Flame-retardant hydrophobic exposed type polymer waterproof coiled material and preparation method thereof

Abstract

The invention relates to the technical field of building waterproof materials, in particular to a flame-retardant hydrophobic exposed type polymer waterproof roll and a preparation method thereof. The thermoplastic composition for the waterproof coiled material is adopted in the flame-retardant macromolecular waterproof coiled material. The thermoplastic composition for the waterproof coiled material comprises a flame-retardant pre-manufactured master batch, the flame-retardant pre-manufactured master batch comprises polyethylene, a flame retardant, graphene and a silane coupling agent; the composite material comprises the following components in parts by weight: 35-52 parts of polyethylene, 40-55 parts of a flame retardant, 2-6 parts of graphene and 2-6 parts of a silane coupling agent, the flame retardant comprises MPP and PER in a mass ratio of (2-5): 1. The flame-retardant pre-manufactured master batch provided by the invention can well solve the problems that the compatibility is poor and the mechanical property, the stability and the weather resistance are reduced after conventional flame-retardant components are introduced into a TPO material, and the prepared TPO waterproof coiled material has excellent mechanical property, ageing resistance, chemical resistance and flame-retardant property at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of building waterproof materials, and in particular to a flame-retardant and hydrophobic exposed polymer waterproof coiled material and a preparation method thereof. Background Art

[0002] Waterproofing membranes are primarily categorized into SBS-modified asphalt membranes, asphalt-based self-adhesive membranes, and polymer membranes. Asphalt-based membranes are the most commonly used waterproofing material, while polymer membranes, a key development area, are experiencing steady growth in market demand. Among polymer membranes, pre-laid, reverse-adhesive polymer membranes are particularly popular due to their ease of installation, and their application in construction projects continues to rise. While polymer waterproofing membranes have become mainstream in some markets, there is still significant room for improvement. Market penetration is closely tied to the technical maturity of the material itself. The industry generally believes that the core advantage of polymer membranes lies in their superior durability. Therefore, improving product stability and extending the effective warranty period of waterproofing systems are key factors driving their wider adoption. With the continuous optimization and improvement of product quality, the market potential of polymer membranes will be further unleashed.

[0003] As a high-performance green building material, polymer waterproofing membranes are experiencing rapid growth, driven by market trends and relevant architectural concepts. Their production and market size are expected to continue to rise. In terms of application scenarios, polymer membranes are currently primarily used for basement and roof waterproofing. In the future, as product performance continues to improve, their application areas will become more diverse, particularly in single-ply roofing systems and planted roofs (green roofs), which demonstrate significant potential. The single-ply roofing segment alone is expected to generate a vast market. Building-integrated photovoltaics (BIPV), which integrates photovoltaic technology with architecture, is currently a core trend in photovoltaic applications. This model offers multiple advantages: it effectively utilizes building surfaces without requiring additional land; photovoltaic modules can replace traditional building materials and eliminate the independent support structures of traditional photovoltaic systems, thus reducing overall costs; distributed generation significantly reduces power losses during transmission and distribution, lowering grid investment and maintenance costs; and it can also enhance the aesthetic value of buildings. Transforming buildings into self-sufficient, independent units is an inevitable trend in the integration of architectural technology and sustainable development concepts. Thermoplastic polyolefin (TPO) waterproofing membrane is a commonly used high-performance material for roof waterproofing combined with photovoltaic systems. It's based on vinyl resin and manufactured using advanced technology. Its core advantage lies in its plasticizer-free formula, fundamentally avoiding the brittleness caused by plasticizer migration and ensuring long-term flexibility and reliability. TPO membrane also boasts a range of excellent properties, including high tensile strength, excellent puncture resistance, strong UV resistance (requiring the addition of a small amount of additives), a smooth surface (still susceptible to contamination even after prolonged exposure), high reflectivity (reflectivity decreases significantly after contamination), environmental friendliness, and weldability.

