Photoaging-resistant thermoplastic polyolefin waterproof coiled material and preparation method thereof

Abstract

The invention discloses a photoaging-resistant thermoplastic polyolefin waterproof coiled material which comprises the following raw materials: basic resin, the material proportion of the basic resin is about 65-75%, and the basic resin comprises high-crystallinity polypropylene, metallocene polyethylene and a cyclic olefin copolymer; the material proportion of the composite stabilizing material and the composite stabilizing agent is about 4-6%, and the composite stabilizing agent comprises a nano cerium oxide coated ultraviolet light absorber, a high molecular weight hindered amine light stabilizer, a novel benzotriazole / triazine hybrid stabilizing agent and a composite antioxidant; the material proportion of the functional filler is about 18-22%, and the functional filler comprises silane coupling agent modified nano kaolin, titanate treated calcium carbonate and graphene modified glass beads; and the material proportion of the special auxiliary agent is about 3-5%, and the special auxiliary agent comprises a hyperbranched polyester plasticizer, a phosphorus-nitrogen intumescent flame retardant and a fluorine surfactant. Compared with the prior art, the invention has the advantages of strong weatherability, high tensile strength and fracture resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of waterproof coiled materials, and particularly to a light-aging resistant thermoplastic polyolefin waterproof coiled material and a preparation method thereof. Background Art

[0002] During the operation of photovoltaic devices, there is usually energy conversion, which causes a huge change in the surrounding environment temperature and accelerates the aging of waterproof coiled materials. These characteristics make high requirements for the aging resistance and wide-temperature elastic properties of the materials for photovoltaic waterproof coiled materials. Thermoplastic polyolefin (TPO) waterproof coiled materials are sheet-shaped thermoplastic rubber elastic waterproof materials made of ethylene resin as the base material by using polymerization technology and a specific formula. The ingredients do not contain plasticizers, so there is no embrittlement caused by plasticizer migration, and they have the characteristics of environmental protection. They are waterproof coiled materials that have developed rapidly in recent years.

[0003] However, the patents under the existing technology have the following several disadvantages:

[0004] (1) The existing invented waterproof coiled materials have poor weather resistance, low tensile strength, are easy to break, and lack the function of self-repair. After being affected by harsh environments, timely maintenance is required. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the above technical defects and provide a light-aging resistant thermoplastic polyolefin waterproof coiled material with strong weather resistance, high tensile strength, and fracture resistance.

[0006] To solve the above problems, the technical solution of the present invention is: a light-aging resistant thermoplastic polyolefin waterproof coiled material, comprising the following raw materials:

[0007] Base resin, the material proportion of the base resin is about 65 - 75%, and the base resin includes high-crystallinity polypropylene, metallocene polyethylene, and cyclic olefin copolymer;

[0008] Composite stabilizer, the material proportion of the composite stabilizer is about 4 - 6%, and the composite stabilizer includes nano-ceria-coated ultraviolet absorber, high-molecular-weight hindered amine light stabilizer, novel benzotriazole / triazine hybrid stabilizer, and composite antioxidant;

[0009] Functional filler, the material proportion of the functional filler is about 18 - 22%, and the functional filler includes silane-coupling-agent-modified nano-kaolin, titanate-treated calcium carbonate, and graphene-modified glass microspheres;

[0010] Special additive, the material proportion of the special additive is about 3 - 5%, and the special additive includes hyperbranched polyester plasticizer, phosphorus-nitrogen-based intumescent flame retardant, and fluorosurfactant.

[0011] Furthermore,

[0012] The proportion of the high-crystallinity polypropylene material is about 45-50%. The high-crystallinity polypropylene provides a rigid skeleton structure. Through the β-crystal form regulation technology, the crystallinity reaches more than 70%, endowing the material with high strength and creep resistance ability;

[0013] The proportion of the metallocene polyethylene material is about 20-25%. The metallocene polyethylene realizes the flexible-rigid dynamic balance. The metallocene polyethylene and the high-crystallinity polypropylene form an interpenetrating network structure, improving the elongation at break;

[0014] The proportion of the cyclic olefin copolymer material is about 5%. The cyclic olefin copolymer reacts with the radical scavenger through the double bond in the cyclic structure to form a self-healing network, enhancing the three-dimensional crosslinking, reducing the water absorption rate, and eliminating the interfacial water vapor erosion.

