High weather-resistant SBS composite modified waterproof membrane and its preparation method

Abstract

This invention belongs to the field of waterproof membrane technology, specifically relating to a high weather-resistant SBS composite modified waterproof membrane and its preparation method. The invention involves coating a modified bitumen compound onto a base layer to obtain a bitumen substrate layer, covering the surface of the bitumen substrate layer with a weather-resistant release film, and then cooling and packaging to obtain a high weather-resistant SBS composite modified waterproof membrane. The multi-arm structure of the modified SBS branched soft segments exhibits excellent low-temperature elasticity. Its mesh structure reduces permanent deformation during long-term use of the waterproof membrane, preventing cracking and brittle fracture caused by prolonged exposure in outdoor environments. The limitation on relative molecular weight avoids excessively high viscosity of the bitumen mixture, which would hinder coating and make it easier to process. The UV-resistant material introduced into the weather-resistant release film contains catechol groups, which absorb ultraviolet light and prevent detachment caused by oxygen and rainwater erosion of the UV-resistant material.

Description

Technical Field

[0001] This invention belongs to the field of waterproof membrane technology, specifically relating to a high weather-resistant SBS composite modified waterproof membrane and its preparation method. Background Technology

[0002] Building waterproofing materials are core functional materials that ensure the safety of building structures, and their performance directly affects the durability and functionality of buildings. One of the most widely used waterproofing materials is styrene-butadiene-styrene block copolymer (SBS) modified waterproofing membrane. SBS modified waterproofing membranes, made with SBS-modified bitumen as the core waterproofing coating and polyester base as the reinforcing material, possess excellent elasticity and ductility.

[0003] Chinese invention patent CN120552463B discloses a method for preparing an aging-resistant modified bitumen waterproof membrane. This aging-resistant modified bitumen waterproof membrane includes a polyethylene film, a base layer, and a modified bitumen matrix. The modified bitumen matrix, by weight, comprises the following raw materials: 45-60 parts bitumen, 10-15 parts SBS elastomer, 8-12 parts softener, 3-5 parts waterproofing agent, 4-6 parts anti-aging agent, 5-9 parts SBR, 5-10 parts composite filler, and 0.03-0.05 parts initiator. The aging-resistant modified bitumen waterproof membrane prepared by this invention possesses excellent waterproof performance, heat aging resistance, and UV aging resistance. Furthermore, this aging-resistant modified bitumen waterproof membrane has a complex network structure, giving the matrix excellent mechanical properties. However, existing technologies suffer from the technical problem that waterproof membranes are prone to aging, cracking, and blistering under prolonged exposure to sunlight. Summary of the Invention

[0004] The purpose of this invention is to provide a high weather-resistant SBS composite modified waterproof membrane and its preparation method, which solves the technical problem that waterproof membranes in the prior art are prone to aging, cracking and blistering under long-term exposure to sunlight.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] The high weather-resistant SBS composite modified waterproof membrane consists of a weather-resistant release membrane, an asphalt substrate layer, and a base layer, from top to bottom.

[0007] The base layer is a polyester felt base.

[0008] The asphalt substrate layer is made from the following components in parts by weight: 80-90 parts asphalt, 3-5 parts modified SBS, 7-15 parts softening oil and 0.5-2 parts antioxidant.

[0009] The weather-resistant insulating membrane is made from the following components in parts by weight: 80-90 parts polyethylene, 0.5-1 part UV-resistant material, 0.5-2 parts micron-sized silica, 0.5-2 parts stearic acid, and 0.5-2 parts antioxidant.

[0010] The antioxidant is any one of antioxidant 1010, antioxidant 168, and antioxidant 264.

[0011] The method for preparing the modified SBS includes the following steps:

[0012] S11. Add solvent cyclohexane to the reactor, purge the air with nitrogen, preheat the temperature, add styrene and initiator n-butyllithium, carry out one-stage polymerization, then add butadiene and carry out two-stage polymerization to obtain styrene-butadiene diblock copolymer.

