Creep-resistant macromolecular self-adhesive waterproof coiled material

Abstract

The invention relates to the technical field of waterproof coiled materials, and discloses a creep-resistant macromolecular self-adhesive waterproof coiled material, which is prepared from the following raw materials in parts by mass: a macromolecular polymer matrix: 30 to 40 parts of thermoplastic elastomer; 5 to 10 parts of a nanometer material; 10 to 20 parts of synthetic asphalt mastic; the self-adhesive glue comprises the following components in parts by weight: 20-30 parts of rubber, 10-15 parts of tackifying resin, 5-10 parts of a softening agent, 1-3 parts of an anti-aging agent, 0.5-2 parts of an antioxidant and 5-15 parts of a filling agent. The waterproof material has good creep resistance, weather resistance and waterproofness, does not generate tensile deformation or cracking under long-term load, is not easy to age in outdoor ultraviolet, temperature difference and other environments, effectively resists water erosion, prolongs the service life, and provides a material choice with more reliable performance and longer service cycle for building waterproof engineering.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, specifically to a creep-resistant polymer self-adhesive waterproof membrane. Background Technology

[0002] In recent years, the construction industry has continued to develop towards higher quality and greater complexity. Whether it's high-rise buildings, underground engineering, tunnel engineering, or building structures in special environments, the performance requirements for waterproofing materials are constantly increasing, especially in terms of self-adhesion, chemical corrosion resistance, and environmental adaptability. In practical applications, building waterproofing membranes need to withstand long-term structural deformation, temperature fluctuations, humidity changes, and chemical erosion, while also adapting to complex structures in different construction scenarios (such as irregular joints, splicing seams, and high and low temperature construction environments). This poses a greater challenge to the overall performance of the membranes. While current polymer self-adhesive waterproof membranes on the market offer some advantages in terms of ease of construction and basic waterproofing performance, several industry pain points remain to be addressed. On one hand, the self-adhesion of most membranes relies on physically blended adhesive layers, which are prone to problems such as adhesive layer migration and decreased bonding strength under long-term use or in complex environments. This can lead to delamination between the membrane and the substrate or between the membrane itself, resulting in leakage risks. On the other hand, existing membranes lack sufficient resistance to chemical corrosion. In environments commonly encountered in underground engineering, such as acidic or alkaline soils and groundwater erosion, or in industrial buildings where they come into contact with chemical media, the materials are prone to aging and degradation, shortening their service life. More critically, traditional polymer membranes suffer from poor creep performance due to defects in their molecular structure design. Under long-term loads (such as structural weight and soil pressure) or stress caused by temperature changes, they are prone to irreversible permanent deformation, leading to tensile cracking and joint displacement, compromising the integrity of the waterproofing system. This problem is particularly pronounced in large-span structures and settlement-sensitive buildings, severely impacting the reliability of waterproofing projects. Furthermore, with the construction industry placing greater emphasis on cost control and construction efficiency, the market has set higher requirements for the cost-effectiveness of waterproofing materials. While some existing high-performance waterproofing membranes can meet certain performance indicators, they often rely on imported raw materials or complex production processes, resulting in high prices and hindering their widespread adoption in large-scale civil buildings. On the other hand, low-priced membranes generally have performance shortcomings, failing to balance self-adhesion, corrosion resistance, and creep resistance, making them unsuitable for diverse construction scenarios. Therefore, developing a waterproofing membrane that combines excellent self-adhesion, chemical corrosion resistance, and creep resistance, adaptable to various structural constructions, and offers high cost-effectiveness, has become a key direction for addressing current industry pain points and meeting the high-quality development needs of building waterproofing projects. This is of great significance for promoting the advancement of building waterproofing technology and ensuring the long-term safety of building structures. Summary of the Invention

[0003] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a creep-resistant polymer self-adhesive waterproof membrane.

[0004] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: a creep-resistant polymer self-adhesive waterproof membrane, comprising the following raw materials in parts by weight: Polymer matrix: 30-40 parts thermoplastic elastomer; Nanomaterials: 5-10 parts; Synthetic asphalt adhesive: 10-20 parts; Self-adhesive: 20-30 parts rubber, 10-15 parts tackifying resin, 5-10 parts softener, 1-3 parts anti-aging agent, 0.5-2 parts antioxidant, and 5-15 parts filler; The method for preparing the self-adhesive includes the following steps: A1. Add rubber to a reaction vessel equipped with a constant temperature control, nitrogen protection device and high-speed stirring, introduce nitrogen gas, heat up and stir evenly; mix 3.5~5% of the total mass of the rubber modifier with 0.8~1.2% of the modifier mass of dicumyl peroxide, add it to the molten rubber at a uniform speed, heat up and stir to react. A2. After the reaction is complete, cool down and stir, add tackifying resin, keep warm and stir evenly, then add softener in three parts, with an interval of 15 minutes between each addition; add preheated synthetic asphalt adhesive, heat up and stir, cool down and add anti-aging agent and antioxidant, stir evenly; finally add filler and stir evenly. The thermoplastic elastomer is selected from one of ethylene-vinyl acetate copolymer, styrene-butadiene-styrene block copolymer, and ethylene-octene copolymer; The rubber is selected from butyl rubber and styrene-butadiene rubber.

