Waterproofing membrane and process for its production

Abstract

The application belongs to the technical field of waterproof materials, and particularly relates to a waterproof coiled material and a production process thereof. The waterproof coiled material provided by the application comprises high-density polyethylene, linear low-density polyethylene, a hydrophobic modifier, a reinforcing agent, a compatibilizer, a filler, a cross-linking agent and an antioxidant. The application adopts fluorine-containing silane-nano-silicon dioxide hybrid particles to construct a low-surface-energy hydrophobic network, and matches modified hydroxyapatite to form a zigzag penetration barrier channel, so that the waterproof stability and mechanical properties of the waterproof coiled material are greatly improved. The application adopts POSS hyperbranched polyamide as the compatibilizer, so that the mechanical properties of the coiled material are significantly improved.

Description

Technical Field

[0001] This invention belongs to the field of waterproof materials technology, specifically relating to a waterproof membrane and its production process. Background Technology

[0002] Waterproof membranes are indispensable functional building materials in fields such as construction engineering, municipal roads and bridges, underground pipe corridors, and water conservancy facilities. They are primarily used to prevent water penetration and avoid problems such as structural leakage, steel corrosion, and concrete freeze-thaw damage, forming a core component of building waterproofing systems. The most widely used waterproof membranes on the market are mainly divided into two categories: modified bitumen waterproof membranes and polymer waterproof membranes. Traditional modified bitumen waterproof membranes have proven unsuitable for complex working conditions and high-standard engineering requirements in long-term practical applications. Compared to traditional bitumen waterproof membranes, polyethylene-based composite waterproof membranes offer advantages such as being non-toxic and environmentally friendly, high strength, good toughness, and long service life, and have now become the mainstream product in the field of engineering waterproofing.

[0003] Currently, most polyethylene waterproof membranes in existing technologies are prepared by simple blending and modification of a single polyethylene matrix or by conventional multi-layer lamination structures. During production, the polyethylene matrix is ​​typically modified by adding common inorganic fillers, conventional antioxidants, and plasticizers, and multi-layer structures are formed using traditional hot-pressing or adhesive bonding processes to meet the basic waterproofing requirements of conventional buildings. However, the fillers have poor compatibility with the polyethylene matrix, and uneven dispersion can easily lead to agglomeration. This results in micropores and structural defects within the formed membrane, insufficient overall density, and limited waterproofing and seepage prevention performance. Prolonged immersion under pressure can easily lead to seepage and leakage. Furthermore, the overall mechanical properties of the membrane are uneven, with weak tensile strength, tear resistance, and puncture resistance. It is prone to damage and cracking under slight foundation deformation, external friction, and bending conditions during construction, resulting in poor waterproofing reliability. Multi-layer composite waterproof membranes are mostly applied by secondary bonding, single-sided thermal bonding, or adhesive bonding. The interlayer interface fusion effect is poor and the bonding force is weak. Under long-term high and low temperature alternation, dry and wet cycle, and outdoor ultraviolet aging environment, the membrane is very prone to defects such as blistering, delamination, and separation between layers, which damages the overall waterproof structure, forms through water seepage channels, causes the waterproof system to fail prematurely, significantly shortens the waterproof life of the project, and increases the cost of later maintenance and repair.

[0004] Chinese patent application CN115304844A discloses a high-density polyethylene waterproof sheet comprising the following raw material components in the indicated weight ratios: 100 parts by weight of high-density polyethylene; 60-70 parts by weight of linear low-density polyethylene; 40-50 parts by weight of polypropylene; 5-20 parts by weight of an olefin copolymer elastomer; 0.1-0.3 parts by weight of a foaming agent; and 1-3 parts by weight of a nucleating agent, including at least one of calcium stearate, talc, calcium carbonate, silica, alum, and titanium dioxide. However, the high-density polyethylene, linear low-density polyethylene, and polypropylene in the disclosed patent application are thermodynamically incompatible systems, with significant differences in their molecular structure, crystallization rate, and melt viscosity. Relying solely on a small amount of toughening agent from the olefin copolymer elastomer cannot solve the problem of phase separation at the polyethylene and polypropylene interface. Furthermore, waterproof membranes require high density, no pores, and water resistance; the foaming agent added to the formula would form a porous structure within the sheet, reducing its waterproof performance. Summary of the Invention

[0005] In order to solve the technical problems of poor waterproof performance and mechanical properties in the prior art, the purpose of this invention is to provide a waterproof membrane and its manufacturing process.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows:

[0007] A waterproof membrane comprising the following components in parts by weight: 80-90 parts high-density polyethylene, 30-50 parts linear low-density polyethylene, 10-15 parts hydrophobic modifier, 8-14 parts reinforcing agent, 5-10 parts compatibilizer, 3-5 parts filler, 1-3 parts crosslinking agent, and 0.5-1.5 parts antioxidant; The hydrophobic modifier is a fluorinated silane-nano silica hybrid particle, and the reinforcing agent is modified hydroxyapatite.

[0008] In the above scheme, high-density polyethylene and linear low-density polyethylene are used as the matrix, balancing the structural strength and low-temperature toughness of the roll material. Fluorosilane-nano silica hybrid particles are used as hydrophobic modifiers to construct a continuous hydrophobic network inside the roll material, filling resin micropores, blocking water penetration channels, and improving waterproof and seepage-proof performance. Modified hydroxyapatite is selected as a reinforcing agent, utilizing its plate-like and layered structure to form a tortuous barrier effect, while improving the interfacial bonding between inorganic fillers and the matrix, significantly improving the tensile strength, tear resistance, and puncture resistance of the roll material. Compatibilizers can effectively solve the defects of poor compatibility and easy agglomeration between inorganic fillers and polyolefin matrix, improving overall density; crosslinking agents can construct a uniform and stable three-dimensional crosslinking network, further enhancing structural stability.

