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

Abstract

The present application relates to the technical field of building waterproof material, and particularly relates to a flame-retardant hydrophobic exposed type high polymer waterproof roll material and a preparation method thereof. The flame-retardant high polymer waterproof roll material uses a thermoplastic composition for waterproof roll material; the thermoplastic composition for waterproof roll material comprises a flame-retardant pre-made masterbatch; the flame-retardant pre-made masterbatch comprises polyethylene, a flame retardant, graphene and a silane coupling agent; the polyethylene is 35-52 parts by weight, the flame retardant is 40-55 parts by weight, the graphene is 2-6 parts by weight, and the silane coupling agent is 2-6 parts by weight; the flame retardant comprises MPP and PER in a mass ratio of (2-5):1. The present application provides a flame-retardant pre-made masterbatch, which can well solve the problems of poor compatibility, and the decline of mechanical properties, stability and weather resistance caused by the introduction of conventional flame-retardant components into TPO material, and the prepared TPO waterproof roll material simultaneously has excellent mechanical properties, anti-aging, chemical resistance and flame-retardant properties.

Description

Technical Field

[0001] This invention relates to the field of building waterproofing materials technology, and in particular to a flame-retardant, hydrophobic exposed polymer waterproof membrane and its preparation method. Background Technology

[0002] In the field of waterproof membranes, they are mainly divided into SBS modified bitumen membranes, bitumen-based self-adhesive membranes, and polymer membranes. Bitumen-based membranes are the most commonly used waterproofing materials, while polymer membranes, as an important development direction, are experiencing steady market demand growth. Particularly among polymer membranes, pre-applied self-adhesive waterproof membranes are highly favored due to their significant ease of construction, and their application demand in construction projects continues to rise. Although polymer waterproof membranes have become mainstream in some markets, there is still considerable room for improvement. Their market penetration rate is closely related to the technological 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 acceptance. With continuous optimization and improvement in product quality, the market potential of polymer membranes will be further released.

[0003] As a high-performance green building material, polymer waterproof membranes are experiencing rapid development driven by the market and related building concepts. Their production volume and market size are expected to continue to climb. In terms of application scenarios, polymer membranes are currently mainly used for waterproofing basements and roofs. In the future, with further enhancements in product performance, their application areas will become more diversified, especially in single-layer roofing systems and green roofs, demonstrating enormous application potential. The single-layer roofing segment alone can generate a vast market space. Building-integrated photovoltaics (BIPV), which combines photovoltaic technology with buildings, is currently the core direction of photovoltaic applications. This model has multiple advantages: it effectively utilizes building surfaces without requiring additional land; photovoltaic modules can replace traditional building materials and eliminate the need for independent support structures in traditional photovoltaic systems, thus saving overall costs; distributed generation significantly reduces power loss during transmission and distribution, lowering grid investment and maintenance costs; and it also enhances the aesthetic value of buildings. Transforming buildings into self-sufficient energy units is an inevitable trend in the integration of building technology and sustainable development concepts. In applications combining roof waterproofing with photovoltaic systems, thermoplastic polyolefin (TPO) waterproof membranes are a commonly used high-performance material. Made from ethylene resin using advanced technology, its core advantage lies in its plasticizer-free formulation, fundamentally avoiding the brittleness caused by plasticizer migration and ensuring long-term flexibility and reliability. Furthermore, TPO membranes integrate a range of excellent properties, including high tensile strength, good puncture resistance, strong UV resistance (requiring the addition of small amounts of additives), a smooth surface (though still susceptible to contamination after prolonged exposure), high reflectivity (which significantly decreases after contamination), environmental friendliness, and weldability.

[0004] In addition, the waterproof layer between the photovoltaic module and the building has a certain flame-retardant function, which can reduce the fire hazard. However, for the existing TPO waterproof layer materials used in the corresponding scenarios, there is a compatibility problem between the flame retardant and the TPO material. The introduction of flame retardant will inevitably lead to a decline in mechanical properties, weather resistance and other aspects of performance. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a flame-retardant, hydrophobic, exposed polymer waterproof membrane and its preparation method.