[0005] Preferably, the nanomaterial is one of nano-silica, nano-zinc oxide, and nano-clay; the nano-silica has a particle size of 5-50 nm and a specific surface area of ​​100-400 m². 2 / g, purity ≥99.5%; the nano zinc oxide particles have a particle size of 10~30nm and a specific surface area of ​​30~80m². 2 / g, purity ≥99.0%; the nano-clay is montmorillonite, with a particle size of 1~10 nm and an interlayer spacing of 1.2~1.8 nm.

[0006] Preferably, the synthetic asphalt adhesive is one of styrene-butadiene rubber modified asphalt adhesive, butyl rubber modified asphalt adhesive, and rosin resin modified asphalt adhesive; the styrene-butadiene rubber modified asphalt adhesive has a styrene-butadiene rubber content of 5-10%; the butyl rubber modified asphalt adhesive has a butyl rubber content of 3-8%; and the rosin resin modified asphalt adhesive has a rosin resin content of 8-15%.

[0007] Preferably, the tackifying resin is one of terpene resin, phenolic resin, and rosin resin; the terpene resin has a softening point of 80~120℃, an acid value ≤10 mgKOH / g, and a hydroxyl value ≤5 mgKOH / g; the phenolic resin has a softening point of 90~130℃, a free phenol content ≤5%, and a hydroxymethyl content of 8~15%; the rosin resin has a softening point of 70~100℃, an acid value of 150~180 mgKOH / g, and a saponification value of 160~190 mgKOH / g.

[0008] Preferably, the softener is one of naphthenic oil, aromatic oil, and paraffin oil; the naphthenic oil has a kinematic viscosity of 20-50 mmHg at 40°C. 2 / s, flash point ≥180℃, pour point ≤-20℃; the aromatic oil: kinematic viscosity at 40℃ 30~60 mm 2 / s, flash point ≥190℃, pour point ≤-15℃; the paraffin oil: kinematic viscosity 15~40 mm at 40℃. 2 / s, flash point ≥200℃, freezing point ≤-25℃.

[0009] Preferably, the anti-aging agent is one of light stabilizer 622, light stabilizer 944, and light stabilizer UV2020.

[0010] Preferably, the antioxidant is one of antioxidant 264, antioxidant 1010, and antioxidant 1076.

[0011] Preferably, the filler is one of calcium carbonate, talc, and kaolin; the calcium carbonate has a particle size of 0.1~5 μm; the talc has a particle size of 1~20 μm; and the kaolin has a particle size of 0.5~10 μm.

[0012] Preferably, the method for preparing the modifier includes the following steps: B1. Add 50-60 parts of hydroxyethyl methacrylate, 100-120 parts of anhydrous toluene, and 0.3-0.5 parts of p-hydroxyanisole to a four-necked flask equipped with a reflux condenser, a nitrogen delivery tube, and a stirrer. Purge with nitrogen, stir, and heat to 50-55°C. Keep warm for 10-15 minutes. B2. Slowly add 30-40 parts of m-chloroperoxybenzoic acid dropwise to the above reaction system, maintaining the temperature at 50-55℃ during the dropwise addition. After the dropwise addition is complete, raise the temperature to 60-65℃ and keep the reaction at this temperature for 5-8 hours. Add saturated sodium carbonate solution to the system, allow it to stand and separate into layers, take the organic phase, wash it three times with deionized water, add anhydrous magnesium sulfate to dry it, filter to remove the drying agent, and obtain the intermediate solution for later use. B3. At a temperature of 50-60℃, slowly add 25-30 parts of 4-amino-2,2,6,6-tetramethylpiperidine and maintain the temperature for 2-3 hours. While maintaining the reaction temperature, add 0.5-1.2 parts of dibutyltin dilaurate catalyst and slowly add 20-25 parts of 3-(perfluorohexyl)propyl isocyanate. Increase the temperature to 70-80℃ and react for 3-5 hours. After the reaction is complete, distill under reduced pressure. Pour the residue into excess anhydrous ethanol to precipitate. After standing for 1-2 hours, filter. Dry the filter cake in a vacuum drying oven at 60-80℃ for 6-8 hours to obtain the modifier.

[0013] Preferably, a method for preparing a creep-resistant polymer self-adhesive waterproof membrane includes the following steps: S1. The thermoplastic elastomer is dried at 80~100℃ for 2~3 h; the nanomaterial is mixed with 1~3% by mass of silane coupling agent KH-550 in a high-speed mixer at 80~90℃ for 20~30 min to obtain the modified nanomaterial. S2. Add the pretreated thermoplastic elastomer, synthetic asphalt rubber, and modified nanomaterials to a twin-screw extruder. Set the extruder temperature gradient as follows: feeding section 150~160℃, melting section 170~180℃, mixing section 180~200℃, and extrusion section 170~180℃. Control the screw speed at 80~120 r / min. Control the material residence time in the extruder at 3~5 min. After water cooling, the extrudate is granulated by a granulator and dried at 60~80℃ for 2~4 h to obtain creep-resistant polymer granules. S3. Add the creep-resistant polymer granules to a single-screw extruder, set the temperature to 160~190℃, and extrude them through a T-die to form a continuous sheet with a thickness of 1.0~2.5 mm. Use a doctor blade coating or roller coating method to evenly coat one side of the sheet with the prepared self-adhesive, control the coating thickness to be 0.5~1.5 mm, and maintain the temperature at 100~120℃ during the coating process to form a self-adhesive layer. S4. Introduce the composite sheet into the cooling roller assembly and control the cooling temperature gradient: the first stage cooling temperature is 60~70℃, the second stage is 30~40℃, and the third stage is room temperature. S5. Apply a silicone oil film as a release agent to the surface of the self-adhesive layer, control the winding tension to 50~100 N, match the winding speed with the extrusion speed, and ensure that the roll is neatly wound with an end face deviation of no more than 3 mm. S6. Finished roll materials should be stored in a well-ventilated and dry warehouse, avoiding direct sunlight. The stacking height should not exceed 5 layers to prevent the roll materials from being deformed by pressure. The storage temperature should be controlled between 5 and 35℃.

