A fiber-reinforced self-adhesive modified bitumen waterproof membrane and its preparation method

Abstract

This application relates to the field of waterproof membrane technology, specifically disclosing a fiber-reinforced self-adhesive modified bitumen waterproof membrane and its preparation method. The fiber-reinforced self-adhesive modified bitumen waterproof membrane includes a modified bitumen layer, a base material, a PET film, and mineral particles. By weight, the modified bitumen layer comprises 25-35 parts of 70# bitumen, 5-8 parts of base oil, 1.5-2 parts of modifier, 5-9 parts of modified basalt fiber, and 6-10 parts of tire powder. The modified basalt fiber is obtained by surface modification of the esterification reaction product of terminal hydroxyl alkylphosphonic acid and palmitic acid. The fiber-reinforced self-adhesive modified bitumen waterproof membrane of this application possesses excellent mechanical properties and resistance to damp heat aging, resulting in a longer service life.

Description

Technical Field

[0001] This application relates to the field of waterproof membrane technology, and more specifically, to a fiber-reinforced self-adhesive modified bitumen waterproof membrane and its preparation method. Background Technology

[0002] Modified bitumen waterproof membranes are among the most widely used materials in the field of building waterproofing. They are made with bitumen as the base material, and polymer modifiers (such as SBS and SBR) are added to improve the high-temperature flowability and low-temperature brittleness of the bitumen. They are then combined with a composite reinforcing material (such as polyester or fiberglass). With the promotion of self-adhesive waterproof membranes, their advantages of requiring no hot-melt application and facilitating cold-applied construction have led to their widespread use in roofing, underground, and tunnel projects.

[0003] However, existing self-adhesive modified bitumen waterproof membranes still have several technical shortcomings. First, conventional self-adhesive modified bitumen coatings struggle to balance cohesion and peel strength during long-term use; increasing adhesion often leads to a decrease in coating cohesive strength, resulting in problems such as edge lifting and water seepage after construction. Second, bitumen itself is a viscoelastic material, prone to softening and flowing at high temperatures and cracking and failing at low temperatures under varying environmental temperatures. Although polymers such as SBS and SBR can partially improve this, the adaptability of a single modified system to extreme temperature environments remains limited. Furthermore, existing products often use large amounts of inert fillers such as heavy calcium carbonate and talc to reduce costs. These fillers have weak interfacial bonding with the bitumen matrix, easily leading to interfacial debonding under stress, resulting in decreased tensile strength and elongation at break of the coating. Uneven filler dispersion further degrades the material's mechanical properties. Additionally, some products use polymer films as reinforcing layers, but the interlayer bonding strength between the film and the modified bitumen coating is insufficient, making it prone to delamination under long-term immersion or humid and hot conditions, affecting the overall durability of the membrane.

[0004] Regarding the aforementioned technologies, the inventors have discovered that existing technologies attempt to reinforce asphalt coatings by adding fibrous materials (such as polyester fibers and lignin fibers). However, conventional short-cut fibers in existing technologies have poor compatibility with the asphalt matrix and are not easily dispersed uniformly, making it difficult to form an effective three-dimensional reinforcing network structure. Summary of the Invention

[0005] To improve the self-adhesive stability and mechanical strength of asphalt waterproof membranes and enhance their durability, this application provides a fiber-reinforced self-adhesive modified asphalt waterproof membrane and its preparation method.

[0006] In a first aspect, this application provides a fiber-reinforced self-adhesive modified bitumen waterproof membrane, employing the following technical solution:

[0007] A fiber-reinforced self-adhesive modified bitumen waterproof membrane includes a modified bitumen layer, a base material, a PET film, and mineral particles. By weight, the raw materials of the modified bitumen layer include 25-35 parts of 70# bitumen, 5-8 parts of base oil, 1.5-2 parts of modifier, 5-9 parts of modified basalt fiber, and 6-10 parts of tire powder. The modified basalt fiber is obtained by surface modification of the esterification reaction product of terminal hydroxyalkylphosphonic acid and palmitic acid.

[0008] By adopting the above technical solution, this application introduces basalt fibers modified by esterification products of terminal hydroxyl alkyl phosphonic acid and palmitic acid. The modifier obtained by the esterification reaction of the terminal hydroxyl groups in the terminal hydroxyl alkyl phosphonic acid and the carboxyl groups in the palmitic acid under specific conditions has long-chain alkyl groups of palmitic acid and long-chain alkyl groups of terminal hydroxyl alkyl phosphonic acid. The phosphonic acid group at one end can chemically bond with the silanol groups on the surface of the basalt fiber to form a stable anchoring structure. At the other end, the carbon chain of the long-chain alkyl phosphonic acid and the alkyl long chain introduced by the palmitic acid together form an oleophilic-hydrophobic molecular brush. This structure transforms the basalt fiber from hydrophilic to hydrophobic-oleophilic, enabling it to spontaneously bond deeply with the asphalt matrix. Furthermore, it promotes the rapid unwinding of the fiber under abrasive action and the construction of a continuous and uniform three-dimensional skeleton network structure. As a waterproof membrane prepared with modified asphalt layer, it can effectively inhibit the slippage of asphalt molecular chains under stress. Through the skeleton support effect, it significantly improves the cohesion and tensile strength of the modified asphalt layer, effectively balancing the relationship between high cohesion and high peel strength.

