Non-asphalt-based aging-resistant waterproof coiled material and preparation method thereof

Abstract

The application discloses a non-asphalt-based aging-resistant waterproof coiled material and a preparation method thereof. The main body layer is composed of a thermoplastic polyolefin resin, an ethylene-vinyl acetate copolymer and a fiber filler; the surface aging-resistant layer is composed of nano titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, a hindered phenol antioxidant, a phosphite auxiliary antioxidant, an organic tin stabilizer, a rare earth stabilizer, a silane coupling agent and a non-ionic surfactant; and the wear-resistant reinforcing layer is composed of methyl methacrylate-butadiene-styrene copolymer, nano aluminum oxide, gamma-methacryloyloxypropyl trimethoxysilane, an epoxy resin, an initiator and an accelerator. The application relates to the technical field of waterproof coiled materials. The methyl methacrylate-butadiene-styrene copolymer is used as a matrix, nano aluminum oxide is added as a wear-resistant filler, and surface modification treatment is carried out, so that a material with excellent wear resistance and comprehensive performance is prepared.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, specifically to a non-bitumen-based aging-resistant waterproof membrane and its preparation method. Background Technology

[0002] Asphalt waterproof membrane is the most important material in the field of building waterproofing applications. It is mainly made by impregnating asphalt with a base material such as paper or fiber felt, and then sprinkling powdery, granular, or sheet-like raw materials on the surface to form a rollable waterproof material. Among asphalt waterproof membranes, those rolls made by impregnating petroleum asphalt with thick paper or fiberglass cloth are called reinforced rolls; while those rolls made by mixing asbestos, rubber powder, etc. into asphalt materials and then rolling them are called roll-formed rolls, or unreinforced rolls. Because modified bitumen, when directly exposed to the atmosphere, undergoes significant aging, its performance deteriorates, leading to waterproofing failure. Therefore, all exposed bitumen waterproofing membranes have an anti-aging barrier material covering the bitumen surface to form a protective layer. This layer prevents the membrane from prolonged exposure to direct ultraviolet radiation and isolates it from most oxygen, thereby reducing the impact of aging factors such as ultraviolet radiation and oxygen. Summary of the Invention

[0003] To solve the above-mentioned technical problems, the present invention provides a non-asphalt-based aging-resistant waterproof membrane, the membrane being composed of a main layer, a surface aging-resistant layer, an adhesive layer, and a wear-resistant reinforcing layer; The main body layer is composed of thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer and fiber filler; The surface anti-aging layer is composed of nano-titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents and nonionic surfactants. The adhesive layer is composed of terpene resin and butyl rubber; The wear-resistant reinforcing layer is composed of methyl methacrylate-butadiene-styrene copolymer, nano-alumina, γ-methacryloyloxypropyltrimethoxysilane, epoxy resin, initiator and accelerator.

[0004] Preferred, a non-bitumen-based aging-resistant waterproof membrane, comprising the following components by weight: 40-45 parts by weight of thermoplastic polyolefin resin, 25-30 parts by weight of ethylene-vinyl acetate copolymer, 10-12 parts by weight of fiber filler, 10-15 parts by weight of nano-titanium dioxide, 5-10 parts by weight of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 3-5 parts by weight of hindered phenolic antioxidant, 2-4 parts by weight of phosphite auxiliary antioxidant, 3-6 parts by weight of organotin stabilizer, and dilute... Soil stabilizer 2-5 parts by weight, silane coupling agent 1-3 parts by weight, nonionic surfactant 1-2 parts by weight, terpene resin 3-5 parts by weight, butyl rubber 2-4 parts by weight, methyl methacrylate-butadiene-styrene copolymer 40-50 parts by weight, nano alumina 10-16 parts by weight, γ-methacryloyloxypropyltrimethoxysilane 3-6 parts by weight, epoxy resin 20-30 parts by weight, initiator 0.5-1.5 parts by weight, and accelerator 0.1-0.4 parts by weight.

[0005] Preferably, the fiber filler is composed of carbon fiber and polyester fiber, the hindered phenolic antioxidant is 2,6-di-tert-butyl-4-methylphenol, the phosphate ester auxiliary antioxidant is triphosphite, the nonionic surfactant is fatty alcohol polyoxyethylene ether, the initiator is benzoyl peroxide, and the accelerator is dimethylaniline.

