Composite waterproofing membrane with layered structure and method for manufacturing the same

Abstract

The application discloses a composite waterproof roll material with a layered structure and a preparation method thereof, and belongs to the field of the layered structure waterproof roll material. The composite waterproof roll material with the layered structure has the layered structure, and comprises, from bottom to top, a base material layer, a first corrosion-resistant modified asphalt layer, a non-woven fabric layer, a second corrosion-resistant asphalt layer and a waterproof film layer; the first corrosion-resistant modified asphalt layer and the second corrosion-resistant modified asphalt layer comprise, in terms of mass fraction, petroleum asphalt 36-40 parts, a modifier 5-8 parts, butadiene styrene rubber 1-2 parts and a compatilizer 2-4 parts; the modifier is obtained by modifying epoxy resin, fluorine-containing polysiloxane and ethylene-vinyl acetate copolymer. The waterproof roll material has a double corrosion-resistant effect through the synergistic effect of the first corrosion-resistant modified asphalt layer and the second corrosion-resistant modified asphalt layer, improves the corrosion-resistant effect of the overall waterproof roll material, and prolongs the service life of the waterproof roll material.

Description

Technical Field

[0001] This application relates to a composite waterproof membrane with a layered structure and its preparation method, belonging to the field of layered waterproof membranes. Background Technology

[0002] The single type of ordinary polymer waterproof membrane used in the existing technology can erode the structure of traditional membranes in harsh environments due to the presence of acidic or alkaline seepage liquids or some corrosive components. This damages the waterproof coating and the underlying material layer, leading to cracking and accelerated aging of the waterproof membrane, causing it to lose its waterproof function.

[0003] Meanwhile, most of the existing waterproof membranes have relatively simple functions and cannot meet multiple requirements such as waterproofing, corrosion prevention, and crack resistance at the same time. With the rapid development of the construction industry, the application scenarios of waterproof membranes are increasing and the application environment is becoming more and more complex. Complex application scenarios not only require materials to have basic waterproofing capabilities, but also strong corrosion resistance.

[0004] Chinese invention patent CN108790349 A discloses a UV-resistant waterproof membrane. The raw material components of the waterproof membrane, by weight, are: 30-35 parts linear high-density polyethylene granules (HDPE), 30-35 parts linear low-density polyethylene granules (LDPE), 25-30 parts ethylene-vinyl acetate (EVA), 3-5 parts polyethylene octene co-elastomer toughening agent (POE), 1.8-2.5 parts carbon black, 2-3 parts antioxidant, 2-3 parts UV resistant agent, and 0.1-0.3 parts stabilizer. This composition ratio results in a UV-resistant waterproof membrane with good tensile strength, good elongation, strong adaptability to substrate expansion or cracking deformation, root penetration resistance, and UV resistance. However, the waterproof membrane in the aforementioned patent contains various additives. The corresponding technical effects are achieved through the combination of these additives with the substrate, and the amount and types of additives added will affect the actual performance of the waterproof membrane in practical applications.

[0005] Furthermore, the waterproof membrane in the aforementioned patent is obtained directly by extruding a hot-melt film from a flat die, followed by calendering and cooling. The waterproof membrane's waterproof and corrosion-resistant properties rely on the membrane itself. Once the surface of the waterproof membrane is corroded and cracked, the entire membrane can easily be destroyed.

[0006] Therefore, there is an urgent need for a composite waterproof membrane with a layered structure that has good waterproof performance, strong corrosion resistance, and synergistic effects between layers. Summary of the Invention

[0007] To address the aforementioned issues, a composite waterproof membrane with a layered structure is provided. This waterproof membrane exhibits dual corrosion resistance through the synergistic effect of a first corrosion-resistant modified bitumen layer and a second corrosion-resistant modified bitumen layer, thereby improving the overall corrosion resistance of the waterproof membrane and extending its service life.

[0008] One aspect of this application provides a composite waterproof membrane with a layered structure, comprising, from bottom to top, a substrate layer, a first corrosion-resistant modified bitumen layer, a non-woven fabric layer, a second corrosion-resistant bitumen layer, and a waterproof membrane layer; the first and second corrosion-resistant modified bitumen layers, by mass fraction, comprise: 36-40 parts petroleum bitumen, 5-8 parts modifier, 1-2 parts styrene-butadiene rubber, and 2-4 parts compatibilizer; the modifier is obtained by modifying epoxy resin with fluorinated polysiloxane and ethylene-vinyl acetate copolymer.

[0009] The waterproof membrane in this application is designed with a layered structure, which can provide multiple protective barriers. When one layer of the layered waterproof membrane is damaged, it will not affect the function of other layers. The waterproof membrane can still play a role in waterproofing and corrosion prevention, thereby extending the service life of the waterproof membrane.