[0009] In addition, the high modulus and heat resistance of basalt fibers endow the modified bitumen layer with excellent high-temperature constraint. When heated, it can effectively limit the viscous flow of bitumen mortar, and when cooled, it can passivate the propagation of microcracks through bridging effect, thereby broadening the applicable temperature range of waterproof membrane.

[0010] Optionally, the preparation method of the modified basalt fiber includes the following steps:

[0011] S1: In an inert atmosphere, terminal hydroxyl alkylphosphonic acid, palmitic acid and catalyst are added to an organic solvent and stirred and mixed. The reaction is heated to obtain a reaction solution. The organic solvent is removed by rotary evaporation under reduced pressure. Then sodium bicarbonate solution is added, stirred and neutralized, and after standing, the mixture is extracted by separation. The solvent is removed again by rotary evaporation under reduced pressure and then placed in a drying oven for constant temperature drying to obtain a surface treatment agent.

[0012] S2: Mix basalt fiber and surface treatment agent, then add to a grinding disc and grind to obtain the desired product.

[0013] Optionally, the grinding conditions for basalt fiber and surface treatment agent in step S2 are 90-110℃ and 1200-1600r / min.

[0014] Optionally, the terminal hydroxyalkylphosphonic acid is selected from any one of 11-hydroxyundecylphosphonic acid, 12-hydroxydodecylphosphonic acid, 13-hydroxytetrazylphosphonic acid, 14-hydroxytetradecylphosphonic acid, 15-hydroxypentadecanylphosphonic acid, and 16-hydroxyhexadecylphosphonic acid.

[0015] By employing the above-mentioned technical solution, the surface treatment agent is mixed with basalt fiber and then surface modified using a butadiene grinding disc. Under the strong shearing and extrusion action of grinding, the surface of the basalt fiber instantly generates localized high pressure, high temperature, and highly active surface, inducing the phosphonic acid end groups in the surface treatment agent to achieve rapid and dense chemical anchoring with the basalt fiber. This mechanically assisted chemical reaction pathway not only greatly shortens the modification time, but more importantly, it constructs a uniformly thick, firmly bonded organic coating film on the fiber surface that cannot be washed away by conventional solvents. In addition, compared with traditional wet modification, the butadiene grinding disc method also significantly reduces the amount of organic solvent used, and the introduction of long palmitic acid chains endows the basalt fiber with superior resistance to damp heat aging.

[0016] Optionally, the modifier comprises SBR particles and SBS particles in a mass ratio of (2-3):(3-4).

[0017] Optionally, the SBS particles include star-shaped SBS particles and linear SBS particles with a mass ratio of (1-2):1.

[0018] By adopting the above technical solutions, star-shaped SBS, with its extremely high crosslinking density and physical crosslinking points, can construct a stable three-dimensional physical network under high temperature conditions, endowing the material with the modulus and cohesive strength required to resist flow deformation. The introduction of an appropriate amount of linear SBS effectively adjusts the problem of excessive rigidity of the star-shaped structure, playing a lubricating and compatibilizing role during processing, promoting the fine distribution of the micro-phase of SBS and SBR in the continuous phase of asphalt, and making the modifier network more evenly interspersed in the voids of the basalt fiber skeleton, which helps to improve the high-temperature deformation resistance and low-temperature crack resistance of the final modified asphalt layer.

[0019] Secondly, this application provides a method for preparing a fiber-reinforced self-adhesive modified bitumen waterproof membrane, employing the following technical solution:

[0020] A method for preparing a fiber-reinforced self-adhesive modified bitumen waterproof membrane includes the following steps:

[0021] S1: Heat 70# asphalt to 130-135℃, then add modified basalt fiber, stir at 300-500r / min for 0.5-1h, then raise the temperature to 190-200℃, add modifier, continue stirring for 1-2h, then add base oil and tire powder, continue stirring for 3-5h to obtain modified asphalt coating;

[0022] S2: After uncoiling and drying the base material, immerse it in the oiling tank and apply modified asphalt coating to both sides of the base material to form a modified asphalt layer on both sides.

[0023] S3: Cover the modified asphalt layers on both sides with PET film, sprinkle mineral granules, cool, emboss, and cool a second time to obtain the final product.

[0024] Optionally, in step S3, the temperature for coating the PET film is 50-70℃, and the temperature for sprinkling the mineral granules is 70-90℃.