[0004] In addition, the waterproof layer between the photovoltaic modules and the building has a certain flame retardant function, which can reduce the risk of fire. However, for the existing TPO waterproof layer materials used in corresponding scenarios, there are compatibility issues between flame retardants and TPO materials. The introduction of flame retardants will inevitably lead to a decline in many aspects of performance such as mechanical properties and weather resistance. Summary of the Invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a flame retardant and hydrophobic exposed polymer waterproof coiled material and a preparation method thereof.

[0006] In a first aspect, the present invention provides a flame-retardant masterbatch comprising: polyethylene, a flame retardant, graphene, and a silane coupling agent; in parts by weight, the polyethylene is 35 to 52 parts, the flame retardant is 40 to 55 parts, the graphene is 2 to 6 parts, and the silane coupling agent is 2 to 6 parts; the flame retardant comprises MPP and PER in a mass ratio of (2 to 5):1.

[0007] Furthermore, the flame retardant masterbatch is composed of the following components, in parts by weight: 35 to 52 parts of polyethylene, 40 to 55 parts of flame retardant, 2 to 6 parts of graphene, and 2 to 6 parts of silane coupling agent; the flame retardant is composed of MPP and PER in a mass ratio of (2 to 5):1.

[0008] Efficiently incorporating flame-retardant materials into TPO (thermoplastic polyolefin) waterproofing membranes presents significant technical challenges. This involves more than a simple physical mixing process; rather, it involves a complex formulation requiring difficult trade-offs between multiple performance indicators. The core advantages of TPO waterproofing membranes lie in their excellent weather resistance, low-temperature flexibility, and high strength. However, the addition of flame retardants, especially the large amounts required to achieve effective flame retardancy, inherently conflicts with these core advantages. For example, the addition of flame retardants can lead to a sharp decline in mechanical properties, poor compatibility, and a decrease in long-term weather resistance and durability. Therefore, the application of flame-retardant materials to TPO waterproofing membranes presents significant technical challenges.

[0009] The present invention provides a flame-retardant prefabricated masterbatch prepared from specific components, wherein polyethylene, a flame retardant, graphene and a silane coupling agent are multi-components that work together to effectively reduce the amount of the flame retardant and provide the masterbatch with better compatibility with TPO materials. When applied to the preparation of a flame-retardant TPO waterproof membrane, the prepared flame-retardant TPO waterproof membrane can have excellent mechanical properties, weather resistance, durability and flame retardant properties.

[0010] The MPP used in this invention is melamine polyphosphate, a nitrogen-phosphorus intumescent flame retardant, and PER is pentaerythritol, the carbon source in the intumescent flame retardant system. The polyethylene, MPP, PER, graphene, and silane coupling agent system provided in this invention achieves excellent compatibility with TPO materials by leveraging the chemical structural similarities between polyethylene and POE (both are non-polar polyolefins), molecular segment interactions (co-crystallization and segment interpenetration), and thermodynamic behavior during blending (driven by entropy increase). Furthermore, surface modification of MPP and PER with a silane coupling agent reduces polarity and improves interfacial adhesion with TPO. However, replacing MPP with APP or MCA (similar intumescent flame retardants) can hinder the production of materials with a combination of mechanical, aging, and flame retardant properties due to poor compatibility, low flame retardant efficiency, and the impact of large-scale use on mechanical and aging resistance.

[0011] In a second aspect, the present invention provides a thermoplastic composition for waterproof membrane, comprising the aforementioned flame retardant masterbatch.

[0012] Furthermore, the composition comprises, in parts by weight: 10 to 18 parts of polypropylene, 25 to 35 parts of the aforementioned flame retardant masterbatch, 40 to 60 parts of polyolefin elastomer, and 3 to 10 parts of functional additives.

[0013] Furthermore, the functional additives include: an antioxidant and a white masterbatch; in parts by weight, the antioxidant is 2 to 6 parts, and the white masterbatch is 1 to 4 parts.

[0014] The antioxidant of the present invention comprises: POE, a high-temperature resistant antioxidant component, an ultraviolet absorber and a light stabilizer.

[0015] The high temperature resistant antioxidant component of the present invention can be selected from hindered phenol antioxidants, aromatic amine antioxidants, thio antioxidants, lactone antioxidants or hydroxylamine antioxidants.