[0013] S12. After mixing hexachlorodisilane and dienylbenzene to prepare a multi-arm coupling agent, it is added to styrene-butadiene diblock copolymer, and tetrahydrofurfuryl ethyl ether is added dropwise. The coupling reaction is carried out under nitrogen atmosphere and the reaction is terminated by adding isopropanol as a terminator to obtain modified SBS.

[0014] Preferably, the mass ratio of styrene, butadiene, and initiator n-butyllithium in S11 is 33~40:60~67:19~25.

[0015] Preferably, in step S11, the temperature is preheated to 60-70°C, the reaction temperature for the first-stage polymerization is 60-70°C, and the reaction time is 30-50 min. The reaction temperature for the second-stage polymerization is 85-100°C, and the reaction time is 15-30 min.

[0016] Preferably, in S12, the mass ratio of hexachlorodisilane to dienylbenzene is 0.5~0.8:1~1.5, the amount of coupling agent added is 80~85% of the mass of the initiator n-butyllithium, the amount of tetrahydrofurfuryl ethyl ether added is 1~3% of the mass of the styrene-butadiene diblock copolymer, and the coupling reaction is carried out at 50~60℃ for 1~1.5h.

[0017] Preferably, the relative molecular mass of the modified SBS in S12 is 1.5~2.5×10⁻⁶. 5 The coupling efficiency is 83-88%.

[0018] Preferably, the method for preparing the UV-resistant material includes the following steps:

[0019] S21. Add zinc nitrate to deionized water, add ammonia dropwise, stir to form a precipitate, filter to collect the precipitate, and dry to obtain nano zinc oxide.

[0020] S22. Dissolve sodium silicate in deionized water, add nano zinc oxide while stirring, add hydrochloric acid dropwise for gelation treatment, add acetone for aging, take out the gel and immerse it in anhydrous ethanol, and dry it to obtain a porous antioxidant material.

[0021] S23. Add porous antioxidant material and dopamine to deionized water, heat to a hydrothermal reaction, filter and dry to obtain UV-resistant material.

[0022] Preferably, the concentration of ammonia in S21 is 20-25%, and the ratio of zinc nitrate, deionized water, and ammonia is (10-15) g: (200-300) mL: (8-15) mL. After stirring for 20-30 min, the mixture is dried at 50-60℃ to obtain nano zinc oxide.

[0023] Preferably, the concentration of hydrochloric acid in S22 is 2-3%, and hydrochloric acid is added dropwise to promote gelation and control the pH to 8-9; the ratio of sodium silicate, nano zinc oxide and acetone is (14-15) g: (10-12) g: (20-30) mL, acetone is added for aging for 4-6 h, the gel is taken out and soaked in anhydrous ethanol for 8-12 h, dried at 50-60℃ for 2-4 h, and then heated to 110-130℃ for 2-4 h.

[0024] Preferably, the mass ratio of porous antioxidant material to dopamine in S23 is 5~7:0.8~1, and the reaction is carried out at 200~220℃ for 20~24h.

[0025] The preparation method of high weather-resistant SBS composite modified waterproof membrane includes the following steps:

[0026] S1. Clean the tire base layer thoroughly and set aside;

[0027] S2. Modified SBS, asphalt, antioxidant, and softening oil are added to a mixing tank and heated and mixed. The mixture is then pumped into a colloid mill and stirred to obtain modified asphalt compound. The modified asphalt compound is then coated onto the base layer to obtain the asphalt substrate layer.

[0028] S3. A weather-resistant barrier film is prepared by mixing polyethylene, anti-UV material, micron-sized silica, stearic acid and antioxidant, casting the mixture, and drying it.

[0029] S4. Cover the surface of the asphalt substrate layer with a weather-resistant release film, compact it, and package it after cooling to obtain a high weather-resistant SBS composite modified waterproof membrane.

[0030] Preferably, in step S2, the temperature is heated to 150~170℃ and stirred in a colloid mill for 20~30 minutes, resulting in an asphalt substrate layer thickness of 2~2.5 mm.

