Capillary crystallization type bio-based modified asphalt pre-paved polymer waterproof coiled material and preparation method thereof

Abstract

The invention relates to the technical field of waterproof coiled materials, and discloses a permeable crystallization type bio-based modified asphalt pre-laid polymer waterproof coiled material and a preparation method thereof.The waterproof coiled material comprises a five-layer structure including a permeable crystal sand layer, an upper bio-based modified asphalt rubber layer, a polymer modified polyethylene base, a lower bio-based modified asphalt rubber layer and a lower isolating membrane; the modified isocyanate polymer is prepared, flame-retardant elements contained in the modified isocyanate polymer and inorganic particles in the cementation sand layer are utilized to synergistically improve the mechanical property of the material, and the modified isocyanate polymer contains an isocyanate structure and a siloxane structure, so that the flame-retardant performance of the material is improved, and the flame-retardant performance of the material is improved. The internal compatibility of the bio-based modified asphalt rubber layer can be improved, and hydrogen bonds can be generated with the crystalline sand layer and the polymer modified polyethylene matrix, so that the comprehensive performance of the waterproof coiled material is improved.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, specifically to a permeable crystalline bio-based modified bitumen pre-laid polymer waterproof membrane and its preparation method. Background Technology

[0002] In the "General Specification for Waterproofing of Building and Municipal Engineering" GB55030-2022 (i.e., the new 55030 specification), regarding the specific structural requirements for Class I waterproofing, the existing technical solutions for underground waterproofing projects stipulate that Class I waterproofing can adopt the method of "waterproof concrete + two external waterproofing layers." The waterproof concrete should meet relevant performance requirements, and the two external waterproofing layers can be a combination of a coating and a roll material, or other combinations of materials that meet the requirements. Traditional coatings and roll materials are incompatible, which may weaken the adhesion between them, thus affecting the overall performance of the waterproofing layer. Furthermore, improper construction of coatings and roll materials, such as uneven application or uneven laying of the roll material, can lead to leaks or weak points in the waterproofing layer. In addition, waterproof concrete requires high-level construction techniques; improper construction may lead to defects such as cracks and voids within the concrete, thus affecting its waterproofing performance.

[0003] Existing technologies typically require waterproof concrete plus two external waterproofing layers for Class I waterproofing, one of which must be a coating or roll material. This invention utilizes a pre-applied polymer waterproofing roll material, composed of polymer sheets and modified bitumen, which is then combined with penetrating crystalline sand. The penetrating crystalline sand is evenly applied on the production line, solving the problem of uneven coating application. The evenly laid upper layer of penetrating crystalline sand bonds with the subsequently poured concrete, repairing structural cracks in the concrete structure. Furthermore, the bio-based polymer-modified bitumen of this invention can perfectly combine with the penetrating crystalline sand coating. Summary of the Invention

[0004] This patent addresses the problems of existing technical solutions by proposing a permeable crystalline bio-based modified asphalt pre-laid polymer waterproof membrane and its preparation method, which is based on a composite of nano-silicate permeable crystalline sand coating, bio-based polymer modified asphalt, and polymer modified polyethylene sheet. Its main advantages are that it allows for uniform application of the permeable coating to the membrane surface, resulting in a smooth membrane installation. Simultaneously, it achieves compatibility between the bio-based polymer asphalt membrane and the coating, ensuring a tight bond between them. When concrete is poured into the permeable sand layer, the silicate molecules in the sand react with calcium ions in the concrete to form permanently stable CSH crystals, filling the pores and cracks in the concrete. This invention reduces construction steps; a single waterproof layer can achieve Class I waterproofing, saving costs and time while also providing excellent waterproof performance, durability, and environmental friendliness.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A permeable crystalline bio-based modified bitumen pre-laid polymer waterproof membrane is provided. The waterproof membrane comprises a five-layer structure consisting of a permeable crystalline sand layer, an upper bio-based modified bitumen adhesive layer, a polymer modified polyethylene base, a lower bio-based modified bitumen adhesive layer, and a lower release membrane. The five-layer structure is obtained by composite co-extrusion calendering, cooling and shaping, and winding.