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

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

[0008] Integrating flame-retardant materials efficiently into TPO (thermoplastic polyolefin) waterproof membranes presents significant technical challenges. It's not a simple physical mixing process, but a complex formulation technology requiring difficult trade-offs between multiple performance indicators. The core advantages of TPO waterproof membranes lie in their excellent weather resistance, low-temperature flexibility, and high strength. However, adding flame retardants, especially the large amounts required to achieve an effective flame-retardant rating, inherently contradicts these core advantages. For example, it may lead to a sharp decline in mechanical properties, poor compatibility, and a decrease in long-term weather resistance and durability. Therefore, applying flame-retardant materials to TPO waterproof membranes presents substantial technical challenges.

[0009] This invention provides a flame-retardant preform masterbatch made from specific components, wherein polyethylene, flame retardant, graphene and silane coupling agent work synergistically to effectively reduce the amount of flame retardant used and make it more compatible with TPO materials. When applied to the preparation of flame-retardant TPO waterproof membranes, the resulting flame-retardant TPO waterproof membranes can have excellent mechanical properties, weather resistance, durability and flame retardant properties.

[0010] The MPP used in this invention is melamine polyphosphate, an intumescent flame retardant based on a nitrogen-phosphorus system, and PER is pentaerythritol, which is the carbon source in the intumescent flame retardant system. In the polyethylene, MPP, PER, graphene, and silane coupling agent system provided by this invention, the chemical structural similarity between polyethylene and POE (both are non-polar polyolefins), the interaction of molecular chain segments (co-crystallization and interpenetration of chain segments), and the thermodynamic behavior during blending (driven by entropy increase), along with the surface modification treatment of MPP and PER through the silane coupling agent to reduce polarity and improve interfacial adhesion with TPO, achieve good compatibility with TPO materials. However, replacing MPP with APP or MCA (similar intumescent flame retardants) results in poor compatibility, low flame retardant efficiency, and problems with mechanical properties and aging resistance due to excessive use, making it difficult to obtain a material that combines mechanical properties, aging resistance, and flame retardant properties.

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

[0012] Further, by weight, it includes: 10-18 parts of polypropylene, 25-35 parts of the aforementioned flame-retardant pre-formulated masterbatch, 40-60 parts of polyolefin elastomer, and 3-10 parts of functional additives.

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

[0014] The antioxidants described in this invention include: POE, high-temperature resistant antioxidant components, ultraviolet absorbers, and light stabilizers.

[0015] The high-temperature resistant antioxidant component described in this invention can be selected from hindered phenolic antioxidants, aromatic amine antioxidants, thiolated antioxidants, lactone antioxidants, or hydroxylamine antioxidants.

[0016] The ultraviolet absorber described in this invention can be selected from benzophenone ultraviolet absorbers, cinnamic acid ester ultraviolet absorbers, salicylic acid ester ultraviolet absorbers, PABA derivatives, triazine ultraviolet absorbers, and benzotriazole ultraviolet absorbers.

[0017] The light stabilizer described in this invention is a hindered ammonia-based light stabilizer.

[0018] This invention combines the aforementioned flame-retardant pre-made masterbatch with polypropylene, polyolefin elastomer, antioxidant, and white masterbatch to prepare the main functional layers of TPO waterproof membrane. The components exhibit excellent compatibility, ensuring satisfactory mechanical properties, weather resistance, durability, and flame retardancy even without the addition of polypropylene. Furthermore, the addition of polypropylene further enhances these properties.

[0019] Thirdly, the present invention provides a TPO material layer, which is prepared from the aforementioned thermoplastic composition.

[0020] Fourthly, the present invention provides a waterproof membrane 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 for the fluorocarbon membrane 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 added flame retardant, such as one or more of butyl rubber, SBC hot melt adhesive, EVA-based hot melt adhesive, PO-based hot melt adhesive, acrylic adhesive or silicone adhesive.

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

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

[0026] This invention adds magnesium hydroxide to butyl rubber, resulting in a butyl rubber layer that combines superior adhesion and flame retardant properties, achieving a B1 flame retardant rating. Furthermore, the waterproof membrane provided by this invention uses multiple layers of different materials with varying thermal conductivity, making heat transfer more difficult. Butyl rubber, with its low thermal conductivity and slow heat transfer, provides superior thermal insulation.

