules by water cooling and dried at 75°C for 7 h to obtain the biological root inhibitor.
[0028] For example, the preparation method of the copper ion-diatomite composite in step A2 is as follows: Diatomaceous earth and copper salt solution were mixed at a mass ratio of 1:2.3 and ultrasonically vibrated at 55°C. After vibration, the mixture was dried at 100°C for 10 hours and calcined in a muffle furnace at 400°C for 1 hour. After cooling, it was ground through a 290-mesh sieve to obtain a copper ion-diatomaceous earth composite.
[0029] Among them, the muffle furnace is an experimental device used for high-temperature heating and heat treatment. It is widely used in the sintering of materials, ash content determination, elemental analysis and chemical experiments. It provides a stable high-temperature environment through electric heating and can realize high-temperature calcination, drying, oxidation or other heat treatment processes of mixtures.
[0030] It should be added that the copper salt solution is prepared by mixing and dissolving copper nitrate trihydrate and deionized water at a mass ratio of 0.8:15. Among them, the azadirachtin extract can be purchased from the azadirachtin extract produced by Lanzhou Waterles Biotechnology Co., Ltd.
[0031] Furthermore, the ethanol solution is prepared by mixing azadirachtin extract with a purity ≥95% with anhydrous ethanol at a mass ratio of 0.4 g / mL.
[0032] Meanwhile, the nano zinc oxide solution in step A2 is prepared by mixing nano zinc oxide and anhydrous ethanol at a solid-liquid ratio of 0.4 g / mL.
[0033] Furthermore, the bio-based polyurethane elastomer comprises hard segments and soft segments, and the preparation method of the bio-based polyurethane elastomer includes the following steps: B1: Castor oil-based polyether polyol and polylactic acid polyol were mixed at a mass ratio of 2.8:1.5 to obtain a multi-component complex. The hydroxyl value of the multi-component complex was adjusted to 60 mg KOH / g to obtain a preliminary soft segment. B2: The hard segment and the initial soft segment are mixed at a mass ratio of 2.5:9 and stirred at 75°C for 1.5 hours. During the stirring process, the molar ratio of isocyanate groups to hydroxyl groups is controlled at 1.1:0.9 to obtain the end-capped prepolymer. B3: After the end-capped prepolymer is cooled to 55°C, add 5% by mass of nitrogen-coordinated boron-oxygen hexacyclic compound (for the hard segment) and 1% by mass of nanofiller (for the end-capped prepolymer). Stir for 20 minutes to disperse. After dispersion, add 3% by mass of 1,4-butanediol and tin tetrachloride and trimethylamine in a mass ratio of 0.8:1.7 to obtain the crosslinked compound.
[0034] B4: Add 1.1% by mass of foaming agent and 0.2% by mass of dimethyl silicone oil to the crosslinking compound, stir at high speed for 50 seconds, pour into a mold and wait for curing for 23 hours to prepare a porous elastomer sponge; wherein, the foaming agent is prepared by mixing water and dichloromethane in a mass ratio of 1:1.5.
[0035] B5: The porous elastomer sponge was dried in a vacuum environment at 75°C for 10 hours. After drying, it was heat-treated at 110°C for 1.5 hours and then ground through a 190-mesh sieve to obtain a bio-based polyurethane elastomer.
[0036] It should be understood that the nanofiller in step B3 is composed of nano-silica and polyurethane matrix mixed in a mass ratio of 0.8:38.5.
[0037] Example 2 The preparation method of the backed adhesive root-penetration resistant pre-laid waterproof membrane provided in this embodiment is basically the same as that in Embodiment 1. The main difference between the two lies in the specific composition and ratio of the raw materials used. The specific composition of the raw materials used in this embodiment is as follows: 45 parts high-density polyethylene, 4 parts polyvinyl chloride, 15 parts maleic anhydride grafted polyethylene, 10 parts bio-based polyurethane elastomer, 11 parts kaolin, 5 parts nano zinc oxide, 13 parts bio-root inhibitor and 6 parts chopped glass fiber. It should be noted that the high-density polyethylene is produced by Hebei Luxin Plastic Products Co., Ltd., the polyvinyl chloride can be sourced from Nanjing Milan New Materials Co., Ltd., the maleic anhydride grafted polyethylene is purchased from Keais Chemical Co., Ltd., the chopped glass fiber is produced by Cangzhou Zhongli New Materials Technology Co., Ltd., and the kaolin is purchased from Lingshou County Zhongshi Hengda Mineral Products Processing Plant.