[0016] The ultraviolet absorber of the present invention can be selected from benzophenone ultraviolet absorbers, cinnamate ultraviolet absorbers, salicylate ultraviolet absorbers, PABA derivatives, triazine ultraviolet absorbers, and benzotriazole ultraviolet absorbers.

[0017] The light stabilizer of the present invention is a hindered ammonia light stabilizer.

[0018] The present invention combines the aforementioned flame-retardant masterbatch with polypropylene, a polyolefin elastomer, an antioxidant, and a white masterbatch to produce the primary functional layer of the TPO waterproof membrane. The components exhibit excellent compatibility, ensuring satisfactory mechanical properties, weather resistance, durability, and flame retardancy even without the addition of polypropylene. The addition of polypropylene further enhances these properties.

[0019] In a third aspect, the present invention provides a TPO material layer, wherein the TPO material layer is prepared from the aforementioned thermoplastic composition.

[0020] In a fourth aspect, the present invention provides a waterproof roll material, comprising: the aforementioned TPO material layer.

[0021] Furthermore, it includes: a fluorocarbon film layer, a flame retardant adhesive layer and the aforementioned TPO material layer.

[0022] The raw material of the fluorocarbon film layer of the present invention can be one or more of polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene or fluorinated ethylene propylene copolymer.

[0023] The flame retardant adhesive layer of the present invention can be a hot melt adhesive with a flame retardant added, such as one or more of butyl adhesive, SBC hot melt adhesive, EVA-based hot melt adhesive, PO-based hot melt adhesive, acrylic adhesive or organic silicone adhesive.

[0024] Furthermore, the fluorocarbon film layer is a porous polytetrafluoroethylene film; and / or the flame-retardant adhesive layer is a flame-retardant butyl adhesive layer.

[0025] Furthermore, the flame retardant butyl rubber layer comprises, in parts by weight: 15-25 parts of butyl rubber, 3-7 parts of SIS, 8-12 parts of C5 hydrogenated resin, 2-8 parts of terpene resin, 15-25 parts of polyisobutylene, 30-40 parts of magnesium hydroxide, 0.1-0.3 parts of silane coupling agent, 0.4-0.8 parts of antioxidant, 0.2-0.5 parts of anti-ultraviolet agent and 1-3 parts of titanium dioxide.

[0026] The present invention adds magnesium hydroxide to butyl rubber, resulting in a butyl rubber layer with excellent bonding and flame retardancy, achieving a B1 flame retardancy rating. Furthermore, the waterproofing membrane provided by the present invention utilizes multiple layers of different materials, each with varying thermal conductivities, making heat conduction more difficult. Butyl rubber has a lower thermal conductivity and conducts heat more slowly, providing superior insulation.

[0027] In a fifth aspect, the present invention provides a method for preparing the aforementioned TPO material layer, comprising: melt-blending and extruding polypropylene, a flame retardant prefabricated masterbatch, a polyolefin elastomer, and a functional additive; The extrusion parameters include: barrel temperature of 170°C to 190°C, three-roll calender temperature of 45°C to 65°C, and tempering roller temperature of 30°C to 45°C.

[0028] In a sixth aspect, the present invention provides the use of the aforementioned thermoplastic composition for waterproof membranes, or the aforementioned TPO material layer in the preparation of waterproof membranes for building roofs, underground projects, artificial water bodies and environmental projects, or transportation and infrastructure projects.

[0029] The present invention has the following beneficial effects: The present invention provides a flame-retardant prefabricated masterbatch, which has excellent compatibility with TPO material. The polymer waterproof membrane prepared by introducing the masterbatch into TPO material has excellent mechanical properties, aging resistance, chemical resistance and flame retardancy, which has important application value in the field of waterproof materials used in scenarios such as building roofs. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the present invention or the prior art, a brief introduction is given below to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0031] Figure 1 It is a schematic structural diagram of the waterproof roll provided in Example 1 of the present invention.

[0032] Figure 2 This is a flow chart of the preparation of the waterproof roll provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0033] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0034] Unless otherwise specified, the experimental methods involved in the following examples are all conventional methods in the art. For example, reference can be made to experimental manuals in the art, or the conditions recommended by the manufacturer's instructions.