[0009] Furthermore, the preparation method of the hydrophobic modifier is as follows: 100g of fumed silica is dispersed in an ethanol aqueous solution and ultrasonically dispersed; 8-12g of perfluorooctyltriethoxysilane and 3-5g of tetraethyl orthosilicate are added, the pH is adjusted to 8-9 with ammonia water, and the mixture is stirred and reacted at 60℃ for 6-7h; the mixture is centrifuged, washed, and dried to obtain the hydrophobic modifier.

[0010] In the above scheme, perfluorooctyltriethoxysilane is hydrolyzed and condensed in an aqueous ethanol solution, grafting fluorocarbon bonds onto the surface of nano-silica to construct a hydrophobic layer with extremely low surface energy, forming superhydrophobic nano-hybrid particles. Tetraethyl orthosilicate is hydrolyzed and condensed in an aqueous ethanol solution, forming a dense silica cross-linked transition layer on the surface of nano-silica, significantly improving the grafting strength of the fluorinated hydrophobic groups and preventing the hydrophobic groups from detaching and failing during high-temperature processing. When these hydrophobic modifier particles are added to the waterproof membrane, they can form a hydrophobic network inside the membrane, increasing the contact angle of the membrane surface, reducing the adsorption and penetration of water molecules on the membrane surface, and thus improving the hydrophobic performance.

[0011] Furthermore, the preparation method of the reinforcing agent is as follows: hexadecyltrimethylammonium bromide template agent is added to Ca(NO3)2 solution and stirred until dissolved. (NH4)2HPO4 solution is added under stirring. After the addition is completed, stirring is continued for 20-30 min. Ammonia water is added to adjust the pH value to 10.0-10.5. The temperature is raised to 80-85℃ and stirred for 12-13 h. After cooling, filtration, washing, and drying, nano-hydroxyapatite powder is obtained. The nano-hydroxyapatite powder is added to chitosan acetic acid aqueous solution and stirred at high speed for 30-50 min. After filtration, the filter cake is soaked in glutaraldehyde and allowed to stand for 10-12 h. After removal, washing, drying, and pulverizing, the reinforcing agent is obtained.

[0012] In the above scheme, the directional adsorption of hexadecyltrimethylammonium bromide on specific crystal faces of hydroxyapatite crystals in aqueous solution is utilized. Hydroxyapatite nanosheets are synthesized through an alkaline hydrothermal reaction using Ca(NO3)2 solution and (NH4)2HPO4 solution. The hydroxyapatite nanosheets are dispersed in a chitosan acetic acid aqueous solution. The active sites on the surface of hydroxyapatite form hydrogen bonds and electrostatic interactions with chitosan molecules, allowing chitosan to uniformly coat and fill the gaps between the hydroxyapatite sheets. After high-speed stirring and vacuum filtration, the disordered sheet-like hydroxyapatite undergoes directional parallel stacking under negative pressure. The flexible polymer phase of chitosan uniformly fills the gaps between the sheets. The nanosheets are then immersed in a glutaraldehyde crosslinking solution and subjected to constant temperature static crosslinking treatment. The dialdehyde groups of glutaraldehyde undergo covalent crosslinking reactions with the amino groups in the chitosan molecules, achieving solidification and shaping of the chitosan molecules, significantly improving the interlayer bonding force and structural stability, and preventing interlayer loosening and peeling. The reinforcing agent prepared by this method, when added to the waterproof membrane, can form a large number of interlaced physical barrier layers, which significantly prolongs the water penetration path and effectively blocks the water pressure penetration channel. In addition, the flaky hydroxyapatite has ultra-high rigidity and hardness, and can serve as a rigid support skeleton inside the membrane, improving the tensile strength and puncture resistance of the membrane. The interlayer cross-linked and cured chitosan flexible network has excellent toughness and deformation buffering capacity, which can effectively consume the impact energy of external forces and inhibit the initiation and propagation of matrix cracks.

[0013] Furthermore, the concentration of the Ca(NO3)2 solution is 0.5-0.6 mol / L, and the concentration of the (NH4)2HPO4 solution is 0.3-0.4 mol / L; the concentration of the hexadecyltrimethylammonium bromide in the Ca(NO3)2 solution is 2-3 g / L; the mass concentration of chitosan in the chitosan acetic acid aqueous solution is 0.5-0.8%, the mass concentration of glacial acetic acid is 1-2%, and the mass ratio of nano-hydroxyapatite powder to chitosan is 19:1.

[0014] Furthermore, the compatibilizer is prepared as follows: N-methylpyrrolidone is added to octaaminophenyl cage-type polysilsesquioxane, stirred evenly, and then 4,4'-diaminodiphenyl ether is added and stirred evenly. A solution of N-methylpyrrolidone in trimesoyl chloride is added dropwise, and the mixture is stirred at -5°C for 1-2 hours. The mixture is then heated to room temperature and stirred for another 4-5 hours. Triethylamine is added until the pH of the solution is neutral. The solution is then poured into ethanol to precipitate, washed, and dried to obtain the compatibilizer.