[0010] Optionally, the substrate layer is a polyester felt layer.

[0011] Optionally, the compatibilizer is one of fully refined paraffin wax or semi-refined paraffin wax.

[0012] Optionally, the thickness of the substrate layer is 0.5-0.8 mm.

[0013] At this thickness, the substrate layer ensures sufficient tensile and tear strength, serving as the base layer of the waterproof membrane. Above the substrate layer are a first corrosion-resistant modified bitumen layer, a non-woven fabric layer, a second corrosion-resistant modified bitumen layer, and a waterproof membrane layer. This prevents deformation and damage to the membrane due to structural weight or external forces during construction after the layers are composited, thus extending the overall service life of the membrane. If the substrate layer thickness is less than 0.5mm, it is prone to tearing during cutting and laying, making it unsuitable as a base layer for waterproof membrane production. If the substrate layer thickness is greater than 0.8mm, it not only increases the weight and construction difficulty of the waterproof membrane but also increases material costs. Furthermore, an excessively thick substrate layer increases the rigidity of the membrane, further complicating production.

[0014] Optionally, the thickness of the first corrosion-resistant modified asphalt layer is 0.2-0.4 mm.

[0015] At this thickness, the first corrosion-resistant modified bitumen layer can form a continuous, non-porous corrosion-resistant coating, effectively blocking corrosive media and preventing corrosion of the substrate layer, thus improving the corrosion resistance of the waterproof roll curtain. At the same time, the modified bitumen in the first corrosion-resistant modified bitumen layer itself has a waterproof function, further improving the corrosion resistance of the waterproof roll curtain while maintaining its own waterproof performance.

[0016] If the thickness of the first corrosion-resistant modified bitumen layer is less than 0.2 mm, it is easy for the first corrosion-resistant modified bitumen layer to be missed, and a continuous corrosion-resistant protective layer cannot be formed. If the thickness of the first corrosion-resistant modified bitumen layer is greater than 0.4 mm, it is easy for the first corrosion-resistant modified bitumen layer to crack after curing. Increasing the thickness will not only increase the weight and material cost of the waterproof membrane, but also affect the adhesion between the first corrosion-resistant modified bitumen layer and the substrate layer.

[0017] Optionally, the thickness of the second corrosion-resistant modified asphalt layer is 0.2-0.4 mm.

[0018] At this thickness, the second corrosion-resistant modified bitumen layer serves several purposes: first, it works synergistically with the first corrosion-resistant modified bitumen layer to improve the corrosion resistance of the waterproof membrane, effectively enhancing its corrosion resistance; second, it prevents cracking of the second corrosion-resistant modified bitumen layer, extending the service life of the waterproof membrane; and third, it fills the fiber gaps on the surface of the non-woven fabric layer, allowing the lower and upper surfaces of the non-woven fabric layer to be covered by the first and second corrosion-resistant modified bitumen layers respectively, forming a sandwich structure. This not only strengthens the adhesion between the first and second corrosion-resistant modified bitumen layers and the non-woven fabric layer but also protects the non-woven fabric layer from absorbing moisture or being eroded by corrosive media through the hydrophobic properties of the first and second corrosion-resistant modified bitumen layers.

[0019] Optionally, the nonwoven fabric layer is 0.3-0.5 mm thick.

[0020] At this thickness, the nonwoven fabric layer not only improves the tensile strength and elongation at break of the waterproof membrane, but also compensates for the low strength and susceptibility to damage of the first and second corrosion-resistant modified bitumen layers, thereby enhancing the strength and toughness of the waterproof membrane and extending its service life. If the thickness is less than 0.3 mm, the fiber density of the nonwoven fabric layer is insufficient, failing to effectively improve the tensile strength of the waterproof membrane. If the thickness is greater than 0.5 mm, the excessive thickness of the nonwoven fabric layer will prevent the first and second corrosion-resistant modified bitumen layers from fully penetrating, leading to a decrease in the adhesion between the first and second corrosion-resistant modified bitumen layers and the nonwoven fabric layer, thus affecting the quality of the waterproof membrane.

[0021] Optionally, the waterproof membrane layer is 0.1-0.2 mm thick.

[0022] At this thickness, the waterproof membrane layer has an extremely low permeability coefficient, which not only directly blocks external water molecules from penetrating inward but also prevents the second corrosion-resistant modified bitumen layer from being directly exposed to the air, reducing the corrosion and oxidation of the modified bitumen by oxygen and moisture. If the thickness of the waterproof membrane layer is less than 0.1 mm, it is easily damaged due to its thinness and cannot form effective protection; if the thickness of the waterproof membrane layer is greater than 0.2 mm, the rigidity of the waterproof membrane layer increases, which reduces the mechanical properties of the waterproof membrane and also affects its adhesion to the second corrosion-resistant modified bitumen layer.