[0038] The preparation method of the biological root inhibitor includes the following steps: A1: Copper chloride dihydrate, β-cyclodextrin, sodium diisooctyl succinate sulfonate, and deionized water were mixed in a mass ratio of 0.18:0.7:0.04:9 and stirred in a water bath at 60°C. During stirring, 0.4 g / mL sodium hydroxide solution was added to adjust the pH to 8.3 to obtain a microemulsion. The microemulsion was then centrifuged for 15 min to collect the precipitate. The precipitate was washed three times with anhydrous ethanol and dried in a vacuum at 60°C for 12 h to obtain a nano-copper-β-cyclodextrin complex. A2: The nano-copper-β-cyclodextrin complex, bio-based polyurethane elastomer and copper ion-diatomite complex were added to a high-speed mixer at a mass ratio of 2.2:1:1 and premixed for 10 min. Then, a nano-zinc oxide solution of 20% by volume of the premix was added and the mixture was continued for 20 min. Finally, an ethanol solution of 15% by mass of the premix was added by spraying and stirred at low speed for 15 min to obtain the complex. A3: The composite was fed into a twin-screw extruder and melt-blended at 190°C for 10 min. The melted composite was then cut into granules by water cooling and dried at 80°C for 8 h to obtain a biological root inhibitor.
[0039] For example, the preparation method of the copper ion-diatomite composite in step A2 is as follows: Diatomaceous earth and copper salt solution were mixed at a mass ratio of 1:2.5 and ultrasonically vibrated at 60°C. After vibration, the mixture was dried at 110°C for 12 hours and calcined in a muffle furnace at 500°C for 2 hours. After cooling, it was ground through a 300-mesh sieve to obtain a copper ion-diatomaceous earth composite.
[0040] Among them, the muffle furnace is an experimental device used for high-temperature heating and heat treatment. It is widely used in the sintering of materials, ash content determination, elemental analysis and chemical experiments. It provides a stable high-temperature environment through electric heating and can realize high-temperature calcination, drying, oxidation or other heat treatment processes of mixtures.
[0041] It should be added that the copper salt solution is prepared by mixing and dissolving copper nitrate trihydrate and deionized water at a mass ratio of 1:17.
[0042] Furthermore, the ethanol solution is prepared by mixing azadirachtin extract with a purity of ≥95% with anhydrous ethanol at a mass ratio of 0.5 g / mL.
[0043] Meanwhile, the nano zinc oxide solution in step A2 is prepared by mixing nano zinc oxide and anhydrous ethanol at a solid-liquid ratio of 0.5 g / mL.
[0044] Furthermore, the bio-based polyurethane elastomer comprises hard segments and soft segments, and the preparation method of the bio-based polyurethane elastomer includes the following steps: B1: Castor oil-based polyether polyol and polylactic acid polyol are mixed at a mass ratio of 3:2 to obtain a multi-component complex. The hydroxyl value of the multi-component complex is adjusted to 65 mg KOH / g to obtain a preliminary soft segment. B2: The hard segment and the initial soft segment are mixed at a mass ratio of 3:10 and stirred at 80°C for 2 hours. During the stirring process, the molar ratio of isocyanate groups to hydroxyl groups is controlled at 1.2:1 to obtain the end-capped prepolymer. B3: After the end-capped prepolymer is cooled to 60°C, add 8% by mass of nitrogen-coordinated boron-oxygen hexacyclic compound (hard segment) and 2% by mass of nanofiller (end-capped prepolymer). Stir for 30 minutes to disperse. After dispersion, add 6% by mass of 1,4-butanediol (end-capped prepolymer) and triphenyltin compound and triphenylamine in a mass ratio of 1:2 to obtain the crosslinked compound.
[0045] B4: Add 1.3% by mass of foaming agent and 0.3% by mass of dimethyl silicone oil to the crosslinking compound, stir at high speed for 60s, pour into a mold and wait for curing for 24h to prepare a porous elastomer sponge; wherein, the foaming agent is prepared by mixing water and dichloromethane in a mass ratio of 1:2.