[0031] Preferably, in step S3, the film is cast at 210~220℃, and the thickness of the weather-resistant isolation film is 5~10μm.

[0032] Preferably, the compaction pressure in step S4 is 1~5MPa and the compaction time is 2~5min.

[0033] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0034] 1. This invention produces a high-weather-resistant SBS composite modified waterproof membrane by coating a modified asphalt binder onto a base layer to form an asphalt substrate layer, covering the surface of the asphalt substrate layer with a weather-resistant release film, and then cooling and packaging it. The multi-arm structure of the modified SBS branched soft segments has excellent low-temperature elasticity. The mesh structure reduces permanent deformation of the waterproof membrane during long-term use, preventing cracking and brittle fracture caused by prolonged exposure in outdoor environments. The limitation of relative molecular weight avoids excessive viscosity of the asphalt mixture, which would make coating difficult and facilitates processing. The UV-resistant material introduced into the weather-resistant release film has catechol groups, which can absorb ultraviolet light and prevent the detachment of materials caused by oxygen and rainwater corrosion.

[0035] 2. After obtaining nano-zinc oxide, this invention loads it onto silica gel and dries it to obtain a porous antioxidant material. This porous antioxidant material has an excellent specific surface area, which increases the contact area between nano-zinc oxide and light, reflects ultraviolet light and reduces radiation damage. The surface obtained by dopamine polymerization rapidly consumes the energy of ultraviolet light through the movement of photogenerated charge carriers in conjunction with nano-zinc oxide, thereby improving the weather resistance of the waterproof membrane. Attached Figure Description

[0036] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0037] Figure 1 A schematic diagram of the layered structure of the high weather-resistant SBS composite modified waterproof membrane of the present invention is shown;

[0038] Figure reference numerals: 1-weather-resistant isolation membrane, 2-asphalt substrate layer and 3-base layer. Detailed Implementation

[0039] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] The polyester felt base of this invention has a thickness of 1 mm, the average diameter of the micron-sized silica is 5 μm, and the softening oil is of type NL-45.

[0041] Example 1, see Figure 1 As shown, the high weather-resistant SBS composite modified waterproof membrane of this embodiment includes, from top to bottom, a weather-resistant isolation membrane 1, an asphalt substrate layer 2, and a base layer 3.

[0042] The asphalt substrate layer is made from the following components: 85g of asphalt, 3g of modified SBS, 12g of softening oil and 2g of antioxidant 1010.

[0043] The weather-resistant insulating membrane is made from the following components: 90g of polyethylene, 1g of UV-resistant material, 2g of micron-sized silica, 2g of stearic acid and 2g of antioxidant 1010.

[0044] The method for preparing modified SBS in this embodiment includes the following steps:

[0045] S11. Add 1L of solvent cyclohexane to the reactor, purge the air with nitrogen, preheat the temperature to 65℃, add 33g of styrene and 20g of initiator n-butyllithium, carry out the first-stage polymerization at 65℃ for 40min, then add 67g of butadiene and carry out the second-stage polymerization at 90℃ for 20min to obtain styrene-butadiene diblock copolymer.

[0046] S12. A multi-arm coupling agent was prepared by mixing 6g of hexachlorodisilane and 10g of dienylbenzene. Then, 100g of styrene-butadiene diblock copolymer was added, followed by the dropwise addition of 3g of tetrahydrofurfuryl ethyl ether. The mixture was heated to 60℃ under a nitrogen atmosphere for 1-1.5 hours for coupling reaction. Isopropanol was added as a terminator to terminate the reaction, yielding modified SBS with a relative molecular mass of 1.6 × 10⁻⁶. 5 The coupling efficiency is 83.5%.

[0047] The method for preparing the UV-resistant material in this embodiment includes the following steps:

[0048] S21. Add 10g of zinc nitrate to 250mL of deionized water, add 8.5mL of 25% ammonia water dropwise, stir for 20min to form a precipitate, filter and collect the precipitate, and dry at 50℃ to obtain nano zinc oxide.

