Epoxy modified vegetable oil based bitumen-free self-adhesive pre-paved waterproofing membrane and preparation method thereof

Abstract

This invention discloses an epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane and its preparation method. The waterproof membrane comprises, from top to bottom, a reverse-adhesive functional layer, an epoxy-modified vegetable oil self-adhesive layer, a main waterproof substrate, a reinforcing layer, and an isolation underlayer. The reverse-adhesive functional layer is composed of silane coupling agent-modified white marble sand. The epoxy-modified vegetable oil self-adhesive layer is mainly prepared from the following raw materials in the following weight ratios: 28-32 parts epoxy-modified vegetable oil, 30-33 parts SIS elastomer, 13-15 parts hydrogenated C5 petroleum resin, 15.5-25.4 parts 200-mesh heavy calcium carbonate, 2.5-3 parts anti-aging additive, 0.6-0.8 parts organic peroxide crosslinking agent, and 0.5-0.8 parts silane coupling agent. The waterproof membrane of this invention is completely free of asphalt and harmful volatiles, exhibiting excellent environmental performance. It not only possesses excellent low-temperature flexibility, heat resistance, and resistance to accelerated aging, but also provides reliable adhesion.

Description

Technical Field

[0001] This application relates to the field of waterproof membrane technology, and in particular to an epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane and its preparation method. Background Technology

[0002] Traditional waterproof membranes mostly use bitumen as the core binding material, but they release harmful volatile organic compounds such as aromatics during production and use, and have significant performance defects such as low-temperature brittleness and high-temperature flowability, making it difficult to meet the needs of green buildings and complex working conditions. To solve these problems, non-bitumen-based waterproof membranes have gradually become a research hotspot, but existing non-bitumen-based membranes still have many shortcomings: some solutions still retain bitumen components (such as the patent with publication number CN1594435A, which uses a formulation system of vegetable oil + rosin + SBS + filler, but still contains bitumen-related components and has not achieved true non-bitumenization), thus limiting their environmental friendliness; some bitumen-free solutions use pure polymer adhesives, which have problems such as poor compatibility with the substrate, insufficient bonding strength, and poor aging resistance.

[0003] Therefore, there is an urgent need to develop a non-asphalt-based waterproof membrane that is completely free of asphalt and asphalt derivatives, uses green and renewable raw materials as its core, and has stable and reliable performance, in order to avoid the defects of existing technologies and meet the market demand for environmentally friendly waterproof materials. Summary of the Invention

[0004] In view of this, this application provides an epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane and its preparation method. The waterproof membrane of the present invention is completely free of asphalt and harmful volatile substances, has excellent environmental performance, and not only has excellent low-temperature flexibility, heat resistance and artificial accelerated aging resistance, but also reliable adhesion.

[0005] To achieve the above objectives, this application employs the following technical solution: An epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane, characterized in that it comprises, from top to bottom, a reverse-adhesive functional layer, an epoxy-modified vegetable oil self-adhesive layer, a main waterproof substrate, a reinforcing layer, and an isolation bottom layer; the reverse-adhesive functional layer is composed of silane coupling agent modified white marble sand; The epoxy-modified vegetable oil self-adhesive layer is mainly prepared from the following raw materials in the following weight ratios: Epoxy-modified vegetable oil, 28-32 parts. 30-33 parts of SIS elastomer 13-15 parts of hydrogenated C5 petroleum resin, Ultrafine heavy calcium carbonate, 15.5-25.4 parts. Anti-aging additives 2.5-3 parts, 0.6-0.8 parts of organic peroxide crosslinking agent, 0.5-0.8 parts of silane coupling agent.

[0006] In the epoxy-modified vegetable oil self-adhesive layer of this invention, epoxy-modified vegetable oil is used to replace asphalt and traditional plasticizers, improving environmental friendliness and compatibility with SIS elastomers; SIS elastomers (i.e., styrene-isoprene-styrene block copolymers) can ensure the cohesive strength and bonding flexibility of the adhesive layer; hydrogenated C5 petroleum resin can improve room temperature adhesion and temperature resistance, avoiding the use of easily aging components such as rosin; the addition of ultrafine heavy calcium carbonate reduces costs and improves the hardness and wear resistance of the adhesive layer; anti-aging additives are used to improve weather resistance; organic peroxide crosslinking agents can improve the heat resistance and dimensional stability of the adhesive layer; silane coupling agents can improve the interfacial bonding force between the adhesive layer and the substrate and functional layers.

[0007] This invention utilizes epoxy-modified vegetable oil to achieve excellent compatibility with SIS elastomers. The principle is as follows: Ordinary vegetable oils (such as soybean oil) contain unsaturated double bonds in their molecular chains, resulting in poor compatibility with SIS elastomers and a tendency for migration and precipitation, leading to a decrease in the adhesive strength of the adhesive layer. This invention introduces epoxy groups (-COC-) into the vegetable oil molecular chains through epoxy modification. The polarity of the epoxy groups interacts with the polarity of the styrene blocks in the SIS elastomer, improving the interfacial compatibility between the two phases and preventing delamination and migration of the adhesive.