[0035] Unless otherwise specified, the experimental materials and reagents involved in the following examples can be obtained from commercial sources.

[0036] Example 1 This embodiment provides a waterproof roll material, such as Figure 1 As shown, it is prepared by the following process: 1. The raw materials are as follows (1) The upper layer uses a porous polytetrafluoroethylene membrane.

[0037] (2) The middle layer is butyl rubber, including: 2 parts of titanium dioxide (R-215), 0.3 parts of UV inhibitor (2020), 0.3 parts of antioxidant (168), 0.3 parts of antioxidant (1010), 0.2 parts of silane coupling agent (KH560), 35 parts of magnesium hydroxide, 20.4 parts of polyisobutylene (1300), 5 parts of terpene resin (T100), 10 parts of C5 hydrogenated resin, 5 parts of SIS (YH1716) and 21.5 parts of butyl rubber (301).

[0038] (3) The lower layer is the TPO material layer, including: 14 parts of polypropylene PP, 30 parts of flame retardant prefabricated masterbatch, 50 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0039] The flame retardant masterbatch includes the following components: 42 parts of polyethylene PE, 50 parts of a mixture of MPP and PER (MPP:PER=3:1), 4 parts of graphene, and 4 parts of a silane coupling agent.

[0040] The components of composite antioxidant masterbatch are as follows: Table 1 Components of composite antioxidant masterbatch

[0041] 2. Preparation method (1) Butyl rubber is prepared by the following process: Butyl rubber blocks were treated at level 5 for 1 h; Titanium dioxide R-902, 1010 antioxidant, 168 antioxidant, 2020 UV inhibitor, C5 hydrogenated resin, SIS, terpene resin and magnesium hydroxide (50%) were added at 130°C and treated at level 6 for 1 hour; Observe whether there are particles. If there are particles, cut until there are no particles. Polyisobutylene (50%) and magnesium hydroxide (25%) were added and treated at level 6 for 0.5 h; Polyisobutylene (the remaining amount, 50%), silane coupling agent, and magnesium hydroxide (the remaining amount, 25%) were added and treated at level 6 for 1 h; Discharge after observing that there are no particles.

[0042] The above process was carried out in a polymer rubber kneader NH2000, with gear 5 corresponding to 25 Hz and gear 6 corresponding to 30 Hz.

[0043] (2) The TPO material layer is prepared by the following method: Polypropylene (PP), flame-retardant masterbatch, polyolefin elastomer (POE), composite antioxidant masterbatch, and white masterbatch are melt-blended in an extruder and extruded to a specified thickness to form a TPO sheet material layer for later use. Extruder parameters are: barrel temperature 170°C to 190°C, three-roll calender temperature 45°C to 65°C, and tempering roll temperature 30°C to 45°C. (Extruder operating parameters are generally set within a range.) (3) The flame retardant masterbatch is prepared by the following method: Polyethylene PE, MPP / PER, graphene and silane coupling agent are pelletized in a twin-screw extruder with the following extruder parameters: barrel temperature 190°C.

[0044] (4) The waterproof membrane is prepared by the following process: like Figure 2 As shown, the process includes the following: Positioning and deviation correction; Install sheets and membranes: Install TPO material layer; Glue coating: The butyl rubber coating process is shown in the following table; Coating with fluorocarbon film and performing alignment and deviation correction; cool down; Rolling: according to the predetermined size and appearance; Package; Weighing, affixing certificates of conformity, and palletizing; Finished product testing and quality control; Enter storage.

[0045] As shown above, the sizes of each layer of the waterproof membrane can be adjusted according to needs. The thickness of the lower layer is 1.2mm, the thickness of the middle layer is 0.3~0.35mm, and the thickness of the upper layer is 0.1mm.

[0046] Table 2 Butyl rubber coating process parameters

[0047] Example 2 This embodiment provides a waterproof roll, which is prepared by the following process: 1. The raw materials are as follows (1) The upper layer uses a porous polytetrafluoroethylene membrane.