[0027] Fifthly, the present invention provides a method for preparing the aforementioned TPO material layer, comprising: melt-blending and extruding polypropylene, flame-retardant pre-fabricated masterbatch, polyolefin elastomer and functional additives;

[0028] The extrusion parameters include: barrel temperature 170℃~190℃, three-roll calender temperature 45℃~65℃, and tempering roll temperature 30℃~45℃.

[0029] In a sixth aspect, the present invention provides the application of the aforementioned thermoplastic composition for waterproof membranes, or the aforementioned TPO material layer, in the preparation of waterproof membranes for building roofs, underground works, artificial water bodies and environmental works, or transportation and infrastructure works.

[0030] The present invention has the following beneficial effects:

[0031] This invention provides a flame-retardant pre-made masterbatch that has excellent compatibility with TPO materials. When introduced into TPO materials, the resulting polymer waterproof membrane exhibits excellent mechanical properties, anti-aging properties, chemical resistance, and flame-retardant properties. This has significant application value in the field of waterproof materials for building roofs and other applications. Attached Figure Description

[0032] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0033] Figure 1This is a schematic diagram of the structure of the waterproof membrane provided in Embodiment 1 of the present invention.

[0034] Figure 2 This is a flowchart illustrating the preparation process of the waterproof membrane provided in Embodiment 1 of the present invention. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0036] Unless otherwise specified, the experimental methods involved in the following embodiments are conventional methods in the art. For example, you can refer to the experimental manual in the art or follow the conditions recommended in the manufacturer's instructions.

[0037] Unless otherwise specified, all experimental materials and reagents used in the following examples are commercially available.

[0038] Example 1

[0039] This embodiment provides a waterproof membrane, such as Figure 1 As shown, it is prepared through the following process:

[0040] 1. Raw materials are as follows

[0041] (1) The upper layer is made of porous polytetrafluoroethylene membrane.

[0042] (2) The intermediate layer is butyl rubber, including: 2 parts of titanium dioxide (R-215), 0.3 parts of UV stabilizer (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).

[0043] (3) The lower layer is a TPO material layer, including: 14 parts of polypropylene (PP), 30 parts of flame retardant pre-made masterbatch, 50 parts of polyolefin elastomer (POE), 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0044] The flame-retardant pre-made 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 silane coupling agent.

[0045] The components of the composite antioxidant masterbatch are as follows:

[0046] Table 1. Components of the Composite Antioxidant Masterbatch

[0047]

[0048] 2. Preparation method

[0049] (1) Butyl rubber is prepared by the following process:

[0050] Butyl rubber blocks were treated under conditions of level 5 for 1 hour;

[0051] Add titanium dioxide R-902, 1010 antioxidant, 168 antioxidant, 2020 UV stabilizer, C5 hydrogenated resin, SIS, terpene resin and magnesium hydroxide (50%) at 130℃, and treat for 1 hour under condition 6.

[0052] Observe for the presence of particles; if particles are present, cut until no particles remain.

[0053] Add polyisobutylene (50%) and magnesium hydroxide (25%), and treat for 0.5 h under conditions of grade 6;

[0054] Add polyisobutylene (remaining, 50%), silane coupling agent and magnesium hydroxide (remaining, 25%), and treat for 1 hour under conditions 6.

[0055] Discharge the material after observing that there are no particles.

[0056] The above process is carried out in the NH2000 polymer rubber kneader, with setting 5 corresponding to 25Hz and setting 6 corresponding to 30Hz.

[0057] (2) The TPO material layer is prepared by the following method:

[0058] Polypropylene (PP), flame-retardant pre-formed masterbatch, polyolefin elastomer (POE), composite antioxidant masterbatch, and white masterbatch are fed into an extruder for melt blending. The mixture is then extruded to a specified thickness to obtain a TPO sheet material layer for later use. The extruder parameters are: barrel temperature 170℃~190℃, three-roll calender temperature 45℃~65℃, and tempering roll temperature 30℃~45℃. (The extruder's operating parameters are generally set to a range.)

[0059] (3) The flame-retardant pre-made masterbatch is prepared by the following method:

[0060] Polyethylene (PE), MPP / PER, graphene, and silane coupling agent are granulated in a twin-screw extruder with the following parameters: barrel temperature 190℃.