[0008] Specifically, the density of the anti-adhesion functional layer is 0.4-0.8 kg / m³. 2 The epoxy-modified vegetable oil self-adhesive layer has a thickness of 0.5-0.8 mm, the main waterproof substrate has a thickness of 1.2-1.5 mm, and the reinforcing layer has a basis weight of 100-150 g / m². 2 The thickness of the insulating base layer is 0.05-0.1mm.

[0009] Specifically, the main waterproof substrate is composed of a thermoplastic polyolefin / ethylene-vinyl acetate copolymer blend composite substrate, wherein the mass ratio of thermoplastic polyolefin to ethylene-vinyl acetate copolymer in the thermoplastic polyolefin / ethylene-vinyl acetate copolymer blend composite substrate is 7:3.

[0010] Specifically, the reinforcing layer is composed of short-fiber needle-punched polyester geotextile; the insulating bottom layer is composed of silicone oil-coated anti-stick PE film.

[0011] Specifically, the preparation method of the thermoplastic polyolefin / ethylene-vinyl acetate copolymer blended composite substrate includes the following steps: mixing thermoplastic polyolefin, ethylene-vinyl acetate copolymer and anti-aging additive in proportion, feeding into a twin-screw extruder, extruding and casting into a film at a temperature of 180-200℃, and cooling and shaping by a cooling roller at 20-30℃ to obtain the thermoplastic polyolefin / ethylene-vinyl acetate copolymer blended composite substrate; In the preparation method of thermoplastic polyolefin / ethylene-vinyl acetate copolymer blended composite substrate: the anti-aging additive is composed of antioxidant 1010 and ultraviolet absorber UV-326 mixed in a mass ratio of 2:1, and the amount of the anti-aging additive added is 0.4%-0.6% of the total weight of the thermoplastic polyolefin / ethylene-vinyl acetate copolymer blended composite substrate.

[0012] This invention employs a thermoplastic polyolefin / ethylene-vinyl acetate copolymer blend composite substrate (i.e., TPO / EVA blend composite substrate) to synergistically achieve excellent weather resistance, low-temperature flexibility, and mechanical properties. The principle is as follows: Thermoplastic polyolefin (TPO) has excellent weather resistance and chemical corrosion resistance, but poor low-temperature flexibility; ethylene-vinyl acetate copolymer (EVA) has good flexibility and processability, but insufficient weather resistance. In this invention, TPO and EVA are blended at a mass ratio of 7:3 to form an "island-type" blend structure: TPO acts as the continuous phase (sea phase), providing core mechanical support and weather resistance for the substrate; EVA acts as the dispersed phase (island phase), uniformly dispersed in the TPO continuous phase. Its vinyl acetate groups can enhance the polarity of the substrate, strengthen the interfacial adhesion with the self-adhesive layer, and improve the low-temperature flexibility of the substrate. The synergistic effect of the two enables the substrate to meet the mechanical requirement of tensile strength ≥15MPa (the tensile strength of the TPO / EVA blend composite substrate of the present invention was tested to be 15.2-16.8MPa), and also achieve the performance index of low-temperature flexibility without cracking at -25℃.

[0013] Specifically, the preparation method of the silane coupling agent modified white marble sand includes the following steps: (1) Dry the white marble sand in an environment of 100-110℃ for 2-3 hours to remove surface moisture, and then cool it to room temperature; (2) Dissolve 0.5-1% of the silane coupling agent by mass of white marble sand in an ethanol aqueous solution, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is 9:1, stir evenly to obtain a diluted silane coupling agent solution. (3) Put the white marble sand treated in step (1) into a high-speed mixer, adjust the speed to 800-1000 r / min, and then add the silane coupling agent dilution at a constant speed of 5-7 mL / min. After the addition is completed, continue stirring for 30-40 min to ensure that the surface of each white marble sand particle is uniformly coated with silane coupling agent. (4) Place the mixed modified white marble sand obtained in step (3) into an oven and dry it at a constant temperature of 75-85℃ for 1-2 hours to solidify and shape it. After cooling to room temperature, remove the agglomerated particles by sieving with a sieve to obtain silane coupling agent modified white marble sand.

[0014] Specifically, the white marble sand in step (1) has a mesh size of 28-55, and the sieve in step (4) has a mesh size of 28.

[0015] Specifically, in the epoxy-modified vegetable oil self-adhesive layer: the epoxy-modified vegetable oil is epoxy soybean oil; the anti-aging additive is a mixture of antioxidant 1010 and ultraviolet absorber UV-326 in a mass ratio of 2:1; the organic peroxide crosslinking agent is dicumyl peroxide; the silane coupling agent is KH-550; and the ultrafine heavy calcium carbonate is 200-mesh heavy calcium carbonate.