[0048] (2) The middle layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of UV inhibitor (2020), 0.3 parts of antioxidant (168), 0.3 parts of antioxidant (1010), 0.2 parts of silane coupling agent, 35 parts of magnesium hydroxide, 20.4 parts of polyisobutylene (1300), 5 parts of terpene resin (T100), 10 parts of C5 hydrogenated resin, 5 parts of SIS (YH1716) and 21.5 parts of butyl rubber.

[0049] (3) The lower layer is the TPO material layer, including: 14 parts of polyethylene PE, 30 parts of flame retardant prefabricated masterbatch, 50 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0050] The flame retardant prefabricated masterbatch and the composite antioxidant masterbatch are the same as those in Example 1.

[0051] 2. The preparation process is the same as that of Example 1.

[0052] Example 3 This embodiment provides a waterproof roll, which is prepared by the following process: 1. The raw materials are as follows (1) The upper layer uses a porous polytetrafluoroethylene membrane.

[0053] (2) The middle layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of UV inhibitor (2020), 0.3 parts of antioxidant (168), 0.3 parts of antioxidant (1010), 0.2 parts of silane coupling agent, 35 parts of magnesium hydroxide, 20.4 parts of polyisobutylene (1300), 5 parts of terpene resin (T100), 10 parts of C5 hydrogenated resin, 5 parts of SIS (YH1716) and 21.5 parts of butyl rubber.

[0054] (3) The lower layer is the TPO material layer, including: 30 parts of flame retardant prefabricated masterbatch, 64 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0055] The flame retardant prefabricated masterbatch and the composite antioxidant masterbatch are the same as those in Example 1.

[0056] 2. The preparation process is the same as that of Example 1.

[0057] Comparative Example 1 This comparative example provides a waterproof roll, which is prepared by the following process: 1. The raw materials are as follows Only the TPO material layer is retained, including: 14 parts of polypropylene PP, 30 parts of heavy calcium, 50 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0058] 2. The preparation process is the same as that of Example 1.

[0059] Comparative Example 2 This comparative example provides a waterproof roll, which is prepared by the following process: 1. The raw materials are as follows The upper layer is the TPO material layer: 14 parts of polypropylene PP, 30 parts of heavy calcium carbonate, 50 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch, and 2 parts of white masterbatch.

[0060] The middle layer is mesh cloth.

[0061] The lower layer is the TPO material layer: 14 parts of polypropylene PP, 29 parts of heavy calcium carbonate, 50 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch, 2 parts of white masterbatch, and 1 part of black masterbatch.

[0062] 2. The preparation process is the same as that of Example 1.

[0063] Comparative Example 3 This comparative example provides a waterproof roll, which has the same raw materials and preparation method as Example 1, except that the raw materials are as follows: (1) The upper layer uses a porous polytetrafluoroethylene membrane.

[0064] (2) The middle layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of UV inhibitor (2020), 0.3 parts of antioxidant (168), 0.3 parts of antioxidant (1010), 0.2 parts of silane coupling agent, 35 parts of magnesium hydroxide, 20.4 parts of polyisobutylene (1300), 5 parts of terpene resin (T100), 10 parts of C5 hydrogenated resin, 5 parts of SIS (YH1716) and 21.5 parts of butyl rubber.

[0065] (3) The lower layer is the TPO material layer, including: 14 parts of polypropylene PP, 50 parts of flame retardant prefabricated masterbatch, 30 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0066] The flame retardant masterbatch includes the following components: 42 parts of polyethylene PE, 21 parts of magnesium hydroxide, 21 parts of decabromodiphenyl ethane, 8 parts of antimony trioxide, 4 parts of graphene, and 4 parts of silane coupling agent.

[0067] Comparative Example 4 This comparative example provides a waterproof roll, which is prepared in the same manner as in Example 1, except that the raw materials are as follows: (1) The upper layer uses a porous polytetrafluoroethylene membrane.

[0068] (2) The middle layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of 2020 anti-ultraviolet agent, 0.3 parts of 168 antioxidant, 0.3 parts of 1010 antioxidant, 0.2 parts of silane coupling agent, 35 parts of magnesium hydroxide, 20.4 parts of polyisobutylene, 5 parts of terpene resin, 10 parts of C5 hydrogenated resin, 5 parts of SIS and 21.5 parts of butyl rubber.