[0015] Furthermore,

[0016] The proportion of the nano-ceria-coated ultraviolet absorber material is about 1.5%. The core-shell structure of the nano-ceria-coated ultraviolet absorber is formed by coating the benzotriazole core with nano-CeO2 shell through plasma spraying. The nano-ceria-coated ultraviolet absorber gradually releases Ce 3 + ions to repair material defects;

[0017] The proportion of the high-molecular-weight hindered amine light stabilizer material is about 1.2%. The high-molecular-weight hindered amine light stabilizer has a seven-membered ring structure and forms a persistent protection by capturing free radicals (·OH, RO·) and regenerating nitroxyl radicals (NOR·), increasing the number of anti-aging cycles;

[0018] The proportion of the benzotriazole / triazine hybrid stabilizer material is about 1.0%. The benzotriazole / triazine hybrid stabilizer connects two functional groups of the benzotriazole unit and the triazine ring through covalent bonds. The hybrid structure enhances the light stability of the material and improves the ultraviolet absorption ability;

[0019] The proportion of the composite antioxidant material is about 0.8%. The composite antioxidant is composed of a phenolic antioxidant that captures alkoxy free radicals and a phosphite antioxidant that decomposes hydroperoxides.

[0020] Furthermore,

[0021] The proportion of the silane coupling agent-modified nano-kaolin material is about 12%. The surface of the silane coupling agent-modified nano-kaolin is grafted with γ-aminopropyltriethoxysilane and chemically bonded to the resin matrix through Si-O-Si bonds. The layered structure forms a maze effect, reducing the oxygen transmission rate by 70% and increasing the flexural modulus to 2200 MPa;

[0022] The proportion of the titanate-treated calcium carbonate material is about 6-8%, and the titanate-treated calcium carbonate forms a "hard core-soft shell" structure, with the impact strength increased by 40%;

[0023] The proportion of the graphene-modified glass microspheres material is about 2%. Three to five layers of graphene are grown on the surface of the microspheres by chemical vapor deposition (CVD). The in-plane thermal conductivity is improved, local hot spots are eliminated, and strain buffering is achieved through the wrinkled structure.

[0024] Furthermore,

[0025] The proportion of the hyperbranched polyester plasticizer material is about 2%. The hyperbranched polyester plasticizer can reduce the melt viscosity without migration, and the hyperbranched polyester plasticizer can form a hydrogen bond network between the terminal hydroxyl groups and the filler surface;

[0026] The proportion of the microencapsulated phosphazene flame retardant material is about 1.5%. When the microencapsulated phosphazene flame retardant encounters fire, the outer shell thermally decomposes and releases the flame retardant components;

[0027] The proportion of the fluorosurfactant material is about 0.5%. The fluorosurfactant reduces the surface tension to 18 mN / m, constructs a hydrophobic surface while maintaining the adhesive property of the back glue.

[0028] A preparation method of a light-fast thermoplastic polyolefin waterproof coiled material is as follows:

[0029] S1. Pretreatment of raw materials. The nano kaolin modified by silane coupling agent, the graphene-modified glass microspheres and the phosphazene intumescent flame retardant are respectively preprocessed;

[0030] Pretreatment of the nano kaolin modified by silane coupling agent: First, the nano kaolin and 3% KH550 silane coupling agent are filled into a high-speed mixer according to the solid-liquid ratio of 1:5 in an ethanol solution. Then, the mixing temperature is maintained at 80 °C, and the stirring paddle speed is maintained at 1200 rpm for 2 hours of mixing to complete grafting. Finally, a spray drying tower is used to maintain the inlet temperature at 180 °C and the outlet temperature at 80 °C for spray drying to obtain activated powder, and the preparation of the nano kaolin modified by silane coupling agent is completed;

[0031] Pretreatment of the graphene-modified glass microspheres: The equipment used is a chemical vapor deposition (CVD) system. Under an Ar / H2 atmosphere, pyrolysis of methane at 1050 °C is carried out according to the flow ratio of 10:1 to grow graphene, and the growth time is controlled for 20 min to obtain a 3-5 layer graphene coating layer, and the preparation of the graphene-modified glass microspheres is completed;