[0016] The anti-adhesion functional layer of this invention is a reactive functional layer. It achieves water resistance and enhanced adhesion through this reactive functional layer. The principle is as follows: The anti-adhesion functional layer uses silane coupling agent-modified white marble sand. Its core principle is that the KH-550 silane coupling agent molecule contains bifunctional groups. The alkoxy group at one end can undergo a hydrolysis-condensation reaction with the hydroxyl groups on the surface of the white marble sand, forming a strong chemical bond, thus firmly grafting the silane coupling agent onto the sand grain surface. The amino group at the other end can undergo a ring-opening reaction with the epoxy groups of the epoxy-modified vegetable oil, achieving chemical adhesion between the sand grains and the adhesive layer. When the subsequent concrete is poured, the sand grains are exposed on the adhesive layer surface. Their rough surface forms a mechanical bond with the concrete. Simultaneously, the cement hydration products in the concrete (such as Ca(OH)2) can further react with the residual hydroxyl groups of the silane coupling agent, forming a chemical bond, ultimately constructing an integrated "roll-concrete" structure, fundamentally eliminating water leakage channels.

[0017] The waterproof membrane of this invention uses epoxy-modified vegetable oil, which can enhance adhesion. The principle is as follows: the epoxy groups in the epoxy-modified vegetable oil can undergo ring-opening reaction with the amino groups in the silane coupling agent, and at the same time can form hydrogen bonds with the hydroxyl groups in the concrete, which significantly enhances the bonding strength between the adhesive layer and the substrate and concrete, and achieves a stable interface bond between the adhesive, substrate and concrete.

[0018] This invention also provides a method for preparing the above-mentioned epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane, comprising the following steps: (1) Premixing of epoxy modified vegetable oil self-adhesive: Add epoxy modified vegetable oil and hydrogenated C5 petroleum resin to a nitrogen-protected internal mixer, heat to 120-130℃, stir at 30-40r / min, and keep warm for 15-25min to ensure that the resin is completely dissolved in the epoxy modified vegetable oil. (2) Melt-mixing and crosslinking of epoxy-modified vegetable oil self-adhesive: Add SIS elastomer to the internal mixer, heat to 135-145℃, keep warm and stir for 60-90min until the elastomer is completely melted and dispersed; then add ultrafine heavy calcium carbonate, anti-aging additives and silane coupling agent, increase the speed to 60-80r / min, stir for 40-60min; finally add organic peroxide crosslinking agent, vacuum to -0.06~-0.1MPa, keep warm and stir for 40-60min to obtain epoxy-modified vegetable oil self-adhesive layer; (3) Composite molding: The epoxy modified vegetable oil self-adhesive layer is hot-melted and coated on the surface of the main waterproof substrate at 150-160℃. Then, the reinforcing layer is hot-pressed on the lower surface of the main waterproof substrate at 120-140℃ and 0.2-0.4Pa. After hot-pressing, before the adhesive material cools down, silane coupling agent modified white marble sand is evenly sprinkled on the upper surface of the epoxy modified vegetable oil self-adhesive layer. The adhesive layer is embedded under pressure of 0.25-0.35MPa. Finally, the isolation bottom layer is composited on the lower surface of the reinforcing layer. (4) Post-processing: The roll material after composite molding in step (3) is cooled through a cooling channel at 20-30℃, and then cut into roll materials of a set width as required. After being rolled up, it is cured at room temperature for 24 hours to obtain epoxy modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof roll material. The room temperature is usually 21-25℃, but the present invention is not limited to this. The room temperature can also be slightly higher or slightly lower than this range. The standard room temperature of 23℃ is generally used for curing.

[0019] The waterproof membrane of this invention is prepared using a solvent-free continuous production process, achieving both environmental protection and stable quality. The principle is as follows: Traditional waterproof membrane adhesive production often uses aromatic solvents (such as xylene) to reduce system viscosity and facilitate processing. However, solvent evaporation causes environmental pollution, and residual solvents can lead to later shrinkage and decreased adhesion of the adhesive layer. This invention employs a solvent-free process of "nitrogen purging protection + vacuum degassing": Nitrogen purging protection isolates oxygen, preventing oxidative degradation of epoxy-modified vegetable oils and SIS elastomers during high-temperature mixing, ensuring stable adhesive performance; vacuum degassing (vacuum degree -0.06 to -0.1 MPa) completely removes air bubbles and trace amounts of low-molecular-weight volatiles generated during adhesive mixing, improving the density of the adhesive layer, while avoiding solvent use and controlling VOC content to ≤8 g / L, meeting green environmental protection requirements.

[0020] In the waterproof membrane of this invention, the core function of the anti-adhesive functional layer is to mechanically interlock and chemically bond with the post-poured concrete to prevent water seepage; the epoxy-modified vegetable oil self-adhesive layer is a core layer without asphalt bonding, ensuring bonding strength and aging resistance; the main waterproof substrate provides a core waterproof barrier and mechanical support; the reinforcing layer improves the membrane's tear resistance and dimensional stability; the isolation layer protects the self-adhesive layer and allows for easy peeling during construction.