[0014] (iii) Beneficial technical effects This invention relates to a creep-resistant polymer self-adhesive waterproof membrane. Through nanomaterial filling and reinforcement and molecular chain movement restriction, it effectively inhibits the creep deformation of the polymer matrix and improves the long-term dimensional stability of the membrane. The epoxy groups contained in the modifier can form stable chemical bonds with the active groups on the substrate surface, the hindered amine groups can capture free radicals generated during aging, and the fluoroalkyl groups can construct a hydrophobic barrier to prevent water penetration. The three types of groups synergistically optimize the adhesion, weather resistance, and water resistance properties. The selection of butyl rubber or styrene-butadiene rubber enhances the elasticity and barrier properties of the membrane due to their molecular structure characteristics. With the precise control of tackifying resins, anti-aging agents, and other additives, the system compatibility and long-term service stability are further enhanced.

[0015] This invention has excellent creep resistance, weather resistance, and waterproof properties, which can prevent the membrane from tensile deformation or cracking under long-term load, ensure a tight bond between the membrane and the substrate, reduce the risk of water seepage at the interface, and make the membrane less prone to aging under outdoor ultraviolet rays, temperature differences, and other environments. It effectively resists water erosion, extends service life, and provides a more reliable material option with a longer service life for building waterproofing projects. Detailed Implementation

[0016] 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.

[0017] The creep-resistant polymer self-adhesive waterproof membrane formulation components in this invention are as follows: The thermoplastic elastomer was purchased from Zhejiang Petrochemical Co., Ltd. The nanomaterials were purchased from Fenghong Group; The synthetic bitumen adhesive was purchased from Beijing Zhonglai Chemical Co., Ltd. Styrene-butadiene rubber was purchased from Jilin Petrochemical Company of China National Petroleum Corporation. The butyl rubber was purchased from Arlanxtech (China) Co., Ltd. The tackifying resin was purchased from Dongguan Dingxin Plastic Raw Materials Co., Ltd. All parts used in this invention are parts by weight; Example 1 A creep-resistant polymer self-adhesive waterproof membrane, comprising the following raw materials in parts by weight: Polymer matrix: 30 parts of ethylene-vinyl acetate copolymer; Nanomaterials: 5 parts; Synthetic asphalt adhesive: 10 parts; Self-adhesive: 20 parts butyl rubber, 10 parts tackifying resin, 5 parts softener, 1 part anti-aging agent, 0.5 parts antioxidant, and 5 parts filler.

[0018] The nanomaterial is nano-silica; the nano-silica has a particle size of 5-50 nm and a specific surface area of ​​100-400 m². 2 / g, purity ≥99.5%.

[0019] The synthetic asphalt adhesive is a butyl rubber modified asphalt adhesive; the butyl rubber modified asphalt adhesive contains 3-8% butyl rubber.

[0020] The tackifying resin is a terpene resin; the terpene resin has a softening point of 80~120℃, an acid value of ≤10 mgKOH / g, and a hydroxyl value of ≤5 mgKOH / g.

[0021] The softener is naphthenic oil; the naphthenic oil has a kinematic viscosity of 20-50 mmHg at 40°C. 2 / s, flash point ≥180℃, freezing point ≤-20℃.

[0022] The anti-aging agent is light stabilizer 622.

[0023] The antioxidant is antioxidant 264.

[0024] The filler is calcium carbonate; the calcium carbonate particle size is 0.1~5 μm.

[0025] The method for preparing the self-adhesive includes the following steps: A1. Add butyl rubber to a reactor equipped with a constant temperature control, nitrogen protection device and high-speed stirring, introduce nitrogen gas, heat to 120℃, stir at 300 r / min for 40 min; mix 3.5% of the total rubber mass of modifier with 0.8% of the modifier mass of dicumyl peroxide, add to the molten rubber at a uniform speed, heat to 155℃, increase the stirring speed to 450 r / min, and stir for 50 min. A2. After the reaction is complete, cool down to 140℃, reduce the stirring speed to 300 r / min, add the tackifying resin, keep warm and stir for 35 min, then add the softener in three batches, with an interval of 15 min between each addition, and maintain the stirring speed at 200 r / min; add the synthetic asphalt adhesive preheated to 70℃, raise the temperature to 135℃, keep warm and stir for 70 min, continue to cool down to 110℃, add the anti-aging agent and antioxidant, and stir for 15 min; finally add the filler, increase the stirring speed to 600 r / min, and stir for 50 min.