[0032] Pretreatment of phosphorus-nitrogen intumescent flame retardant: The equipment used is a microfluidic emulsification system. First, APP / MPP is mixed at a ratio of 4:1, and the core material is dispersed in toluene. It is injected into the isocyanate / amine monomer interface polymerization through a microchannel with a diameter of 200 μm, maintaining a reaction temperature of 45 °C and reacting for 6 h to form a 200-nm-thick polyurea shell layer, completing the preparation of the pretreatment of the phosphorus-nitrogen intumescent flame retardant;

[0033] S2. Premixing process: The equipment used is a vacuum three-dimensional motion mixer. The base resin is premixed for 3 minutes, then the composite stabilizer is added to the mixer in three portions at intervals of 2 minutes for mixing. Finally, the functional filler and special additives are added, with the rotation speed maintained at 900 rpm and the vacuum degree maintained at -0.08 MPa for 20 minutes of mixing;

[0034] S3. Melt blending: The equipment used is a co-rotating twin-screw extruder with L / D = 40. The premixed raw materials are sheared, stretched, and kneaded, realizing the precise dispersion and interfacial bonding of the light-resistant aging functional components and constructing a multi-scale protection system;

[0035] S4. Extrusion and calendering molding: The equipment used is a three-roll calender capable of controlling the roll temperature gradient. The upper roll is set at a temperature of 100 °C and a rotation speed of 8 rpm, the middle roll is set at a temperature of 110 °C and a rotation speed of 10 rpm, and the lower roll is set at a temperature of 90 °C and a rotation speed of 12 rpm. The melt-blended raw materials are extruded and calendered, and a 50-kHz alternating magnetic field is applied in the calendering gap to align the nano-fillers along the MD direction;

[0036] S5. Surface microstructure treatment: The equipment used is a femtosecond laser processing system. The wavelength is set at 1030 nm, the pulse energy is 50 μJ, and the scanning speed is 200 mm / s to generate a hexagonal pit array with a spacing of 20 μm, and a 500-nm fluff structure is secondarily processed in the pits;

[0037] S6. Cooling and shaping: First, cooling is carried out by an air knife with a wind speed of 15 m / s and a temperature of 60 °C, and then cooling is carried out by a water-cooled roll with a water temperature of 25 °C and a contact time of 8 s to complete the cooling preparation of the coil.

[0038] The advantages of the present invention compared with the existing technology are as follows:

[0039] (1) The thermoplastic polyolefin waterproofing membrane with light aging resistance of the present invention uses highly crystalline polypropylene, metallocene polyethylene and cyclic olefin copolymer as the matrix, and realizes high-temperature stability and low-temperature crack resistance through the COC self-healing network. It innovatively uses nano-ceria-coated ultraviolet absorber and high molecular weight HALS to cooperate to form a three-level protection of reflection-absorption-repair. After 5000h of ultraviolet aging, the strength retention rate > 90%, which is 20% higher than that of traditional waterproofing membranes. Silane-modified nano-kaolin reduces oxygen penetration by 70%, graphene glass microspheres build a heat conduction network to eliminate thermal stress, and microcapsule flame retardants achieve intelligent fire protection. It is suitable for extreme environments such as photovoltaic roofs, and the comprehensive cost is reduced by 40%, promoting the long-term upgrade of waterproof materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 It is the raw material ratio diagram of the thermoplastic polyolefin waterproofing membrane with light aging resistance of the present invention.

[0041] Figure 2 It is the preparation flow chart of the thermoplastic polyolefin waterproofing membrane with light aging resistance of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0042] The following will further illustrate the specific embodiments of the present invention with reference to the accompanying drawings. Among them, the same components are denoted by the same reference numerals.

[0043] It should be noted that the words "front", "rear", "left", "right", "up" and "down" used in the following description refer to the directions in the drawings, and the words "inner" and "outer" refer to the directions towards or away from the geometric center of the specific component respectively.