[0049] S22. Dissolve 14.5g of sodium silicate in 20mL of deionized water, add 10g of nano zinc oxide and stir while adding 3% hydrochloric acid to control the pH to 8 for gelation treatment, add 20mL of acetone for aging for 4h, take out the gel and soak it in anhydrous ethanol for 10h, dry it at 60℃ for 2h, and then heat it to 130℃ for 4h to obtain a porous antioxidant material.

[0050] S23. Add 7g of porous antioxidant material and 0.85g of dopamine to deionized water, heat to 220℃ and react for 24h, filter and dry to obtain UV-resistant material.

[0051] The preparation method of the high weather-resistant SBS composite modified waterproof membrane in this embodiment includes the following steps:

[0052] S1. Clean the tire base layer thoroughly and set aside;

[0053] S2. Add modified SBS, asphalt, antioxidant, and softening oil to a mixing tank and heat to 160°C to mix. Pump the mixture into a colloid mill and stir for 20 minutes to obtain modified asphalt compound. Coat the modified asphalt compound onto the base layer to obtain an asphalt substrate layer with a thickness of 2 mm.

[0054] S3. Polyethylene, UV-resistant material, micron-sized silica, stearic acid and antioxidant are mixed and cast into a film at 220°C. After drying, a weather-resistant isolation film is obtained with a thickness of 6μm.

[0055] S4. Cover the surface of the asphalt substrate layer with a weather-resistant isolation film, press it with a pressure of 1MPa for 2 minutes, cool it, and then package it to obtain a high weather-resistant SBS composite modified waterproof membrane.

[0056] Example 2: The high weather-resistant SBS composite modified waterproof membrane of this example includes, from top to bottom, a weather-resistant isolation membrane, an asphalt substrate layer, and a base layer.

[0057] The asphalt substrate layer is made from the following components: 80g of asphalt, 5g of modified SBS, 15g of softening oil and 0.5g of antioxidant 168.

[0058] The weather-resistant insulating membrane is made from the following components: 80g of polyethylene, 0.5g of UV-resistant material, 0.5g of micron-sized silica, 0.5g of stearic acid and 0.5g of antioxidant 168.

[0059] The method for preparing modified SBS in this embodiment includes the following steps:

[0060] S11. Add 1L of solvent cyclohexane to the reactor, purge the air with nitrogen, preheat the temperature to 70℃, add 35g of styrene and 21.5g of initiator n-butyllithium, carry out the first-stage polymerization at 60℃ for 50min, then add 65g of butadiene and carry out the second-stage polymerization at 95℃ for 30min to obtain styrene-butadiene diblock copolymer.

[0061] S12. A multi-arm coupling agent was prepared by mixing 7g of hexachlorodisilane and 12g of dienylbenzene. Then, 100g of styrene-butadiene diblock copolymer was added, followed by the dropwise addition of 2g of tetrahydrofurfuryl ethyl ether. The mixture was heated to 50℃ under a nitrogen atmosphere and the coupling reaction was carried out for 1.5h. Isopropanol was added as a terminator to terminate the reaction, yielding modified SBS with a relative molecular mass of 2.3 × 10⁻⁶. 5 The coupling efficiency is 85%.

[0062] The method for preparing the UV-resistant material in this embodiment includes the following steps:

[0063] S21. Add 12g of zinc nitrate to 200mL of deionized water, add 10mL of 20% ammonia water dropwise, stir for 20min to generate a precipitate, filter and collect the precipitate, and dry at 60℃ to obtain nano zinc oxide.

[0064] S22. Dissolve 14g of sodium silicate in 20mL of deionized water, add 10g of nano zinc oxide and stir while adding 3% hydrochloric acid to control the pH to 8 for gelation treatment, add 25mL of acetone for aging for 6h, take out the gel and soak it in anhydrous ethanol for 12h, dry it at 50℃ for 4h, and then heat it to 110℃ for 4h to obtain a porous antioxidant material.

[0065] S23. Add 6g of porous antioxidant material and 0.9g of dopamine to deionized water, heat to 210℃ and react for 22h, filter and dry to obtain UV-resistant material.