[0061] (4) The waterproof membrane is prepared through the following process:

[0062] like Figure 2 As shown, the process includes the following:

[0063] Alignment and correction;

[0064] Installing sheets and films: Installing TPO material layers;

[0065] Adhesive Coating: The process for coating butyl rubber is shown in the table below;

[0066] Apply fluorocarbon film and perform alignment and correction;

[0067] cool down;

[0068] Rewinding: according to the predetermined size and appearance;

[0069] Package;

[0070] Weighing, affixing certificates of conformity, and stacking;

[0071] Finished product inspection and quality control;

[0072] Stored in the warehouse.

[0073] The dimensions of each layer of the waterproof membrane can be adjusted according to requirements. The thickness of the bottom layer is 1.2mm, the thickness of the middle layer is 0.3~0.35mm, and the thickness of the top layer is 0.1mm.

[0074] Table 2 Butyl Rubber Coating Process Parameters

[0075]

[0076] Example 2

[0077] This embodiment provides a waterproof membrane, which is prepared through the following process:

[0078] 1. Raw materials are as follows

[0079] (1) The upper layer is made of porous polytetrafluoroethylene membrane.

[0080] (2) The intermediate layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of UV stabilizer (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.

[0081] (3) The lower layer is a TPO material layer, including: 14 parts of polyethylene (PE), 30 parts of flame retardant pre-made masterbatch, 50 parts of polyolefin elastomer (POE), 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0082] The flame-retardant pre-formed masterbatch and the composite antioxidant masterbatch are the same as those in Example 1.

[0083] 2. The preparation process is the same as in Example 1.

[0084] Example 3

[0085] This embodiment provides a waterproof membrane, which is prepared through the following process:

[0086] 1. Raw materials are as follows

[0087] (1) The upper layer is made of porous polytetrafluoroethylene membrane.

[0088] (2) The intermediate layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of UV stabilizer (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.

[0089] (3) The lower layer is a TPO material layer, including: 30 parts of flame retardant pre-made masterbatch, 64 parts of polyolefin elastomer POE, 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0090] The flame-retardant pre-formed masterbatch and the composite antioxidant masterbatch are the same as those in Example 1.

[0091] 2. The preparation process is the same as in Example 1.

[0092] Comparative Example 1

[0093] This comparative example provides a waterproof membrane, which is prepared through the following process:

[0094] 1. Raw materials are as follows

[0095] Only the TPO material layer is retained, including: 14 parts polypropylene (PP), 30 parts heavy calcium carbonate, 50 parts polyolefin elastomer (POE), 4 parts composite antioxidant masterbatch, and 2 parts white masterbatch.

[0096] 2. The preparation process is the same as in Example 1.

[0097] Comparative Example 2

[0098] This comparative example provides a waterproof membrane, which is prepared through the following process:

[0099] 1. Raw materials are as follows

[0100] The upper layer is a TPO material layer: 14 parts polypropylene (PP), 30 parts heavy calcium carbonate, 50 parts polyolefin elastomer (POE), 4 parts composite antioxidant masterbatch, and 2 parts white masterbatch.

[0101] The middle layer is a mesh fabric.

[0102] The lower layer is a TPO material layer: 14 parts polypropylene (PP), 29 parts heavy calcium carbonate, 50 parts polyolefin elastomer (POE), 4 parts composite antioxidant masterbatch, 2 parts white masterbatch, and 1 part black masterbatch.

[0103] 2. The preparation process is the same as in Example 1.

[0104] Comparative Example 3

[0105] This comparative example provides a waterproof membrane, which uses the same raw materials and preparation method as Example 1, except that the raw materials are as follows:

[0106] (1) The upper layer is made of porous polytetrafluoroethylene membrane.

[0107] (2) The intermediate layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of UV stabilizer (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.

[0108] (3) The lower layer is a TPO material layer, including: 14 parts of polypropylene (PP), 50 parts of flame retardant pre-made masterbatch, 30 parts of polyolefin elastomer (POE), 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0109] The flame-retardant pre-made masterbatch includes the following components: 42 parts polyethylene (PE), 21 parts magnesium hydroxide, 21 parts decabromodiphenyl ethane, 8 parts antimony trioxide, 4 parts graphene, and 4 parts silane coupling agent.