[0015] In the above scheme, octaaminophenyl cage-type polysilsesquioxane, 4,4'-diaminodiphenyl ether, and trimesoyl chloride are used as reactants for polycondensation to form a highly branched, multi-terminated, three-dimensional cage-type-hyperbranched structure. When added to the waterproof membrane, the cage-type POSS inorganic silica skeleton in its molecular structure can interact with the filler, while the multi-terminated amino groups of the hyperbranched polyamide at the other end can entangle the polyethylene molecular chains, significantly improving the interfacial bonding force between the inorganic and organic phases. This solves the problems of filler agglomeration, interfacial voids, and water seepage channels, significantly improving the density and waterproofness of the waterproof membrane. Furthermore, the hyperbranching degree and high content of terminal amino groups in the molecular structure can form multi-point crosslinks with reinforcing agents and crosslinking agents, constructing a three-dimensional network within the membrane and improving its mechanical properties.

[0016] Furthermore, in the preparation method of the compatibilizer, the mass ratio of the octaaminophenyl cage-type polysilsesquioxane, 4,4'-diaminodiphenyl ether, and trimesoyl chloride is (2-4):(8-10):(5-7); and the mass concentration of the N-methylpyrrolidone solution of trimesoyl chloride is 10-11 g / mL.

[0017] Furthermore, the filler is one or more of nano-silica, nano-titanium dioxide, nano-calcium carbonate, and nano-alumina.

[0018] Furthermore, the crosslinking agent is composed of diphenylthiazole disulfide and bis(4-mercaptophenyl) disulfide in a mass ratio of (0.8-1.2):(1.9-2.3).

[0019] In the above scheme, diphenylthiazole disulfide and bis(4-mercaptophenyl) disulfide are used together to form a crosslinking agent, which enhances the crosslinking and bonding between the membrane matrix, filler, reinforcing agent, compatibilizer and hydrophobic modifier in the waterproof membrane, effectively improving the density of the waterproof membrane and thus improving the waterproof performance.

[0020] Furthermore, the antioxidant is one of antioxidant 1010, antioxidant 1076, and antioxidant 3114.

[0021] The present invention also provides a manufacturing process for the above-mentioned waterproof membrane, comprising the following steps: S1: Place the hydrophobic modifier, reinforcing agent, filler, and antioxidant in a high-speed mixer and premix for 5-10 minutes to obtain a powder mixture; S2: Add high-density polyethylene, linear low-density polyethylene and compatibilizer to a twin-screw extruder, set the temperature as follows: Zone 1 160-165℃, Zone 2 165-170℃, Zone 3 175℃, Zone 4 175-180℃, Zone 5 180-185℃, Zone 6 190℃, screw speed 200-300 rpm, melt, add the powder mixture and crosslinking agent obtained in step S1, continue to melt and blend for 10-15 minutes to obtain the melt material; S3: The molten material obtained in step S2 is extruded through a die at a temperature of 190°C to form a rolled material. The rolled material is then calendered at a temperature of 50-70°C, cooled, and wound up to obtain a waterproof rolled material.

[0022] The above-mentioned method, employing pre-mixing of powder followed by twin-screw melt blending, effectively avoids the agglomeration of nanofillers such as hydrophobic modifiers and reinforcing agents. Segmented temperature control ensures thorough resin plasticization while guaranteeing gentle crosslinking of the crosslinking agent, preventing excessive crosslinking that could reduce melt fluidity. The calendering and cooling processes eliminate internal stress in the roll material, improving thickness uniformity and surface smoothness. This preparation process is simple, continuous, and highly efficient, resulting in roll materials with good density, excellent mechanical properties, and stable waterproofing and seepage prevention effects.

[0023] Compared with the prior art, the waterproof membrane and its preparation method provided by the present invention have the following technical advantages: (1) The present invention uses fluorinated silane-nano silica hybrid particles to construct a low surface energy hydrophobic network, and combines it with modified hydroxyapatite to form a tortuous permeation barrier channel, which greatly improves the waterproof stability of the waterproof membrane. (2) The present invention utilizes the ultra-high rigidity and hardness of flaky hydroxyapatite, combined with fillers as the internal rigid support skeleton of the roll material, to improve the tensile strength and puncture resistance of the roll material. (3) The present invention uses POSS hyperbranched polyamide as a compatibilizer, which effectively solves the problems of poor compatibility and easy agglomeration between nanofillers and polyolefin matrix. It can form a uniform and dense three-dimensional cross-linked network between matrix, filler and reinforcing agent, which significantly improves the mechanical properties of roll material. Attached Figure Description

[0024] Figure 1 The XRD pattern of the hydrophobic modifier prepared in Example 3; Figure 2 TEM image of the hydrophobic modifier prepared in Example 3; Figure 3 XRD pattern of the reinforcing agent prepared in Example 7; Figure 4 The infrared spectrum of the compatibilizer prepared in Example 11. Detailed Implementation

[0025] The following description, in conjunction with embodiments, provides further details, but the present invention is not limited to these embodiments. Those skilled in the art can make various modifications based on the fundamental principles of the present invention, but such modifications are all within the scope of the invention as long as they do not depart from its basic principles.

[0026] The particle size of the filler described in this specific embodiment is 20-50 nm.

[0027] Preparation Example 1 The preparation method of the hydrophobic modifier is as follows: 100g of fumed silica with a particle size of 15nm is dispersed in 1000g of ethanol / water (volume ratio 9:1) mixed solvent and ultrasonically dispersed for 40min at a power of 300w; 8g of perfluorooctyltriethoxysilane and 3g of tetraethyl orthosilicate are added, the pH is adjusted to 8 with ammonia water, and the reaction is stirred at 60℃ for 6h; after centrifugation and washing with ethanol 3 times, it is vacuum dried at 110℃ for 6h to obtain a fluorinated silane-nano silica hybrid hydrophobic agent with a surface water contact angle of more than 155°.