[0021] The core performance indicators of the waterproof membrane of this invention are as follows:

[0022] As can be seen from the above technical solution, this application has at least the following advantages and positive effects: 1. This invention employs an epoxy-modified vegetable oil green adhesive system (replacing traditional asphalt + ordinary rubber oil), overcoming the problems of traditional asphalt adhesives relying on petroleum asphalt base materials and the difficulty in balancing environmental protection and compatibility. Using renewable epoxy soybean oil as the core, it completely eliminates asphalt and its derivatives, while simultaneously improving compatibility with SIS elastomers through modification. Therefore, the waterproof membrane of this invention exhibits excellent environmental performance: completely free of asphalt and harmful volatile organic compounds, with a VOC content ≤8g / L, and using renewable epoxy-modified vegetable oil as the core raw material, aligning with the trend of green building development.

[0023] 2. This invention optimizes the design of the anti-adhesion functional layer, replacing the traditional single mechanical interlocking with a reactive composite functional layer structure, and uses silane coupling agent to modify white marble sand to achieve the dual function of "mechanical interlocking + chemical bonding", thus solving the defect of insufficient water resistance of traditional pre-laid roll materials.

[0024] 3. This invention uses a TPO / EVA blended composite substrate, overcoming the shortcomings of single substrates and abandoning traditional roll material substrates. By blending TPO and EVA in a 7:3 mass ratio, it balances the weather resistance of TPO with the flexibility of EVA, improving the interfacial bonding between the substrate and the adhesive layer. Therefore, the waterproof roll material of this invention exhibits outstanding weather resistance: excellent flexibility at -25℃, stable heat resistance at 85℃, strength retention rate ≥90% after 1000 hours of artificial aging, and a long service life.

[0025] 4. This invention employs a solvent-free continuous production process, improving upon the solvent-based pollution problems of conventional mixing processes. It offers high production efficiency, stable product quality, and is easily scaled up for industrial applications. Specifically, the integrated nitrogen purging and vacuum degassing process avoids the use of aromatic solvents, resolving the environmental pollution and unstable product quality issues inherent in traditional production methods.

[0026] 5. The waterproof membrane of this invention has reliable adhesion: the peel strength with the post-poured concrete is ≥1.8MPa, and it has strong resistance to water seepage. It is suitable for pre-laid reverse bonding construction in underground engineering. Detailed Implementation

[0027] The exemplary embodiments of the present invention are described in more detail below. These embodiments are intended to provide a more thorough understanding of the invention and to fully convey the scope of the invention to those skilled in the art. While exemplary embodiments of the present invention are shown, it should be understood that the invention should not be limited to the embodiments set forth herein.

[0028] Table 1. Formulations of epoxy-modified vegetable oil self-adhesive layers in Examples 1-3 and Comparative Examples 1-5 (parts by weight)

[0029] Table 2 Formulations of epoxy-modified vegetable oil self-adhesive layers in Comparative Examples 6-12 (parts by weight)

[0030] Table 3 Formulation of ordinary bitumen-based self-adhesive layer in Comparative Example 13 (parts by weight)

[0031] Example 1 The preparation method of epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane is as follows: 1. Preparation of anti-adhesion functional layer: (1) 28-55 (1) Dry the white marble sand at 105℃ for 2.5h to remove surface moisture, and then cool it to room temperature; (2) Dissolve KH-550 in an ethanol aqueous solution with the mass of silane coupling agent (KH-550) being 0.75% of the mass of white marble sand. The volume ratio of ethanol to water in the ethanol aqueous solution is 9:1. Stir evenly to prepare a silane coupling agent dilution; (3) Put the pretreated white marble sand obtained in step (1) into a high-speed mixer, adjust the speed to 900r / min, and add the prepared coupling agent dilution at a uniform speed of 6mL / min. After the addition is completed, continue stirring for 35min to ensure that the surface of each sand grain is evenly coated with silane coupling agent; (4) Put the mixed modified white marble sand into an oven and dry it at 80℃ for 1.5h to solidify and shape it. After cooling to room temperature, pass it through a 28-mesh sieve to remove agglomerated particles to obtain silane coupling agent modified white marble sand, which can be directly used for the application of the anti-adhesion functional layer of the roll material; 2. Preparation of the substrate: TPO, EVA, and anti-aging additives are mixed evenly in a certain proportion, fed into a twin-screw extruder, and extruded and cast into a film at 190°C. The film is then cooled and shaped by a 25°C cooling roller to obtain a TPO / EVA blended composite substrate. The mass ratio of TPO to EVA in the TPO / EVA blended composite substrate is 7:3. The anti-aging additives consist of antioxidant 1010 and ultraviolet absorber UV-326 in a mass ratio of 2:1, and the amount of anti-aging additives added is 0.5% of the total weight of the TPO / EVA blended composite substrate. 3. Premixing of epoxy-modified vegetable oil self-adhesive: Add epoxy soybean oil and hydrogenated C5 petroleum resin to a nitrogen-protected internal mixer, heat to 125°C, stir at 35 r / min, and keep warm for 20 min to ensure that the resin is completely dissolved in the epoxy soybean oil. 4. Melt-mixing and crosslinking of epoxy-modified vegetable oil self-adhesive compound: Add SIS elastomer to a mixer, heat to 140℃, and stir for 75 minutes until the elastomer is completely melted and dispersed; then add 200-mesh heavy calcium carbonate, anti-aging additives and silane coupling agent, increase the speed to 70 r / min and stir for 50 minutes; finally add organic peroxide crosslinking agent, vacuum to -0.08 MPa, and stir for 50 minutes to obtain epoxy-modified vegetable oil self-adhesive layer; 5. Composite Molding: The epoxy-modified vegetable oil self-adhesive layer is hot-melt coated onto the surface of the TPO / EVA blended composite substrate at 155℃. Then, the short-fiber needle-punched polyester geotextile reinforcement layer is hot-pressed at 130℃ and 0.3MPa. After hot-pressing, before the adhesive material cools, silane coupling agent modified white marble sand is evenly sprinkled on the surface of the epoxy-modified vegetable oil self-adhesive layer and embedded into the adhesive layer under pressure of 0.3MPa. Finally, a silicone oil-coated anti-stick PE film is laminated onto the lower surface of the reinforcement layer. 6. Post-treatment: The composite membrane is cooled at 25°C through a cooling channel and cut into 1.0-2.0m wide rolls as required. After rolling, it is cured at room temperature (23°C) for 24 hours to obtain epoxy modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane.