[0006] A method for preparing a non-bitumen-based aging-resistant waterproof membrane includes the following steps: Step 1: Raw material procurement and inspection. Procurement of thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer, fiber filler, nano titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents, nonionic surfactants, terpene resins, butyl rubber, methyl methacrylate-butadiene-styrene copolymer, nano alumina, γ-methacryloyloxypropyltrimethoxysilane, epoxy resin, initiators, and accelerators according to the formula requirements. Step 2: Preparation of the main body layer. Thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer and fiber filler are added to a high-speed mixer and mixed for 15-20 minutes at a temperature of 80-100℃ and a speed of 1000-1500r / min. The mixed material is then added to a special extruder for the main body layer. After being heated and plasticized in the extruder, the material is extruded through a die to form a sheet of the main body layer, and then cooled and shaped. Step 3: Preparation of the surface anti-aging layer. Nano titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidant, phosphite auxiliary antioxidant, organotin stabilizer, rare earth stabilizer, silane coupling agent and nonionic surfactant are added to another high-speed mixer and mixed at 60-80℃ for 10-15 minutes. The mixed material is then added to a special extruder for the anti-aging layer and extruded to form an anti-aging layer sheet, which is then dried. Step 4: Preparation of the adhesive layer. Add the terpene resin and butyl rubber to a small mixer and mix at room temperature for 5-10 minutes. Step 5: Preparation of wear-resistant reinforcing layer. Add nano-alumina to an appropriate amount of ethanol and disperse it ultrasonically. Slowly add γ-methacryloxypropyltrimethoxysilane to the above dispersion while stirring continuously. After the addition is complete, continue stirring and reflux the mixed solution to react. After the reaction is complete, obtain the surface-modified nano-alumina by centrifugation. Wash with ethanol 3-5 times to remove unreacted γ-methacryloxypropyltrimethoxysilane and impurities, and then vacuum dry for later use. Prepolymerization reaction: Methyl methacrylate-butadiene-styrene copolymer is added to a reactor and heated until completely melted. Epoxy resin is added to the reactor and stirred evenly. Then an initiator is added, and stirring and heating are continued to carry out the prepolymerization reaction. Blending reaction: The surface-modified nano-alumina is added to the above prepolymer, and an accelerator is added at the same time. The mixture is thoroughly mixed under high-speed stirring, and then the temperature is raised to continue the reaction. After the reaction is completed, it is naturally cooled to room temperature to obtain a wear-resistant reinforcing layer. The prepared wear-resistant reinforcing layer is added to a special extruder for wear-resistant reinforcing layers and extruded to form wear-resistant reinforcing layer sheets; Step Six: Roll lamination. The prepared main layer, surface aging-resistant layer, adhesive layer and wear-resistant reinforcing layer are laminated in the order of main layer-adhesive layer-wear-resistant reinforcing layer-adhesive layer-surface aging-resistant layer through a lamination equipment. The laminated roll is then further calendered by a calender. Step 7: Post-treatment, cooling treatment is performed on the composite waterproof membrane.

[0007] Preferably, the ultrasonic dispersion time in step five is 30-60 minutes, and the stirring time after the addition is completed is set to 2-3 hours; The reflux reaction temperature of the mixed solution was set to 60-80℃, and the reflux reaction time was set to 4-6 hours. The vacuum drying temperature is set to 80-100℃, and the vacuum drying time is set to 6-8 hours.

[0008] Preferably, in the prepolymerization reaction, the heating temperature is set to 80-100℃, the temperature rise is set to 120-130℃, and the prepolymerization reaction time is set to 1-2 hours.

[0009] Preferably, the heating temperature in the blending reaction is set to 140-150°C, and the reaction time is set to 2-3 hours.

[0010] Preferredly, the preparation method of 2,6-di-tert-butyl-4-methylphenol involves adding p-cresol to a reaction vessel, then slowly adding concentrated sulfuric acid as a catalyst while stirring to ensure uniform dispersion. Next, isobutylene gas is slowly introduced under specific temperature and pressure conditions. The reaction temperature is generally controlled at 50-70°C, the pressure is maintained at 0.2-0.5 MPa, and the reaction time is 4-6 hours. After the reaction, the system is neutralized with sodium hydroxide solution to achieve a pH of approximately neutral. Following neutralization, a water washing operation is performed to remove water-soluble impurities such as salts generated during the reaction. This washing process is typically repeated multiple times until the pH of the washing solution remains essentially constant. Finally, the system is separated and purified using vacuum distillation to obtain 2,6-di-tert-butyl-4-methylphenol.

[0011] Preferredly, the method for preparing the triphosphite involves adding toluene as solvent to a reaction vessel, then slowly adding 2,4-di-tert-butylphenol and stirring until dissolved. Next, phosphorus trichloride is slowly added dropwise at a low temperature of 0-10°C, with strict temperature control during the addition process. After the addition is complete, the temperature is slowly raised to the reflux temperature, which is approximately 110-112°C, and the reaction is carried out for 3-5 hours. After the reaction, the mixture is neutralized and washed with water, and then separated and purified by vacuum distillation to obtain the triphosphite.

[0012] Preferably, the method for preparing the fatty alcohol polyoxyethylene ether involves adding a fatty alcohol and an alkaline catalyst to a reaction vessel, closing the reaction vessel and drawing a vacuum to remove air and moisture from the reaction system, then slowly introducing ethylene oxide at a temperature of 120-180℃ and a pressure of 0.2-0.5MPa to carry out the reaction, followed by neutralization and washing with water, and then separation and purification by vacuum distillation to obtain the fatty alcohol polyoxyethylene ether.

[0013] This invention provides a non-asphalt-based aging-resistant waterproof membrane and its preparation method, which has the following advantages: 1. Material Innovation: A novel modified polymer material is used in the wear-resistant reinforcing layer. Using methyl methacrylate-butadiene-styrene copolymer as the matrix, nano-alumina is added as a wear-resistant filler, and surface modification is performed. Combined with epoxy resin and other components, a material with excellent wear resistance and comprehensive performance is prepared. The application of this new material is innovative in the field of non-asphalt-based waterproof membranes, breaking through the performance limitations of traditional materials, improving the surface wear resistance of the membrane, and making it possible to apply waterproof membranes in some special environments.