[0007] Preferably, the separator is a PE separator.

[0008] Preferably, the method for preparing the crystallized sand layer includes the following steps:

[0009] 425 cement, activated calcium oxide, nano-grade sodium silicate, anhydrous powdered aluminum sulfate, decanteric acid conjugated salt, and water-reducing agent YT-1003 are added to a planetary mixer. Deionized water is then added and the mixture is stirred until homogeneous. The mixture is then poured into a mold, allowed to dry and harden naturally, and crushed using a large jaw crusher to control the particle size at 16-50 mesh, thus obtaining a crystallized sand layer.

[0010] In this step, decanoisoester conjugated acid salt is used. It can be understood as the "transport captain" and "start switch" of the entire infiltration crystallization system. As a "permeation carrier" and "reaction catalyst", it specifically performs the following functions: 1. Deep penetration: It reduces the surface tension of the active chemical solution, enabling it to carry these active components and actively and rapidly penetrate deep into the concrete through capillary action; 2. Catalysis and transport: It creates a reaction environment and promotes the crystallization reaction; 3. Crystallization optimization: It helps to form a denser, more uniform, and cross-linked crystal structure, thereby more effectively blocking pores and increasing crystal density.

[0011] Preferably, the ratio of 425 cement, activated calcium oxide, nano-grade sodium silicate, anhydrous powdered aluminum sulfate, decanter conjugated acid salt, and water-reducing agent is 100g:(13-15)g:(5-7)g:(21-23)g:(7-9)g:(2-4)g.

[0012] Preferably, the method for preparing the polymer-modified polyethylene base is as follows:

[0013] Polyethylene resin, polypropylene resin, ethylene-propylene copolymer, titanium dioxide, and ethylene-vinyl acetate copolymer are added to a granulator and mixed evenly. The mixture is then placed in a feeder, extruded and plasticized, and rolled into rolls to obtain a high-molecular-weight modified polyethylene base.

[0014] Preferably, the ratio of the amount of polyethylene resin, polypropylene resin, ethylene-propylene copolymer, titanium dioxide, and ethylene-vinyl acetate copolymer is 100g:(150-180)g:(15-20)g:(2-3)g:(150-180)g.

[0015] Preferably, the preparation method of the bio-based modified bitumen adhesive layer is as follows:

[0016] (1) Nitrogen gas was introduced as a protective gas. Tris(2-hydroxyethyl) isocyanurate, mercaptoacetic acid, methylbenzenesulfonic acid, and dithiothreitol were added to toluene solvent and stirred to disperse. The reaction was carried out at 100-110℃ for 10-12 h. After the reaction was completed, sodium bicarbonate aqueous solution and ethyl acetate were added to extract the product 2-3 times. The organic phase was collected and then deionized water was added to extract the product 2-3 times. The product was filtered, rotary evaporated, and dried to obtain intermediate product 1. In this reaction process, dithiothreitol was used as a reducing agent, methylbenzenesulfonic acid was used as a catalyst, and tris(2-hydroxyethyl) isocyanurate and mercaptoacetic acid were used as reactants. The hydroxyl groups in tris(2-hydroxyethyl) isocyanurate were used to react with the carboxyl groups in mercaptoacetic acid to form intermediate product 1. The reaction formula is as follows:

[0017] ;

[0018] (2) KH-560 (γ-glycidoxypropyltrimethoxysilane), intermediate 1, and triethylamine were added to dichloromethane solvent and reacted at 35-40℃ under nitrogen for 18-20 h. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water, and dried to obtain intermediate 2. In this reaction, the thiol group contained in intermediate 1 was used to undergo a ring-opening reaction with KH-560 to obtain intermediate 2. The reaction formula is as follows:

[0019] ,in, .