[0028] Preparation Example 2 The preparation method of the hydrophobic modifier is as follows: 100g of fumed silica with a particle size of 25nm is dispersed in 1000g of ethanol / water (volume ratio 9:1) mixed solvent and ultrasonically dispersed for 40min at a power of 300w; 12g of perfluorooctyltriethoxysilane and 5g of tetraethyl orthosilicate are added, the pH is adjusted to 9 with ammonia water, and the reaction is stirred at 60℃ for 7h; after centrifugation and washing with ethanol 3 times, it is vacuum dried at 110℃ for 6h to obtain a fluorinated silane-nano silica hybrid hydrophobic agent with a surface water contact angle of more than 155°.

[0029] Preparation Example 3 The preparation method of the hydrophobic modifier is as follows: 100g of fumed silica with a particle size of 20nm is dispersed in 1000g of ethanol / water (volume ratio 9:1) mixed solvent and ultrasonically dispersed for 40min under a power of 300w; 9g of perfluorooctyltriethoxysilane and 4g of tetraethyl orthosilicate are added, the pH is adjusted to 8.8 with ammonia water, and the reaction is stirred at 60℃ for 6.5h; after centrifugation and washing with ethanol 3 times, it is vacuum dried at 110℃ for 6h to obtain a fluorinated silane-nano silica hybrid hydrophobic agent with a surface water contact angle of more than 155°.

[0030] Preparation Example 4 The preparation method of the hydrophobic modifier is as follows: 100g of fumed silica with a particle size of 23nm is dispersed in 1000g of ethanol / water (volume ratio 9:1) mixed solvent and ultrasonically dispersed for 40min under a power of 300w; 11g of perfluorooctyltriethoxysilane and 4.5g of tetraethyl orthosilicate are added, the pH is adjusted to 8.5 with ammonia water, and the reaction is stirred at 60℃ for 6.7h; after centrifugation and washing with ethanol 3 times, it is vacuum dried at 110℃ for 6h to obtain a fluorinated silane-nano silica hybrid hydrophobic agent with a surface water contact angle of more than 155°.

[0031] Preparation Example 5 The preparation method of the reinforcing agent is as follows: Hexadecyltrimethylammonium bromide template agent is added to 1000 mL of 0.5 mol / L Ca(NO3)2 solution until the concentration of the hexadecyltrimethylammonium bromide template agent is 2 g / L. The mixture is stirred until dissolved. Then, 1000 mL of 0.3 mol / L (NH4)2HPO4 solution is slowly added while stirring. After the addition is complete, stirring is continued for 20 min. Ammonia water is added to adjust the pH to 10.0. The mixture is heated to 80℃ and stirred for 12 h. After cooling to room temperature, it is filtered, washed three times with deionized water and anhydrous ethanol colloid by centrifugation, and dried at 60℃ to obtain nano-hydroxyapatite powder. The nano-hydroxyapatite... Hydroxyapatite powder was added to a chitosan-acetic acid aqueous solution (chitosan mass concentration was 0.5%, glacial acetic acid mass concentration was 1%) (the mass ratio of nano-hydroxyapatite powder to chitosan was 19:1). The mixture was stirred at 1500 rpm for 30 min, filtered, and the sheet-like nano-hydroxyapatite was driven to stack and arrange in a parallel manner in a horizontal direction using negative pressure. Chitosan filled the spaces between the nano-hydroxyapatite nanosheets. The filter cake was soaked in glutaraldehyde and allowed to stand for 10 h. The dialdehyde groups of glutaraldehyde reacted with the amino groups in the chitosan molecules to form a cross-linking reaction. After removal, the mixture was washed with deionized water, vacuum dried at 100℃, pulverized, and passed through a 200-mesh sieve to obtain the reinforcing agent.

[0032] Preparation Example 6 The preparation method of the reinforcing agent is as follows: Hexadecyltrimethylammonium bromide template agent is added to 1000 mL of a 0.6 mol / L Ca(NO3)2 solution until the concentration of the hexadecyltrimethylammonium bromide template agent is 3 g / L. The mixture is stirred until dissolved. Then, 1000 mL of a 0.4 mol / L (NH4)2HPO4 solution is slowly added while stirring. After the addition is complete, stirring is continued for 30 min. Ammonia water is added to adjust the pH to 10.5. The mixture is heated to 85℃ and stirred for 13 h. After cooling to room temperature, it is filtered, washed five times with deionized water and anhydrous ethanol colloid by centrifugation, and dried at 60℃ to obtain nano-hydroxyapatite powder. The nano-hydroxyapatite... Hydroxyapatite powder was added to a chitosan-acetic acid aqueous solution (chitosan mass concentration was 0.8%, glacial acetic acid mass concentration was 2%) (the mass ratio of nano-hydroxyapatite powder to chitosan was 19:1). The mixture was stirred at 2000 rpm for 50 min, filtered, and the sheet-like nano-hydroxyapatite was driven to stack and arrange in a parallel manner in a horizontal direction using negative pressure. Chitosan filled the spaces between the nano-hydroxyapatite nanosheets. The filter cake was soaked in glutaraldehyde and allowed to stand for 12 h. The dialdehyde groups of glutaraldehyde reacted with the amino groups in the chitosan molecules to form a cross-linking reaction. After removal, the mixture was washed with deionized water, vacuum dried at 120℃, pulverized, and passed through a 200-mesh sieve to obtain the reinforcing agent.