[0032] The density of the anti-adhesion functional layer is 0.6 kg / m³. 2 The epoxy-modified vegetable oil self-adhesive layer has a thickness of 0.65mm, the main waterproof substrate has a thickness of 1.35mm, and the reinforcing layer has a basis weight of 125g / m². 2 The thickness of the isolation layer is 0.075mm. Example

[0033] The preparation method of epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane is as follows: 1. Preparation of anti-adhesion functional layer: (1) Dry 28-55 mesh white marble sand at 100℃ for 2h to remove surface moisture, and then cool to room temperature; (2) Dissolve KH-550 in ethanol aqueous solution at 0.5% of the mass of white marble sand, with the volume ratio of ethanol to water in the ethanol aqueous solution being 9:1, stir evenly, and prepare silane coupling agent dilution solution; (3) Put the pretreated white marble sand into a high-speed mixer, adjust the speed to 800r / min, and mix at 5mL / min Add the prepared silane coupling agent dilution solution at a uniform speed. After the addition is completed, continue stirring for 30 minutes to ensure that the surface of each sand grain is uniformly coated with silane coupling agent; (4) Put the mixed modified white marble sand into the oven and dry it at 75°C for 1 hour to solidify and shape it. After cooling to room temperature, pass it through a 28-mesh sieve to remove the clumps and obtain silane coupling agent modified white marble sand, which can be directly used for the application of the anti-adhesion functional layer of the roll material; 2. Preparation of the substrate: TPO, EVA, and anti-aging additives are mixed evenly in a certain proportion, fed into a twin-screw extruder, and extruded and cast into a film at 180°C. The film is then cooled and shaped by a 20°C cooling roller to obtain a TPO / EVA blended composite substrate. The mass ratio of TPO to EVA in the TPO / EVA blended composite substrate is 7:3. The anti-aging additives consist of antioxidant 1010 and ultraviolet absorber UV-326 in a mass ratio of 2:1, and the amount of anti-aging additives added is 0.4% of the total weight of the TPO / EVA blended composite substrate. 3. Premixing of epoxy-modified vegetable oil self-adhesive: Add epoxy soybean oil and hydrogenated C5 petroleum resin to a nitrogen-protected internal mixer, heat to 120°C, stir at 30 r / min, and keep warm for 15 min to ensure that the resin is completely dissolved in the epoxy soybean oil. 4. Melt-mixing and crosslinking of epoxy-modified vegetable oil self-adhesive compound: Add SIS elastomer to a mixer, heat to 135℃, and stir for 60 minutes until the elastomer is completely melted and dispersed; then add 200-mesh heavy calcium carbonate, anti-aging additives and silane coupling agent, increase the speed to 60 r / min and stir for 40 minutes; finally add organic peroxide crosslinking agent, vacuum to -0.06 MPa, and stir for 40 minutes to obtain epoxy-modified vegetable oil self-adhesive layer; 5. Composite Molding: The epoxy-modified vegetable oil self-adhesive layer is hot-melted and coated onto the surface of the TPO / EVA blended composite substrate at 150℃. Then, the short-fiber needle-punched polyester geotextile reinforcement layer is hot-pressed at 120℃ and 0.2MPa. After hot-pressing, before the adhesive material cools, silane coupling agent modified white marble sand is evenly sprinkled on the surface of the epoxy-modified vegetable oil self-adhesive layer and embedded into the adhesive layer under pressure of 0.25MPa. Finally, a silicone oil-coated anti-stick PE film is laminated onto the lower surface of the reinforcement layer. 6. Post-processing: The composite membrane is cooled at 20°C through a cooling channel and cut into 1.0-2.0m wide rolls as required. After rolling, it is cured at room temperature (23°C) for 24 hours to obtain epoxy modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane.