[0020] (3) Nitrogen gas was introduced as a protective gas. Intermediate product 2, isophorone diisocyanate (IDPI), and dibutyltin dilaurate (DBTDL) were added to toluene solvent, stirred and dispersed, and the temperature was controlled at 40-50℃. The reaction was stirred for 1-2 hours. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water, and dried to obtain the modified isocyanate polymer. In this reaction, the hydroxyl group contained in intermediate product 2 and IDPI under the catalysis of DBTDL under controlled molar ratio underwent an addition reaction to obtain the modified isocyanate polymer. The flame-retardant sulfur and nitrogen elements contained in this substance can synergistically improve the flame retardancy of the material. In addition, this substance contains more polar structures (such as urethane esters) and active isocyanate groups to facilitate the subsequent mixing process. The chemical reaction route is as follows:

[0021] ;

[0022] (4) Add oil, PLA (polylactic acid), PHA (polyhydroxy fatty acid ester), SBS, SBR, plasticizer, and modified isocyanate polymer to asphalt, keep the temperature at 180-190℃, stir for 1-2 hours, grind for 1 hour, and finally add talc powder and continue stirring for 1-2 hours to obtain bio-based modified asphalt adhesive layer.

[0023] Styrene-butadiene-styrene block copolymer (SBS) is a thermoplastic elastomer whose main function is to significantly improve low-temperature flexibility and high-temperature stability; styrene-butadiene rubber (SBR) is a synthetic rubber with a relatively uniform molecular chain structure, mainly used to improve the plastic behavior of asphalt and increase viscosity and cohesion; PLA mainly serves as the matrix of composite materials, providing structural framework and strength; PHA mainly serves as an excellent barrier layer, contributing high elasticity and corrosion resistance.

[0024] During this process, due to the poor compatibility between asphalt and PLA / PHA, the overall performance of the mixture formed by the two is poor. Based on this, the present invention prepares a modified isocyanate polymer. First, it contains flame-retardant elements (sulfur and nitrogen) which are introduced into the adhesive layer to improve the flame-retardant performance of the material. Second, the modified isocyanate polymer contains active isocyanate groups and siloxane structures. Asphalt contains hydroxyl groups, and the isocyanate groups and siloxane structures can link with the hydroxyl groups in asphalt to form aminomethyl ester bonds and siloxane bonds, which have good chemical affinity. The aminomethyl ester bonds can form hydrogen bonds with the polar ester bonds contained in PLA / PHA, improving the compatibility between asphalt and PLA / PHA, thereby improving the overall performance of the bio-based modified asphalt adhesive layer.

[0025] Furthermore, the bio-based modified asphalt adhesive layer comprises an upper bio-based modified asphalt adhesive layer and a lower bio-based modified asphalt adhesive layer. The upper bio-based modified asphalt adhesive layer is linked to the crystallized sand layer. The unreacted siloxane structures in the bio-based modified asphalt adhesive layer can combine with the hydroxyl groups on the surface of the crystallized sand layer, increasing the bonding strength between the upper bio-based modified asphalt adhesive layer and the crystallized sand layer. Specifically, the unreacted siloxane structures act like a "molecular bridge," with one end chemically bonded to the bio-based modified asphalt adhesive layer and the other end firmly gripping the crystallized sand layer, thereby greatly enhancing the interfacial adhesion between the crystallized sand layer and the bio-based modified asphalt adhesive layer. By preventing moisture intrusion into the interface, the strength significantly improves the resistance to water damage, indirectly ensuring the durability of the bonding performance and increasing the overall performance of the waterproof membrane. The upper bio-based modified bitumen adhesive layer is connected to the polymer-modified polyethylene base. The numerous polar structures contained in the upper bio-based modified bitumen adhesive layer can form hydrogen bonds with the polar structures contained in the polymer-modified polyethylene base, increasing the bonding performance between the two. Therefore, the modified polymer sheet layer and the bio-based modified bitumen layer are firmly bonded, and there is no risk of water seepage at the bonding point, thus improving the overall performance of the waterproof membrane (the same principle applies to the connection between the lower bio-based modified bitumen adhesive layer and the polymer-modified polyethylene base).

[0026] Preferably, in (1), the molar amounts of tris(2-hydroxyethyl) isocyanurate, mercaptoacetic acid, methylbenzenesulfonic acid, and dithiothreitol are 1:3-3.2:0.01-0.02:0.05-0.07.

[0027] Preferably, in step (2), the molar amounts of KH-560, intermediate product 1, and triethylamine are 3.2-3.4:1:0.25-0.4.

