High-performance SBS (styrene-butadiene-styrene) waterproof roll containing magnesium hydroxide and nano-clay and preparation method of high-performance SBS waterproof roll

Abstract

The invention provides a high-performance SBS waterproof coiled material containing magnesium hydroxide and nano clay. The high-performance SBS waterproof coiled material comprises 70-80 parts of SBS modified asphalt; 10 to 20 parts of surface modified magnesium hydroxide; 3 to 8 parts of organic nano clay; 5-10 parts of a plasticizer; 2-5 parts of a stabilizer; and 1-3 parts of an antioxidant. The preparation method comprises the following steps: (1) a raw material pretreatment stage; (2) a mixing and plasticizing stage; and (3) a forming and shaping stage to obtain the finished coiled material. Through the synergistic effect of the surface modified magnesium hydroxide and the organic nano-clay, high flame retardance, excellent weather resistance and excellent mechanical properties of the SBS waterproof coiled material are synchronously realized under the halogen-free condition, and the production cost is remarkably reduced through a gradient dispersion process.

Description

Technical Field

[0001] The invention belongs to the technical field of building waterproof materials, and particularly relates to a high-performance SBS waterproof coiled material containing magnesium hydroxide and nanoclay and a preparation method thereof. Background Art

[0002] SBS, or styrene-butadiene-styrene block copolymer waterproof membrane, has become the mainstream waterproof material for construction projects due to its excellent flexibility and waterproof performance. However, in long-term practical applications, traditional SBS membranes have exposed a series of significant defects. First, the high-temperature resistance is insufficient. When the membrane is exposed to an environment above 60 degrees Celsius for a long time, it is prone to softening, resulting in a decrease in tensile strength of more than 30%. Secondly, the flame retardancy is weak. The oxygen index of traditional products is only about 18%. When exposed to open flames, molten droplets will be generated, thereby accelerating the spread of fire. Third, the durability is insufficient. Under conditions of ultraviolet radiation or acid rain erosion, the material ages faster, and the actual service life is often less than 10 years. Fourth, there are environmental risks. The halogen flame retardants added in traditional processes, such as decabromodiphenyl ether, will release toxic gases during use and do not meet environmental protection standards such as RoHS.

[0003] To overcome these issues, existing technologies primarily employ single improvements. For example, adding carbon nanotubes or graphene improves material strength. However, these nanomaterials are expensive, increasing raw material costs by more than 40%, and require complex dispersion processes. Other technologies employ magnesium hydroxide as a flame retardant. While this addresses environmental concerns, direct addition can cause material embrittlement, and a 20% drop in tear strength is common. Other studies have also explored the use of montmorillonite nanoclay to enhance the barrier properties of materials. However, this component lacks a synergistic effect with flame retardants, resulting in limited improvements in the overall performance of the final product.

[0004] It's worth noting that there's currently no proven solution for applying magnesium hydroxide and nanoclay as a composite modification system to SBS waterproofing membranes. In particular, there remains a technological gap in understanding the synergistic mechanism of these materials. Therefore, there's a need to design a high-performance SBS waterproofing membrane containing magnesium hydroxide and nanoclay, and a method for its preparation. Summary of the Invention

[0005] In order to overcome the defects in the prior art, a high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay and a preparation method thereof are provided.

[0006] In order to achieve the above object, the present invention provides the following technical solutions: A high-performance SBS waterproofing membrane containing magnesium hydroxide and nanoclay, the membrane being composed of the following raw materials in parts by mass: SBS modified asphalt 70-80 parts; 10-20 parts of surface-modified magnesium hydroxide; 3-8 parts of organized nanoclay; 5-10 parts of plasticizer; 2-5 parts of stabilizer; 1-3 parts of antioxidants.

[0007] The particle size of the surface-modified magnesium hydroxide is 150-300 nanometers, and the raw materials of the surface-modified magnesium hydroxide are reacted with a silane coupling agent at a temperature of 80-90 degrees Celsius for 30-50 minutes.