[0023] Optionally, the modifier is prepared as follows:

[0024] (1) After the epoxy resin is mixed evenly in the solvent, fluorinated polysiloxane is added and mixed evenly. Then, phosphoric acid solution is added dropwise, and the mixture is stirred at 100-110℃ for 5-10 hours. After washing with water and drying, intermediate A is obtained.

[0025] (2) Add ethylene-vinyl acetate copolymer to intermediate A and ball mill and mix at 25-35℃ for 30-60h to obtain the modifier.

[0026] The epoxy groups of epoxy resin react with the active groups of fluorinated polysiloxane under phosphoric acid catalysis, causing the fluorinated polysiloxane to graft onto the epoxy resin molecular chain. The fluorine atoms in the epoxy resin molecular chain form a dense protective layer, which can improve the corrosion resistance of the material. At the same time, the siloxane bond has excellent chemical stability and can resist oxidation, hydrolysis and high temperature aging, making up for the defects of poor weather resistance and susceptibility to strong acid and alkali corrosion of epoxy resin. By modifying epoxy resin, its corrosion resistance and weather resistance can be improved, thereby improving the performance of the final product.

[0027] In addition, fluorinated polysiloxanes have low surface energy, which further improves the hydrophobicity of the material. The high bond energy of the siloxane bonds makes them less prone to aging and decomposition even when used in high-temperature environments, thus extending the service life of the waterproof membrane.

[0028] By blending intermediate A with ethylene-vinyl acetate copolymer, the elasticity and flexibility of the material are increased, thereby improving the elongation at break of the waterproof membrane. This reduces the stress caused by deformation during use and prevents the waterproof membrane from cracking. At the same time, ethylene-vinyl acetate has good weather resistance, making the prepared waterproof membrane less prone to yellowing, embrittlement, and cracking in outdoor exposure environments.

[0029] Optionally, the mass ratio of the epoxy resin to the fluorinated polysiloxane is 1:(0.5-1).

[0030] At this ratio, the synergistic effect between fluorinated polysiloxane and epoxy resin is the best. Excessive epoxy resin will increase the rigidity of the system, increase the processing difficulty of the material, and the effect of increasing the amount of epoxy resin added is not obvious in enhancing the corrosion resistance of the system. The low surface energy of the fluorocarbon chain on the fluorinated polysiloxane and the chemical stability of the siloxane bond can effectively improve the corrosion resistance, water resistance and weather resistance of the material. If too much fluorinated polysiloxane is added, it will reduce the bonding strength and compatibility, and it is also easy to agglomerate when blended with ethylene-vinyl acetate in the later stage, which cannot be effectively dispersed, thus affecting the performance of the material.

[0031] Optionally, the mass ratio of intermediate A to ethylene-vinyl acetate copolymer is 1:(0.3-0.5).

[0032] At this ratio, the system's flexibility and crack resistance are significantly improved, reducing cracking and breakage, while also enhancing the system's corrosion resistance and adhesion. If the amount of ethylene-vinyl acetate copolymer added is small, the toughness enhancement is not significant, and the waterproof membrane is prone to brittleness during use; if the amount of ethylene-vinyl acetate copolymer added is large, it will dilute the crosslinking density of intermediate A, resulting in insufficient tensile strength of the modifier, thus affecting the performance of the waterproof membrane.

[0033] Optionally, the fluorinated polysiloxane includes trifluoropropylmethylcyclotrisiloxane.

[0034] Optionally, the vinyl acetate monomer content in the ethylene-vinyl acetate copolymer is 32-36 wt%.

[0035] The ester groups in the vinyl acetate linkages of the ethylene-vinyl acetate copolymer can enhance compatibility with intermediate A, and also enhance compatibility and adhesion with petroleum asphalt. When preparing the first and second corrosion-resistant modified asphalt layers, it can enhance the bonding strength with the nonwoven fabric layer, prevent the waterproof membrane from detaching or cracking during use, improve the quality of the waterproof membrane, and extend its service life.

[0036] Another aspect of this application provides a method for preparing a composite waterproof membrane with a layered structure, comprising the following steps:

[0037] S1: Petroleum asphalt, modifier, styrene-butadiene rubber, and compatibilizer are added to a twin-screw extruder for blending, melted at 170-180℃ for 4-6 minutes, and extruded to obtain the first corrosion-resistant modified asphalt layer and the second corrosion-resistant modified asphalt layer.