[0044] In order to make the content of the present invention more clearly understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0045] As Figures 1 to 2 shown, a thermoplastic polyolefin waterproofing membrane with light aging resistance includes the following raw materials:

[0046] Base resin, the material proportion of the base resin is about 65 - 75%, and the base resin includes high-crystallinity polypropylene, metallocene polyethylene, and cyclic olefin copolymer; the material proportion of high-crystallinity polypropylene is about 45 - 50%, and high-crystallinity polypropylene provides a rigid skeleton structure. Through the β-crystal form control technology, the crystallinity reaches more than 70%, endowing the material with high strength and creep resistance; the material proportion of metallocene polyethylene is about 20 - 25%, and metallocene polyethylene realizes the flexible-rigid dynamic balance. Metallocene polyethylene and high-crystallinity polypropylene form an interpenetrating network structure to improve the elongation at break; the material proportion of cyclic olefin copolymer is about 5%, and the cyclic olefin copolymer reacts with a radical scavenger through the double bond in the cyclic structure to form a self-healing network, enhance three-dimensional crosslinking, reduce the water absorption rate, and eliminate the interface water vapor erosion.

[0047] Composite stabilizer material, the material proportion of the composite stabilizer is about 4 - 6%, and the composite stabilizer includes nano-ceria-coated ultraviolet absorber, high-molecular-weight hindered amine light stabilizer, novel benzotriazole / triazine hybrid stabilizer, and composite antioxidant; the material proportion of nano-ceria-coated ultraviolet absorber is about 1.5%, and the core-shell structure of the nano-ceria-coated ultraviolet absorber is formed by coating the benzotriazole core with nano-CeO2 shell through plasma spraying. The nano-ceria-coated ultraviolet absorber gradually releases Ce 3 + ions to repair material defects; the material proportion of high-molecular-weight hindered amine light stabilizer is about 1.2%, and the high-molecular-weight hindered amine light stabilizer has a seven-membered ring structure. It forms a lasting protection by capturing free radicals (·OH, RO·) and regenerating nitroxyl radicals (NOR·), increasing the number of anti-aging cycles; the material proportion of benzotriazole / triazine hybrid stabilizer is about 1.0%, and the benzotriazole / triazine hybrid stabilizer connects two functional groups, the benzotriazole unit and the triazine ring, through a covalent bond. The hybrid structure enhances the light stability of the material and improves the ultraviolet absorption ability; the material proportion of the composite antioxidant is about 0.8%, and the composite antioxidant is composed of a phenolic antioxidant that captures alkoxy free radicals and a phosphite antioxidant that decomposes hydroperoxides.

[0048] Functional fillers, the material proportion of the functional fillers is about 18 - 22%, and the functional fillers include nano kaolin modified by silane coupling agent, calcium carbonate treated with titanate, and graphene modified glass microspheres; the material proportion of nano kaolin modified by silane coupling agent is about 12%, the surface of nano kaolin modified by silane coupling agent is grafted with γ-aminopropyltriethoxysilane, chemically bonded to the resin matrix through Si-O-Si bonds, and the layered structure forms a maze effect, reducing the oxygen transmission rate by 70% and increasing the flexural modulus to 2200 MPa; the material proportion of calcium carbonate treated with titanate is about 6 - 8%, and the calcium carbonate treated with titanate forms a "hard core - soft shell" structure, increasing the impact strength by 40%; the material proportion of graphene modified glass microspheres is about 2%, and 3 - 5 layers of graphene are grown on the surface of the microspheres by chemical vapor deposition, increasing the in-plane thermal conductivity, eliminating local hot spots, and achieving strain buffering through the wrinkled structure.

[0049] Special additives, the material proportion of the special additives is about 3 - 5%, and the special additives include hyperbranched polyester plasticizer, phosphorus - nitrogen based intumescent flame retardant, and fluorosurfactant; the material proportion of hyperbranched polyester plasticizer is about 2%, and the hyperbranched polyester plasticizer can reduce the melt viscosity without migration, and the hyperbranched polyester plasticizer can form a hydrogen bond network between the terminal hydroxyl groups and the filler surface; the material proportion of microencapsulated phosphorus - nitrogen based flame retardant is about 1.5%, and when the microencapsulated phosphorus - nitrogen based flame retardant encounters fire, the outer shell thermally decomposes and releases the flame retardant components; the material proportion of fluorosurfactant is about 0.5%, and the fluorosurfactant reduces the surface tension to 18 mN / m, constructing a hydrophobic surface while maintaining the adhesive property of the back glue.