[0069] (3) The lower layer is a TPO material layer, including: 14 parts of polypropylene PP, 40 parts of flame retardant prefabricated masterbatch, 40 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0070] The flame retardant masterbatch includes the following components: 34.4 parts of LLDPE, 12 parts of conductive carbon black, 12 parts of expandable graphite, 30 parts of phosphorus-nitrogen intumescent flame retardant (polyammonium phosphate (APP), melamine (MEL), and pentaerythritol (PER) are mixed in the ratio of APP:MEL:PER=7:3:4 by weight), 2.0 parts of antistatic agent HDC-100K, 1.0 parts of silane coupling agent, 6.0 parts of POE-g-GMA, 2.0 parts of PE wax, and 0.6 parts of antioxidant (1010).

[0071] Comparative Example 5 This comparative example provides a waterproof roll, which is prepared in the same manner as in Example 1, and the raw materials are as follows: (1) The upper layer uses a porous polytetrafluoroethylene membrane.

[0072] (2) The middle layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of 2020 anti-ultraviolet agent, 0.3 parts of 168 antioxidant, 0.3 parts of 1010 antioxidant, 0.2 parts of silane coupling agent, 35 parts of magnesium hydroxide, 20.4 parts of polyisobutylene, 5 parts of terpene resin, 10 parts of C5 hydrogenated resin, 5 parts of SIS and 21.5 parts of butyl rubber.

[0073] (3) The lower layer is the TPO material layer, including: 14 parts of polypropylene PP, 30 parts of heavy calcium (1000 mesh), 50 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0074] The main difference from Example 1 is that the flame retardant masterbatch is replaced with an equal amount of heavy calcium carbonate.

[0075] Comparative Example 6 This comparative example provides a waterproof roll, which is prepared in the same manner as in Example 1, and the raw materials are as follows: (1) The upper layer uses a porous polytetrafluoroethylene membrane.

[0076] (2) The middle layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of 2020 anti-ultraviolet agent, 0.3 parts of 168 antioxidant, 0.3 parts of 1010 antioxidant, 0.2 parts of silane coupling agent, 35 parts of magnesium hydroxide, 20.4 parts of polyisobutylene, 5 parts of terpene resin, 10 parts of C5 hydrogenated resin, 5 parts of SIS and 21.5 parts of butyl rubber.

[0077] (3) The lower layer is the TPO material layer, including: 14 parts of polypropylene PP, 30 parts of flame retardant prefabricated masterbatch, 50 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0078] The flame retardant masterbatch includes the following components: 42 parts of polyethylene PE, 50 parts of APP and MEL mixture (APP:PER=3:1), 4 parts of graphene, and 4 parts of silane coupling agent.

[0079] The main difference from Example 1 is that MPP is replaced by an equal amount of APP.

[0080] Experimental Example 1 In this experimental example, the performance of the TPO waterproof membranes prepared in Examples 1-3 and Comparative Examples 1 and 2 was tested in accordance with the provisions of GB 27789-2011 "Thermoplastic polyolefin (TPO) waterproof membranes", GBT 23260-2009 "Waterproof membranes with self-adhesive layer", GB / T 30693-2014 "Measurement of the contact angle of plastic films with water" and GB 8624-2012 "Classification of the burning behavior of building materials and products". The results are shown in the following table: Table 3-1 Performance test results of Examples 1-3 and Comparative Examples 1 and 2 - Part 1

[0081] Table 3-2 Performance test results of Examples 1-3 and Comparative Examples 1 and 2 - Part II

[0082] Note: Pull-out strength test method: Use a 6.3mm diameter carbon steel screw to penetrate the coil, place it under standard test environment for 48 hours, and then test the nail pulling force value.

[0083] Watertightness after nailing: Use a 6.3mm diameter carbon steel screw to penetrate the coil. After leaving it under standard test environment for 48 hours, test the watertightness of the nailed part.