[0110] Comparative Example 4

[0111] This comparative example provides a waterproof membrane, prepared using the same method as in Example 1, except that the raw materials are as follows:

[0112] (1) The upper layer is made of porous polytetrafluoroethylene membrane.

[0113] (2) The intermediate layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of 2020 UV stabilizer, 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.

[0114] (3) The lower layer is a TPO material layer, including: 14 parts of polypropylene (PP), 40 parts of flame retardant pre-made masterbatch, 40 parts of polyolefin elastomer (POE), 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0115] The flame-retardant pre-made masterbatch includes the following components: 34.4 parts LLDPE, 12 parts conductive carbon black, 12 parts expandable graphite, 30 parts phosphorus-nitrogen intumescent flame retardant (ammonia polyphosphate (APP), melamine (MEL), pentaerythritol (PER) mixed in a weight ratio of APP:MEL:PER = 7:3:4), 2.0 parts antistatic agent HDC-100K, 1.0 part silane coupling agent, 6.0 parts POE-g-GMA, 2.0 parts PE wax, and 0.6 parts antioxidant (1010).

[0116] Comparative Example 5

[0117] This comparative example provides a waterproof membrane, prepared using the same method as in Example 1, with the following raw materials:

[0118] (1) The upper layer is made of porous polytetrafluoroethylene membrane.

[0119] (2) The intermediate layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of 2020 UV stabilizer, 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.

[0120] (3) The lower layer is a TPO material layer, including: 14 parts of polypropylene (PP), 30 parts of heavy calcium carbonate (1000 mesh), 50 parts of polyolefin elastomer (POE), 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0121] The main difference from Example 1 is that the flame-retardant pre-made masterbatch is replaced with an equal amount of heavy calcium carbonate.

[0122] Comparative Example 6

[0123] This comparative example provides a waterproof membrane, prepared using the same method as in Example 1, with the following raw materials:

[0124] (1) The upper layer is made of porous polytetrafluoroethylene membrane.

[0125] (2) The intermediate layer is butyl rubber, including: 2 parts of titanium dioxide, 0.3 parts of 2020 UV stabilizer, 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.

[0126] (3) The lower layer is a TPO material layer, including: 14 parts of polypropylene (PP), 30 parts of flame retardant pre-made masterbatch, 50 parts of polyolefin elastomer (POE), 4 parts of composite antioxidant masterbatch and 2 parts of white masterbatch.

[0127] The flame-retardant pre-made masterbatch includes the following components: 42 parts of polyethylene (PE), 50 parts of a mixture of APP and MEL (APP:PER=3:1), 4 parts of graphene, and 4 parts of silane coupling agent.

[0128] The main difference from Example 1 is that MPP is replaced with an equal amount of APP.

[0129] Experimental Example 1

[0130] This experiment tested the performance of the TPO waterproof membranes prepared in Examples 1-3 and Comparative Examples 1 and 2. The tests were conducted according to the standards GB 27789-2011 "Thermoplastic Polyolefin (TPO) Waterproof Membranes", GB / T 23260-2009 "Waterproof Membranes with Self-Adhesive Layers", GB / T 30693-2014 "Measurement of the Contact Angle between Plastic Films and Water", and GB 8624-2012 "Classification of Burning Performance of Building Materials and Products". The results are shown in the table below.

[0131] Table 3-1 Performance test results of Examples 1-3 and Comparative Examples 1 and 2 - Part 1

[0132]

[0133] Table 3-2 Performance test results of Examples 1-3 and Comparative Examples 1 and 2 - Part 2

[0134]

[0135] Note: Pull-out strength test method: Use a 6.3mm diameter carbon steel screw to penetrate the roll material, place it under standard test conditions for 48 hours, and then test the screw pull-out force value.

[0136] Water impermeability after nailing: The roll material is penetrated by a 6.3mm diameter carbon steel screw. After being placed under standard test conditions for 48 hours, the water impermeability of the nailed area is tested.