[0014] 2. Synergistic use of multiple high-performance additives: The formulation comprehensively utilizes a variety of high-performance additives, such as nano-titanium dioxide, benzotriazole UV absorbers, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, and rare earth stabilizers. These additives improve the performance of the membrane from different aspects, and their synergistic effect gives the waterproof membrane significant advantages in aging resistance, oxidation resistance, and stability. This design concept of synergistic use of multiple additives is innovative in waterproof membrane formulation, providing new ideas and methods for improving product performance.

[0015] 3. Surface Modification and Dispersion Processes for Nanomaterials: Specific surface modification processes and dispersion methods were employed to address the unique characteristics of nano-titanium dioxide and nano-alumina. Through ultrasonic dispersion and surface modification using silane coupling agents (such as KH570), the problem of easy agglomeration of nanomaterials in the polymer matrix was effectively solved, improving their dispersion uniformity and compatibility with the matrix. This nanomaterial processing technology is innovative in the production of waterproof membranes, providing technical support for fully utilizing the superior properties of nanomaterials and also offering a reference for nano-applications in other related materials fields.

[0016] 4. The fabrication process of the multi-layer composite structure: This solution employs a unique multi-layer composite structure fabrication process, rationally combining and compositing the main layer, surface aging-resistant layer, adhesive layer, and wear-resistant reinforcing layer. By precisely controlling the fabrication process parameters of each layer, as well as the pressure and temperature conditions during interlayer bonding, a tight bond and synergistic effect between the layers are achieved, giving the waterproof membrane a variety of superior properties. This multi-layer composite structure design and fabrication process is innovative in the field of non-bitumen-based waterproof membranes, breaking through the limitations of traditional single-layer or simple multi-layer structures and opening up new avenues for improving the comprehensive performance of waterproof membranes.

[0017] 5. Significantly Improved Overall Performance: Through material and process innovation, the non-bitumen-based aging-resistant waterproof membrane prepared using this method exhibits significant improvements in aging resistance, abrasion resistance, waterproof performance, and mechanical strength. Compared to traditional waterproof membranes, it boasts a longer service life, better abrasion resistance, and more reliable waterproofing, meeting the needs of specialized building projects with high performance requirements for waterproof membranes. This innovative improvement in overall performance provides a superior solution for the building waterproofing field, driving the development and advancement of waterproof membrane technology.

[0018] 6. Multifunctional: This waterproof membrane not only possesses basic waterproofing capabilities but also integrates multiple functions such as aging resistance and abrasion resistance by adding different functional layers and materials. This multifunctional design concept aligns with the development trend of modern building materials, providing users with a multifunctional integrated product. It reduces the need for using and combining various functional materials during construction, improves construction efficiency and project quality, and possesses strong market competitiveness and application prospects. Detailed Implementation

[0019] The following embodiments further illustrate the present invention in detail. The embodiments of the present invention are given for illustrative and descriptive purposes only and are not intended to be exhaustive or to limit the invention to the disclosed forms. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described to better illustrate the principles and practical application of the invention, and to enable those skilled in the art to understand the invention and design various embodiments with various modifications suitable for a particular purpose.

[0020] Example 1: A non-asphalt-based aging-resistant waterproof membrane, the membrane being composed of a main layer, a surface aging-resistant layer, an adhesive layer, and a wear-resistant reinforcing layer; The main body layer is composed of thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer and fiber filler; The surface anti-aging layer is composed of nano-titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents and nonionic surfactants. The adhesive layer is composed of terpene resin and butyl rubber; The wear-resistant reinforcing layer is composed of methyl methacrylate-butadiene-styrene copolymer, nano-alumina, γ-methacryloyloxypropyltrimethoxysilane, epoxy resin, initiator and accelerator.

[0021] A non-asphalt-based aging-resistant waterproof membrane comprises the following components by weight: 40 parts by weight of thermoplastic polyolefin resin, 25 parts by weight of ethylene-vinyl acetate copolymer, 10 parts by weight of fiber filler, 10 parts by weight of nano-titanium dioxide, 5 parts by weight of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 3 parts by weight of hindered phenolic antioxidant, 2 parts by weight of phosphite auxiliary antioxidant, 3 parts by weight of organotin stabilizer, 2 parts by weight of rare earth stabilizer, 1 part by weight of silane coupling agent, 1 part by weight of nonionic surfactant, 3 parts by weight of terpene resin, 2 parts by weight of butyl rubber, 40 parts by weight of methyl methacrylate-butadiene-styrene copolymer, 10 parts by weight of nano-alumina, 3 parts by weight of γ-methacryloyloxypropyltrimethoxysilane, 20 parts by weight of epoxy resin, 0.5 parts by weight of initiator, and 0.1 parts by weight of accelerator.