[0066] The preparation method of the high weather-resistant SBS composite modified waterproof membrane in this embodiment includes the following steps:

[0067] S1. Clean the tire base layer thoroughly and set aside;

[0068] S2. Add modified SBS, asphalt, antioxidant, and softening oil to a mixing tank and heat to 170°C to mix. Pump the mixture into a colloid mill and stir for 30 minutes to obtain modified asphalt compound. Coat the modified asphalt compound onto the base layer to obtain an asphalt substrate layer with a thickness of 2 mm.

[0069] S3. Polyethylene, UV-resistant material, micron-sized silica, stearic acid and antioxidant are mixed and cast into a film at 210°C. After drying, a weather-resistant isolation film is obtained with a thickness of 7μm.

[0070] S4. Cover the surface of the asphalt substrate layer with a weather-resistant isolation film, press it with a pressure of 2MPa for 5 minutes, cool it, and then package it to obtain a high weather-resistant SBS composite modified waterproof membrane.

[0071] Example 3: The high weather-resistant SBS composite modified waterproof membrane of this example includes, from top to bottom, a weather-resistant isolation membrane, an asphalt substrate layer, and a base layer.

[0072] The asphalt substrate layer is made from the following components: 85g of asphalt, 5g of modified SBS, 10g of softening oil and 1.5g of antioxidant 264.

[0073] The weather-resistant insulating membrane is made from the following components: 90g of polyethylene, 1g of UV-resistant material, 1g of micron-sized silica, 1.5g of stearic acid and 2g of antioxidant 264.

[0074] The method for preparing modified SBS in this embodiment includes the following steps:

[0075] S11. Add 1L of solvent cyclohexane to the reactor, purge the air with nitrogen, preheat the temperature to 70℃, add 38g of styrene and 23.5g of initiator n-butyllithium, carry out the first-stage polymerization at 70℃ for 45min, then add 62g of butadiene and carry out the second-stage polymerization at 85℃ for 30min to obtain styrene-butadiene diblock copolymer.

[0076] S12. A multi-arm coupling agent was prepared by mixing 8g of hexachlorodisilane and 10g of dienylbenzene. This mixture was then added to 100g of styrene-butadiene diblock copolymer, and 1.5g of tetrahydrofurfuryl ethyl ether was added dropwise. The mixture was heated to 60℃ under a nitrogen atmosphere and the coupling reaction was carried out for 1.5h. The reaction was terminated by adding isopropanol to obtain modified SBS. The relative molecular mass of the modified SBS was 2.1 × 10⁻⁶. 5 The coupling efficiency is 86.2%.

[0077] The method for preparing the UV-resistant material in this embodiment includes the following steps:

[0078] S21. Add 14g of zinc nitrate to 300mL of deionized water, add 15mL of 25% ammonia water dropwise, stir for 30min to generate a precipitate, filter and collect the precipitate, and dry at 60℃ to obtain nano zinc oxide.

[0079] S22. Dissolve 15g of sodium silicate in 30mL of deionized water, add 12g of nano zinc oxide and stir while adding 2% hydrochloric acid to control the pH to 8.5 for gelation treatment, add 30mL of acetone for aging for 4h, take out the gel and soak it in anhydrous ethanol for 12h, dry it at 55℃ for 3h, and then heat it to 115℃ for 3h to obtain a porous antioxidant material.

[0080] S23. Add 5g of porous antioxidant material and 1g of dopamine to deionized water, heat to 220℃ and react for 20h, filter and dry to obtain UV-resistant material.

[0081] The preparation method of high weather-resistant SBS composite modified waterproof membrane includes the following steps:

[0082] S1. Clean the tire base layer thoroughly and set aside;

[0083] S2. Add modified SBS, asphalt, antioxidant, and softening oil to a mixing tank and heat to 160°C to mix. Pump the mixture into a colloid mill and stir for 30 minutes to obtain modified asphalt compound. Coat the modified asphalt compound onto the base layer to obtain an asphalt substrate layer with a thickness of 2~2.5mm.