[0038] S2: The substrate layer and the first corrosion-resistant modified asphalt layer are hot-pressed together by a three-roll mill, and then the non-woven fabric layer and the second corrosion-resistant modified asphalt layer are hot-pressed together by a three-roll mill to form the substrate layer.

[0039] S3: Apply a waterproof coating to the second corrosion-resistant modified bitumen layer, which will form a waterproof film layer after curing;

[0040] S4: After cooling, correction, edge trimming, cutting, rolling, and packaging, a composite waterproof membrane with a layered structure is prepared.

[0041] Melting petroleum asphalt, modifier, styrene-butadiene rubber (SBR), and compatibilizer at 170-180℃ allows them to mix. The compatibilizer and modifier work synergistically to improve the compatibility of petroleum asphalt and SBR, thereby enhancing the density, water resistance, and corrosion resistance of the first and second corrosion-resistant modified asphalt layers.

[0042] Optionally, the waterproof coating, by mass fraction, comprises 40-50 parts acrylic acid, 20-25 parts epoxy resin, 10-15 parts modified fluorocarbon polymer, 8-10 parts defoamer, 30-40 parts curing agent, and 50-70 parts water.

[0043] Optionally, the defoamer is one of polysiloxane defoamers or polyether defoamers.

[0044] Optionally, the curing agent is one of diethylenetriamine, triethylenetetraamine, and tetraethylenepentamine.

[0045] Optionally, the fluorocarbon polymer is at least one of polytetrafluoroethylene, polyvinylidene fluoride, and ethylene-tetrafluoroethylene copolymer.

[0046] Optionally, the fluorocarbon polymer is prepared as follows:

[0047] The fluorocarbon polymer was impregnated in a strong oxidant at 40-45°C for 2-3 hours, then washed and dried. After that, it was added to an aqueous acrylic acid solution at 60-65°C, and an initiator was added. The reaction was carried out for 1-2 hours, followed by washing and drying to obtain the modified fluorocarbon polymer.

[0048] The surface of fluorocarbon polymers is oxidized by strong oxidants to generate polar active groups such as hydroxyl and carboxyl groups. Initiators generate free radicals, which trigger the reaction between the double bonds of acrylic monomers and the active groups on the surface of fluorocarbon polymers, grafting acrylic segments onto the surface of fluorocarbon polymers and improving the dispersibility of fluorocarbon polymers. The CF bonds in fluorocarbon polymers can resist the erosion of ultraviolet rays, oxygen, and moisture, while acrylic acid itself has anti-aging properties. The combination of the two further improves the corrosion resistance, waterproofness, and anti-aging properties of the waterproof film layer.

[0049] Optionally, the strong oxidant is one of hydrogen peroxide and potassium permanganate.

[0050] Optionally, the initiator is one of potassium persulfate or sodium persulfate.

[0051] The beneficial effects of this application include, but are not limited to:

[0052] 1. According to the composite waterproof membrane with a layered structure of this application, when one layer of the waterproof membrane is damaged, it will not affect the function of other layers, and the waterproof membrane can still function effectively, thus extending the service life of the waterproof membrane.

[0053] 2. The composite waterproof membrane with a layered structure according to this application has a dual corrosion resistance effect through the synergistic effect of the first corrosion-resistant modified bitumen layer and the second corrosion-resistant modified bitumen layer, thereby improving the overall corrosion resistance of the waterproof membrane and extending its service life.

[0054] 3. The composite waterproof membrane with a layered structure according to this application, by grafting fluorinated polysiloxane onto the epoxy resin molecular chain, the fluorine atoms in the epoxy resin molecular chain will form a dense protective layer. When blended with ethylene-vinyl acetate copolymer, it can not only improve the corrosion resistance, oxidation resistance and waterproofness of the waterproof membrane, but also improve the elasticity, flexibility and elongation at break of the material.

[0055] 4. According to the composite waterproof membrane with a layered structure of this application, acrylic acid is used to modify the fluorocarbon polymer to improve the dispersibility of the fluorocarbon polymer in the waterproof coating system. The synergistic effect of fluorocarbon polymer and acrylic acid can improve the corrosion resistance, waterproofness and anti-aging performance of the waterproof film layer. Attached Figure Description

[0056] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings:

[0057] Figure 1 This is a schematic diagram of the composite waterproof membrane with a layered structure involved in the embodiments of this application.

[0058] List of components and reference numerals:

[0059] 1. Substrate layer; 2. First corrosion-resistant modified bitumen layer; 3. Non-woven fabric layer; 4. Second corrosion-resistant modified bitumen layer; 5. Waterproof membrane layer. Detailed Implementation

[0060] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0061] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application were all purchased commercially.