[0033] Preparation Example 7 The preparation method of the reinforcing agent is as follows: Hexadecyltrimethylammonium bromide template agent is added to 1000 mL of 0.53 mol / L Ca(NO3)2 solution until the concentration of the hexadecyltrimethylammonium bromide template agent is 2.6 g / L. The mixture is stirred until dissolved. Then, 1000 mL of 0.32 mol / L (NH4)2HPO4 solution is slowly added while stirring. After the addition is complete, stirring is continued for 25 min. Ammonia water is added to adjust the pH to 10.2. The mixture is heated to 83℃ and stirred for 12.5 h. After cooling to room temperature, the mixture is filtered, washed four times with deionized water and anhydrous ethanol colloid by centrifugation, and dried at 60℃ to obtain nano-hydroxyapatite powder. The nano-hydroxyapatite powder is then... Apatite powder was added to a chitosan-acetic acid aqueous solution (chitosan mass concentration was 0.7%, glacial acetic acid mass concentration was 1.6%) (the mass ratio of nano-hydroxyapatite powder to chitosan was 19:1). The mixture was stirred at 1800 rpm for 45 min, filtered, and the sheet-like nano-hydroxyapatite was driven to stack and arrange in a parallel manner in a horizontal direction using negative pressure. Chitosan filled the spaces between the nano-hydroxyapatite nanosheets. The filter cake was soaked in glutaraldehyde and allowed to stand for 11.5 h. The dialdehyde groups of glutaraldehyde reacted with the amino groups in the chitosan molecules to form a cross-linking reaction. After removal, the mixture was washed with deionized water, vacuum dried at 115 °C, pulverized, and passed through a 200-mesh sieve to obtain the reinforcing agent.

[0034] Preparation Example 8 The preparation method of the reinforcing agent is as follows: Hexadecyltrimethylammonium bromide template agent is added to 1000 mL of 0.56 mol / L Ca(NO3)2 solution until the concentration of the hexadecyltrimethylammonium bromide template agent is 2.8 g / L. The mixture is stirred until dissolved. Then, 1000 mL of 0.35 mol / L (NH4)2HPO4 solution is slowly added while stirring. After the addition is complete, stirring is continued for 25 min. Ammonia water is added to adjust the pH to 10.3. The mixture is heated to 83℃ and stirred for 12.5 h. After cooling to room temperature, the mixture is filtered, washed five times with deionized water and anhydrous ethanol colloid by centrifugation, and dried at 60℃ to obtain nano-hydroxyapatite powder. The nano-hydroxyapatite powder is then further processed. Hydroxyapatite powder was added to a chitosan-acetic acid aqueous solution (chitosan mass concentration was 0.6%, glacial acetic acid mass concentration was 1.4%) (the mass ratio of nano-hydroxyapatite powder to chitosan was 19:1). The mixture was stirred at 1600 rpm for 40 min, filtered, and the sheet-like nano-hydroxyapatite was driven to stack and arrange in a parallel manner in a horizontal direction by negative pressure. Chitosan filled the spaces between the nano-hydroxyapatite nanosheets. The filter cake was soaked in glutaraldehyde and allowed to stand for 11 h. The dialdehyde groups of glutaraldehyde reacted with the amino groups in the chitosan molecules to form a cross-linking reaction. After removal, the mixture was washed with deionized water, vacuum dried at 110 °C, pulverized, and passed through a 200-mesh sieve to obtain the reinforcing agent.

[0035] Preparation Example 9 The compatibilizer was prepared as follows: 200 mL of N-methylpyrrolidone was added to 4 g of octaaminophenyl cage-type polysilsesquioxane and stirred until homogeneous. Then, 16 g of 4,4'-diaminodiphenyl ether was added and stirred until homogeneous to obtain a mixture. 10 g of trimesoyl chloride was dissolved in N-methylpyrrolidone to form a trimesoyl chloride N-methylpyrrolidone solution with a mass concentration of 10 g / mL. The trimesoyl chloride N-methylpyrrolidone solution was added dropwise to the mixture and stirred at -5℃ for 1 h. The temperature was raised to room temperature and stirred for another 4 h. Triethylamine was added until the pH of the solution was neutral. The reaction solution was poured into a large amount of ethanol to precipitate the polymer. The polymer was washed three times with anhydrous ethanol and dried under vacuum at 80℃ for 12 h to obtain the compatibilizer.

[0036] Preparation Example 10 The compatibilizer was prepared as follows: 200 mL of N-methylpyrrolidone was added to 8 g of octaaminophenyl cage-type polysilsesquioxane and stirred until homogeneous. Then, 20 g of 4,4'-diaminodiphenyl ether was added and stirred until homogeneous to obtain a mixture. 14 g of trimesoyl chloride was dissolved in N-methylpyrrolidone to form a trimesoyl chloride N-methylpyrrolidone solution with a mass concentration of 11 g / mL. The trimesoyl chloride N-methylpyrrolidone solution was added dropwise to the mixture and stirred at -5℃ for 2 h. The temperature was raised to room temperature and stirred for another 5 h. Triethylamine was added until the pH of the solution was neutral. The reaction solution was poured into a large amount of ethanol to precipitate the polymer. The polymer was washed 5 times with anhydrous ethanol and dried under vacuum at 80℃ for 12 h to obtain the compatibilizer.