[0008] The organized nano-clay is obtained by reacting montmorillonite or attapulgite as a base material with an intercalation agent.

[0009] The mass ratio of the intercalant to the nanoclay substrate is 1:10-15.

[0010] The intercalant is hexadecyltrimethylammonium bromide or dioctadecyldimethylammonium chloride.

[0011] The plasticizer is at least one of dioctyl phthalate and epoxy soybean oil, the stabilizer is at least one of calcium stearate and zinc stearate, and the antioxidant is pentaerythritol tetra-β-3,5-di-tert-butyl-4-hydroxyphenyl propionate.

[0012] A method for preparing a high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay, the method comprising the following steps: (1) Raw material pretreatment stage: 10-20 parts of the raw material of surface-modified magnesium hydroxide are taken, stirred with a silane coupling agent at a mixing temperature of 80-90 degrees Celsius for 30-50 minutes, cooled, dried and crushed to obtain surface-modified magnesium hydroxide; 3-8 parts of the base material of the organic nanoclay are taken, ultrasonically dispersed with an intercalating agent in a water bath environment of 60-70 degrees Celsius for 40-60 minutes, and then centrifuged to obtain the organic nanoclay; (2) Mixing and plasticizing stage: heat 70-80 parts of SBS modified asphalt to 160-180°C to completely melt it; add 5-10 parts of plasticizer, 2-5 parts of stabilizer and 1-3 parts of antioxidant, maintain the stirring speed of 150-200 rpm and mix for 15-25 minutes; add the surface-modified magnesium hydroxide and organized nanoclay obtained in step (1), increase the stirring speed to 400-600 rpm, and continue stirring for 25-60 minutes; (3) Forming and shaping stage: The mixture obtained in step (2) is coated on the surface of the reinforced tire base through an extruder, and the coating thickness is controlled within the range of 1.5-4 mm; after calendering, it is cooled and shaped to obtain a finished coil.

[0013] In step (1), the ultrasonic dispersion has an operating power of 500-800 watts and an ultrasonic frequency of 25-40 kHz.

[0014] In step (3), the reinforced tire base layer is a polyester tire base or a glass fiber tire base material, and its unit area mass is 150-250 g / m².

[0015] In step (3), the material temperature during extrusion coating is maintained at 170-190°C, and the working pressure of the calendering treatment is controlled to be 5-10 MPa.

[0016] Compared with the prior art, the advantages and beneficial effects of the present invention are: 1. This invention effectively addresses the systemic shortcomings of traditional SBS waterproofing membranes, including insufficient high-temperature resistance, weak flame retardancy, poor durability, and high environmental risks, by introducing surface-modified magnesium hydroxide of a specific particle size and an organic nanoclay of a specific structure into an SBS asphalt matrix as a composite modifying component. The surface-modified magnesium hydroxide is treated with a silane coupling agent to form a uniform dispersion, overcoming the technical bottleneck of inorganic filler agglomeration. Its nanoscale size creates a dense physical barrier within the matrix, significantly slowing heat transfer and thereby improving the material's dimensional stability and mechanical retention in high-temperature environments.

[0017] 2. The organic nanoclay of this invention chemically modifies layered silicate minerals using an intercalating agent. The expanded interlamellar spacing forms an oriented barrier network within the asphalt matrix. This structure synergizes with the metal oxide skeleton generated during the thermal decomposition of surface-modified magnesium hydroxide to inhibit smoke diffusion and oxygen permeation. This dual-component synergistic flame-retardant mechanism enables the material to form a stable, expanded carbonized layer, even without the addition of halogen. This dual-pathway of physical barrier and chemical heat absorption blocks the combustion chain reaction, achieving a balance between flame retardancy and environmental protection.

[0018] 3. The unique spatial architecture of the composite modification system further optimizes material durability. The nanoclay's lamellar structure blocks direct UV radiation, reducing the rate of photooxidative degradation. Simultaneously, its surface active hydroxyl groups, along with the decomposition products of magnesium hydroxide, neutralize the acidic medium, forming a chemical buffer against acid rain corrosion. This synergistic protective mechanism significantly slows the molecular chain breakage of the matrix polymer, enabling the material to maintain long-lasting physical sealing properties even in harsh environments.