[0084] S3. Polyethylene, UV-resistant material, micron-sized silica, stearic acid and antioxidant are mixed and cast into a film at 215°C. After drying, a weather-resistant isolation film is obtained with a thickness of 7.5μm.

[0085] S4. Cover the surface of the asphalt substrate layer with a weather-resistant release film, press it with a pressure of 3MPa for 5 minutes, cool it, and then package it to obtain a high weather-resistant SBS composite modified waterproof membrane.

[0086] Example 4: The high weather-resistant SBS composite modified waterproof membrane of this example includes, from top to bottom, a weather-resistant isolation membrane, an asphalt substrate layer, and a base layer.

[0087] The asphalt substrate layer is made from the following components: 90g of asphalt, 3g of modified SBS, 7g of softening oil and 0.5g of antioxidant 1010.

[0088] The weather-resistant insulating membrane is made from the following components: 80g of polyethylene, 0.8g of UV-resistant material, 2g of micron-sized silica, 2g of stearic acid and 1.5g of antioxidant 1010.

[0089] The method for preparing modified SBS in this embodiment includes the following steps:

[0090] S11. Add 1L of solvent cyclohexane to the reactor, purge the air with nitrogen, preheat the temperature to 65℃, add 40g of styrene and 25g of initiator n-butyllithium, carry out the first-stage polymerization at 65℃ for 50min, then add 60g of butadiene and carry out the second-stage polymerization at 85℃ for 15min to obtain styrene-butadiene diblock copolymer.

[0091] S12. A multi-arm coupling agent was prepared by mixing 8g of hexachlorodisilane and 14g of dienylbenzene. This mixture was then added to 100g of styrene-butadiene diblock copolymer, and 1g of tetrahydrofurfuryl ethyl ether was added dropwise. The mixture was heated to 60℃ under a nitrogen atmosphere and the coupling reaction was carried out for 1 hour. Isopropanol was added as a terminator to terminate the reaction, yielding modified SBS with a relative molecular mass of 1.6 × 10⁻⁶. 5 The coupling efficiency is 83.9%.

[0092] The method for preparing the UV-resistant material in this embodiment includes the following steps:

[0093] S21. Add 11.5g of zinc nitrate to 220mL of deionized water, add 13mL of 25% ammonia water dropwise, stir for 30min to generate a precipitate, filter and collect the precipitate, and dry at 60℃ to obtain nano zinc oxide.

[0094] S22. Dissolve 14g of sodium silicate in 20mL of deionized water, add 10g of nano zinc oxide and stir while adding 3% hydrochloric acid to control the pH to 8 for gelation treatment, add 30mL of acetone for aging for 6h, take out the gel and soak it in anhydrous ethanol for 8h, dry it at 50~60℃ for 2h, and then heat it to 130℃ for 4h to obtain a porous antioxidant material.

[0095] S23. Add 7g of porous antioxidant material and 0.8g of dopamine to deionized water, heat to 220℃ and react for 22h, filter and dry to obtain UV-resistant material.

[0096] The preparation method of high weather-resistant SBS composite modified waterproof membrane includes the following steps:

[0097] S1. Clean the tire base layer thoroughly and set aside;

[0098] S2. Add modified SBS, asphalt, antioxidant, and softening oil to a mixing tank and heat to 160°C to mix. Pump the mixture into a colloid mill and stir for 30 minutes to obtain modified asphalt compound. Coat the modified asphalt compound onto the base layer to obtain an asphalt substrate layer with a thickness of 2.5 mm.

[0099] S3. Polyethylene, UV-resistant material, micron-sized silica, stearic acid and antioxidant are mixed and cast into a film at 210~220℃. After drying, a weather-resistant isolation film is obtained with a thickness of 10μm.

[0100] S4. Cover the surface of the asphalt substrate layer with a weather-resistant release film, press it with a pressure of 5MPa for 3 minutes, cool it, and then package it to obtain a high weather-resistant SBS composite modified waterproof membrane.