[0062] Unless otherwise specified, the methods used in the embodiments and comparative examples of this application are conventional methods in the prior art.

[0063] Trifluoropropylmethylcyclotrisiloxane CAS No.: 2374-14-3; Petroleum asphalt CAS No.: 8052-42-4; Styrene-butadiene rubber CAS No.: 9003-55-8; Butyl acetate CAS No.: 123-86-4; n-Butanol CAS No.: 71-36-3; Bisphenol A type epoxy resin CAS No.: 25085-99-8; Acrylic acid CAS No.: 79-10-7; Polytetrafluoroethylene CAS No.: CAS No.: 9002-84-0; Diethylenetriamine CAS No.: 111-40-0; Potassium permanganate CAS No.: 7722-64-7; Ammonium persulfate CAS No.: 7727-54-0; Potassium persulfate CAS No.: 7727-21-1; Polyvinylidene fluoride CAS No.: 24937-79-9; Hydrogen peroxide CAS No.: 7722-84-1; Polysiloxane CAS No.: 63148-62-9.

[0064] Example 1

[0065] This embodiment relates to a composite waterproof membrane with a layered structure. The composite waterproof membrane with a layered structure includes, from bottom to top, a base layer (polyester felt layer) 1 with a thickness of 0.5 mm, a first corrosion-resistant modified bitumen layer 2 with a thickness of 0.4 mm, a non-woven fabric layer 3 with a thickness of 0.5 mm, a second corrosion-resistant bitumen layer with a thickness of 0.4 mm, and a waterproof film layer 5 with a thickness of 0.1 mm.

[0066] The first corrosion-resistant modified asphalt layer 2 and the second corrosion-resistant modified asphalt layer 4, by mass fraction, include: 36 parts of petroleum asphalt, 5 parts of modifier, 1 part of styrene-butadiene rubber, and 2 parts of fully refined paraffin wax.

[0067] The preparation method of composite waterproof membrane with layered structure includes the following steps:

[0068] S1: Petroleum asphalt, modifier, styrene-butadiene rubber, and fully refined paraffin wax are added to a twin-screw extruder for blending, melted at 170°C for 6 minutes, and extruded and calendered at 180°C to obtain a first corrosion-resistant modified asphalt layer 2 and a second corrosion-resistant modified asphalt layer 4 with a thickness of 0.4 mm.

[0069] The preparation method of the modifier is as follows:

[0070] (1) After mixing bisphenol A type epoxy resin evenly in a mixed solution of butyl acetate and n-butanol with a mass ratio of 1:1, trifluoropropylmethylcyclotrisiloxane is added and mixed evenly. The mass ratio of bisphenol A type epoxy resin to trifluoropropylmethylcyclotrisiloxane is 1:0.5. Then, an 85% phosphoric acid solution is added dropwise, and the mixture is stirred at 100°C for 10 h. After washing with water and drying, intermediate A is obtained.

[0071] (2) Add ethylene-vinyl acetate copolymer (vinyl acetate chain segment content is 32wt%) to intermediate A and ball mill and mix at 25°C for 30h to obtain modifier. The mass ratio of intermediate A to ethylene-vinyl acetate copolymer (vinyl acetate chain segment content is 32wt%) is 1:0.3.

[0072] S2: Take a 0.5mm thick base material layer (polyester felt layer) 1 and a 0.4mm thick first corrosion-resistant modified bitumen layer 2, and hot press them together with a 0.5mm thick non-woven fabric layer 3 and a 0.4mm thick second corrosion-resistant modified bitumen layer 4, and then hot press them together with a three-roll mill to form the final product.

[0073] S3: Apply waterproof coating to the second corrosion-resistant modified bitumen layer 4, control the thickness of the waterproof coating to be 0.1 mm, and form a waterproof film layer 5 after curing at 130℃;

[0074] The waterproof coating comprises 40 parts acrylic acid, 20 parts bisphenol A type epoxy resin, 10 parts modified polytetrafluoroethylene, 8 parts polysiloxane defoamer, 30 parts diethylenetriamine, and 50 parts water. The modified polytetrafluoroethylene is prepared by immersing polytetrafluoroethylene in a 0.8 mol / L potassium permanganate solution at 40°C for 3 hours, followed by washing and drying. Then, it is added to a 2 mol / L acrylic acid aqueous solution, and after adding 0.2 wt% ammonium persulfate at 65°C, the reaction is carried out for 1 hour, followed by washing and drying to obtain the modified polytetrafluoroethylene.

[0075] S4: After cooling, correction, edge trimming, cutting, rolling, and packaging, a composite waterproof membrane with a layered structure is prepared.