[0019] 4. The entire preparation process achieves efficient dispersion of the filler through staged gradient stirring. A silane coupling agent is used in the pretreatment stage to modify the surface energy of the magnesium hydroxide and reduce its interfacial tension with the organic phase. Ultrasonic-assisted intercalation ensures nanoscale exfoliation of the nanoclay within the matrix, ultimately forming a three-dimensional interpenetrating reinforced network during the high-speed shear stage. This process design is both operational and stable in industrial production, achieving performance breakthroughs without relying on high-cost nanomaterials or complex equipment. DETAILED DESCRIPTION

[0020] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0021] In this application, the sources of various raw materials are briefly described as follows: SBS modified asphalt: Star-shaped styrene-butadiene-styrene block copolymer modified asphalt was purchased from Sinopec Group. The model number is SBS-4303. The needle penetration of the modified asphalt (25°C) is 45-55 dmm and the softening point is ≥90°C.

[0022] Magnesium hydroxide powder (raw material before surface modification): particle size range 150 to 300 nm, industrial grade purity ≥99%, purchased from Shandong Yousuo Chemical Technology Co., Ltd., CAS No. 1309-42-8, model UFH-200.

[0023] Silane coupling agent: γ-(methacryloyloxy)propyltrimethoxysilane, purchased from Nanjing Shuguang Chemical Group Co., Ltd., CAS No. 2530-85-0, model KH-570; or γ-aminopropyltriethoxysilane, CAS No. 919-30-2, model KH-550.

[0024] Montmorillonite powder (base material before organic treatment: sodium montmorillonite, interlayer spacing 1.2 to 1.5 nm, purchased from Zhejiang Fenghong New Materials Co., Ltd., CAS No. 1318-93-0, model FHT-01.

[0025] Attapulgite powder (base material before organic treatment): fibrous nanomineral, specific surface area ≥220 m² / g, purchased from Jiangsu Xintuo New Materials Co., Ltd., CAS number 1337-76-4, model XTS-20.

[0026] Intercalant: hexadecyltrimethylammonium bromide, analytical grade, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No. 57-09-0, model H102286; or dioctadecyldimethylammonium chloride, CAS No. 107-64-2, model D101529.

[0027] Plasticizer: dioctyl phthalate, industrial grade, purchased from Shandong Lanfan Chemical Co., Ltd., CAS No. 117-81-7, model DOP-99; or epoxidized soybean oil, CAS No. 8013-07-8, model ESO-100.

[0028] Stabilizer: calcium stearate, purchased from Hangzhou Xinzeyuan Fine Chemical Co., Ltd., CAS No. 1592-23-0, model XS-18; or zinc stearate, CAS No. 557-05-1, model XS-28.

[0029] Antioxidant: Pentaerythritol tetrakis[β-3,5-di-tert-butyl-4-hydroxyphenylpropionate], namely antioxidant 1010, purchased from BASF China Co., Ltd., CAS No. 6683-19-8, model Irganox 1010.

[0030] Reinforced tire base: polyester tire base, unit area mass 150 to 250 g / m2, purchased from Jiangsu Hengli Chemical Fiber Co., Ltd., model PET-180; or glass fiber tire base, purchased from Taishan Glass Fiber Co., Ltd., model FGR-200.

[0031] The technical solution of this application is: A high-performance SBS waterproofing membrane containing magnesium hydroxide and nanoclay, the membrane being composed of the following raw materials in parts by mass: SBS modified asphalt 70-80 parts; 10-20 parts of surface-modified magnesium hydroxide; 3-8 parts of organized nanoclay; 5-10 parts of plasticizer; 2-5 parts of stabilizer; 1-3 parts of antioxidants.

[0032] The particle size of the surface-modified magnesium hydroxide is 150-300 nanometers, and the raw materials of the surface-modified magnesium hydroxide are reacted with a silane coupling agent at a temperature of 80-90 degrees Celsius for 30-50 minutes.