[0137] As shown in the above results, the flame-retardant pre-made masterbatch provided by this invention exhibits superior compatibility when applied to TPO material layers, effectively addressing the issue of conventional flame-retardant materials affecting the mechanical properties and aging resistance of TPO materials. In particular, as demonstrated in Example 3, even after removing polypropylene from the TPO material layer, it still possesses satisfactory mechanical properties and aging resistance. Furthermore, because the upper layer utilizes a porous polytetrafluoroethylene membrane with a contact angle index approaching the superhydrophobic standard, superior to the comparative example, it can be considered an excellent antifouling and self-cleaning layer.

[0138] Table 4 Qualified Technical Indicators

[0139]

[0140] Experiment Example 2

[0141] The present invention replicated the experiment shown in Experimental Example 1 for Comparative Examples 3-6, and obtained the results shown in the table below:

[0142] Table 5-1 Performance Test Results of Comparative Example 3-6 - Part 1

[0143]

[0144] Table 5-1 Performance Test Results of Comparative Example 3-6 - Part Two

[0145]

[0146] As shown in the results above, compared with Comparative Example 5, which did not use flame-retardant pre-made masterbatch, the waterproof membrane provided by this invention significantly improves the flame retardant rating while maintaining mechanical properties and aging resistance. Comparative Examples 3, 4, and 6 represent other types of flame-retardant components used in this invention during the research process (the amount of flame-retardant pre-made masterbatch in Comparative Examples 3 and 4 was experimentally optimized to maximize their flame-retardant, mechanical, and aging resistance properties), but they clearly have poor compatibility with other components in the TPO waterproof membrane, and their introduction significantly reduces mechanical properties and aging resistance.

[0147] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A thermoplastic composition for waterproof membranes, characterized in that, By weight, it includes: 10-18 parts of polypropylene, 25-35 parts of flame retardant preformed masterbatch, 40-60 parts of polyolefin elastomer and 3-10 parts of functional additives. The flame-retardant pre-fabricated masterbatch comprises: polyethylene, flame retardant, graphene, and silane coupling agent; by weight, the polyethylene comprises 35-52 parts, the flame retardant comprises 40-55 parts, the graphene comprises 2-6 parts, and the silane coupling agent comprises 2-6 parts; the flame retardant comprises melamine polyphosphate and pentaerythritol in a mass ratio of (2-5):

1.

2. The thermoplastic composition for waterproof membranes according to claim 1, characterized in that, The functional additives include: antioxidants and white masterbatch; by weight, the antioxidants are 2 to 6 parts and the white masterbatch is 1 to 4 parts.

3. A TPO material layer, characterized in that, The TPO material layer is prepared from the thermoplastic composition according to claim 1 or 2.

4. A waterproof membrane, characterized in that, include: The TPO material layer as described in claim 3.

5. The waterproof membrane according to claim 4, characterized in that, include: Fluorocarbon film layer, adhesive layer and TPO material layer.

6. The waterproof membrane according to claim 5, characterized in that, The fluorocarbon membrane layer is a porous polytetrafluoroethylene membrane; and / or, the adhesive layer is a flame-retardant butyl rubber layer.

7. The waterproof membrane according to claim 6, characterized in that, By weight, the flame-retardant butyl rubber layer comprises: 15-25 parts butyl rubber, 3-7 parts SIS, 8-12 parts C5 hydrogenated resin, 2-8 parts terpene resin, 15-25 parts polyisobutylene, 30-40 parts magnesium hydroxide, 0.1-0.3 parts silane coupling agent, 0.4-0.8 parts antioxidant, 0.2-0.5 parts UV stabilizer, and 1-3 parts titanium dioxide.

8. The method for preparing the TPO material layer according to claim 3, characterized in that, include: Polypropylene, flame-retardant preformed masterbatch, polyolefin elastomer and functional additives are melt-blended and extruded; The extrusion parameters include: barrel temperature 170℃~190℃, three-roll calender temperature 45℃~65℃, and tempering roll temperature 30℃~45℃.

9. The application of the thermoplastic composition for waterproof membranes according to claim 1 or 2, or the TPO material layer according to claim 3, in the preparation of waterproof membranes for building roofs, underground works, artificial water bodies and environmental works, or transportation and infrastructure works.

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