[0037] Preparation Example 11 The compatibilizer was prepared as follows: 200 mL of N-methylpyrrolidone was added to 6 g of octaaminophenyl cage-type polysilsesquioxane and stirred until homogeneous. Then, 17 g of 4,4'-diaminodiphenyl ether was added and stirred until homogeneous to obtain a mixture. 13 g of trimesoyl chloride was dissolved in N-methylpyrrolidone to form a trimesoyl chloride N-methylpyrrolidone solution with a mass concentration of 10.5 g / mL. The trimesoyl chloride N-methylpyrrolidone solution was added dropwise to the mixture and stirred at -5℃ for 1.4 h. The temperature was raised to room temperature and stirred for another 4.3 h. Triethylamine was added until the pH of the solution was neutral. The reaction solution was poured into a large amount of ethanol to precipitate the polymer. The polymer was washed four times with anhydrous ethanol and dried under vacuum at 80℃ for 12 h to obtain the compatibilizer.

[0038] Preparation Example 12 The compatibilizer was prepared as follows: 200 mL of N-methylpyrrolidone was added to 7 g of octaaminophenyl cage-type polysilsesquioxane and stirred until homogeneous. Then, 18 g of 4,4'-diaminodiphenyl ether was added and stirred until homogeneous to obtain a mixture. 12 g of trimesoyl chloride was dissolved in N-methylpyrrolidone to form a trimesoyl chloride N-methylpyrrolidone solution with a mass concentration of 10.7 g / mL. The trimesoyl chloride N-methylpyrrolidone solution was added dropwise to the mixture and stirred at -5 °C for 1.6 h. The temperature was raised to room temperature and stirred for another 4.7 h. Triethylamine was added until the pH of the solution was neutral. The reaction solution was poured into a large amount of ethanol to precipitate the polymer. The polymer was washed five times with anhydrous ethanol and dried under vacuum at 80 °C for 12 h to obtain the compatibilizer.

[0039] Example 1 A waterproof membrane comprising the following components in parts by weight: 80g of high-density polyethylene, 50g of linear low-density polyethylene, 10g of hydrophobic modifier, 8g of reinforcing agent, 5g of compatibilizer, 3g of nano-silica, 1g of crosslinking agent, and 0.5g of antioxidant 1010; the hydrophobic modifier was prepared in Preparation Example 1, the reinforcing agent was prepared in Preparation Example 5, and the compatibilizer was prepared in Preparation Example 9; the crosslinking agent was composed of diphenylthiazole disulfide and bis(4-mercaptophenyl) disulfide in a mass ratio of 0.8:1.9.

[0040] The production process of waterproof membrane is as follows: S1: Place the hydrophobic modifier, reinforcing agent, nano silica, and antioxidant 1010 in a high-speed mixer and premix for 5 minutes to obtain a powder mixture; S2: Add high-density polyethylene, linear low-density polyethylene and compatibilizer to a twin-screw extruder, set the temperature as follows: Zone 1 160℃, Zone 2 165℃, Zone 3 175℃, Zone 4 175℃, Zone 5 180℃, Zone 6 190℃, screw speed 200 rpm, melt, add the powder mixture and crosslinking agent obtained in step S1, continue to melt and blend for 10 min to obtain the melt material; S3: The molten material obtained in step S2 is extruded through a die head at a temperature of 190°C to form a rolled material. The rolled material is then calendered at a temperature of 50°C, cooled, and wound up to obtain a waterproof rolled material.

[0041] Example 2 A waterproof membrane comprising the following components in parts by weight: 90g of high-density polyethylene, 30g of linear low-density polyethylene, 15g of hydrophobic modifier, 14g of reinforcing agent, 10g of compatibilizer, 5g of nano-titanium dioxide, 3g of crosslinking agent, and 1.5g of antioxidant 1076; the hydrophobic modifier was prepared in Preparation Example 2, the reinforcing agent was prepared in Preparation Example 6, and the compatibilizer was prepared in Preparation Example 10; the crosslinking agent was composed of diphenylthiazole disulfide and bis(4-mercaptophenyl) disulfide in a mass ratio of 1.2:2.3.

[0042] The production process of waterproof membrane is as follows: S1: Place the hydrophobic modifier, reinforcing agent, nano titanium dioxide, and antioxidant 1076 in a high-speed mixer and premix for 10 minutes to obtain a powder mixture; S2: Add high-density polyethylene, linear low-density polyethylene and compatibilizer to a twin-screw extruder, set the temperature as follows: zone 1 165℃, zone 2 170℃, zone 3 175℃, zone 4 180℃, zone 5 185℃, zone 6 190℃, screw speed 300 rpm, melt, add the powder mixture and crosslinking agent obtained in step S1, continue to melt and blend for 15 min to obtain the melt material; S3: The molten material obtained in step S2 is extruded through a die at a temperature of 190°C to form a rolled material. The rolled material is then calendered at a temperature of 70°C, cooled, and wound up to obtain a waterproof rolled material.

[0043] Example 3 A waterproof membrane comprising the following components in parts by weight: 83g of high-density polyethylene, 34g of linear low-density polyethylene, 12g of hydrophobic modifier, 11g of reinforcing agent, 8g of compatibilizer, 4g of nano-calcium carbonate, 2g of crosslinking agent, and 1.2g of antioxidant 3114; the hydrophobic modifier was prepared in Preparation Example 3, the reinforcing agent was prepared in Preparation Example 7, and the compatibilizer was prepared in Preparation Example 11; the crosslinking agent was composed of diphenylthiazole disulfide and bis(4-mercaptophenyl) disulfide in a mass ratio of 1:2.