[0022] The fiber filler is composed of carbon fiber and polyester fiber, the hindered phenolic antioxidant is 2,6-di-tert-butyl-4-methylphenol, the phosphate ester auxiliary antioxidant is triphosphite, the nonionic surfactant is fatty alcohol polyoxyethylene ether, the initiator is benzoyl peroxide, and the accelerator is dimethylaniline.

[0023] Example 2: A non-asphalt-based aging-resistant waterproof membrane, the membrane being composed of a main layer, a surface aging-resistant layer, an adhesive layer, and a wear-resistant reinforcing layer; The main body layer is composed of thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer and fiber filler; The surface anti-aging layer is composed of nano-titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents and nonionic surfactants. The adhesive layer is composed of terpene resin and butyl rubber; The wear-resistant reinforcing layer is composed of methyl methacrylate-butadiene-styrene copolymer, nano-alumina, γ-methacryloyloxypropyltrimethoxysilane, epoxy resin, initiator and accelerator.

[0024] A non-asphalt-based aging-resistant waterproof membrane comprises the following components by weight: 45 parts by weight of thermoplastic polyolefin resin, 30 parts by weight of ethylene-vinyl acetate copolymer, 12 parts by weight of fiber filler, 15 parts by weight of nano-titanium dioxide, 10 parts by weight of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5 parts by weight of hindered phenolic antioxidant, 4 parts by weight of phosphite auxiliary antioxidant, 6 parts by weight of organotin stabilizer, 5 parts by weight of rare earth stabilizer, 3 parts by weight of silane coupling agent, 2 parts by weight of nonionic surfactant, 5 parts by weight of terpene resin, 4 parts by weight of butyl rubber, 50 parts by weight of methyl methacrylate-butadiene-styrene copolymer, 16 parts by weight of nano-alumina, 6 parts by weight of γ-methacryloyloxypropyltrimethoxysilane, 30 parts by weight of epoxy resin, 1.5 parts by weight of initiator, and 0.4 parts by weight of accelerator.

[0025] The fiber filler is composed of carbon fiber and polyester fiber, the hindered phenolic antioxidant is 2,6-di-tert-butyl-4-methylphenol, the phosphate ester auxiliary antioxidant is triphosphite, the nonionic surfactant is fatty alcohol polyoxyethylene ether, the initiator is benzoyl peroxide, and the accelerator is dimethylaniline.

[0026] Example 3: A non-asphalt-based aging-resistant waterproof membrane, the membrane being composed of a main layer, a surface aging-resistant layer, an adhesive layer, and a wear-resistant reinforcing layer; The main body layer is composed of thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer and fiber filler; The surface anti-aging layer is composed of nano-titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents and nonionic surfactants. The adhesive layer is composed of terpene resin and butyl rubber; The wear-resistant reinforcing layer is composed of methyl methacrylate-butadiene-styrene copolymer, nano-alumina, γ-methacryloyloxypropyltrimethoxysilane, epoxy resin, initiator and accelerator.

[0027] A non-asphalt-based aging-resistant waterproof membrane comprises the following components by weight: 42.5 parts by weight of thermoplastic polyolefin resin, 27.5 parts by weight of ethylene-vinyl acetate copolymer, 11 parts by weight of fiber filler, 12.5 parts by weight of nano-titanium dioxide, 7.5 parts by weight of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 4 parts by weight of hindered phenolic antioxidant, 3 parts by weight of phosphite auxiliary antioxidant, 4.5 parts by weight of organotin stabilizer, 3.5 parts by weight of rare earth stabilizer, 2 parts by weight of silane coupling agent, 1.5 parts by weight of nonionic surfactant, 4 parts by weight of terpene resin, 3 parts by weight of butyl rubber, 45 parts by weight of methyl methacrylate-butadiene-styrene copolymer, 13 parts by weight of nano-alumina, 4.5 parts by weight of γ-methacryloyloxypropyltrimethoxysilane, 25 parts by weight of epoxy resin, 1 part by weight of initiator, and 0.25 parts by weight of accelerator.

[0028] The fiber filler is composed of carbon fiber and polyester fiber, the hindered phenolic antioxidant is 2,6-di-tert-butyl-4-methylphenol, the phosphate ester auxiliary antioxidant is triphosphite, the nonionic surfactant is fatty alcohol polyoxyethylene ether, the initiator is benzoyl peroxide, and the accelerator is dimethylaniline.

[0029] Example 4, based on Examples 1, 2, and 3, describes a method for preparing a non-asphalt-based aging-resistant waterproof membrane, comprising the following steps: I. Preparatory Work Raw material procurement and inspection Procurement of high-quality thermoplastic polyolefin (TPO) resin, ethylene-vinyl acetate copolymer (EVA), fiber filler, nano titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents, nonionic surfactants, terpene resins, butyl rubber, methyl methacrylate-butadiene-styrene copolymer (MBS), nano alumina, γ-methacryloyloxypropyltrimethoxysilane (KH570), epoxy resin (E-44), initiator (benzoyl peroxide, BPO), and accelerator (dimethylaniline, DMA) in accordance with formulation requirements.

[0030] Inspect the purchased raw materials to ensure that their quality meets relevant standards and formulation requirements, such as checking the molecular weight and purity of the resin, and the content of active ingredients in the additives.