[0034] The density of the anti-adhesion functional layer is 0.4 kg / m³. 2 The epoxy-modified vegetable oil self-adhesive layer is 0.5mm thick, the main waterproof substrate is 1.2mm thick, and the reinforcing layer has a basis weight of 100g / m². 2 The thickness of the insulating base layer is 0.05mm. Example

[0035] The preparation method of epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane is as follows: 1. Preparation of anti-adhesion functional layer: (1) Dry 28-55 mesh white marble sand at 110℃ for 3h to remove surface moisture, and then cool to room temperature; (2) Dissolve KH-550 in ethanol aqueous solution at 1% of the mass of white marble sand, with the volume ratio of ethanol to water in the ethanol aqueous solution being 9:1, stir evenly, and prepare silane coupling agent dilution; (3) Put the pretreated white marble sand into a high-speed mixer, adjust the speed to 1000r / min, and add the prepared silane coupling agent dilution at a uniform rate of 7mL / min. After the addition is completed, continue stirring for 40min to ensure that the surface of each sand grain is uniformly coated with silane coupling agent; (4) Put the mixed modified white marble sand into an oven, dry at 85℃ for 2h, solidify and shape, and cool to room temperature before passing through 28 The silane coupling agent-modified white marble sand was obtained by sieving to remove agglomerated particles and then directly applied to the anti-adhesion functional layer of the roll material. 2. Preparation of the substrate: TPO, EVA, and anti-aging additives are mixed evenly in a certain proportion, fed into a twin-screw extruder, and extruded and cast into a film at 200°C. The film is then cooled and shaped by a 30°C cooling roller to obtain a TPO / EVA blended composite substrate. The mass ratio of TPO to EVA in the TPO / EVA blended composite substrate is 7:3. The anti-aging additives consist of antioxidant 1010 and ultraviolet absorber UV-326 in a mass ratio of 2:1, and the amount of anti-aging additives added is 0.6% of the total weight of the TPO / EVA blended composite substrate. 3. Premixing of epoxy-modified vegetable oil self-adhesive: Add epoxy soybean oil and hydrogenated C5 petroleum resin to a nitrogen-protected internal mixer, heat to 130℃, stir at 40r / min, and keep warm for 25min to ensure that the resin is completely dissolved in the epoxy soybean oil. 4. Melt-mixing and crosslinking of epoxy-modified vegetable oil self-adhesive compound: Add SIS elastomer to a mixer, heat to 145℃, and stir for 90 minutes until the elastomer is completely melted and dispersed; then add 200-mesh heavy calcium carbonate, anti-aging additives and silane coupling agent, increase the speed to 80 r / min and stir for 60 minutes; finally add organic peroxide crosslinking agent, vacuum to -0.1 MPa, and stir for 60 minutes to obtain epoxy-modified vegetable oil self-adhesive layer; 5. Composite Molding: The epoxy-modified vegetable oil self-adhesive layer is hot-melted and coated onto the surface of the TPO / EVA blended composite substrate at 160℃. Then, the short-fiber needle-punched polyester geotextile reinforcement layer is hot-pressed at 140℃ and 0.4MPa. After hot-pressing, before the adhesive material cools, silane coupling agent modified white marble sand is evenly sprinkled on the surface of the epoxy-modified vegetable oil self-adhesive layer and embedded into the adhesive layer under pressure of 0.35MPa. Finally, a silicone oil-coated anti-stick PE film is laminated onto the lower surface of the reinforcement layer. 6. Post-processing: The composite membrane is cooled at 30°C through a cooling channel and cut into 1.0-2.0m wide rolls as required. After rolling, it is cured at room temperature (23°C) for 24 hours to obtain epoxy modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane.

[0036] The density of the anti-adhesion functional layer is 0.8 kg / m³. 2 The epoxy-modified vegetable oil self-adhesive layer is 0.8mm thick, the main waterproof substrate is 1.5mm thick, and the reinforcing layer has a basis weight of 150g / m². 2 The thickness of the isolation layer is 0.1mm.

[0037] Comparative Examples 1-12: The preparation method of the waterproof membrane is the same as that in Example 1.

[0038] Comparative Example 13: The other steps are the same as those in Example 1 for preparing the waterproof membrane, except that a common bitumen-based self-adhesive layer (formulation shown in Table 3) is used instead of the epoxy-modified vegetable oil self-adhesive layer of the present invention.