[0046] B5: The porous elastomer sponge was dried in a vacuum environment at 80℃ for 12 hours. After drying, it was heat-treated at 120℃ for 2 hours and then ground through a 200-mesh sieve to obtain a bio-based polyurethane elastomer.
[0047] It should be understood that the nanofiller in step B3 is a mixture of nano-silica and polyurethane matrix in a mass ratio of 1:39.
[0048] Example 3 The preparation method of the backed adhesive root-penetration resistant pre-laid waterproof membrane provided in this embodiment is basically the same as that in Embodiment 1. The main difference between the two lies in the specific composition and ratio of the raw materials used. The specific composition of the raw materials used in this embodiment is as follows: 50 parts high-density polyethylene, 5 parts polyvinyl chloride, 20 parts maleic anhydride grafted polyethylene, 15 parts bio-based polyurethane elastomer, 12 parts illite, 7 parts nano zinc oxide, 15 parts bio-root inhibitor and 9 parts chopped glass fiber. It should be noted that the high-density polyethylene is produced by Hebei Luxin Plastic Products Co., Ltd., the polyvinyl chloride can be sourced from Nanjing Milan New Materials Co., Ltd., the maleic anhydride-grafted polyethylene is purchased from Keais Chemical Co., Ltd., the chopped glass fiber is produced by Cangzhou Zhongli New Materials Technology Co., Ltd., and the illite is sourced from Hebei Leijiang New Materials Technology Co., Ltd.
[0049] The preparation method of the biological root inhibitor includes the following steps: A1: Copper chloride dihydrate, β-cyclodextrin, hexadecyltrimethylammonium bromide, and deionized water were mixed in a mass ratio of 0.20:0.9:0.05:10 and stirred in a water bath at 65°C. During stirring, 0.048 g / mL sodium hydroxide solution was added to adjust the pH to 8.5 to obtain a microemulsion. The microemulsion was then centrifuged for 20 min to collect the precipitate. The precipitate was washed four times with anhydrous ethanol and dried in a vacuum at 65°C for 14 h to obtain a nano-copper-β-cyclodextrin complex. A2: The nano-copper-β-cyclodextrin complex, bio-based polyurethane elastomer and copper ion-diatomite complex were added to a high-speed mixer at a mass ratio of 2.3:1:1 and premixed for 12 min. Then, a nano-zinc oxide solution of 25% by volume of the premix was added and the mixture was continued for 25 min. Finally, an ethanol solution of 20% by mass of the premix was added by spraying and stirred at low speed for 18 min to obtain the complex. A3: The composite is fed into a twin-screw extruder and melt-blended at 200°C for 15 min. The melted composite is then cut into granules by water cooling and dried at 75–85°C for 7–9 h to obtain a biological root inhibitor.
[0050] For example, the preparation method of the copper ion-diatomite composite in step A2 is as follows: Diatomaceous earth and copper salt solution were mixed at a mass ratio of 1:2.7 and ultrasonically vibrated at 65°C. After vibration, the mixture was dried at 120°C for 14 hours and calcined in a muffle furnace at 600°C for 3 hours. After cooling, it was ground through a 310-mesh sieve to obtain a copper ion-diatomaceous earth composite.
[0051] Among them, the muffle furnace is an experimental device used for high-temperature heating and heat treatment. It is widely used in the sintering of materials, ash content determination, elemental analysis and chemical experiments. It provides a stable high-temperature environment through electric heating and can realize high-temperature calcination, drying, oxidation or other heat treatment processes of mixtures.
[0052] It should be added that the copper salt solution is prepared by mixing and dissolving copper nitrate trihydrate and deionized water in a mass ratio of 1.2:18.
[0053] Furthermore, the ethanol solution is prepared by mixing azadirachtin extract with a purity of ≥95% with anhydrous ethanol at a mass ratio of 0.6 g / mL.
[0054] Meanwhile, the nano zinc oxide solution in step A2 is prepared by mixing nano zinc oxide and anhydrous ethanol at a solid-liquid ratio of 0.6 g / mL.