[0028] Preferably, in step (3), the molar ratio of intermediate product 2 to IDPI is 1:3.2-3.5.

[0029] Preferably, in step (4), the mass ratio of asphalt, oil, PLA, PHA, SBS, SBR, plasticizer, modified isocyanate polymer, and talc is 100g:(10-12)g:(3-5)g:(3-5)g:(5-7)g:(7-10)g:(20-25)g:(10-20)g:(50-60)g, wherein the oil is naphthenic oil and the plasticizer is an environmentally friendly aromatic plasticizer.

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

[0031] The waterproof membrane prepared by this invention contains five components. In the crystallized sand layer, the nano-silicate crystallized sand is modified by nano-ultrafine modification technology to make crystallized sand that can be uniformly coated on the surface of the asphalt membrane. When concrete is poured in the crystallized sand layer, the silicate molecules in the crystallized sand react with the calcium ions in the concrete to form permanent and stable CSH crystals, which fill the pores and cracks in the concrete and improve the density and durability of the concrete.

[0032] The bio-based modified asphalt adhesive layer of this invention uses bio-based polymers, such as PLA (polylactic acid) and PHA (polyhydroxyalkanoate), which are derived from renewable resources. These bio-based polymers possess renewable and excellent environmental performance, representing an important transformation of asphalt-based materials towards green and sustainable development. The addition of these polymers not only endows the material with superior environmental characteristics but also, through their unique molecular structure, achieves multi-dimensional optimization and improvement of the comprehensive performance of the asphalt adhesive layer, specifically:

[0033] The role of bio-based polymers goes far beyond simple physical blending; they penetrate deep into the microstructure of asphalt, bringing about fundamental improvements: (1) Enhanced adhesion and cohesion: The molecular chains of semi-rigid polymers such as PLA can interact with the oil in asphalt to form a denser network structure, which significantly improves the cohesive strength and adhesion of the asphalt adhesive layer and effectively resists water intrusion and delamination caused by load. (2) The polar functional groups such as ester bonds (-COO-) and urethane esters in the molecular structure of bio-based polymers have extremely high chemical affinity with the active silicate anions in the penetrating crystallizing coating and the calcium cations (Ca²⁺) in the cement hydration products. This affinity allows the two to not only form physical anchoring at the interface, but also induce strong interactions such as ionic bonding and coordination bonding. As a result, a strong interface with chemical bond bridging and gradient transition is constructed between the bio-based asphalt adhesive layer and the penetrating crystallizing coating. This interface can more effectively guide the bidirectional penetration and deposition of crystalline active substances, forming a through-type overall waterproof structure, thereby greatly improving the reliability and service life of the waterproof system. In summary, the addition of bio-based polymers to asphalt can effectively improve the asphalt's bonding performance, anti-aging ability, weather resistance, durability and stability.

[0034] The bio-based modified asphalt adhesive layer prepared by this invention contains flame-retardant elements. In the event of a fire, these elements initially act to prevent the spread of flames. As the fire progresses, the flame-retardant elements form a glassy substance on the surface of the inorganic particles in the crystallized sand layer, preventing flammable substances from escaping from the gaps between the inorganic particles. The two elements work synergistically to enhance the flame-retardant properties of the material. Furthermore, the bio-based modified asphalt adhesive layer prepared by this invention contains numerous polar structures, which can form chemical bonds with the crystallized sand layer and the polymer-modified polyethylene base, thereby improving the overall performance of the material. The five-layer structure, obtained through composite co-extrusion calendering, cooling and shaping, and winding, produces a waterproof membrane. The five layers support and interact with each other, synergistically enhancing the overall performance of the waterproof membrane and demonstrating broad application prospects. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the structure of a waterproof membrane product. Detailed Implementation

[0036] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0037] Example 1

[0038] This embodiment provides a method for preparing a crystallized sand layer, including the following steps:

[0039] 425 cement, activated calcium oxide, nano-sized sodium silicate, anhydrous powdered aluminum sulfate, decanteryl conjugated acid salt, and water-reducing agent YT-1003 were added to a planetary mixer. Deionized water was then added and the mixture was stirred until homogeneous. The mixture was poured into a mold, allowed to dry and harden naturally, and then crushed using a large jaw crusher to obtain a 50-mesh infiltrated crystal sand layer. The sand layer contained 125g of 425 cement, 17.5g of activated calcium oxide, 7.5g of nano-sized sodium silicate, 27.5g of anhydrous powdered aluminum sulfate, 10g of decanteryl conjugated acid salt, and 3.75g of water-reducing agent.