[0026] The preparation method of the modifier includes the following steps: B1. Add 50 parts of hydroxyethyl methacrylate, 100 parts of anhydrous toluene, and 0.3 parts of p-hydroxyanisole to a four-necked flask equipped with a reflux condenser, a nitrogen delivery tube, and a stirrer. Purge with nitrogen, stir, and heat to 50°C. Keep warm for 10 min. B2. Slowly add 30 parts of m-chloroperoxybenzoic acid to the above reaction system, keeping the temperature at 50°C during the addition. After the addition is complete, raise the temperature to 60°C and keep the reaction at this temperature for 5 hours. Add saturated sodium carbonate solution to the system, let it stand and separate into layers, take the organic phase, wash it three times with deionized water, add anhydrous magnesium sulfate to dry it, filter to remove the desiccant, and obtain the intermediate solution for later use. B3. At 50°C, 25 parts of 4-amino-2,2,6,6-tetramethylpiperidine were slowly added dropwise to the above intermediate solution. The reaction was maintained at this temperature for 2 hours. While maintaining the reaction temperature, 0.5 parts of dibutyltin dilaurate catalyst were added, followed by 20 parts of 3-(perfluorohexyl)propyl isocyanate. The temperature was raised to 70°C and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was distilled under reduced pressure. The residue was poured into excess anhydrous ethanol to precipitate. After standing for 1 hour, the mixture was filtered. The filter cake was dried in a vacuum drying oven at 60°C for 6 hours to obtain the modifier.

[0027] A method for preparing a creep-resistant polymer self-adhesive waterproof membrane includes the following steps: S1. The ethylene-vinyl acetate copolymer was dried at 80°C for 2 hours. The nanomaterial was mixed with 1% by mass of silane coupling agent KH-550 in a high-speed mixer at 80°C for 20 minutes to obtain the modified nanomaterial. S2. The pretreated ethylene-vinyl acetate copolymer, synthetic asphalt rubber and modified nanomaterials are added to a twin-screw extruder. The extruder temperature gradient is set as follows: feeding section 150℃, melting section 170℃, mixing section 180℃, extrusion section 170℃. The screw speed is controlled at 80 r / min. The residence time of the material in the extruder is controlled at 3 min. After the extrudate is cooled by water, it is granulated by a granulator and dried at 60℃ for 2 h to obtain creep-resistant polymer granules. S3. Add the creep-resistant polymer granules to a single-screw extruder, set the temperature to 160℃, and extrude them through a T-die to form a continuous sheet with a thickness of 1.0 mm. Use a roller coating method to evenly coat the prepared self-adhesive on one side of the sheet, control the coating thickness to 0.5 mm, and maintain the temperature at 100℃ during the coating process to form a self-adhesive layer. S4. Introduce the composite sheet into the cooling roller assembly and control the cooling temperature gradient: the first stage cooling temperature is 60℃, the second stage is 30℃, and the third stage is room temperature. S5. Apply a silicone oil film as a release agent to the surface of the self-adhesive layer, control the winding tension to 50 N, match the winding speed with the extrusion speed, and ensure that the roll is neatly wound with an end face deviation of no more than 3 mm. S6. Finished roll materials should be stored in a well-ventilated and dry warehouse, avoiding direct sunlight. The stacking height should not exceed 5 layers to prevent the roll materials from being deformed by pressure. The storage temperature should be controlled at 5℃.

[0028] Example 2 A creep-resistant polymer self-adhesive waterproof membrane, comprising the following raw materials in parts by weight: Polymer matrix: 35 parts of styrene-butadiene-styrene block copolymer; Nanomaterials: 8 parts; Synthetic asphalt adhesive: 15 parts; Self-adhesive: 25 parts styrene-butadiene rubber, 12 parts tackifying resin, 8 parts softener, 2 parts anti-aging agent, 1 part antioxidant, and 10 parts filler.

[0029] The nanomaterial is zinc oxide nanoparticles; the zinc oxide nanoparticles have a particle size of 10-30 nm and a specific surface area of ​​30-80 m². 2 / g, purity ≥99.0%.

[0030] The synthetic asphalt adhesive is a styrene-butadiene rubber-modified asphalt adhesive; the styrene-butadiene rubber-modified asphalt adhesive contains 5-10% styrene-butadiene rubber.

[0031] The tackifying resin is a phenolic resin; the phenolic resin has a softening point of 90~130℃, a free phenol content of ≤5%, and a hydroxymethyl content of 8~15%.

[0032] The softener is an aromatic oil; the aromatic oil has a kinematic viscosity of 30~60 mm at 40°C. 2 / s, flash point ≥190℃, freezing point ≤-15℃.

[0033] The anti-aging agent is light stabilizer 944.

[0034] The antioxidant is antioxidant 1010.

[0035] The filler is talc; the talc particle size is 1~20 μm.

[0036] The method for preparing the self-adhesive includes the following steps: A1. Add styrene-butadiene rubber to a reactor equipped with a constant temperature control, nitrogen protection device and high-speed stirring, introduce nitrogen, heat to 125℃, stir at 350 r / min for 45 min; mix 4% of the total rubber mass of modifier with 1% of the modifier mass of dicumyl peroxide, add to the molten rubber at a uniform speed, heat to 160℃, increase the stirring speed to 500 r / min, and stir for 55 min. A2. After the reaction is complete, cool down to 145℃, reduce the stirring speed to 350 r / min, add the tackifying resin, keep warm and stir for 40 min, then add the softener in three batches, with an interval of 15 min between each addition, and maintain the stirring speed at 250 r / min; add the synthetic asphalt adhesive preheated to 75℃, raise the temperature to 140℃, keep warm and stir for 80 min, continue to cool down to 115℃, add the anti-aging agent and antioxidant, and stir for 20 min; finally add the filler, increase the stirring speed to 800 r / min, and stir for 60 min.