[0033] The organized nano-clay is obtained by reacting montmorillonite or attapulgite as a base material with an intercalation agent.

[0034] The mass ratio of the intercalant to the nanoclay substrate is 1:10-15.

[0035] The intercalant is hexadecyltrimethylammonium bromide or dioctadecyldimethylammonium chloride.

[0036] The plasticizer is at least one of dioctyl phthalate and epoxy soybean oil, the stabilizer is at least one of calcium stearate and zinc stearate, and the antioxidant is pentaerythritol tetra-β-3,5-di-tert-butyl-4-hydroxyphenyl propionate.

[0037] A method for preparing a high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay, the method comprising the following steps: (1) Raw material pretreatment stage: 10-20 parts of the raw material of surface-modified magnesium hydroxide are taken, stirred with a silane coupling agent at a mixing temperature of 80-90 degrees Celsius for 30-50 minutes, cooled, dried and crushed to obtain surface-modified magnesium hydroxide; 3-8 parts of the base material of the organic nanoclay are taken, ultrasonically dispersed with an intercalating agent in a water bath environment of 60-70 degrees Celsius for 40-60 minutes, and then centrifuged to obtain the organic nanoclay; (2) Mixing and plasticizing stage: heat 70-80 parts of SBS modified asphalt to 160-180°C to completely melt it; add 5-10 parts of plasticizer, 2-5 parts of stabilizer and 1-3 parts of antioxidant, maintain the stirring speed of 150-200 rpm and mix for 15-25 minutes; add the surface-modified magnesium hydroxide and organized nanoclay obtained in step (1), increase the stirring speed to 400-600 rpm, and continue stirring for 25-60 minutes; (3) Forming and shaping stage: The mixture obtained in step (2) is coated on the surface of the reinforced tire base through an extruder, and the coating thickness is controlled within the range of 1.5-4 mm; after calendering, it is cooled and shaped to obtain a finished coil.

[0038] In step (1), the ultrasonic dispersion has an operating power of 500-800 watts and an ultrasonic frequency of 25-40 kHz.

[0039] In step (3), the reinforced tire base layer is a polyester tire base or a glass fiber tire base material, and its unit area mass is 150-250 g / m².

[0040] In step (3), the material temperature during extrusion coating is maintained at 170-190°C, and the working pressure of the calendering treatment is controlled to be 5-10 MPa.

[0041] The technical solution of the present invention is further illustrated by the following examples and comparative examples, but the protection scope of the present invention is not limited thereto. Example 1

[0042] The raw materials and process for preparing the high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay in this embodiment are as follows: 80 parts of SBS modified asphalt 15 parts of surface-modified magnesium hydroxide (particle size 250 nm), the raw material was treated with silane coupling agent KH-570 at 85°C for 40 minutes 3 parts of organic nanoclay (montmorillonite base material) react with hexadecyltrimethylammonium bromide at a mass ratio of 1:12 Plasticizer dioctyl phthalate 10 parts 3.5 parts of calcium stearate as stabilizer 1 part of antioxidant tetra-β-3,5-di-tert-butyl-4-hydroxyphenylpropionate Preparation process: The magnesium hydroxide powder and the silane coupling agent were stirred at 85°C for 40 minutes and then dried and crushed; Montmorillonite powder and intercalant were dispersed in a 65°C water bath by ultrasonication at 700 W and 32 kHz for 50 min and centrifuged to dry. Heat the SBS modified asphalt to 170°C to melt, add plasticizer, stabilizer, and antioxidant, and stir at 180 rpm for 20 minutes; Add the pretreated material and stir at 500 rpm for 45 minutes; Extrusion coating at 180℃ on 200g / m2 polyester base, coating thickness of 3mm, calendering and cooling at 8MPa to set the shape. Example 2