[0040] Example 2

[0041] This embodiment provides a method for preparing a polymer-modified polyethylene base material, comprising the following steps:

[0042] Polyethylene resin, polypropylene resin, ethylene-propylene copolymer, titanium dioxide, and ethylene-vinyl acetate copolymer are added to a granulator and mixed evenly. The mixture is then placed in a feeder, extruded and plasticized, and rolled into rolls to obtain modified polymer sheets, wherein the polyethylene resin is 23.5g, polypropylene resin is 35.3g, ethylene-propylene copolymer is 3.7g, titanium dioxide is 0.5g, and ethylene-vinyl acetate copolymer is 37g.

[0043] Example 3

[0044] This embodiment provides a method for preparing a bio-based modified asphalt adhesive layer, comprising the following steps:

[0045] (1) Nitrogen gas was introduced as a protective gas. Tris(2-hydroxyethyl) isocyanurate, mercaptoacetic acid, toluenesulfonic acid and dithiothreitol were added to toluene solvent, stirred and dispersed, and reacted at 105℃ for 11 h. After the reaction was completed, sodium bicarbonate aqueous solution and ethyl acetate were added to extract the product three times. The organic phase was collected, and deionized water was added to extract the product twice. The product was filtered, rotary evaporated and dried to obtain intermediate product 1, which contained 0.1 mol of tris(2-hydroxyethyl) isocyanurate, 0.32 mol of mercaptoacetic acid, 0.002 mol of toluenesulfonic acid and 0.007 mol of dithiothreitol.

[0046] (2) KH-560, intermediate product 1 and triethylamine were added to dichloromethane solvent and reacted at 40°C under nitrogen for 18 h. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water and dried to obtain intermediate product 2, in which KH-560 was 2.56 mol, intermediate product 1 was 0.8 mol and triethylamine was 0.32 mol.

[0047] (3) Nitrogen gas was introduced as a protective gas, and intermediate product 2, IDPI and DBTDL were added to toluene solvent, stirred and dispersed, and the temperature was controlled at 45℃. The reaction was stirred for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water and dried to obtain modified isocyanate polymer, wherein intermediate product 2 was 0.5 mol, IDPI was 0.17 mol and the mass fraction of DBTDL was 0.08%.

[0048] (4) Add naphthenic oil, PLA, PHA, SBS, SBR, environmentally friendly aromatic plasticizer diisononyl phthalate, and modified isocyanate polymer to asphalt, keep the temperature at 180-190℃, stir for 1-2 hours, then grind for 1 hour, and finally add talc powder and continue stirring for 1-2 hours to obtain a bio-based modified asphalt adhesive layer, wherein asphalt 50g, oil 6g, PLA 2g, PHA 1.5g, SBS 3.5g, SBR 4g, plasticizer 12g, modified isocyanate polymer 5g, and talc powder 28g.

[0049] Example 4

[0050] This embodiment provides a method for preparing a bio-based modified asphalt adhesive layer, comprising the following steps:

[0051] (1) Nitrogen gas was introduced as a protective gas. Tris(2-hydroxyethyl) isocyanurate, mercaptoacetic acid, toluenesulfonic acid and dithiothreitol were added to toluene solvent, stirred and dispersed, and reacted at 110°C for 10 h. After the reaction was completed, sodium bicarbonate aqueous solution and ethyl acetate were added to extract the product three times. The organic phase was collected and then deionized water was added to extract the product three times. The product was filtered, rotary evaporated and dried to obtain intermediate product 1, which contained 0.1 mol of tris(2-hydroxyethyl) isocyanurate, 0.3 mol of mercaptoacetic acid, 0.001 mol of toluenesulfonic acid and 0.006 mol of dithiothreitol.