[0031] Equipment debugging Prepare a high-speed mixer, an extruder (with different screw structures and specifications for each layer), a calender, a laminating equipment, a drying equipment, a winding equipment, etc.

[0032] The temperature control system, pressure control system, and speed control system of the equipment are debugged to ensure stable operation during production and to meet the required process parameters. For example, the screw temperature of the extruder should be set according to the characteristics of the raw materials in different layers, and the temperature generally increases gradually from the feeding section to the die head.

[0033] II. Preparation of Each Layer Preparation of the main layer Thermoplastic polyolefin (TPO) resin, ethylene-vinyl acetate copolymer (EVA), and fiber filler are added to a high-speed mixer.

[0034] Mix for 15-20 minutes at a certain temperature (80-100℃) and rotation speed (1000-1500r / min) to ensure the raw materials are fully and evenly mixed.

[0035] The mixed materials are added to the main body layer special extruder. The screw speed of the extruder is adjusted to 30-50 r / min according to the production speed requirements, and the machine body temperature is controlled at 180-220℃.

[0036] After being heated and plasticized in the extruder, the material is extruded through a die to form the main sheet, and then cooled and shaped. Air cooling or water cooling can be used to reduce its temperature to room temperature.

[0037] Preparation of surface aging-resistant layer Nano-titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents, and nonionic surfactants are added to another high-speed mixer.

[0038] Mix at a low temperature (60-80℃) for 10-15 minutes to avoid excessively high temperatures that could cause some additives to decompose or become ineffective.

[0039] The mixed material is added to a special extruder for aging-resistant layers. The extruder temperature is controlled at 160-190℃ and the screw speed is 20-40r / min.

[0040] The aging-resistant sheet is formed by extrusion, and the thickness is controlled according to the design requirements. After extrusion, it can be slightly stretched to orient its molecular chains and improve its performance. Then it is dried to remove moisture and volatile components. The drying temperature is 80-100℃ and the time is 2-3 hours.

[0041] Adhesive layer preparation Add the terpene resin and butyl rubber to a small mixer and mix at room temperature for 5-10 minutes to ensure uniform mixing.

[0042] The mixed adhesive is evenly applied to one side of the main layer or wear-resistant reinforcing layer using a coating device. The coating thickness is 0.1-0.3 mm, which can be adjusted according to the bonding performance requirements.

[0043] Preparation of wear-resistant reinforcing layer (novel modified polymer material) Nano-alumina surface modification: Add nano-alumina to an appropriate amount of ethanol and ultrasonically disperse for 30-60 minutes to ensure uniform dispersion in the ethanol solution.

[0044] Slowly add KH570 dropwise to the above dispersion, using 3-6 parts of the mass of nano-alumina. Stir continuously during the dropwise addition, and continue stirring for 2-3 hours after the addition is complete.

[0045] The mixed solution is then refluxed at 60-80℃ for 4-6 hours to allow KH570 to fully react with the hydroxyl groups on the surface of nano-alumina.

[0046] After the reaction is complete, the surface-modified nano-alumina is obtained by centrifugation, washed with ethanol 3-5 times to remove unreacted KH570 and impurities, and then vacuum dried at 80-100℃ for 6-8 hours for later use.

[0047] Prepolymerization reaction: Add MBS to a reaction vessel equipped with a stirrer, thermometer and condenser, and heat to 80-100℃ to melt it completely.

[0048] Add a certain amount of epoxy resin (E-44) to the reactor and stir until homogeneous.

[0049] Then add the initiator BPO, continue stirring and heat to 120-130℃, and carry out the prepolymerization reaction for 1-2 hours.

[0050] Blending reaction: Surface-modified nano-alumina was added to the prepolymer, with the amount of nano-alumina being 10-16 parts by mass of MBS. Accelerator DMA was also added.

[0051] The mixture is thoroughly mixed under high-speed stirring, then heated to 140-150℃ and reacted for 2-3 hours to allow the nano-alumina to be uniformly dispersed in the polymer matrix and to interact with the polymer.

[0052] After the reaction was completed, the mixture was naturally cooled to room temperature to obtain a novel modified polymer material.

[0053] The prepared novel modified polymer material is added to a special extruder for wear-resistant reinforcing layers. The extruder temperature is controlled at 170-200℃, and the screw speed is 25-45 r / min. The material is extruded to form a wear-resistant reinforcing layer sheet, with the thickness controlled according to design requirements.

[0054] III. Roll-on composite The prepared main layer, surface aging-resistant layer, adhesive layer and wear-resistant reinforcing layer are laminated in the order from bottom to top (main layer-adhesive layer-wear-resistant reinforcing layer-adhesive layer-surface aging-resistant layer) using a lamination device.

[0055] During the lamination process, appropriate pressure and temperature must be applied to ensure a tight bond between the layers. The pressure is generally controlled between 0.2 and 0.5 MPa, and the temperature is set according to the characteristics of the adhesive layer, typically between 100 and 130°C.

[0056] The composite roll material undergoes further calendering through a calendering machine to make the bonding between the layers tighter and the surface smoother. The calendering pressure is 0.3-0.6 MPa.