[0037] The preparation method of the modifier includes the following steps: B1. Add 55 parts of hydroxyethyl methacrylate, 110 parts of anhydrous toluene, and 0.4 parts of p-hydroxyanisole to a four-necked flask equipped with a reflux condenser, a nitrogen delivery tube, and a stirrer. Purge with nitrogen, stir, and heat to 55°C. Keep warm for 10 min. B2. Slowly add 35 parts of m-chloroperoxybenzoic acid to the above reaction system, maintaining the temperature at 55°C during the addition. After the addition is complete, raise the temperature to 60°C and keep the reaction at this temperature for 6 hours. Add saturated sodium carbonate solution to the system, allow it to stand and separate into layers, take the organic phase, wash it three times with deionized water, add anhydrous magnesium sulfate to dry it, filter to remove the drying agent, and obtain the intermediate solution for later use. B3. At a temperature of 55°C, 28 parts of 4-amino-2,2,6,6-tetramethylpiperidine were slowly added dropwise, and the reaction was maintained at this temperature for 3 hours. While maintaining the reaction temperature, 1 part of dibutyltin dilaurate catalyst was added, followed by 22 parts of 3-(perfluorohexyl)propyl isocyanate. The temperature was raised to 75°C and the reaction was carried out for 4 hours. After the reaction was completed, the mixture was distilled under reduced pressure, and the residue was poured into excess anhydrous ethanol to precipitate. After standing for 2 hours, the mixture was filtered, and the filter cake was dried in a vacuum drying oven at 70°C for 7 hours to obtain the modifier.

[0038] A method for preparing a creep-resistant polymer self-adhesive waterproof membrane includes the following steps: S1. The styrene-butadiene-styrene block copolymer was dried at 90°C for 2 h. The nanomaterial was mixed with 2% by mass of silane coupling agent KH-550 in a high-speed mixer at 85°C for 25 min to obtain the modified nanomaterial. S2. The pretreated styrene-butadiene-styrene block copolymer, synthetic asphalt rubber and modified nanomaterials are added to a twin-screw extruder. The extruder temperature gradient is set as follows: feeding section 155℃, melting section 175℃, mixing section 190℃, extrusion section 175℃. The screw speed is controlled at 100 r / min. The residence time of the material in the extruder is controlled at 4 min. After the extrudate is cooled by water, it is granulated by a granulator and dried at 70℃ for 3 h to obtain creep-resistant polymer granules. S3. Add the creep-resistant polymer granules to a single screw extruder, set the temperature to 180℃, and extrude them into a continuous sheet with a thickness of 2 mm through a T-die. Use a roller coating method to evenly coat the prepared self-adhesive on one side of the sheet, control the coating thickness to 1 mm, and maintain the temperature at 110℃ during the coating process to form a self-adhesive layer. S4. Introduce the composite sheet into the cooling roller assembly and control the cooling temperature gradient: the first stage cooling temperature is 65℃, the second stage is 35℃, and the third stage is room temperature. S5. Apply a silicone oil film as a release agent to the surface of the self-adhesive layer, control the winding tension to 60 N, match the winding speed with the extrusion speed, and ensure that the roll is neatly wound with an end face deviation of no more than 3 mm. S6. Finished roll materials should be stored in a well-ventilated and dry warehouse, avoiding direct sunlight. The stacking height should not exceed 5 layers to prevent the roll materials from being deformed by pressure. The storage temperature should be controlled at 20℃.

[0039] Example 3 A creep-resistant polymer self-adhesive waterproof membrane, comprising the following raw materials in parts by weight: Polymer matrix: 40 parts of ethylene-octene copolymer; Nanomaterials: 10 parts; Synthetic asphalt adhesive: 20 parts; Self-adhesive: 30 parts butyl rubber, 15 parts tackifying resin, 10 parts softener, 3 parts anti-aging agent, 2 parts antioxidant, and 15 parts filler.

[0040] The nanomaterial is nano-clay; the nano-clay is montmorillonite with a particle size of 1~10 nm and an interlayer spacing of 1.2~1.8 nm.

[0041] The synthetic asphalt adhesive is a rosin resin modified asphalt adhesive; the rosin resin modified asphalt adhesive contains 8-15% rosin resin.

[0042] The tackifying resin is rosin resin; the rosin resin has a softening point of 70~100℃, an acid value of 150~180 mgKOH / g, and a saponification value of 160~190 mgKOH / g.

[0043] The softener is paraffin oil; the paraffin oil has a kinematic viscosity of 15~40 mmHg at 40°C. 2 / s, flash point ≥200℃, freezing point ≤-25℃.

[0044] The anti-aging agent is the light stabilizer UV2020.

[0045] The antioxidant is antioxidant 1076.

[0046] The filler is kaolin; the kaolin particle size is 0.5~10 μm.