[0052] (2) KH-560, intermediate product 1 and triethylamine were added to dichloromethane solvent and reacted at 35°C under nitrogen for 20 h. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water and dried to obtain intermediate product 2, in which KH-560 was 2.72 mol, intermediate product 1 was 0.8 mol and triethylamine was 0.2 mol.

[0053] (3) Nitrogen gas was introduced as a protective gas, and intermediate product 2, IDPI and DBTDL were added to toluene solvent, stirred and dispersed, and the temperature was controlled at 40℃. The reaction was stirred for 2 hours. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water and dried to obtain modified isocyanate polymer, wherein intermediate product 2 was 0.5 mol, IDPI was 1.75 mol and the mass fraction of DBTDL was 0.08%.

[0054] (4) Add naphthenic oil, PLA, PHA, SBS, SBR, environmentally friendly aromatic plasticizer diisononyl phthalate, and modified isocyanate polymer to asphalt, keep the temperature at 185℃, stir for 1 hour, then grind for 1 hour, and finally add talc powder and continue stirring for 2 hours to obtain a bio-based modified asphalt adhesive layer, wherein asphalt 50g, oil 6g, PLA 1.5g, PHA 2.5g, SBS 2.5g, SBR 3.5g, plasticizer 12.5g, modified isocyanate polymer 8g, and talc powder 25g.

[0055] Example 5

[0056] This embodiment provides a method for preparing a bio-based modified asphalt adhesive layer, comprising the following steps:

[0057] (1) Nitrogen gas was introduced as a protective gas. Tris(2-hydroxyethyl) isocyanurate, mercaptoacetic acid, toluenesulfonic acid and dithiothreitol were added to toluene solvent, stirred and dispersed, and reacted at 100℃ for 12 h. After the reaction was completed, sodium bicarbonate aqueous solution and ethyl acetate were added to extract twice. The organic phase was collected and then deionized water was added to extract three times. The mixture was filtered, rotary evaporated and dried to obtain intermediate product 1, which contained 0.1 mol of tris(2-hydroxyethyl) isocyanurate, 0.32 mol of mercaptoacetic acid, 0.002 mol of toluenesulfonic acid and 0.005 mol of dithiothreitol.

[0058] (2) KH-560, intermediate product 1 and triethylamine were added to dichloromethane solvent and reacted at 35°C under nitrogen for 19 h. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water and dried to obtain intermediate product 2, which contained 2.6 mol of KH-560, 0.8 mol of intermediate product 1 and 0.3 mol of triethylamine.

[0059] (3) Nitrogen gas was introduced as a protective gas. Intermediate product 2, IDPI and DBTDL were added to toluene solvent, stirred and dispersed, and the temperature was controlled at 50℃. The reaction was stirred for 1 h. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water and dried to obtain modified isocyanate polymer, wherein intermediate product 2 was 0.5 mol, IDPI was 0.16 mol and the mass fraction of DBTDL was 0.08%.

[0060] (4) Add naphthenic oil, PLA, PHA, SBS, SBR, environmentally friendly aromatic plasticizer diisononyl phthalate, and modified isocyanate polymer to asphalt, keep the temperature at 180℃, stir for 2 hours, then grind for 1 hour, and finally add talc powder and continue stirring for 1 hour to obtain a bio-based modified asphalt adhesive layer, wherein asphalt 50g, oil 6g, PLA 2.5g, PHA 2g, SBS 3g, SBR 5g, plasticizer 10g, modified isocyanate polymer 10g, and talc powder 30g.

[0061] Comparative Example 1

[0062] The difference between this comparative example and Example 3 is that intermediate product 2 is used instead of modified isocyanate polymer in step (4).

[0063] Comparative Example 2

[0064] The difference between this comparative example and Example 3 is that IDPI is used instead of the modified isocyanate polymer in step (4).