[0055] Furthermore, the bio-based polyurethane elastomer comprises hard segments and soft segments, and the preparation method of the bio-based polyurethane elastomer includes the following steps: B1: Castor oil-based polyether polyol and polylactic acid polyol were mixed at a mass ratio of 3.2:2.5 to obtain a multi-component complex. The hydroxyl value of the multi-component complex was adjusted to 70 mg KOH / g to obtain a preliminary soft segment. B2: The hard segment and the initial soft segment are mixed at a mass ratio of 3.5:11 and stirred at 85°C for 2.5 hours. During the stirring process, the molar ratio of isocyanate groups to hydroxyl groups is controlled at 1.3:1.1 to obtain the end-capped prepolymer. B3: After the end-capped prepolymer is cooled to 65°C, 10% by weight of nitrogen-coordinated boron-oxygen hexacyclic compound (based on the mass of the hard segment) is added, along with 3% by weight of nanofiller (based on the mass of the end-capped prepolymer). The mixture is stirred for 40 minutes to disperse the prepolymer. After dispersion, 8% by weight of 1,4-butanediol and tetraethyltin and tetramethylammonium chloride (based on the mass ratio of the end-capped prepolymer) are added to obtain the crosslinked compound.
[0056] B4: Add 1.6% by mass of foaming agent and 0.4% by mass of dimethyl silicone oil to the crosslinking compound, stir at high speed for 70s, pour into a mold and wait for curing for 25h to prepare a porous elastomer sponge; wherein, the foaming agent is prepared by mixing water and dichloromethane in a mass ratio of 1:2.5.
[0057] B5: The porous elastomer sponge was dried in a vacuum environment at 85℃ for 14 hours. After drying, it was heat-treated at 130℃ for 2.5 hours and then ground through a 210-mesh sieve to obtain a bio-based polyurethane elastomer.
[0058] It should be understood that the nanofiller in step B3 is a mixture of nano-silica and polyurethane matrix in a mass ratio of 1.2:39.6.
[0059] Comparative Example 1: The preparation method and specific ratio of raw materials of the root-penetration resistant layer provided in this example are roughly the same as those in Example 1. The main difference is that in this example, an equal amount of commercially available biological root-barrier agent is used instead of biological root-barrier agent, which was purchased from Beijing Antpuna Science and Trade Co., Ltd.
[0060] Comparative Example 2: The preparation method and specific ratio of raw materials of the root penetration resistant layer provided in this example are roughly the same as those in Example 1. The main difference is that an equal amount of ordinary polyurethane elastomer is used instead of bio-based polyurethane elastomer, which is purchased from Shanghai Yongyi Industrial Co., Ltd.
[0061] Comparative Example 3: The preparation method and specific ratio of raw materials of the root penetration resistant layer provided in this example are roughly the same as those in Example 1. The main difference is that in step A2, an equal amount of diatomaceous earth is used instead of copper ion-diatomaceous earth composite material, which is selected from Lingshou County Huixin New Material Co., Ltd.
[0062] Performance testing The root-penetration resistant layers prepared by Examples 1 to 3 of the present invention are designated as Experimental Examples 1 to 3; the root-penetration resistant layers prepared by Comparative Examples 1 to 3 are designated as Comparative Examples 1 to 3; and then the performance of equal amounts of root-penetration resistant layers is tested.
[0063] 1. Root penetration resistance test: In this embodiment, the test method is carried out according to the test method provided by GB / T35468-2017, that is, the root growth of firethorn is simulated for 2 years in a standard greenhouse and the root penetration is observed. 2. Water resistance: The water resistance test shall be conducted in accordance with the test method in GB / T328.27-2007, namely, the water absorption rate test (immersion in water at 23℃ for 4 hours). 3. Flexibility: The low-temperature bending performance is tested according to the test method provided in GB / T1731-2020, namely the shaft bar method. 4. Corrosion resistance: The test method is to make circular pieces with a diameter of 50 mm and a thickness of 0.05 mm for each group of root penetration resistant layers. Multiple samples are immersed in 5% sulfuric acid (acid resistant), 5% sodium hydroxide (alkali resistant), and 3% sodium chloride (salt resistant) solutions. The mass change rate is measured after 7 days.