[0057] IV. Post-processing The composite waterproof membrane can be cooled by air cooling or water cooling to reduce its temperature to room temperature.

[0058] Quality inspection of the roll material includes visual inspection (for defects such as bubbles, wrinkles, and delamination), thickness measurement (to ensure it meets design requirements), and performance testing (such as tensile strength, elongation at break, aging resistance, and waterproof performance).

[0059] Based on the test results, qualified roll materials should be wound up and packaged. During winding, attention should be paid to tension control to avoid loosening or excessive stretching. Packaging materials can include plastic film or kraft paper to protect the roll materials from damage during transportation and storage.

[0060] The above preparation method yields a non-bitumen-based composite waterproof membrane with excellent aging resistance, abrasion resistance, and waterproofing properties. In actual production, strict control of process parameters at each stage is crucial to ensure product quality stability and reliability. Furthermore, the formula and preparation process can be appropriately adjusted and optimized based on actual production conditions and product performance requirements.

[0061] The preparation method of hindered phenolic antioxidants typically involves reactions carried out in a reactor equipped with a stirrer, thermometer, and reflux condenser. The stirrer ensures thorough mixing of the raw materials, the thermometer monitors the reaction temperature, and the reflux condenser allows volatile substances generated during the reaction to flow back into the reaction system, improving the utilization rate of the raw materials.

[0062] p-Cresol is added to the reaction vessel, followed by the slow addition of concentrated sulfuric acid as a catalyst, with stirring to ensure uniform dispersion. Then, isobutylene gas is slowly introduced under specific temperature and pressure conditions. The reaction temperature is generally controlled between 50-70℃, and the pressure is maintained at 0.2-0.5 MPa. Within this temperature and pressure range, the reaction proceeds smoothly, which is beneficial for improving the selectivity and yield of the reaction.

[0063] Reaction Time and Monitoring: The reaction time is typically 4-6 hours. During the reaction, the progress needs to be controlled by observing phenomena within the reactor (such as color changes, the presence of bubbles, etc.) and monitoring the reaction temperature and pressure. Gas chromatography and other analytical methods can be used to periodically monitor the content of raw materials and products in the reaction system. When the conversion rate of p-cresol reaches a certain level (e.g., above 90%) and the content of BHT no longer increases significantly, the reaction can be considered essentially complete.

[0064] Post-processing Neutralization and Washing: After the reaction is complete, the reaction mixture must first be neutralized to remove the concentrated sulfuric acid catalyst. Sodium hydroxide solution is typically used for neutralization to bring the pH of the reaction system to approximately neutral. After neutralization, a water washing process is performed to remove water-soluble impurities such as salts generated during the reaction. Washing is usually repeated several times until the pH of the washing solution remains essentially constant.

[0065] Separation and Purification: The reaction mixture after water washing contains BHT, unreacted raw materials, and a small amount of impurities. Vacuum distillation is used for separation and purification. Because BHT has a relatively high boiling point, vacuum distillation can separate BHT from other low-boiling-point substances at a lower temperature. The fraction collected within a specific temperature and pressure range (determined based on the boiling point of BHT and the vacuum conditions) is the preliminarily purified BHT product.

[0066] Crystallization and Drying: To further improve the purity of BHT, the pre-purified BHT product undergoes crystallization. Generally, BHT is dissolved in a suitable amount of hot organic solvent (such as ethanol), and then the solution is slowly cooled to allow BHT to crystallize out. The crystallized BHT is then filtered and finally dried in a vacuum drying oven at 50-60℃ for 4-6 hours to obtain high-purity 2,6-di-tert-butyl-4-methylphenol.

[0067] The preparation method of phosphate ester-based auxiliary antioxidants typically involves a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas absorption device. The stirrer ensures thorough mixing of the raw materials, the thermometer monitors the reaction temperature, the reflux condenser allows the organic solvent in the reaction system to be refluxed to maintain the stability of the reaction system, and the gas absorption device absorbs the hydrogen chloride gas generated during the reaction, preventing its leakage into the environment.

[0068] Addition sequence and reaction conditions: First, add the solvent (such as toluene) to the reactor, then slowly add 2,4-di-tert-butylphenol and stir until dissolved. Next, slowly add phosphorus trichloride dropwise at a low temperature (generally 0-10℃). Strict temperature control is crucial during the addition process, as phosphorus trichloride reacts violently with water and releases a large amount of heat. Excessive temperature may lead to runaway reaction. After the addition is complete, slowly raise the temperature to the reflux temperature (the reflux temperature of toluene is approximately 110-112℃) and react for several hours (generally 3-5 hours).

[0069] Post-processing Neutralization and Washing: After the reaction is complete, the reaction system contains hydrogen chloride and needs to be neutralized. This is usually done using an alkaline solution (such as sodium hydroxide solution) to bring the pH of the reaction system to neutral. After neutralization, a water washing process is performed to remove salt impurities generated during the reaction and unreacted raw materials. Washing is generally repeated several times until the pH of the washing solution remains essentially constant.