[0047] The method for preparing the self-adhesive includes the following steps: A1. Add butyl rubber to a reactor equipped with a constant temperature control, nitrogen protection device and high-speed stirring, introduce nitrogen gas, heat to 130℃, stir at 400 r / min for 50 min; mix 5% of the total rubber mass of modifier with 1.2% of the modifier mass of dicumyl peroxide, add to the molten rubber at a uniform speed, heat to 165℃, increase the stirring speed to 550 r / min, and stir for 60 min. A2. After the reaction is complete, cool down to 150℃, reduce the stirring speed to 400 r / min, add the tackifying resin, keep warm and stir for 45 min, then add the softener in three batches, with an interval of 15 min between each addition, and maintain the stirring speed at 300 r / min; add the synthetic asphalt adhesive preheated to 80℃, raise the temperature to 145℃, keep warm and stir for 80 min, continue to cool down to 120℃, add the anti-aging agent and antioxidant, and stir for 25 min; finally add the filler, increase the stirring speed to 900 r / min, and stir for 70 min.

[0048] The preparation method of the modifier includes the following steps: B1. Add 60 parts of hydroxyethyl methacrylate, 120 parts of anhydrous toluene, and 0.5 parts of p-hydroxyanisole to a four-necked flask equipped with a reflux condenser, a nitrogen delivery tube, and a stirrer. Purge with nitrogen, stir, and heat to 55°C. Keep warm for 15 min. B2. Slowly add 40 parts of m-chloroperoxybenzoic acid to the above reaction system, maintaining the temperature at 55°C during the addition. After the addition is complete, raise the temperature to 65°C and keep the reaction at this temperature for 8 hours. Add saturated sodium carbonate solution to the system, let it stand and separate into layers, take the organic phase, wash it three times with deionized water, add anhydrous magnesium sulfate to dry it, filter to remove the desiccant, and obtain the intermediate solution for later use. B3. At 60°C, 30 parts of 4-amino-2,2,6,6-tetramethylpiperidine were slowly added dropwise to the above intermediate solution. The reaction was maintained at this temperature for 3 h. While maintaining the reaction temperature, 1.2 parts of dibutyltin dilaurate catalyst were added, followed by 25 parts of 3-(perfluorohexyl)propyl isocyanate. The temperature was raised to 80°C and the reaction was carried out for 5 h. After the reaction was completed, the mixture was distilled under reduced pressure. The residue was poured into excess anhydrous ethanol to precipitate. After standing for 2 h, the mixture was filtered. The filter cake was dried in a vacuum drying oven at 80°C for 8 h to obtain the modifier.

[0049] A method for preparing a creep-resistant polymer self-adhesive waterproof membrane includes the following steps: S1. The ethylene-octene copolymer was dried at 100°C for 3 hours. The nanomaterial was mixed with 3% by mass of silane coupling agent KH-550 in a high-speed mixer at 90°C for 30 minutes to obtain the modified nanomaterial. S2. The pretreated ethylene-octene copolymer, synthetic asphalt rubber and modified nanomaterials are added to a twin-screw extruder. The extruder temperature gradient is set as follows: feeding section 160℃, melting section 180℃, mixing section 200℃, extrusion section 180℃. The screw speed is controlled at 120 r / min. The residence time of the material in the extruder is controlled at 5 min. After the extrudate is cooled by water, it is granulated by a granulator and dried at 80℃ for 4 h to obtain creep-resistant polymer granules. S3. Add the creep-resistant polymer granules to a single screw extruder, set the temperature to 190℃, and extrude them through a T-die to form a continuous sheet with a thickness of 2.5 mm. Use a roller coating method to evenly coat the prepared self-adhesive on one side of the sheet, control the coating thickness to 1.5 mm, and maintain the temperature at 120℃ during the coating process to form a self-adhesive layer. S4. Introduce the composite sheet into the cooling roller assembly and control the cooling temperature gradient: the first stage cooling temperature is 70℃, the second stage is 40℃, and the third stage is room temperature. S5. Apply a silicone oil film as a release agent to the surface of the self-adhesive layer, control the winding tension to 100 N, match the winding speed with the extrusion speed, and ensure that the roll is neatly wound with an end face deviation of no more than 3 mm. S6. Finished roll materials should be stored in a well-ventilated and dry warehouse, avoiding direct sunlight. The stacking height should not exceed 5 layers to prevent the roll materials from being deformed by pressure. The storage temperature should be controlled at 35℃.

[0050] Comparative Example 1: No modifier was added in the preparation of the self-adhesive, and the composition, dosage and preparation process of the other raw materials were the same as in Example 1.

[0051] Comparative Example 2: No nanomaterials were added to the raw materials, and the composition, amount and preparation process of the other raw materials were the same as in Example 1.

[0052] Comparative Example 3: The butyl rubber in the self-adhesive was replaced with an equal amount of natural rubber, and the modifier was replaced with an equal amount of glycidyl methacrylate. The composition, dosage and preparation process of the remaining raw materials were the same as in Example 1.