[0050] A preparation method of a light - aging resistant thermoplastic polyolefin waterproof coil, the specific steps are as follows:

[0051] S1. Pretreatment of raw materials, respectively pre - process nano kaolin modified by silane coupling agent, graphene modified glass microspheres, and phosphorus - nitrogen based intumescent flame retardant;

[0052] Pretreatment of nano kaolin modified by silane coupling agent: First, load nano kaolin and 3% KH550 silane coupling agent into a high - speed mixer at a solid - liquid ratio of 1:5 in an ethanol solution. Then, keep the mixing temperature at 80 °C and the stirring paddle speed at 1200 rpm for 2 hours of mixing to complete the grafting. Finally, use a spray drying tower, keep the inlet temperature at 180 °C and the outlet temperature at 80 °C for spray drying to obtain activated powder, and complete the preparation of nano kaolin modified by silane coupling agent;

[0053] Pretreatment of graphene-modified glass microspheres: The equipment used is a chemical vapor deposition (CVD) system. Under an Ar / H2 atmosphere, pyrolysis of methane is carried out at 1050 °C to grow graphene according to a flow ratio of 10:1, and the growth time is controlled for 20 min to obtain a 3-5 layer graphene coating layer, thus completing the preparation of graphene-modified glass microspheres;

[0054] Pretreatment of phosphorus-nitrogen intumescent flame retardants: The equipment used is a microfluidic emulsification system. First, APP / MPP is mixed at a ratio of 4:1, and the core material is dispersed in toluene. It is injected into the isocyanate / amine monomer interface polymerization through a microchannel with a diameter of 200 μm, and the reaction temperature is maintained at 45 °C for 6 h of reaction to form a 200 nm thick polyurea shell layer, thus completing the preparation of the pretreatment of phosphorus-nitrogen intumescent flame retardants;

[0055] S2. Premixing process: The equipment used is a vacuum three-dimensional motion mixer. The base resin is premixed for 3 minutes, and then the composite stabilizer is added to the mixer in three portions at intervals of 2 minutes for mixing. Finally, the functional filler and special additives are added, the rotation speed is maintained at 900 rpm, and the vacuum degree is maintained at -0.08 MPa for 20 minutes of mixing;

[0056] S3. Melt blending: The equipment used is a co-rotating twin-screw extruder with L / D = 40. The premixed raw materials are sheared, stretched, and kneaded to achieve precise dispersion and interfacial bonding of the light-aging resistant functional components, and a multi-scale protection system is constructed;

[0057] S4. Extrusion and calendering: The equipment used is a three-roll calender capable of controlling the roll temperature gradient. The temperature of the upper roll is set at 100 °C, the rotation speed is 8 rpm, the temperature of the middle roll is set at 110 °C, the rotation speed is 10 rpm, and the temperature of the lower roll is set at 90 °C, the rotation speed is 12 rpm. The melt-blended raw materials are extruded and calendered, and a 50 kHz alternating magnetic field is applied in the calendering gap to align the nano-fillers in the MD direction;

[0058] S5. Surface microstructure treatment: The equipment used is a femtosecond laser processing system. The wavelength is set at 1030 nm, the pulse energy is 50 μJ, and the scanning speed is 200 mm / s to generate a hexagonal pit array with a spacing of 20 μm, and a 500 nm fluff structure is processed secondarily in the pits;

[0059] S6. Cooling and shaping: First, cooling is carried out through an air knife with a wind speed of 15 m / s and a temperature of 60 °C, and then cooling is carried out through a water-cooled roll with a water temperature of 25 °C and a contact time of 8 s to complete the cooling preparation of the coil.

[0060] The above describes the present invention and its embodiments. Such description is not restrictive. What is shown in the accompanying drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Generally speaking, if those of ordinary skill in the art are inspired by it and, without departing from the gist of the present invention, design structures and embodiments similar to the technical solution without creative efforts, they shall fall within the protection scope of the present invention.