[0084] The above results demonstrate that the flame-retardant masterbatch provided by the present invention exhibits excellent compatibility when applied to TPO material layers, effectively addressing the problem of conventional flame retardants affecting the mechanical properties and aging resistance of TPO materials. In particular, as shown in Example 3, even after removing the polypropylene from the TPO material layer, satisfactory mechanical properties and aging resistance were still achieved. Furthermore, due to the porous polytetrafluoroethylene membrane used in the upper layer, the contact angle index approaches the superhydrophobic standard, surpassing that of the comparative example, making it an excellent antifouling and self-cleaning layer.

[0085] Table 4 Qualified technical indicators

[0086] Experimental Example 2 The present invention repeated the experiment shown in Experimental Example 1 for Comparative Examples 3-6, and obtained the results shown in the following table: Table 5-1 Performance test results of comparative examples 3-6 - Part 1

[0087] Table 5-1 Performance test results of comparative examples 3-6 - Part 2

[0088] As shown above, compared to Comparative Example 5, which did not use a flame-retardant masterbatch, the waterproof membrane provided by the present invention significantly improves its flame retardancy while maintaining both mechanical and aging resistance. Comparative Examples 3, 4, and 6 utilize other types of flame-retardant ingredients previously employed in the present invention's research (the amounts of the flame-retardant masterbatch in Comparative Examples 3 and 4 were experimentally optimized to maximize their flame retardancy, mechanical properties, and aging resistance). However, these ingredients clearly exhibit poor compatibility with other components in the TPO waterproof membrane, significantly reducing mechanical and aging resistance after their introduction.

[0089] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A flame retardant prefabricated masterbatch, characterized in that: include: polyethylene, flame retardants, graphene, and silane coupling agents; In parts by weight, the polyethylene is 35 to 52 parts, the flame retardant is 40 to 55 parts, the graphene is 2 to 6 parts, and the silane coupling agent is 2 to 6 parts; the flame retardant includes MPP and PER in a mass ratio of (2 to 5):

1.

2. A thermoplastic composition for waterproof roll, characterized in that: The flame retardant masterbatch according to claim 1 is included.

3. The thermoplastic composition for waterproof membrane according to claim 2, characterized in that: In parts by weight, it comprises: 10-18 parts of polypropylene, 25-35 parts of the flame retardant masterbatch according to claim 1, 40-60 parts of polyolefin elastomer and 3-10 parts of functional additives; Preferably, the functional additives include: an antioxidant and a white masterbatch; in parts by weight, the antioxidant is 2 to 6 parts, and the white masterbatch is 1 to 4 parts.

4. A TPO material layer, characterized in that: The TPO material layer is prepared from the thermoplastic composition according to claim 3.

5. A waterproof roll, characterized in that: include: The TPO material layer according to claim 4.

6. The waterproof roll according to claim 5, characterized in that: include: A fluorocarbon film layer, an adhesive layer and the TPO material layer.

7. The waterproof roll according to claim 6, characterized in that: The fluorocarbon film layer is a porous polytetrafluoroethylene film; and / or the adhesive layer is a flame-retardant butyl adhesive layer.

8. The waterproof roll according to claim 7, characterized in that: In parts by weight, the flame retardant butyl rubber layer includes: 15-25 parts of butyl rubber, 3-7 parts of SIS, 8-12 parts of C5 hydrogenated resin, 2-8 parts of terpene resin, 15-25 parts of polyisobutylene, 30-40 parts of magnesium hydroxide, 0.1-0.3 parts of silane coupling agent, 0.4-0.8 parts of antioxidant, 0.2-0.5 parts of anti-ultraviolet agent and 1-3 parts of titanium dioxide.

9. The method for preparing the TPO material layer according to claim 4, characterized in that: include: The polypropylene, flame retardant masterbatch, polyolefin elastomer and functional additive are melt-blended and extruded; The extrusion parameters include: barrel temperature of 170°C to 190°C, three-roll calender temperature of 45°C to 65°C, and tempering roller temperature of 30°C to 45°C.

10. Use of the thermoplastic composition for waterproof membrane according to claim 2 or 3, or the TPO material layer according to claim 4, in the preparation of waterproof membrane for building roofs, underground engineering, artificial water bodies and environmental engineering, or transportation and infrastructure engineering.

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