[0053] Performance testing: 1. Creep resistance Test standard: Appendix C of GB / T 19250-2013 "Polyurethane Waterproof Coatings" Test conditions: 23℃, 10% tensile stress applied, for 1000 h. Evaluation index: Creep rate (%) = (Elongation at 1000 h / Initial elongation) × 100%; 2. Adhesion performance Testing Standard: GB / T 23441-2009 "Self-adhesive Polymer-Modified Bitumen Waterproof Membrane" Test conditions: 25℃, peel test on concrete substrate. Evaluation indicators: peel strength (kN / m), bond failure mode (interfacial failure / cohesive failure); 3. Weather resistance Test standard: GB / T 18244-2000 "Test Method for Aging of Building Waterproofing Materials" Test conditions: Xenon lamp aging for 168 hours (irradiance 0.71 W / (m²)) 2 •nm), blackboard temperature 65℃, relative humidity 65±5% Evaluation index: Peel strength retention rate after aging (%) = (Aging strength / Initial strength) × 100%; 4. Water resistance Testing Standard: GB / T 18173.1-2012 "Polymer Waterproofing Materials - Part 1: Sheets" Test conditions: Soaked in distilled water at 23℃ for 7 days Evaluation index: Water absorption rate (%) = (Mass after soaking - Initial mass) / Initial mass × 100% Peel strength loss rate after water immersion (%) = (initial strength - strength after immersion) / initial strength × 100%; Table 1. Test results of creep resistance and adhesion properties Group Creep rate (%) Peel strength (kN / m) Bond failure modes Example 1 3.2 2.8 Cohesion destruction Example 2 2.8 3.1 Cohesion destruction Example 3 2.5 3.3 Cohesion destruction Comparative Example 1 3.7 2.5 Partial interface damage Comparative Example 2 3.5 2.3 Partial interface damage Comparative Example 3 5.1 2.1 Interface destruction Table 2 Results of weather resistance and water resistance tests Group Peel strength retention rate after aging (%) Water absorption rate (%) Peel strength loss rate after water immersion (%) Example 1 92 1.2 8 Example 2 94 1.0 7 Example 3 95 0.8 6 Comparative Example 1 65 3.5 35 Comparative Example 2 78 2.3 22 Comparative Example 3 68 4.2 40 The test results show that Examples 1-3 exhibit significantly better overall performance than Comparative Examples 1-3. Regarding creep resistance and adhesion, Examples 1-3 show lower creep rates and higher peel strength, with all adhesion failures occurring through cohesive failure, indicating strong internal bonding of the roll material. Comparative Examples 1-3 show higher creep rates and lower peel strength, with most failures occurring at interfaces or partially at interfaces, indicating weaker bonding with the substrate and weaker internal cohesiveness. In terms of weather resistance and water resistance, Examples 1-3 show higher peel strength retention after aging, lower water absorption, and less peel strength loss after water immersion, demonstrating excellent anti-aging and water penetration resistance. Comparative Examples 1-3 show poor strength retention after aging, more significant water absorption, and greater strength loss after water immersion, indicating insufficient weather resistance and water resistance. In summary, Examples 1-3, through reasonable formulation and process design, achieve synergistic advantages in creep resistance, adhesion, weather resistance, and water resistance.

[0054] 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 creep-resistant polymer self-adhesive waterproof membrane, characterized in that, Includes the following quantities of raw materials: Polymer matrix: 30-40 parts thermoplastic elastomer; Nanomaterials: 5-10 parts; Synthetic asphalt adhesive: 10-20 parts; Self-adhesive: 20-30 parts rubber, 10-15 parts tackifying resin, 5-10 parts softener, 1-3 parts anti-aging agent, 0.5-2 parts antioxidant, and 5-15 parts filler; The method for preparing the self-adhesive includes the following steps: A1. Add rubber to a reaction vessel equipped with a constant temperature control, nitrogen protection device and high-speed stirring, introduce nitrogen gas, heat up and stir evenly; mix 3.5~5% of the total mass of the rubber modifier with 0.8~1.2% of the modifier mass of dicumyl peroxide, add it to the molten rubber at a uniform speed, heat up and stir to react. A2. After the reaction is complete, cool down and stir, add tackifying resin, keep warm and stir evenly, then add softener in three parts, with an interval of 15 minutes between each addition; add preheated synthetic asphalt adhesive, heat up and stir, cool down and add anti-aging agent and antioxidant, stir evenly; finally add filler and stir evenly. The thermoplastic elastomer is selected from one of ethylene-vinyl acetate copolymer, styrene-butadiene-styrene block copolymer, and ethylene-octene copolymer; The rubber is selected from butyl rubber and styrene-butadiene rubber.

2. The creep-resistant polymer self-adhesive waterproof membrane according to claim 1, characterized in that: The nanomaterial is one of nano-silica, nano-zinc oxide, and nano-clay; the nano-silica has a particle size of 5-50 nm and a specific surface area of ​​100-400 m². 2 / g, purity ≥99.5%; the nano zinc oxide particles have a particle size of 10~30 nm and a specific surface area of ​​30~80 m² / g. 2 / g, purity ≥99.0%; the nano-clay is montmorillonite, with a particle size of 1~10 nm and an interlayer spacing of 1.2~1.8 nm.

3. The creep-resistant polymer self-adhesive waterproof membrane according to claim 1, characterized in that: The synthetic asphalt adhesive is one of styrene-butadiene rubber modified asphalt adhesive, butyl rubber modified asphalt adhesive, and rosin resin modified asphalt adhesive; the styrene-butadiene rubber modified asphalt adhesive has a styrene-butadiene rubber content of 5-10%; the butyl rubber modified asphalt adhesive has a butyl rubber content of 3-8%; and the rosin resin modified asphalt adhesive has a rosin resin content of 8-15%.