Claims

1. A light aging-resistant thermoplastic polyolefin waterproofing membrane, characterized in that, It includes the following raw materials: Base resin, the material proportion of the base resin is about 65 - 75%, and the base resin includes high-crystallinity polypropylene, metallocene polyethylene, and cyclic olefin copolymer; Composite stabilizer, the material proportion of the composite stabilizer is about 4 - 6%, and the composite stabilizer includes nano-ceria-coated ultraviolet absorber, high molecular weight hindered amine light stabilizer, novel benzotriazole / triazine hybrid stabilizer, and composite antioxidant; Functional filler, the material proportion of the functional filler is about 18 - 22%, and the functional filler includes silane-coupled nano-kaolin, titanate-treated calcium carbonate, and graphene-modified glass microspheres; Special additive, the material proportion of the special additive is about 3 - 5%, and the special additive includes hyperbranched polyester plasticizer, phosphorus-nitrogen intumescent flame retardant, and fluorosurfactant.

2. A light-aging-resistant thermoplastic polyolefin waterproof coil according to claim 1, characterized in that: The material proportion of the high-crystallinity polypropylene is about 45 - 50%, and the high-crystallinity polypropylene provides a rigid skeleton structure. Through the β-crystal form control technology, the crystallinity reaches more than 70%, endowing the material with high strength and creep resistance; The material proportion of the metallocene polyethylene is about 20 - 25%, and the metallocene polyethylene realizes the flexible-rigid dynamic balance. The metallocene polyethylene and the high-crystallinity polypropylene form an interpenetrating network structure, improving the elongation at break; The material proportion of the cyclic olefin copolymer is about 5%, and the cyclic olefin copolymer reacts with the free radical scavenger through the double bond in the cyclic structure to form a self-healing network, enhancing the three-dimensional crosslinking, reducing the water absorption rate, and eliminating the interfacial water vapor erosion.

3. A light-aging-resistant thermoplastic polyolefin waterproof coil according to claim 1, characterized in that: The material proportion of the nano-ceria-coated ultraviolet absorber is about 1.5%. The core-shell structure of the nano-ceria-coated ultraviolet absorber is formed by coating a benzotriazole core with a nano-CeO2 shell through plasma spraying. The nano-ceria-coated ultraviolet absorber gradually releases Ce 3 + ions to repair material defects; The material proportion of the high molecular weight hindered amine light stabilizer is about 1.2%, and the high molecular weight hindered amine light stabilizer has a seven-membered cyclic structure. By capturing free radicals (·OH, RO·) and regenerating nitroxyl free radicals (NOR·), it forms a lasting protection and increases the number of anti-aging cycles; The material proportion of the benzotriazole / triazine hybrid stabilizer is about 1.0%, and the benzotriazole / triazine hybrid stabilizer connects the benzotriazole unit and the triazine ring through covalent bonds. The hybrid structure enhances the light stability of the material and improves the ultraviolet absorption ability; The material proportion of the composite antioxidant is about 0.8%, and the composite antioxidant is composed of a phenolic antioxidant that captures alkoxy free radicals and a phosphite antioxidant that decomposes hydroperoxides.

4. A light-aging-resistant thermoplastic polyolefin waterproof coil according to claim 1, characterized in that: The material proportion of the silane-coupled nano-kaolin is about 12%, and the surface of the silane-coupled nano-kaolin is grafted with γ-aminopropyltriethoxysilane. It is chemically bonded to the resin matrix through the Si-O-Si bond, and the layered structure forms a maze effect, reducing the oxygen transmission rate by 70% and increasing the flexural modulus to 2200 MPa; The proportion of the titanate-treated calcium carbonate material is about 6-8%, and the titanate-treated calcium carbonate forms a "hard core-soft shell" structure, with the impact strength increased by 40%; The proportion of the graphene-modified glass microbeads material is about 2%. Three to five layers of graphene are grown on the surface of the microbeads by chemical vapor deposition. The in-plane thermal conductivity is increased, local hot spots are eliminated, and strain buffering is achieved through the wrinkled structure.