[0039] The information on some raw materials involved in the various embodiments and comparative examples of the present invention is shown in Table 3 below.

[0040] Table 4. Partial raw material information for Examples 1-3 and Comparative Examples 1-12

[0041] Table 5. Test results of various performance characteristics of the waterproof membranes in Examples 1-3 and Comparative Examples 1-5

[0042] Table 6. Test results of various performance characteristics of the waterproof membranes in Comparative Examples 6-13

[0043] Based on the comparative analysis of the data in Tables 5 and 6, we can conclude that: 1. Example 1 is the optimal ratio. From Comparative Examples 1-2, it can be seen that the content of epoxidized soybean oil has a significant impact on high and low temperature performance. When the addition ratio is 27% (Comparative Example 1), its heat resistance is qualified but its low temperature flexibility is unqualified; when the addition ratio is 33% (Comparative Example 2), its low temperature flexibility is qualified but its heat resistance is unqualified.

[0044] 2. Comparative Examples 3-4 show that if SIS elastomer is used as the main modifier to construct the macromolecular framework, its chain segments are relatively long, resulting in better flexibility and a significant impact on both low-temperature performance and peel performance. When the addition amount is 29%, its cohesive force is much smaller than its interfacial adhesive force, leading to both unsatisfactory low-temperature flexibility and impermeability. When the addition amount is 34%, the material skeleton strength is too high, resulting in unsatisfactory peel performance and correspondingly unsatisfactory impermeability.

[0045] 3. Comparative Examples 5-6 show that hydrogenated C5 petroleum resin can improve the viscosity and temperature resistance of modified adhesives within a certain range. When the addition amount is 12%, its heat resistance, peel strength with post-cast concrete, and impermeability are all unqualified. When the addition amount is increased to 16%, the cohesion of the adhesive increases, and the peel effect and impermeability show a downward trend and are also unqualified.

[0046] 4. Based on Comparative Examples 7-8, it can be seen that the addition of anti-aging additives can significantly improve the anti-aging performance of materials. When the addition amount is 2.4%, the material fails to meet the requirements for artificial accelerated aging. However, when the addition amount is increased to 3.1%, the anti-aging performance of the material does not improve significantly. From an economic perspective, the optimal addition ratio is set at 3%.

[0047] 5. Comparative Examples 9-10 show that when the amount of dicumyl peroxide (DCP) added is 0.5%, the heat resistance of the material fails to meet the requirements. When the proportion is increased to 0.9%, the heat resistance also meets the requirements, but there is no significant improvement. From an economic point of view, the addition amount of 0.7% is the optimal proportion.

[0048] 6. Comparative Examples 11-12 show that silane coupling agents can improve the interfacial adhesion of materials. When the addition amount is 0.4%, the low interfacial adhesion leads to unqualified peel strength and impermeability of the material. When the addition amount is increased to 0.9%, the improvement in material performance is not significant. From an economic point of view, the addition amount of 0.7% is the optimal ratio.

[0049] 7. As shown in Comparative Example 13, after replacing the epoxy-modified vegetable oil self-adhesive layer of the present invention with an ordinary asphalt-based self-adhesive layer, the low-temperature flexibility, peel strength from concrete, impermeability, and artificial accelerated aging performance of the roll material are significantly reduced, and the VOC content far exceeds the standard of the present invention, which fully demonstrates the inventiveness, advancement, and environmental friendliness of the adhesive system of the present invention.

[0050] In summary, Example 1 represents the optimal ratio.

[0051] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. An epoxy-modified vegetable oil-based, bituminous-free, self-adhesive pre-laid waterproof membrane, characterized in that: It includes, from top to bottom, an anti-adhesion functional layer, an epoxy-modified vegetable oil self-adhesive layer, a main waterproof substrate, a reinforcing layer, and an isolation bottom layer; the anti-adhesion functional layer is composed of silane coupling agent modified white marble sand; The epoxy-modified vegetable oil self-adhesive layer is mainly prepared from the following raw materials in the following weight ratios: Epoxy-modified vegetable oil, 28-32 parts. 30-33 parts of SIS elastomer 13-15 parts of hydrogenated C5 petroleum resin, Ultrafine heavy calcium carbonate, 15.5-25.4 parts. Anti-aging additives 2.5-3 parts, 0.6-0.8 parts of organic peroxide crosslinking agent, 0.5-0.8 parts of silane coupling agent.

2. The epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that: The density of the anti-adhesion functional layer is 0.4-0.8 kg / m³. 2 The epoxy-modified vegetable oil self-adhesive layer has a thickness of 0.5-0.8 mm, the main waterproof substrate has a thickness of 1.2-1.5 mm, and the reinforcing layer has a basis weight of 100-150 g / m². 2 The thickness of the insulating base layer is 0.05-0.1mm.

3. The epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that: The main waterproof substrate is composed of a thermoplastic polyolefin / ethylene-vinyl acetate copolymer blend composite substrate, wherein the mass ratio of thermoplastic polyolefin to ethylene-vinyl acetate copolymer in the thermoplastic polyolefin / ethylene-vinyl acetate copolymer blend composite substrate is 7:

3.