[0076] Example 2

[0077] This embodiment relates to a composite waterproof membrane with a layered structure. The composite waterproof membrane with a layered structure includes, from bottom to top, a base layer (polyester felt layer) 1 with a thickness of 0.8 mm, a first corrosion-resistant modified bitumen layer 2 with a thickness of 0.2 mm, a non-woven fabric layer 3 with a thickness of 0.3 mm, a second corrosion-resistant bitumen layer 4 with a thickness of 0.2 mm, and a waterproof film layer 5 with a thickness of 0.2 mm.

[0078] The first corrosion-resistant modified asphalt layer 2 and the second corrosion-resistant modified asphalt layer 4, by mass fraction, include: 40 parts petroleum asphalt, 8 parts modifier, 2 parts styrene-butadiene rubber, and 4 parts semi-refined paraffin wax.

[0079] The preparation method of composite waterproof membrane with layered structure includes the following steps:

[0080] S1: Petroleum asphalt, modifier, styrene-butadiene rubber, and semi-refined paraffin wax are added to a twin-screw extruder for blending, melted at 180°C for 4 minutes, and extruded and calendered at 180°C to obtain the first corrosion-resistant modified asphalt layer 2 and the second corrosion-resistant modified asphalt layer 4 with a diameter of 0.2 mm.

[0081] The preparation method of the modifier is as follows:

[0082] (1) After mixing bisphenol A type epoxy resin evenly in a mixed solution of butyl acetate and n-butanol with a mass ratio of 1:1, trifluoropropylmethylcyclotrisiloxane is added and mixed evenly. The mass ratio of bisphenol A type epoxy resin to trifluoropropylmethylcyclotrisiloxane is 1:1. Then, an 85% phosphoric acid solution is added dropwise, and the mixture is stirred at 110°C for 5 hours. After washing with water and drying, intermediate A is obtained.

[0083] (2) Add ethylene-vinyl acetate copolymer (vinyl acetate chain segment content is 36wt%) to intermediate A and ball mill and mix at 35°C for 30h to obtain modifier. The mass ratio of intermediate A to ethylene-vinyl acetate copolymer (vinyl acetate chain segment content is 36wt%) is 1:0.5.

[0084] S2: Take a 0.8mm thick base material layer (polyester felt layer) 1 and a 0.2mm thick first corrosion-resistant modified bitumen layer 2, and hot press them together with a three-roll mill. Then, take a 0.3mm thick non-woven fabric layer 3 and a 0.2mm thick second corrosion-resistant modified bitumen layer 4, and hot press them together with a three-roll mill to form the final product.

[0085] S3: Apply a waterproof coating to the second corrosion-resistant modified bitumen layer 4, control the thickness of the waterproof coating to be 0.2 mm, and form a waterproof film layer 5 after curing at 130℃;

[0086] The waterproof coating comprises 50 parts acrylic acid, 25 parts bisphenol A type epoxy resin, 15 parts modified polyvinylidene fluoride, 10 parts polyether defoamer, 40 parts triethylenetetramine, and 70 parts water. The modified polyvinylidene fluoride is prepared by immersing polyvinylidene fluoride in an 8 mol / L hydrogen peroxide solution at 40°C for 3 hours, followed by washing and drying. Then, it is added to a 2 mol / L acrylic acid solution at 65°C, and 0.2 wt% potassium persulfate is added. The reaction is carried out for 1 hour, followed by washing and drying to obtain the modified polyvinylidene fluoride.

[0087] S4: After cooling, correction, edge trimming, cutting, rolling, and packaging, a composite waterproof membrane with a layered structure is prepared.

[0088] Example 3

[0089] This embodiment relates to a composite waterproof membrane with a layered structure. The composite waterproof membrane with a layered structure includes, from bottom to top, a base layer (polyester felt layer) 1 with a thickness of 0.6 mm, a first corrosion-resistant modified bitumen layer 2 with a thickness of 0.3 mm, a non-woven fabric layer 3 with a thickness of 0.4 mm, a second corrosion-resistant bitumen layer with a thickness of 0.3 mm, and a waterproof film layer 5 with a thickness of 0.15 mm.

[0090] The first corrosion-resistant modified asphalt layer 2 and the second corrosion-resistant modified asphalt layer 4, by mass fraction, include: 38 parts petroleum asphalt, 6 parts modifier, 1.5 parts styrene-butadiene rubber, and 3 parts fully refined paraffin wax.

[0091] The preparation method of composite waterproof membrane with layered structure includes the following steps:

[0092] S1: Petroleum asphalt, modifier, styrene-butadiene rubber, and fully refined paraffin wax are added to a twin-screw extruder for blending, melted at 175°C for 5 minutes, and extruded and calendered at 180°C to obtain a first corrosion-resistant modified asphalt layer 2 and a second corrosion-resistant modified asphalt layer 4 with a thickness of 0.3 mm.