[0101] Comparative Example 1 differs from Example 1 in that the modified SBS is replaced with SBS of type 3501F.

[0102] Comparative Example 2 differs from Example 1 in that it does not contain any UV-resistant materials.

[0103] Comparative Example 3 differs from Example 1 in that it directly applies porous antioxidant materials to the weather-resistant membrane.

[0104] Performance testing

[0105] According to GB / T 23457-2017 "Pre-laid Waterproof Membranes", the waterproof membranes prepared in various examples and comparative examples were tested for their resistance to water seepage. A 10mm diameter hole was made in the middle of the waterproof membrane, and mortar was poured onto the bonding surface of the membrane specimen. After compaction and curing for 28 days, the pressure was increased to 0.4MPa and maintained for 24 hours. For every additional 0.1MPa, the pressure was maintained for 4 hours until the pressure gradient was 0.8MPa / 35mm. After maintaining the pressure for 4 hours, the water seepage was recorded.

[0106] After the waterproof membranes prepared in each embodiment and comparative example were adhered to the cement-based surface, they were soaked in water for 28 days. After being removed and dried, the joint peel strength and tensile strength retention rate were tested according to GB / T 328.20-2007 "Test Methods for Building Waterproof Membranes Part 20: Peel Performance of Bitumen Waterproof Membranes".

[0107] The waterproof membranes prepared in each embodiment and comparative example were heat-aged at 80℃ for 168 hours, and the joint peel strength and tensile strength retention rate were tested according to GB / T 328.20-2007 "Test Methods for Building Waterproof Membranes Part 20: Peel Performance of Bitumen Waterproof Membranes".

[0108] The test results are shown in Table 1 below:

[0109] Table 1 Test Results

[0110]

[0111] As shown in the table above, the waterproof membranes prepared in Examples 1-4 are waterproof under a pressure gradient of 0.8 MPa / 35 mm, indicating that the waterproof membranes prepared by this invention have excellent waterproof performance. In Comparative Example 1, the modified SBS was replaced with SBS of type 3501F, resulting in a layered structure of SBS with poor peel resistance. The seam peel strength in the water resistance test was only 1.9 N / mm, and the peeled surface had a layered peel structure. The waterproof membranes prepared in Examples 1-4 had a seam peel strength of 3.2-3.4 N / mm and a tensile strength retention rate of 90.4-91.3% after immersion in water for 28 days. After heat aging, the seam peel strength was 4.0-4.2 N / mm and the tensile strength retention rate was 92.2-92.6%, indicating that the waterproof membranes prepared by this invention can maintain their bonding and deformation properties under prolonged immersion in water and high temperature conditions in outdoor environments.

[0112] 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.

[0113] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high weather-resistant SBS composite modified waterproof membrane, characterized in that, From top to bottom, it includes a weather-resistant isolation membrane, an asphalt substrate layer, and a base layer; The asphalt substrate layer is made from the following components in parts by weight: 80-90 parts asphalt, 3-5 parts modified SBS, 7-15 parts softening oil and 0.5-2 parts antioxidant; The weather-resistant insulating membrane is made from the following components in parts by weight: 80-90 parts polyethylene, 0.5-1 part UV-resistant material, 0.5-2 parts micron-sized silica, 0.5-2 parts stearic acid, and 0.5-2 parts antioxidant; The method for preparing the modified SBS includes the following steps: S11. Add solvent cyclohexane to the reactor, purge the air with nitrogen, preheat the temperature, add styrene and initiator n-butyllithium, carry out one-stage polymerization, then add butadiene and carry out two-stage polymerization to obtain styrene-butadiene diblock copolymer. S12. After mixing hexachlorodisilane and dienylbenzene to prepare a multi-arm coupling agent, it is added to styrene-butadiene diblock copolymer, tetrahydrofurfuryl ethyl ether is added dropwise, and the coupling reaction is carried out under nitrogen atmosphere. The reaction is terminated by adding isopropanol as a terminator to obtain modified SBS. The method for preparing the UV-resistant material includes the following steps: S21. Add zinc nitrate to deionized water, add ammonia dropwise, stir to form a precipitate, filter to collect the precipitate, and dry to obtain nano zinc oxide. S22. Dissolve sodium silicate in deionized water, add nano zinc oxide while stirring, add hydrochloric acid dropwise for gelation treatment, add acetone for aging, take out the gel and immerse it in anhydrous ethanol, and dry it to obtain a porous antioxidant material. S23. Add porous antioxidant material and dopamine to deionized water, heat to a hydrothermal reaction, filter and dry to obtain UV-resistant material.