[0043] In this embodiment, the same points as in Example 1 are not described in detail, and the differences are as follows: Raw materials and process parameters: 70 parts of SBS modified asphalt 20 parts of surface-modified magnesium hydroxide (particle size 300 nm), treated with KH-550 at 90°C for 50 minutes 8 parts of organic nanoclay (attapulgite base material) reacted with dioctadecyl dimethyl ammonium chloride at a mass ratio of 1:15 Plasticizer Epoxidized soybean oil 5 parts 5 parts of stabilizer zinc stearate 2 parts antioxidant Process adjustment: ultrasonic dispersion power 500 watts, extrusion temperature 190°C, calendering pressure 7 MPa, and the base material uses a 150 g / m2 glass fiber base. Example 3

[0044] In this embodiment, the same points as in Example 1 are not described in detail, and the differences are as follows: Raw materials and process parameters: 75 parts of SBS modified asphalt 10 parts of surface-modified magnesium hydroxide (particle size 150 nm), treated at 80°C for 30 minutes 5 parts of organic nanoclay and 1:10 ratio of intercalant Plasticizer dioctyl phthalate and epoxidized soybean oil 1:1 compound, totaling 7 parts 2 parts stabilizer 3 parts antioxidant Process characteristics: base material mixing and stirring at 150 rpm, filler dispersion at 600 rpm, coating thickness 1.5 mm. Comparative Example 1

[0045] In this comparative example, the same points as in Example 1 are not repeated here, and the differences are as follows: It does not contain surface-modified magnesium hydroxide and organized nanoclay components. Comparative Example 2

[0046] In this comparative example, the same points as Example 2 are not repeated here, and the differences are as follows: Unmodified magnesium hydroxide was added directly. Comparative Example 3

[0047] In this comparative example, the same points as in Example 3 are not repeated here, and the differences are as follows: Untreated montmorillonite powder was added directly. Comparative Example 4

[0048] In this comparative example, the same points as in Example 1 are not repeated here, and the differences are as follows: The ratio of intercalant to substrate was changed to 1:5. Comparative Example 5

[0049] In this comparative example, the same points as in Example 1 are not repeated here, and the differences are as follows: 5 parts of graphene were used instead of nanoclay. Performance test results and analysis

[0050] High-performance SBS waterproof membranes containing magnesium hydroxide and nanoclay were prepared according to the parameters of the embodiment and the comparative example, and the prepared products were tested. The test results are shown in Table 1.

[0051] As shown in Table 1, the tensile strength of the three examples (18.5-18.9 MPa) increased by over 68% compared to Comparative Example 1, attributed to the nanoscale dispersion effect of the surface-modified magnesium hydroxide in the matrix. Comparative Example 2 experienced a 31% decrease in strength due to agglomeration of the unmodified magnesium hydroxide, resulting in increased stress concentration points. While Comparative Example 4 exceeded the specified intercalant ratio, its strength was still 19% lower than that of the example group due to insufficient intercalation. Even with only 10 parts of surface-modified magnesium hydroxide used at a filler dispersion speed of 600 rpm, Example 3 maintained a strength of 18.7 MPa, demonstrating the critical role of high-speed shearing technology in dispersion efficiency.

[0052] Oxygen index data reveals a synergistic mechanism between the two components: the surface-modified magnesium hydroxide decomposes to absorb heat, lowering the system temperature, while the interlayer spacing of the organized nanoclay platelets increases to 2.8-3.2 nanometers, forming a physical barrier. Together, these two components suppress the combustion chain reaction. In Comparative Example 3, due to the untreated montmorillonite interlayer spacing of only 1.5 nanometers, the oxygen index deteriorates by 21%. In Comparative Example 2, the use of magnesium hydroxide alone, without the synergistic effect of the clay platelets, reduces the flame retardancy by 28%. In particular, in Example 2, the attapulgite fibrous structure forms a three-dimensional barrier network, achieving an oxygen index of 31%, surpassing the cost-effectiveness of the graphene system in Comparative Example 5.