[0070] Separation and Purification: The reaction mixture after water washing contains antioxidant 168, solvent, and a small amount of impurities. Separation and purification are performed using vacuum distillation. First, the solvent is removed by distillation. Then, under vacuum conditions, the product fraction is collected based on the boiling point range of antioxidant 168 (approximately 180-200℃, which decreases under reduced pressure), yielding preliminarily purified antioxidant 168.

[0071] Crystallization and Drying: To further improve the purity of antioxidant 168, the pre-purified product undergoes crystallization. Antioxidant 168 is dissolved in an appropriate amount of hot solvent (such as ethanol or methanol), and then the solution is slowly cooled to allow antioxidant 168 to crystallize out. The crystallized antioxidant 168 is obtained by filtration and then dried in a vacuum drying oven at a temperature generally controlled at 50-70℃ for 4-6 hours to obtain high-purity tris(2,4-di-tert-butylphenyl) phosphite.

[0072] The method for preparing nonionic surfactants involves a reaction carried out in a high-pressure reactor equipped with a stirrer, thermometer, pressure gauge, and cooling device. The stirrer ensures thorough mixing of the raw materials, while the thermometer and pressure gauge monitor the reaction temperature and pressure, respectively. The cooling device controls the temperature during the reaction to prevent runaway reaction.

[0073] Feeding sequence and reaction conditions: First, add the fatty alcohol and catalyst to the reactor, close the reactor, and evacuate to remove air and moisture from the reaction system. Then, slowly introduce ethylene oxide at a specific temperature (generally 120-180℃) and pressure (generally 0.2-0.5MPa). Controlling the reaction temperature and pressure is crucial; excessively high temperatures may increase side reactions, while excessively high pressures pose safety risks. The rate of ethylene oxide introduction should be moderate to ensure a stable reaction.

[0074] Reaction Time and Monitoring: The reaction time depends on the amount of ethylene oxide added and the reaction rate, and generally requires several hours. During the reaction, the progress is judged by monitoring parameters such as pressure, temperature, and stirring power inside the reactor. When the pressure stops decreasing, it indicates that the ethylene oxide has reacted essentially completely.

[0075] Post-processing Neutralization and Washing: After the reaction is complete, the reaction products must first be neutralized to remove the catalyst. This is typically done using an acid (such as acetic acid) to bring the pH of the reaction system close to neutral. After neutralization, a water washing process is performed to remove salt impurities generated during the reaction and unreacted raw materials. Washing usually needs to be repeated several times until the pH of the washing solution remains essentially constant.

[0076] Separation and Purification: The reaction mixture after water washing contains fatty alcohol polyoxyethylene ether, a small amount of impurities, and water. Separation and purification are performed using vacuum distillation. First, water and low-boiling-point impurities are removed by distillation. Then, under vacuum conditions, the product fraction is collected according to the boiling point range of the fatty alcohol polyoxyethylene ether to obtain preliminarily purified fatty alcohol polyoxyethylene ether.

[0077] Filtration and drying: The pre-purified product is filtered to remove any possible solid impurities, and then dried in a vacuum drying oven. The drying temperature is generally controlled at 50-70℃, and the drying time is 4-6 hours to obtain a high-purity fatty alcohol polyoxyethylene ether product.

[0078] The three examples of non-bitumen-based aging-resistant waterproof membranes each have their own characteristics and advantages. Example 1, while having relatively weaker performance in various aspects, may have a lower cost, making it suitable for short-term or temporary construction projects and small projects where cost is sensitive. Example 2 boasts excellent overall performance, exhibiting outstanding abrasion resistance, aging resistance, and oxidation resistance, and is highly reliable, making it suitable for large public buildings, critical infrastructure, and construction projects in harsh environments. Example 3 offers a balance between performance and cost, placing it at a moderate level, and is suitable for general use environments, including general commercial and residential projects, as well as medium-sized projects with certain cost requirements. In practical applications, a comprehensive consideration based on specific circumstances is necessary to achieve the best balance between waterproofing effect and economic benefits.

[0079] Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art and related fields based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention. Structures, devices, and operating methods not specifically described and explained in the present invention, unless otherwise specified or limited, shall be implemented according to conventional means in the art.