2. The high weather-resistant SBS composite modified waterproof membrane according to claim 1, characterized in that, The base layer is a polyester felt base, and the antioxidant is any one of antioxidant 1010, antioxidant 168, and antioxidant 264.

3. The high weather-resistant SBS composite modified waterproof membrane according to claim 1, characterized in that, In S11, the mass ratio of styrene, butadiene, and initiator n-butyllithium is 33-40:60-67:19-25. The temperature is preheated to 60-70°C. The reaction temperature for the first-stage polymerization is 60-70°C, and the reaction time is 30-50 min. The reaction temperature for the second-stage polymerization is 85-100°C, and the reaction time is 15-30 min. In S12, the mass ratio of hexachlorodisilane and dienylbenzene is 0.5-0.8:1-1.

5. The amount of coupling agent added is 80-85% of the mass of the initiator n-butyllithium. The coupling reaction is carried out at 50-60°C for 1-1.5 h. The relative molecular mass of the modified SBS is 1.5-2.5 × 10⁻⁶. 5 The coupling efficiency is 83-88%.

4. The high weather-resistant SBS composite modified waterproof membrane according to claim 1, characterized in that, In step S21, the ammonia concentration is 20-25%, and the ratio of zinc nitrate, deionized water, and ammonia is (10-15) g : (200-300) mL : (8-15) mL. The mixture is stirred for 20-30 minutes and then dried at 50-60℃ to obtain nano-zinc oxide. In step S22, the hydrochloric acid concentration is 2-3%, and hydrochloric acid is added dropwise to promote gelation, controlling the pH to 8-9. The ratio of sodium silicate, nano-zinc oxide, and acetone is... The ratio of porous antioxidant material to dopamine in S23 is (14~15)g:(10~12)g:(20~30)mL. The mixture is aged in acetone for 4~6h, the gel is removed and soaked in anhydrous ethanol for 8~12h, dried at 50~60℃ for 2~4h, and then heated to 110~130℃ for 2~4h. The mass ratio of porous antioxidant material to dopamine in S23 is 5~7:0.8~1. The mixture is reacted at 200~220℃ for 20~24h.

5. The method for preparing high weather-resistant SBS composite modified waterproof membrane according to any one of claims 1-4, characterized in that, Includes the following steps: S1. Clean the tire base layer thoroughly and set aside; S2. Modified SBS, asphalt, antioxidant, and softening oil are added to a mixing tank and heated and mixed. The mixture is then pumped into a colloid mill and stirred to obtain modified asphalt compound. The modified asphalt compound is then coated onto the base layer to obtain the asphalt substrate layer. S3. A weather-resistant barrier film is prepared by mixing polyethylene, anti-UV material, micron-sized silica, stearic acid and antioxidant, casting the mixture, and drying it. S4. Cover the surface of the asphalt substrate layer with a weather-resistant release film, compact it, and package it after cooling to obtain a high weather-resistant SBS composite modified waterproof membrane.

6. The preparation method of the high weather-resistant SBS composite modified waterproof membrane according to claim 5, characterized in that, In step S2, the temperature is heated to 150-170°C and stirred in a colloid mill for 20-30 minutes, resulting in an asphalt substrate layer thickness of 2-2.5 mm. In step S3, the film is cast at 210-220°C, resulting in a weather-resistant isolation film thickness of 5-10 μm. In step S4, the compaction pressure is 1-5 MPa and the compaction time is 2-5 minutes.

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