[0093] The preparation method of the modifier is as follows:

[0094] (1) Bisphenol A type epoxy resin was mixed evenly in a mixed solution of butyl acetate and n-butanol with a mass ratio of 1:1, and then trifluoropropylmethylcyclotrisiloxane was added and mixed evenly. The mass ratio of bisphenol A type epoxy resin to trifluoropropylmethylcyclotrisiloxane was 1:0.7. Then, an 85% phosphoric acid solution was added dropwise, and the mixture was stirred at 105°C for 6 hours. After washing with water and drying, intermediate A was obtained.

[0095] (2) Add ethylene-vinyl acetate copolymer (vinyl acetate chain segment content is 34wt%) to intermediate A and ball mill and mix at 30°C for 35h to obtain modifier. The mass ratio of intermediate A to ethylene-vinyl acetate copolymer (vinyl acetate chain segment content is 34wt%) is 1:0.8.

[0096] S2: Take a 0.6mm thick base material layer (polyester felt layer) 1 and a 0.3mm thick first corrosion-resistant modified bitumen layer 2, and hot press them together with a 0.4mm thick non-woven fabric layer 3 and a 0.3mm thick second corrosion-resistant modified bitumen layer 4, and then hot press them together with a three-roll mill to form the final product.

[0097] S3: Apply waterproof coating to the second corrosion-resistant modified bitumen layer 4, control the thickness of the waterproof coating to be 0.15mm, and form a waterproof film layer 5 after curing at 130℃;

[0098] The waterproof coating comprises 45 parts acrylic acid, 23 parts bisphenol A type epoxy resin, 13 parts modified polytetrafluoroethylene, 9 parts polyether defoamer, 35 parts triethylenetetramine, and 60 parts water. The modified polytetrafluoroethylene is prepared by immersing polytetrafluoroethylene in an 8 mol / L hydrogen peroxide solution at 40°C for 3 hours, followed by washing and drying. Then, it is added to a 2 mol / L acrylic acid solution at 65°C, and 0.2 wt% potassium persulfate is added. The reaction is carried out for 1 hour, followed by washing and drying to obtain the modified polytetrafluoroethylene.

[0099] S4: After cooling, correction, edge trimming, cutting, rolling, and packaging, a composite waterproof membrane with a layered structure is prepared.

[0100] Example 4

[0101] The difference between this embodiment and embodiment 3 is that the thickness of the first corrosion-resistant modified asphalt layer 2 and the second corrosion-resistant modified asphalt layer 4 is 0.1 mm, while the rest is the same as in embodiment 3.

[0102] Example 5

[0103] The difference between this embodiment and Example 3 is that the modifier is obtained by ball milling and mixing bisphenol A type epoxy resin, trifluoropropylmethylcyclotrisiloxane and ethylene-vinyl acetate copolymer (vinyl acetate chain segment content is 34wt%) at 25°C for 40h, and the rest is the same as in Example 3.

[0104] Example 6

[0105] The difference between this embodiment and Embodiment 3 is that the mass ratio of bisphenol A epoxy resin to trifluoropropylmethylcyclotrisiloxane is 1:0.1, while the rest is the same as in Embodiment 3.

[0106] Example 7

[0107] The difference between this embodiment and Embodiment 3 is that the modified polytetrafluoroethylene is replaced with polytetrafluoroethylene in the waterproof coating, while the rest is the same as in Embodiment 3.

[0108] Comparative Example 1

[0109] The difference between this comparative example and Example 3 is that the composite waterproof membrane with a layered structure is the first corrosion-resistant bitumen layer, while the rest is the same as in Example 3.

[0110] Comparative Example 2

[0111] The difference between this comparative example and Example 3 is that the composite waterproof membrane with a layered structure includes a substrate layer, a first corrosion-resistant modified bitumen layer 2, a non-woven fabric layer 3, and a waterproof film layer 5, while the rest is the same as in Example 3.

[0112] Comparative Example 3

[0113] The difference between this comparative example and Example 3 is that trifluoropropylmethylcyclotrisiloxane is not added to the modifier, while the rest is the same as in Example 3.

[0114] Comparative Example 4

[0115] The difference between this comparative example and Example 3 is that trifluoropropylmethylcyclotrisiloxane is replaced with polysiloxane, while the rest is the same as in Example 3.

[0116] Test Example 1

[0117] The waterproof membranes prepared in Examples 1-7 and Comparative Examples 1-4 were subjected to the following tests, and the results are shown in Table 1.