[0064] The obtained experimental data are summarized in Table 1: For its corrosion resistance test results, please refer to Table 2: Results analysis: In summary, based on Tables 1-2 and... Figures 1-2 It can be seen that none of the examples of the root penetration resistant layer prepared by the present invention underwent root penetration after testing, and the plant growth met the standard requirements, proving that it has good root penetration resistance. In contrast, the comparative sample failed the root penetration resistance test due to insufficient modification of its biological root inhibitor, polyurethane elastomer and diatomaceous earth.
[0065] Secondly, the water absorption rate of the embodiment is between 0.3% and 0.55%, which is much lower than that of the comparative sample (0.8% to 1.2%), showing excellent waterproof performance. Furthermore, the embodiment showed no cracks on a 1-2 mm shaft, while the comparative sample required a larger diameter.
[0066] Corrosion resistance: Comparative Example 1, lacking root-barrier components such as nano-copper-β-cyclodextrin complex, showed a significant decrease in acid, alkali, and salt corrosion resistance, with a mass change rate of 3.5% to 5.1%, exceeding the standard limit; Comparative Example 2, using ordinary polyurethane elastomer, lacked bio-based materials, resulting in reduced corrosion resistance; Comparative Example 3, lacking diatomaceous earth modification and copper ion loading, exhibited the worst acid, alkali, and salt corrosion resistance, with a mass change rate of 4.2% to 5.1%.
[0067] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0068] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims
1. A root puncture resistant pre-paved waterproofing membrane characterized in that: The back adhesive root-puncture-resistant type pre-laid waterproof roll material comprises a base material layer and a root-puncture-resistant layer, the top of the root-puncture-resistant layer is fixedly connected with a self-adhesive layer, and the top of the self-adhesive layer is provided with a protective layer. The root-puncture-resistant layer is made of the following raw materials in parts by weight: 40-50 parts of high-density polyethylene, 3-5 parts of polyvinyl chloride, 10-20 parts of maleic anhydride grafted polyethylene, 5-15 parts of bio-based polyurethane elastomer, 10-12 parts of nano clay, 3-7 parts of nano zinc oxide, 10-15 parts of biological root inhibitor, and 3-9 parts of chopped glass fiber. The preparation method of the root-puncture-resistant layer is as follows: The high-density polyethylene and polyvinyl chloride are dry-mixed, and the maleic anhydride grafted polyethylene is added to obtain an adhesive, and the bio-based polyurethane elastomer is mixed in the adhesive, and then the nano clay and nano zinc oxide are added after mixing to obtain a composite raw material; The composite raw material is sent into an extruder for melt treatment at a temperature of 180-220 DEG C, and the chopped glass fiber is added during the extrusion process to obtain a composite material, which is made into a film through a film blowing process; The biological root inhibitor is coated on the surface of the film using an immersion process, and is dried and cured to obtain the root-puncture-resistant layer.
2. The root resistant puncture type pre-paved waterproofing membrane with back adhesive according to claim 1, characterized in that, The preparation method of the biological root inhibitor comprises the following steps: A1: The copper chloride dihydrate, beta-cyclodextrin, surfactant and deionized water are mixed in a mass ratio of 0.15-0.20:0.5-0.9:0.03-0.05:8-10, and water bath stirring is carried out at 55-65 DEG C, and 0.032-0.048 g / mL sodium hydroxide solution is added during stirring to adjust the pH value to 8.0-8.5 to obtain a microemulsion, and then the microemulsion is centrifuged for 10-20 min to collect the precipitate, and the precipitate is washed with anhydrous ethanol for 2-4 times, and is dried in a vacuum at 55-65 DEG C for 10-14 h to obtain a nano copper-beta-cyclodextrin composite; A2: The nano copper-beta-cyclodextrin composite, bio-based polyurethane elastomer and copper ion-diatomic earth composite are added into a high-speed mixer in a mass ratio of 2.1-2.3:1:1 for 8-12 min of pre-mixing, a nano zinc oxide solution with a volume of 15%-25% of the pre-mixture is added, and mixing is continued for 15-25 min, finally, an ethanol solution with a mass of 10%-20% of the pre-mixture is added in a spraying manner, and low-speed stirring is carried out for 12-18 min to obtain a composite; A3: The composite is sent into a twin-screw extruder for melt blending at 180-200 DEG C for 5-15 min, the melted composite is cut into particles through water cooling, and is dried at 75-85 DEG C for 7-9 h to obtain the biological root inhibitor.