4. The epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that: The reinforcing layer is composed of short-fiber needle-punched polyester geotextile; the insulating bottom layer is composed of silicone oil-coated anti-stick PE film.

5. The epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane according to claim 3, characterized in that: The preparation method of the thermoplastic polyolefin / ethylene-vinyl acetate copolymer blended composite substrate includes the following steps: mixing thermoplastic polyolefin, ethylene-vinyl acetate copolymer and anti-aging additive in proportion, feeding into a twin-screw extruder, extruding and casting into a film at a temperature of 180-200℃, and cooling and shaping by a cooling roller at 20-30℃ to obtain the thermoplastic polyolefin / ethylene-vinyl acetate copolymer blended composite substrate; In the preparation method of thermoplastic polyolefin / ethylene-vinyl acetate copolymer blended composite substrate: the anti-aging additive is composed of antioxidant 1010 and ultraviolet absorber UV-326 mixed in a mass ratio of 2:1, and the amount of the anti-aging additive added is 0.4%-0.6% of the total weight of the thermoplastic polyolefin / ethylene-vinyl acetate copolymer blended composite substrate.

6. The epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that: The preparation method of the silane coupling agent modified white marble sand includes the following steps: (1) Dry the white marble sand in an environment of 100-110℃ for 2-3 hours to remove surface moisture, and then cool it to room temperature; (2) Dissolve 0.5-1% of the silane coupling agent by mass of white marble sand in an ethanol aqueous solution, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is 9:1, stir evenly to obtain a diluted silane coupling agent solution. (3) Put the white marble sand treated in step (1) into a high-speed mixer, adjust the speed to 800-1000 r / min, and then add the silane coupling agent dilution at a constant speed of 5-7 mL / min. After the addition is completed, continue stirring for 30-40 min to ensure that the surface of each white marble sand particle is uniformly coated with silane coupling agent. (4) Place the mixed modified white marble sand obtained in step (3) into an oven and dry it at a constant temperature of 75-85℃ for 1-2 hours to solidify and shape it. After cooling to room temperature, remove the agglomerated particles by sieving with a sieve to obtain silane coupling agent modified white marble sand.

7. The epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane according to claim 6, characterized in that: The white marble sand in step (1) has a mesh size of 28-55, and the sieve in step (4) has a mesh size of 28.

8. The epoxy-modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that: In epoxy-modified vegetable oil self-adhesive layers: The epoxy-modified vegetable oil is epoxidized soybean oil; The anti-aging additive is composed of antioxidant 1010 and ultraviolet absorber UV-326 mixed in a mass ratio of 2:

1. The organic peroxide crosslinking agent is dicumyl peroxide; The silane coupling agent is KH-550; The ultrafine heavy calcium carbonate is 200 mesh heavy calcium carbonate.

9. The method for preparing epoxy-modified vegetable oil-based bituminous-free self-adhesive pre-laid waterproof membrane according to any one of claims 1-8, characterized in that: Includes the following steps: (1) Premixing of epoxy modified vegetable oil self-adhesive: Add epoxy modified vegetable oil and hydrogenated C5 petroleum resin to a nitrogen-protected internal mixer, heat to 120-130℃, stir at 30-40r / min, and keep warm for 15-25min to ensure that the resin is completely dissolved in the epoxy modified vegetable oil. (2) Melt-mixing and crosslinking of epoxy-modified vegetable oil self-adhesive: Add SIS elastomer to the internal mixer, heat to 135-145℃, keep warm and stir for 60-90min until the elastomer is completely melted and dispersed; then add ultrafine heavy calcium carbonate, anti-aging additives and silane coupling agent, increase the speed to 60-80r / min, stir for 40-60min; finally add organic peroxide crosslinking agent, vacuum to -0.06~-0.1MPa, keep warm and stir for 40-60min to obtain epoxy-modified vegetable oil self-adhesive layer; (3) Composite molding: The epoxy modified vegetable oil self-adhesive layer is hot-melted and coated on the surface of the main waterproof substrate at 150-160℃. Then, the reinforcing layer is hot-pressed on the lower surface of the main waterproof substrate at 120-140℃ and 0.2-0.4MPa. After hot-pressing, before the adhesive material cools down, silane coupling agent modified white marble sand is evenly sprinkled on the upper surface of the epoxy modified vegetable oil self-adhesive layer. It is then embedded into the adhesive layer under pressure of 0.25-0.35MPa. Finally, the isolation bottom layer is composited on the lower surface of the reinforcing layer. (4) Post-processing: The roll material after composite molding in step (3) is cooled through a cooling channel at 20-30℃, and then cut into roll materials of a set width as required. After being rolled up, it is cured at room temperature for 24 hours to obtain epoxy modified vegetable oil-based asphalt-free self-adhesive pre-laid waterproof roll material.

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