5. A light-fast thermoplastic polyolefin waterproof coil according to claim 1, characterized in that: The proportion of the hyperbranched polyester plasticizer material is about 2%. The hyperbranched polyester plasticizer can reduce the melt viscosity without migration, and the hyperbranched polyester plasticizer can form a hydrogen bond network between the terminal hydroxyl groups and the filler surface; The proportion of the microencapsulated phosphorus-nitrogen-based flame retardant material is about 1.5%. When the microencapsulated phosphorus-nitrogen-based flame retardant encounters fire, the outer shell thermally decomposes and releases the flame retardant components; The proportion of the fluorosurfactant material is about 0.5%. The fluorosurfactant reduces the surface tension to 18 mN / m, constructs a hydrophobic surface while maintaining the adhesiveness of the back glue.

6. A preparation method of a light-fast thermoplastic polyolefin waterproof coil according to claims 1 to 5, the specific steps are as follows: S1. Pretreatment of raw materials, respectively preprocess the silane-coupled agent modified nano kaolin, graphene-modified glass microbeads and phosphorus-nitrogen-based intumescent flame retardant; Pretreatment of silane-coupled agent modified nano kaolin: First, load nano kaolin and 3% KH550 silane coupling agent into a high-speed mixer at a solid-liquid ratio of 1:5 in an ethanol solution. Then, keep the mixing temperature at 80 °C and the stirring paddle speed at 1200 rpm for 2 hours of mixing to complete grafting. Finally, use a spray drying tower, keep the inlet temperature at 180 °C and the outlet temperature at 80 °C for spray drying to obtain activated powder, and complete the preparation of silane-coupled agent modified nano kaolin; Pretreatment of graphene-modified glass microbeads: The equipment used is a chemical vapor deposition (CVD) system. Under an Ar / H2 atmosphere, pyrolyze methane at 1050 °C to grow graphene according to a flow ratio of 10:1, control the growth time for 20 min, and obtain a 3-5 layer graphene coating layer to complete the preparation of graphene-modified glass microbeads; Pretreatment of phosphorus-nitrogen-based intumescent flame retardant: The equipment used is a microfluidic emulsification system. First, mix APP / MPP at a ratio of 4:1, disperse the core material in toluene, inject it into the isocyanate / amine monomer interfacial polymerization through a 200-μm microchannel, keep the reaction temperature at 45 °C, and react for 6 h to form a 200-nm-thick polyurea shell layer to complete the preparation of the pretreatment of the phosphorus-nitrogen-based intumescent flame retardant; S2. Premixing process, the equipment used is a vacuum three-dimensional motion mixer. Premix the base resin for 3 minutes, then add the composite stabilizer to the mixer in three portions at intervals of 2 minutes for mixing. Finally, add the functional filler and special additives, keep the rotation speed at 900 rpm and the vacuum degree at -0.08 MPa for 20 minutes of mixing; S3. Melt blending is carried out using a co-rotating twin-screw extruder with L / D = 40. The premixed raw materials are sheared, stretched and kneaded to achieve precise dispersion and interfacial bonding of the light aging-resistant functional components, and a multi-scale protection system is constructed. S4. Extrusion and calendering molding is carried out using a three-roll calender capable of controlling the roll temperature gradient. The temperature of the upper roll is set at 100 °C, the rotation speed is 8 rpm, the temperature of the middle roll is set at 110 °C, the rotation speed is 10 rpm, the temperature of the lower roll is set at 90 °C, and the rotation speed is 12 rpm. The melt-blended raw materials are extruded and calendered, and a 50 kHz alternating magnetic field is applied in the calendering gap to orient the nano-fillers along the MD direction. S5. Surface microstructure treatment is carried out using a femtosecond laser processing system. The wavelength is set at 1030 nm, the pulse energy is 50 μJ, and the scanning speed is 200 mm / s to generate a hexagonal pit array with a 20 μm pitch. A 500 nm fluff structure is processed secondarily in the pits. S6. Cooling and shaping: First, cooling is carried out using an air knife with a wind speed of 15 m / s and a temperature of 60 °C, and then cooling is carried out using a water-cooled roll with a water temperature of 25 °C and a contact time of 8 s to complete the cooling preparation of the coil.

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