3. The root resistant puncture type pre-paved waterproofing membrane with back adhesive according to claim 2, characterized in that, The surfactant in A1 is selected from any one of sodium dodecyl sulfate, sodium diisooctyl sulfosuccinate, cetyltrimethylammonium bromide and polyoxyethylene ether.
4. The root resistant puncture type pre-paved waterproofing membrane with back adhesive according to claim 2, characterized in that, The preparation method of the copper ion-diatomic earth composite in step A2 is as follows: The diatomite and the copper salt solution are mixed in a mass ratio of 1:2.3-2.7, and ultrasonic oscillation is carried out at 55-65°C. After the oscillation is completed, the obtained mixture is dried at 100-120°C for 10-14h, calcined in a muffle furnace at 400-600°C for 1-3h, cooled, and ground through a 290-310 mesh sieve to obtain a copper ion-diatomite composite.
5. The root resistant puncture type pre-paved waterproofing membrane with back adhesive according to claim 4, characterized in that, The copper salt solution is prepared by mixing copper nitrate trihydrate and deionized water in a mass ratio of 0.8-1.2:15-18.
6. The root resistant puncture type pre-paved waterproofing membrane with back adhesive according to claim 2, characterized in that, The ethanol solution is prepared by mixing a toosendan fruit extract with a purity of ≥95% and anhydrous ethanol in a mass ratio of 0.4-0.6g / mL.
7. The root resistant, puncture resistant, pre-rolled waterproofing membrane according to claim 2, wherein the backing adhesive is a hot melt adhesive. The nanometer zinc oxide solution in step A2 is prepared by mixing nanometer zinc oxide and anhydrous ethanol in a solid-liquid ratio of 0.4-0.6g / mL.
8. The root resistant puncture type pre-paved waterproofing membrane according to claim 2, characterized in that, The bio-based polyurethane elastomer comprises hard segments and soft segments, and the preparation method of the bio-based polyurethane elastomer comprises the following steps: B1: castor oil-based polyether polyol and polylactic acid polyol are mixed in a mass ratio of 2.8-3.2:1.5-2.5 to obtain a polyhydric compound, and the hydroxyl value of the polyhydric compound is adjusted to 60-70mgKOH / g to obtain a preliminary soft segment; B2: the hard segment and the preliminary soft segment are mixed in a mass ratio of 2.5-3.5:9-11, stirred at 75-85°C for 1.5-2.5h, and in the stirring process, the molar ratio of isocyanate groups to hydroxyl groups is controlled to be 1.1-1.3:0.9-1.1 to obtain a capped prepolymer; B3: after the capped prepolymer is cooled to 55-65°C, 5%-10% of the hard segment of nitrogen-coordinated boroxine is added, and 1%-3% of the capped prepolymer of nanometer filler is added, stirred for 20-40min for dispersion, and after the dispersion is completed, 3%-8% of the capped prepolymer of 1,4-butanediol and 0.8-1.2:1.7-2.3 of the organic tin catalyst and the tertiary amine catalyst are added to obtain a crosslinked compound; B4: 1.1%-1.6% of the crosslinked compound of foaming agent and 0.2%-0.4% of the crosslinked compound of dimethyl silicone oil are added to the crosslinked compound, high-speed stirring is carried out for 50-70s, and the mixture is poured into a mold to wait for curing for 23-25h to prepare a porous elastomer sponge; B5: the porous elastomer sponge is dried in a vacuum environment at 75-85°C for 10-14h, after the drying is completed, heat treatment is carried out at 110-130°C for 1.5-2.5h, and the mixture is ground through a 190-210 mesh sieve to obtain a bio-based polyurethane elastomer.
9. The root resistant puncture type pre-paved waterproofing membrane according to claim 8, characterized in that, The nanometer filler in step B3 is prepared by mixing nanometer silicon dioxide and a polyurethane matrix in a mass ratio of 0.8-1.2:38.5-39.
6.
10. The root resistant puncture type pre-paved waterproofing membrane according to claim 1, characterized in that, The nanometer clay is selected from any one of montmorillonite, kaolin, bentonite, illite and optically active clay.