Claims

1. A non-bitumen-based aging-resistant waterproof membrane, characterized in that: The roll material consists of a main layer, a surface aging-resistant layer, an adhesive layer, and a wear-resistant reinforcing layer; The main body layer is composed of thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer and fiber filler; The surface anti-aging layer is composed of nano-titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents and nonionic surfactants. The adhesive layer is composed of terpene resin and butyl rubber; The wear-resistant reinforcing layer is composed of methyl methacrylate-butadiene-styrene copolymer, nano-alumina, γ-methacryloyloxypropyltrimethoxysilane, epoxy resin, initiator and accelerator. The product comprises the following components by weight: 40-45 parts by weight of thermoplastic polyolefin resin, 25-30 parts by weight of ethylene-vinyl acetate copolymer, 10-12 parts by weight of fiber filler, 10-15 parts by weight of nano-titanium dioxide, 5-10 parts by weight of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 3-5 parts by weight of hindered phenolic antioxidant, 2-4 parts by weight of phosphite auxiliary antioxidant, 3-6 parts by weight of organotin stabilizer, and 2-5 parts by weight of rare earth stabilizer. The following components are present: 1-3 parts by weight of silane coupling agent, 1-2 parts by weight of nonionic surfactant, 3-5 parts by weight of terpene resin, 2-4 parts by weight of butyl rubber, 40-50 parts by weight of methyl methacrylate-butadiene-styrene copolymer, 10-16 parts by weight of nano alumina, 3-6 parts by weight of γ-methacryloyloxypropyltrimethoxysilane, 20-30 parts by weight of epoxy resin, 0.5-1.5 parts by weight of initiator and 0.1-0.4 parts by weight of accelerator; The preparation method of this non-asphalt-based aging-resistant waterproof membrane Includes the following steps, Step 1: Raw material procurement and inspection. Procurement of thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer, fiber filler, nano titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidants, phosphite auxiliary antioxidants, organotin stabilizers, rare earth stabilizers, silane coupling agents, nonionic surfactants, terpene resins, butyl rubber, methyl methacrylate-butadiene-styrene copolymer, nano alumina, γ-methacryloyloxypropyltrimethoxysilane, epoxy resin, initiators, and accelerators according to the formula requirements. Step 2: Preparation of the main body layer. Thermoplastic polyolefin resin, ethylene-vinyl acetate copolymer and fiber filler are added to a high-speed mixer and mixed for 15-20 minutes at a temperature of 80-100℃ and a speed of 1000-1500r / min. The mixed material is then added to a special extruder for the main body layer. After being heated and plasticized in the extruder, the material is extruded through a die to form a sheet of the main body layer, and then cooled and shaped. Step 3: Preparation of the surface anti-aging layer. Nano titanium dioxide, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, hindered phenolic antioxidant, phosphite auxiliary antioxidant, organotin stabilizer, rare earth stabilizer, silane coupling agent and nonionic surfactant are added to another high-speed mixer and mixed at 60-80℃ for 10-15 minutes. The mixed material is then added to a special extruder for the anti-aging layer and extruded to form an anti-aging layer sheet, which is then dried. Step 4: Preparation of the adhesive layer. Add the terpene resin and butyl rubber to a small mixer and mix at room temperature for 5-10 minutes. Step 5: Preparation of wear-resistant reinforcing layer. Add nano-alumina to an appropriate amount of ethanol and disperse it ultrasonically. Slowly add γ-methacryloxypropyltrimethoxysilane to the above dispersion while stirring continuously. After the addition is complete, continue stirring and reflux the mixed solution to react. After the reaction is complete, obtain the surface-modified nano-alumina by centrifugation. Wash with ethanol 3-5 times to remove unreacted γ-methacryloxypropyltrimethoxysilane and impurities, and then vacuum dry for later use. Prepolymerization reaction: Methyl methacrylate-butadiene-styrene copolymer is added to a reactor and heated until completely melted. Epoxy resin is added to the reactor and stirred evenly. Then an initiator is added, and stirring and heating are continued to carry out the prepolymerization reaction. Blending reaction: The surface-modified nano-alumina is added to the above prepolymer, and an accelerator is added at the same time. The mixture is thoroughly mixed under high-speed stirring, and then the temperature is raised to continue the reaction. After the reaction is completed, it is naturally cooled to room temperature to obtain a wear-resistant reinforcing layer. The prepared wear-resistant reinforcing layer is added to a special extruder for wear-resistant reinforcing layers and extruded to form wear-resistant reinforcing layer sheets; Step Six: Roll lamination. The prepared main layer, surface aging-resistant layer, adhesive layer and wear-resistant reinforcing layer are laminated in the order of main layer-adhesive layer-wear-resistant reinforcing layer-adhesive layer-surface aging-resistant layer through a lamination equipment. The laminated roll is then further calendered by a calender. Step 7: Post-treatment, cooling treatment is performed on the composite waterproof membrane.

2. The non-bitumen-based aging-resistant waterproof membrane according to claim 1, characterized in that: The fiber filler is composed of carbon fiber and polyester fiber, the hindered phenolic antioxidant is 2,6-di-tert-butyl-4-methylphenol, the phosphite auxiliary antioxidant is triphosphite, the nonionic surfactant is fatty alcohol polyoxyethylene ether, the initiator is benzoyl peroxide, and the accelerator is dimethylaniline.

3. The non-bitumen-based aging-resistant waterproof membrane according to claim 2, characterized in that: In step five, the ultrasonic dispersion time is 30-60 minutes, and the stirring time after the droplet addition is set to 2-3 hours. The reflux reaction temperature of the mixed solution was set to 60-80℃, and the reflux reaction time was set to 4-6 hours. The vacuum drying temperature is set to 80-100℃, and the vacuum drying time is set to 6-8 hours.

4. The non-bitumen-based aging-resistant waterproof membrane according to claim 2, characterized in that: In the prepolymerization reaction, the heating temperature is set to 80-100℃, the temperature rise is set to 120-130℃, and the prepolymerization reaction time is set to 1-2 hours.

5. The non-bitumen-based aging-resistant waterproof membrane according to claim 2, characterized in that: The heating temperature in the blending reaction is set to 140-150℃, and the reaction time is set to 2-3 hours.

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