[0065] Referring to GB / T23457-2017, the properties of the bio-based modified asphalt adhesive layers in Examples 3-5 and Comparative Examples 1-2 were tested as follows:

[0066] Table 1:

[0067] Seam peel strength (N / mm) Example 3 2.13 Example 4 2.44 Example 5 2.59 Comparative Example 1 1.85 Comparative Example 2 1.62 Comparative Example 3 0.94

[0068] Comparative Example 3 is a commercially available ordinary adhesive layer.

[0069] The greater the joint peel strength, the better the bonding performance. As shown in Table 1, the bio-based modified asphalt adhesive layer prepared by this invention has excellent bonding performance.

[0070] Examples 6-8 and Comparative Examples 4-5 are five-layer structures of waterproof membranes. The five-layer structure is obtained by composite co-extrusion calendering, cooling and shaping, and winding.

[0071] Table 2:

[0072] Crystalline Sand Layer Bio-based modified bitumen layer Polymer modified polyethylene base Bio-based modified bitumen layer Separating membrane Example 6 Example 1 Example 3 Example 2 Example 3 PE release film Example 7 Example 1 Example 4 Example 2 Example 4 PE release film Example 8 Example 1 Example 5 Example 2 Example 5 PE release film Comparative Example 4 Example 1 Comparative Example 1 Example 2 Comparative Example 1 PE release film Comparative Example 5 Example 1 Comparative Example 2 Example 2 Comparative Example 2 PE release film

[0073] The tensile strength of the waterproof membrane was tested in accordance with GB / T 328.9-2007.

[0074] The tear strength of the waterproof membrane was tested in accordance with GB / T 328.19-2007.

[0075] The fire performance rating of building waterproof membranes was tested in accordance with GB 8624-2012.

[0076] Table 3:

[0077] Tensile strength (MPa) Tear strength (N) Combustion performance rating Example 6 18.46 473 A Example 7 19.30 492 A Example 8 20.07 510 A Comparative Example 4 15.67 425 A Comparative Example 5 13.24 386 B1

[0078] As can be seen from the tensile strength and tear strength data, the modified isocyanate polymer prepared using this invention exhibits superior mechanical properties. This is because the modified isocyanate polymer contains active isocyanate groups and siloxane structures. Asphalt contains hydroxyl groups, and the isocyanate groups and siloxane structures can link with the hydroxyl groups in asphalt to form aminomethyl ester bonds and siloxane bonds, exhibiting good chemical affinity. The aminomethyl ester bonds can form hydrogen bonds with the polar ester bonds contained in PLA and PHA, which not only improves the compatibility between asphalt and PLA and PHA, but also the chemical cross-linking network formed between various hydrogen bonds and chemical bonds has good binding force. When subjected to external stress, the stress can be dispersed along the chemical cross-linking network in the five-layer structure and... Effective dispersion between layers improves the mechanical properties of the material. In Comparative Example 4, the bio-based modified asphalt adhesive layer does not contain active isocyanate groups, but only active siloxane structures. In Comparative Example 5, the bio-based modified asphalt adhesive layer uses ordinary IDPI instead of modified isocyanate polymer. Firstly, it does not contain active siloxane structures, and secondly, IDPI has a linear structure, while the modified isocyanate polymer of this invention has a non-linear structure. During the reaction, the non-linear structure generates more branches, and the physical cross-linking degree between branches and between branches and the main chain is greater. Therefore, when subjected to external stress, the stress can be dispersed through the physical cross-linking network structure. Thus, Comparative Example 5 has the worst mechanical properties. Based on this, the waterproof membrane prepared by this invention has excellent mechanical properties.

[0079] The flame retardant data show that the waterproof membrane prepared by this invention has excellent flame retardant properties.

[0080] In summary, the waterproof membrane prepared by this invention has excellent mechanical properties and flame retardant properties, and has broad application value in the field of waterproof membranes.

[0081] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A permeable crystalline bio-based modified bitumen pre-laid polymer waterproof membrane, characterized in that, The waterproof membrane comprises a five-layer structure consisting of a crystallized sand layer, an upper bio-based modified bitumen adhesive layer, a polymer-modified polyethylene base, a lower bio-based modified bitumen adhesive layer, and a lower release membrane. The five-layer structure is obtained by composite co-extrusion calendering, cooling and shaping, and winding.

2. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen as described in claim 1, characterized in that, The method for preparing the crystallized sand layer includes the following steps: 425 cement, activated calcium oxide, nano-grade sodium silicate, anhydrous powdered aluminum sulfate, decanteric acid conjugated salt, and water-reducing agent YT-100 are added to a planetary mixer. Deionized water is then added and the mixture is stirred until homogeneous. The mixture is then poured into a mold, allowed to dry and harden naturally, and crushed using a large jaw crusher to control the particle size at 16-50 mesh, thus obtaining a crystallized sand layer.

3. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen as described in claim 2, characterized in that, The ratio of the following components to water-reducing agent is 100g:(13-15)g:(5-7)g:(21-23)g:(7-9)g:(2-4)g.

4. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen as described in claim 1, characterized in that, The preparation method of the polymer-modified polyethylene base is as follows: Polyethylene resin, polypropylene resin, ethylene-propylene copolymer, titanium dioxide, and ethylene-vinyl acetate copolymer are added to a granulator and mixed evenly. The mixture is then placed in a feeder, extruded and plasticized, and rolled into rolls to obtain a high-molecular-weight modified polyethylene base.

5. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen as described in claim 4, characterized in that, The ratio of the amount of polyethylene resin, polypropylene resin, ethylene-propylene copolymer, titanium dioxide, and ethylene-vinyl acetate copolymer is 100g:(150-180)g:(15-20)g:(2-3)g:(150-180)g.

6. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen as described in claim 1, characterized in that, The preparation method of the bio-based modified asphalt adhesive layer is as follows: (1) Nitrogen gas was introduced as a protective gas. Tris(2-hydroxyethyl) isocyanurate, mercaptoacetic acid, methylbenzenesulfonic acid and dithiothreitol were added to toluene solvent, stirred and dispersed, and reacted at 100-110℃ for 10-12h. After the reaction was completed, sodium bicarbonate aqueous solution and ethyl acetate were added to extract 2-3 times. The organic phase was collected, and deionized water was added to extract 2-3 times. The mixture was filtered, rotary evaporated and dried to obtain intermediate product 1. (2) KH-560, intermediate product 1 and triethylamine were added to dichloromethane solvent and reacted at 35-40℃ under nitrogen for 18-20 h. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water and dried to obtain intermediate product 2. (3) Nitrogen gas was introduced as a protective gas, and intermediate product 2, IDPI and DBTDL were added to toluene solvent, stirred and dispersed, and the temperature was controlled at 40-50℃. The reaction was stirred for 1-2 hours. After the reaction was completed, the solvent was removed under reduced pressure, washed with deionized water and dried to obtain modified isocyanate polymer. (4) Add oil, PLA, PHA, SBS, SBR, plasticizer, and modified isocyanate polymer to asphalt, keep the temperature at 180-190℃, stir for 1-2 hours, grind for 1 hour, and finally add talc powder and continue stirring for 1-2 hours to obtain bio-based modified asphalt adhesive layer.

7. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen as described in claim 6, characterized in that, In (1), the molar amounts of tris(2-hydroxyethyl) isocyanurate, mercaptoacetic acid, methylbenzenesulfonic acid, and dithiothreitol are 1:3-3.2:0.01-0.02:0.05-0.

07.

8. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen as described in claim 6, characterized in that, In (2), the molar amounts of KH-560, intermediate product 1, and triethylamine are 3.2-3.4:1:0.25-0.

4.

9. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen as described in claim 6, characterized in that, In step (3), the molar ratio of intermediate product 2 to IDPI is 1:3.2-3.

5.

10. The pre-laid polymer waterproof membrane with penetrating crystalline bio-based modified bitumen according to claim 6, characterized in that, In (4), the mass ratio of asphalt, oil, PLA, PHA, SBS, SBR, plasticizer, modified isocyanate polymer, and talc is 100g:(10-12)g:(3-5)g:(3-5)g:(5-7)g:(7-10)g:(20-25)g:(10-20)g:(50-60)g, the oil is naphthenic oil, and the plasticizer is an environmentally friendly aromatic plasticizer.

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