[0118] (1) Heat resistance test: The heat resistance performance shall be tested in accordance with the method in GB / T328.11-2007;

[0119] (2) Peel strength test: The glass strength shall be tested according to the method in GB / T328.20-2007;

[0120] (3) Impermeability test: The impermeability test shall be conducted in accordance with the method in GB18242-2008;

[0121] (4) Crack resistance test: 100cm sections of the waterproof membranes prepared in Examples 1-7 and Comparative Examples 1-4 were cut. 2 Crack resistance performance was tested according to the methods in GB / T23457-2017;

[0122] (5) Corrosion resistance test: Cut 100cm sections of the waterproof membranes prepared in Examples 1-7 and Comparative Examples 1-4. 2 Corrosion resistance tests were conducted according to the methods in GB / T2951.25-1994.

[0123] Table 1

[0124]

[0125] The above description is merely an embodiment of this application, and the scope of protection of this application is not limited to these specific embodiments, but is determined by the claims of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the technical concept and principles of this application should be included within the scope of protection of this application.

Claims

1. A composite waterproof membrane with a layered structure, characterized in that, It includes, from bottom to top, a substrate layer, a first corrosion-resistant modified bitumen layer, a non-woven fabric layer, a second corrosion-resistant modified bitumen layer, and a waterproof membrane layer; The first and second corrosion-resistant modified asphalt layers, by mass fraction, consist of: 36-40 parts petroleum asphalt, 5-8 parts modifier, 1-2 parts styrene-butadiene rubber, and 2-4 parts compatibilizer. The preparation method of the modifier is as follows: (1) After the epoxy resin is mixed evenly in the solvent, fluorinated polysiloxane is added and mixed evenly. Then, phosphoric acid solution is added dropwise, and the mixture is stirred at 100-110℃ for 5-10 hours. After washing with water and drying, intermediate A is obtained. (2) Add ethylene-vinyl acetate copolymer to intermediate A and ball mill and mix at 25-35℃ for 30-60h to obtain the modifier; The method for preparing the composite waterproof membrane with a layered structure includes the following steps: S1: Petroleum asphalt, modifier, styrene-butadiene rubber, and compatibilizer are added to a twin-screw extruder for blending, melted at 170-180℃ for 4-6 minutes, and extruded to obtain the first corrosion-resistant modified asphalt layer and the second corrosion-resistant modified asphalt layer. S2: The substrate layer and the first corrosion-resistant modified asphalt layer are hot-pressed together by a three-roll mill, and then the non-woven fabric layer and the second corrosion-resistant modified asphalt layer are hot-pressed together by a three-roll mill to form the substrate layer. S3: Apply a waterproof coating to the second corrosion-resistant modified bitumen layer, which will form a waterproof film layer after curing; S4: After cooling, correction, edge trimming, cutting, rolling, and packaging, a composite waterproof membrane with a layered structure is prepared. The waterproof coating, by mass fraction, comprises 40-50 parts acrylic acid, 20-25 parts epoxy resin, 10-15 parts modified fluorocarbon polymer, 8-10 parts defoamer, 30-40 parts curing agent, and 50-70 parts water. The modified fluorocarbon polymer is prepared as follows: The fluorocarbon polymer was impregnated in a strong oxidant at 40-45°C for 2-3 hours, then washed and dried. After that, it was added to an aqueous acrylic acid solution at 60-65°C, and an initiator was added. The reaction was carried out for 1-2 hours, followed by washing and drying to obtain the modified fluorocarbon polymer.

2. The composite waterproof membrane with a layered structure according to claim 1, characterized in that, The thickness of the substrate layer is 0.5-0.8 mm; The thickness of the first corrosion-resistant modified asphalt layer is 0.2-0.4 mm; The thickness of the second corrosion-resistant modified asphalt layer is 0.2-0.4 mm; The nonwoven fabric layer is 0.3-0.5 mm thick; The waterproof membrane layer is 0.1-0.2 mm thick.

3. The composite waterproof membrane with a layered structure according to claim 1, characterized in that, The mass ratio of the epoxy resin to the fluorinated polysiloxane is 1:(0.5-1).

4. The composite waterproof membrane with a layered structure according to claim 1, characterized in that, The mass ratio of intermediate A to ethylene-vinyl acetate copolymer is 1:(0.3-0.5).

5. The composite waterproof membrane with a layered structure according to claim 1, characterized in that, The fluorinated polysiloxane includes trifluoropropylmethylcyclotrisiloxane.

6. The composite waterproof membrane with a layered structure according to claim 1, characterized in that, The vinyl acetate copolymer contains 32-36 wt% vinyl acetate units.

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