[0044] The production process of waterproof membrane is as follows: S1: Place the hydrophobic modifier, reinforcing agent, nano calcium carbonate, and antioxidant 3114 in a high-speed mixer and premix for 8 minutes to obtain a powder mixture; S2: Add high-density polyethylene, linear low-density polyethylene and compatibilizer to a twin-screw extruder, set the temperature as follows: Zone 1 163℃, Zone 2 168℃, Zone 3 175℃, Zone 4 177℃, Zone 5 183℃, Zone 6 190℃, screw speed 260 rpm, melt, add the powder mixture and crosslinking agent obtained in step S1, continue to melt and blend for 13 minutes to obtain the melt material; S3: The molten material obtained in step S2 is extruded through a die head at a temperature of 190°C to form a rolled material. The rolled material is then calendered at a temperature of 60°C, cooled, and wound up to obtain a waterproof rolled material.

[0045] Example 4 A waterproof membrane comprising the following components in parts by weight: 87g of high-density polyethylene, 36g of linear low-density polyethylene, 13g of hydrophobic modifier, 10g of reinforcing agent, 7g of compatibilizer, 4g of nano-alumina, 2g of crosslinking agent, and 1g of antioxidant 1076; the hydrophobic modifier was prepared in Preparation Example 4, the reinforcing agent was prepared in Preparation Example 8, and the compatibilizer was prepared in Preparation Example 12; the crosslinking agent was composed of diphenylthiazole disulfide and bis(4-mercaptophenyl) disulfide in a mass ratio of 1.1:2.3.

[0046] The production process of the waterproof membrane is the same as that in Example 3.

[0047] Comparative Example 1 The formulation and preparation method of the waterproof membrane in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that no hydrophobic modifier was added in this comparative example.

[0048] Comparative Example 2 The formulation and preparation method of the waterproof membrane in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that an equal amount of nano hydroxyapatite powder is used to replace the reinforcing agent in this comparative example.

[0049] Comparative Example 3 The formulation and preparation method of the waterproof membrane in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that anhydrous ethanol is used instead of glutaraldehyde in the preparation method of the reinforcing agent in this comparative example.

[0050] Comparative Example 4 The formulation and preparation method of the waterproof membrane in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that an equal amount of maleic anhydride-grafted polyethylene is used instead of the compatibilizer in this comparative example.

[0051] Comparative Example 5 The formulation and preparation method of the waterproof membrane in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that no crosslinking agent was added in this comparative example.

[0052] Test case Test samples: Waterproof membranes prepared in Examples 1-4 and Comparative Examples 1-5; Performance testing: The water impermeability, tensile strength, elongation at break, tear strength and puncture resistance of the test samples were tested according to GB / T 181.73-2012; the test results are shown in Table 1.

[0053] Table 1 Performance Test Results

[0054] As shown in Table 1, under a water pressure of 0.3 MPa, the waterproof membranes prepared in Examples 1-4 have a water permeability time of 228-243 min, which is far higher than the national standard requirement of 30 min, demonstrating outstanding waterproof and seepage prevention capabilities. The tensile strength is 22.3-23.4 MPa, the elongation at break is 604.3%-612.3%, the tear strength is 13.5-15.1 MPa, and the puncture resistance is 10.1-11.8 MPa, exhibiting excellent mechanical properties.

[0055] In addition, the hydrophobic modifier prepared in Example 3 was subjected to XRD and transmission electron microscopy tests, and the test results are shown in [Figure number missing]. Figure 1 and Figure 2 .Depend on Figure 1It can be seen that a wide and diffuse, dome-shaped diffuse diffraction pattern appears in the 2θ = 15-20° range, with a weak bulge in the 0-10° range. The diffraction intensity gradually decreases after 20°, with no obvious sharp crystalline peaks throughout. This is a typical XRD pattern characteristic of amorphous (non-crystalline) silica. The fumed silica used in the hydrophobic modifier of this invention is amorphous (non-crystalline) silica. This indicates that the modification process of the hydrophobic modifier does not affect the crystal structure of silica; the grafting reaction only occurs on the surface of the nano-silica particles, avoiding agglomeration and performance degradation caused by crystallization. Figure 2 It can be seen that the nano-silica particles in the hydrophobic modifier have a uniform particle size and no obvious agglomeration phenomenon.

[0056] The reinforcing agent prepared in Preparation Example 7 was also subjected to XRD testing, and the test results are shown in [Figure number missing]. Figure 3 .Depend on Figure 3 It can be seen that characteristic diffraction peaks appear at 2θ≈31.8° (corresponding to the (002) crystal plane) and 2θ≈39.8° (corresponding to the (211) crystal plane), which are completely consistent with the standard PDF card of hydroxyapatite. This indicates that the main component of the reinforcing agent is hydroxyapatite, and the subsequent modification processes such as chitosan coating and glutaraldehyde crosslinking only occur on the crystal surface and do not change the crystal structure and phase purity of hydroxyapatite. Moreover, the (002) peak and (211) peak in the spectrum are both sharp and strong peaks, indicating that the crystal preferentially grows along the c-axis direction to form a high aspect ratio sheet / rod nanostructure, which is completely consistent with the design of this invention that uses hexadecyltrimethylammonium bromide as a template to induce anisotropic growth.