4. The creep-resistant polymer self-adhesive waterproof membrane according to claim 1, characterized in that: The tackifying resin is one of terpene resin, phenolic resin, and rosin resin; the terpene resin has a softening point of 80~120℃, an acid value of ≤10mgKOH / g, and a hydroxyl value of ≤5 mgKOH / g; the phenolic resin has a softening point of 90~130℃, a free phenol content of ≤5%, and a hydroxymethyl content of 8~15%; the rosin resin has a softening point of 70~100℃, an acid value of 150~180 mgKOH / g, and a saponification value of 160~190 mgKOH / g.

5. The creep-resistant polymer self-adhesive waterproof membrane according to claim 1, characterized in that: The softener is one of naphthenic oil, aromatic oil, and paraffin oil; the naphthenic oil has a kinematic viscosity of 20-50 mmHg at 40°C. 2 / s, flash point ≥180℃, pour point ≤-20℃; the aromatic oil: kinematic viscosity at 40℃ 30~60 mm 2 / s, flash point ≥190℃, pour point ≤-15℃; the paraffin oil: kinematic viscosity 15~40 mm at 40℃. 2 / s, flash point ≥200℃, freezing point ≤-25℃.

6. The creep-resistant polymer self-adhesive waterproof membrane according to claim 1, characterized in that: The anti-aging agent is one of light stabilizer 622, light stabilizer 944, and light stabilizer UV2020.

7. The creep-resistant polymer self-adhesive waterproof membrane according to claim 1, characterized in that: The antioxidant is one of antioxidant 264, antioxidant 1010, and antioxidant 1076.

8. The creep-resistant polymer self-adhesive waterproof membrane according to claim 1, characterized in that: The filler is one of calcium carbonate, talc, and kaolin; the calcium carbonate has a particle size of 0.1~5 μm; the talc has a particle size of 1~20 μm; and the kaolin has a particle size of 0.5~10 μm.

9. The creep-resistant polymer self-adhesive waterproof membrane according to claim 1, characterized in that, The preparation method of the modifier includes the following steps: B1. Add 50-60 parts of hydroxyethyl methacrylate, 100-120 parts of anhydrous toluene, and 0.3-0.5 parts of p-hydroxyanisole to a four-necked flask equipped with a reflux condenser, a nitrogen delivery tube, and a stirrer. Purge with nitrogen, stir, and heat to 50-55°C. Keep warm for 10-15 minutes. B2. Slowly add 30-40 parts of m-chloroperoxybenzoic acid dropwise to the above reaction system, maintaining the temperature at 50-55℃ during the dropwise addition. After the dropwise addition is complete, raise the temperature to 60-65℃ and keep the reaction at this temperature for 5-8 hours. Add saturated sodium carbonate solution to the system, allow it to stand and separate into layers, take the organic phase, wash it three times with deionized water, add anhydrous magnesium sulfate to dry it, filter to remove the drying agent, and obtain the intermediate solution for later use. B3. At a temperature of 50-60℃, slowly add 25-30 parts of 4-amino-2,2,6,6-tetramethylpiperidine and maintain the temperature for 2-3 hours. While maintaining the reaction temperature, add 0.5-1.2 parts of dibutyltin dilaurate catalyst and slowly add 20-25 parts of 3-(perfluorohexyl)propyl isocyanate. Increase the temperature to 70-80℃ and react for 3-5 hours. After the reaction is complete, distill under reduced pressure. Pour the residue into excess anhydrous ethanol to precipitate. After standing for 1-2 hours, filter. Dry the filter cake in a vacuum drying oven at 60-80℃ for 6-8 hours to obtain the modifier.

10. A method for preparing a creep-resistant polymer self-adhesive waterproof membrane according to any one of claims 1 to 9, characterized in that, Includes the following steps: S1. The thermoplastic elastomer is dried at 80~100℃ for 2~3 h; the nanomaterial is mixed with 1~3% by mass of silane coupling agent KH-550 in a high-speed mixer at 80~90℃ for 20~30 min to obtain the modified nanomaterial. S2. Add the pretreated thermoplastic elastomer, synthetic asphalt rubber, and modified nanomaterials to a twin-screw extruder. Set the extruder temperature gradient as follows: feeding section 150~160℃, melting section 170~180℃, mixing section 180~200℃, and extrusion section 170~180℃. Control the screw speed at 80~120 r / min. Control the material residence time in the extruder at 3~5 min. After water cooling, the extrudate is granulated by a granulator and dried at 60~80℃ for 2~4 h to obtain creep-resistant polymer granules. S3. Add the creep-resistant polymer granules to a single-screw extruder, set the temperature to 160~190℃, and extrude them through a T-die to form a continuous sheet with a thickness of 1.0~2.5 mm. Use a doctor blade coating or roller coating method to evenly coat one side of the sheet with the prepared self-adhesive, control the coating thickness to be 0.5~1.5 mm, and maintain the temperature at 100~120℃ during the coating process to form a self-adhesive layer. S4. Introduce the composite sheet into the cooling roller assembly and control the cooling temperature gradient: the first stage cooling temperature is 60~70℃, the second stage is 30~40℃, and the third stage is room temperature. S5. Apply a silicone oil film as a release agent to the surface of the self-adhesive layer, control the winding tension to 50~100 N, match the winding speed with the extrusion speed, and ensure that the roll is neatly wound with an end face deviation of no more than 3 mm. S6. Finished roll materials should be stored in a well-ventilated and dry warehouse, avoiding direct sunlight. The stacking height should not exceed 5 layers to prevent the roll materials from being deformed by pressure. The storage temperature should be controlled between 5 and 35℃.