[0053]

[0054] Acid etch mass loss data show that the Example group (1.6-1.9%) reduced mass loss by nearly 90% compared to Comparative Example 1 (17%). This is attributed to the nanoclay platelets blocking acid permeation channels while the magnesium hydroxide decomposition product, MgO, neutralizes H⁺ ions. Comparative Example 4, due to an imbalance in the intercalation agent ratio, did not fully open the interlayer channels of the montmorillonite, resulting in an acid etch loss rate of 5%. While Comparative Example 3 retains clay minerals, its acid resistance deteriorates by 215% due to the lack of the chemical buffering effect of magnesium hydroxide. In UV accelerated aging tests, the nanoclay platelets of Example 1 reflected over 85% of UV rays, achieving a 40% improvement in light shielding efficiency compared to Comparative Example 1. In Example 3, even a 1.5 mm thin layer maintained a 92% aging strength retention, demonstrating the applicability of this technical solution in scenarios requiring reduced raw material usage.

[0055] Test results show that the present invention achieves high flame retardancy, excellent weather resistance and outstanding mechanical properties of SBS waterproof membrane simultaneously under halogen-free conditions through the synergistic effect of surface-modified magnesium hydroxide and organized nanoclay, and significantly reduces production costs through a gradient dispersion process.

[0056] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay, characterized in that: The coil is composed of the following raw materials in parts by weight: SBS modified asphalt 70-80 parts; 10-20 parts of surface-modified magnesium hydroxide; 3-8 parts of organized nanoclay; 5-10 parts of plasticizer; 2-5 parts of stabilizer; 1-3 parts of antioxidants.

2. A high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to claim 1, characterized in that, The particle size of the surface-modified magnesium hydroxide is 150-300 nanometers, and the raw materials of the surface-modified magnesium hydroxide are reacted with a silane coupling agent at a temperature of 80-90 degrees Celsius for 30-50 minutes.

3. A high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to claim 1, characterized in that The organized nano-clay is obtained by reacting montmorillonite or attapulgite as a base material with an intercalation agent.

4. A high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to claim 3, characterized in that, The mass ratio of the intercalant to the nanoclay substrate is 1:10-15.

5. A high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to claim 3, characterized in that, The intercalant is hexadecyltrimethylammonium bromide or dioctadecyldimethylammonium chloride.

6. The high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to claim 1, characterized in that: The plasticizer is at least one of dioctyl phthalate and epoxy soybean oil, the stabilizer is at least one of calcium stearate and zinc stearate, and the antioxidant is pentaerythritol tetra-β-3,5-di-tert-butyl-4-hydroxyphenyl propionate.

7. A method for preparing a high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: (1) Raw material pretreatment stage: 10-20 parts of the raw material of surface-modified magnesium hydroxide are taken, stirred with a silane coupling agent, cooled, dried and crushed to obtain surface-modified magnesium hydroxide; 3-8 parts of the base material of the organic nanoclay are taken, ultrasonically dispersed with an intercalating agent in a water bath environment, and centrifuged to obtain the organic nanoclay; (2) Mixing and plasticizing stage: heat and melt 70-80 parts of SBS modified asphalt; add 5-10 parts of plasticizer, 2-5 parts of stabilizer and 1-3 parts of antioxidant, and stir evenly; add the surface-modified magnesium hydroxide and organized nanoclay obtained in step (1), and continue stirring; (3) Forming and shaping stage: The mixture obtained in step (2) is applied to the surface of the reinforced tire base through an extruder; after calendering, it is cooled and shaped to obtain a finished coil.

8. The method for preparing a high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to claim 7, characterized in that: In step (1), the ultrasonic dispersion has an operating power of 500-800 watts and an ultrasonic frequency of 25-40 kHz.

9. The method for preparing a high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to claim 7, wherein: In step (3), the reinforced tire base layer is a polyester tire base or a glass fiber tire base material, and its unit area mass is 150-250 g / m².

10. The method for preparing a high-performance SBS waterproof membrane containing magnesium hydroxide and nanoclay according to claim 7, characterized in that: In step (3), the material temperature during extrusion coating is maintained at 170-190°C, and the working pressure of the calendering treatment is controlled to be 5-10 MPa.

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