[0057] The present invention also subjected the compatibilizer prepared in Preparation Example 11 to infrared spectroscopy testing, and the test results are shown in [Figure number missing]. Figure 4 .Depend on Figure 4 It can be seen that at 1650cm -1 A stretching vibration peak of C=O appeared at 1550 cm⁻¹, which is a characteristic peak of the amide bond formed by the reaction of trimesoyl chloride with the amino group of 4,4'-diaminodiphenyl ether. -1 A bending vibration peak of NH appears at 1000-1100 cm⁻¹, which originates from the residual amino group and the generated amide bond in the reaction system. -1 The strong absorption peak at this point corresponds to the stretching vibration peak of Si-O-Si, which is a characteristic peak of the octaaminophenyl cage-type polysilsesquioxane skeleton. This indicates that the octaaminophenyl cage-type polysilsesquioxane, 4,4'-diaminodiphenyl ether, and pyromellitic tricarboxylic acid chloride all participated in the polymerization reaction.

[0058] This specific embodiment is merely an explanation of the present invention and not a limitation thereof. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A waterproof membrane, characterized in that, The components include the following parts by weight: 80-90 parts high-density polyethylene, 30-50 parts linear low-density polyethylene, 10-15 parts hydrophobic modifier, 8-14 parts reinforcing agent, 5-10 parts compatibilizer, 3-5 parts filler, 1-3 parts crosslinking agent, and 0.5-1.5 parts antioxidant; The hydrophobic modifier is a fluorinated silane-nano silica hybrid particle. The preparation method of the hydrophobic modifier is as follows: 100g of fumed silica is dispersed in an ethanol aqueous solution and ultrasonically dispersed; 8-12g of perfluorooctyltriethoxysilane and 3-5g of tetraethyl orthosilicate are added, the pH is adjusted to 8-9 with ammonia water, and the reaction is stirred at 60℃ for 6-7h; centrifugation, washing, and drying are performed to obtain the hydrophobic modifier. The reinforcing agent is modified hydroxyapatite. The preparation method of the reinforcing agent is as follows: add hexadecyltrimethylammonium bromide template agent to Ca(NO3)2 solution and stir until dissolved. Add (NH4)2HPO4 solution while stirring. After the addition is completed, continue stirring for 20-30 min. Add ammonia water to adjust the pH value to 10.0-10.

5. Heat to 80-85℃ and stir for 12-13 h. Cool, filter, wash, and dry to obtain nano hydroxyapatite powder. Add the nano hydroxyapatite powder to chitosan acetate aqueous solution and stir at high speed for 30-50 min. Filter. Soak the filter cake in glutaraldehyde and let it stand for 10-12 h. Take it out, wash, dry, and pulverize to obtain the reinforcing agent. The compatibilizer is prepared as follows: N-methylpyrrolidone is added to octaaminophenyl cage-type polysilsesquioxane, and after stirring evenly, 4,4'-diaminodiphenyl ether is added and stirred evenly. A solution of N-methylpyrrolidone in trimesoyl chloride is added dropwise, and the mixture is stirred at -5°C for 1-2 hours. The temperature is then raised to room temperature and the mixture is stirred for another 4-5 hours. Triethylamine is added until the pH of the solution is neutral. The solution is then poured into ethanol to precipitate, washed, and dried to obtain the compatibilizer.

2. The waterproof membrane according to claim 1, characterized in that, The concentration of the Ca(NO3)2 solution is 0.5-0.6 mol / L, and the concentration of the (NH4)2HPO4 solution is 0.3-0.4 mol / L; the concentration of the hexadecyltrimethylammonium bromide in the Ca(NO3)2 solution is 2-3 g / L; the mass concentration of chitosan in the chitosan acetic acid aqueous solution is 0.5-0.8%, the mass concentration of glacial acetic acid is 1-2%, and the mass ratio of nano-hydroxyapatite powder to chitosan is 19:

1.

3. The waterproof membrane according to claim 1, characterized in that, The mass ratio of the octaaminophenyl cage-type polysilsesquioxane, 4,4'-diaminodiphenyl ether, and trimesoyl chloride is (2-4):(8-10):(5-7); the mass concentration of the N-methylpyrrolidone solution of trimesoyl chloride is 10-11 g / mL.

4. The waterproof membrane according to claim 1, characterized in that, The filler is one or more of nano-silica, nano-titanium dioxide, nano-calcium carbonate, and nano-alumina.

5. The waterproof membrane according to claim 1, characterized in that, The crosslinking agent is composed of diphenylthiazole disulfide and bis(4-mercaptophenyl) disulfide in a mass ratio of (0.8-1.2):(1.9-2.3).

6. The waterproof membrane according to claim 1, characterized in that, The antioxidant is one of antioxidant 1010, antioxidant 1076, and antioxidant 3114.

7. The manufacturing process of the waterproof membrane according to any one of claims 1-6, characterized in that, Includes the following steps: S1: Place the hydrophobic modifier, reinforcing agent, filler, and antioxidant in a high-speed mixer and premix for 5-10 minutes to obtain a powder mixture; S2: Add high-density polyethylene, linear low-density polyethylene and compatibilizer to a twin-screw extruder, set the temperature as follows: Zone 1 160-165℃, Zone 2 165-170℃, Zone 3 175℃, Zone 4 175-180℃, Zone 5 180-185℃, Zone 6 190℃, screw speed 200-300 rpm, melt, add the powder mixture and crosslinking agent obtained in step S1, continue to melt and blend for 10-15 minutes to obtain the melt material; S3: The molten material obtained in step S2 is extruded through a die at a temperature of 190°C to form a rolled material. The rolled material is then calendered at a temperature of 50-70°C, cooled, and wound up to obtain a waterproof rolled material.

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