[0025] By adopting the above technical solution, the modified basalt fiber was first dispersed at low temperature to effectively protect the integrity of the fiber, and then the SBS / SBR was completely swollen at high temperature to form a strong elastic network, ensuring the fullness of modification and effectively improving the durability of the waterproof membrane.

[0026] In summary, this application has the following beneficial effects:

[0027] 1. Because this application uses terminal hydroxyl alkyl phosphonic acid and palmitate esterification products as surface treatment agents to modify the surface of basalt fibers, the phosphonic acid groups form a chemical anchor with the surface of basalt fibers. The long-chain alkyl groups endow the fibers with excellent hydrophobic and oleophilic properties, which makes the basalt fibers uniformly dispersed in the asphalt and spontaneously form a continuous three-dimensional skeleton network. This effectively constrains the slippage of the asphalt molecular chains, efficiently transfers the external load to the high-strength fibers, and significantly improves the cohesion and tensile strength of the modified asphalt layer.

[0028] 2. In this application, the surface treatment agent is mixed with basalt fiber and then surface modified by grinding with a grinding disc. Under the strong shearing and extrusion of the grinding, the surface of the basalt fiber is instantly generated with local high pressure, high temperature and high activity, which induces the phosphonic acid end group in the surface treatment agent to achieve rapid and dense chemical anchoring with the basalt fiber. A uniform thickness and a strong organic coating film are constructed on the fiber surface. Compared with the traditional wet modification, it not only greatly shortens the modification time, but also significantly reduces the amount of organic solvent used. The introduction of palmitic acid long chain also endows the basalt fiber with better resistance to humid heat aging.

[0029] 3. In this application, a modified basalt fiber skeleton and an SBR / SBS composite elastomer modifier are preferably used to form an interpenetrating network structure. Under high temperature conditions, the fiber network can effectively constrain the viscous flow of asphalt, and the star-shaped SBS provides physical cross-linking support to prevent flow deformation. Under low temperature conditions, SBR can play a toughening role, and fiber bridging inhibits the propagation of microcracks. The synergistic effect of the two enables the waterproof membrane to have both excellent heat resistance and low temperature flexibility, improving the durability of the waterproof membrane in extreme temperature difference environments. Detailed Implementation

[0030] The present application will be further described in detail below with reference to embodiments and comparative examples.

[0031] raw material

[0032] Unless otherwise specified, all raw materials used in the embodiments and comparative examples in this application are commercially available products, specifically:

[0033] The base oil is a naphthenic oil, selected from Dongguan Beishan Lubricating Oil Co., Ltd., A1004;

[0034] SBR particles were selected from Guangdong Chuan'ao High-Tech Co., Ltd.

[0035] Linear SBS particles, selected from PB-5301 of Chi Mei Industrial Co., Ltd. in Taiwan, with a molecular weight of 150,000-200,000;

[0036] Star-shaped SBS particles, selected from Yanshan Petrochemical SBS 4402, with a molecular weight of 200,000-250,000;

[0037] Palmitic acid, selected from Aladdin Chemical Reagents, P432957;

[0038] 11-Hydroxyundecylphosphonic acid, selected from Aladdin Chemical Reagent, H463752;

[0039] Undecylphosphonic acid, selected from Aladdin Reagent, U162890;

[0040] Stearic acid, selected from Jiangsu Taike Palm Chemical Co., Ltd., grade 1840.

[0041] Preparation example of modified basalt fiber

[0042] Preparation Example 1

[0043] The preparation method of modified basalt fiber includes the following steps:

[0044] S1: In a 500mL four-necked flask, N2 was continuously introduced to replace the air in the flask at a flow rate of 30m / min to maintain the N2 atmosphere. 0.12mol of 11-hydroxyundecylphosphonic acid and 0.1mol of palmitic acid were added sequentially, along with 200mL of toluene as a solvent. After stirring and mixing until completely dissolved, 0.2wt% of p-toluenesulfonic acid (total mass of terminal hydroxyalkylphosphonic acid and palmitic acid) was added. The mixture was heated to 105℃ and stirred at a constant temperature for 5 hours to obtain a reaction solution. Methane was then removed by rotary evaporation under reduced pressure. 5wt% sodium bicarbonate solution was added, and the mixture was stirred to neutralize the solution. The pH was adjusted to 6.5-7. After standing and separating the layers, the mixture was extracted and washed. Residual water and trace amounts of solvent were removed by rotary evaporation under reduced pressure again. The mixture was then dried in a drying oven at a constant temperature to obtain the surface treatment agent.

[0045] S2: Mix basalt fiber and surface treatment agent at a mass ratio of 1:0.15 and add them to a grinding disc. Set the temperature to 100℃ and the rotation speed to 1400r / min and grind for 30min. The surface treatment agent will be evenly coated and anchored on the surface of the basalt fiber.

[0046] Preparation Example 2

[0047] The preparation method of modified basalt fiber includes the following steps:

[0048] S1: In a 500mL four-necked flask, N2 was continuously introduced to replace the air in the flask at a flow rate of 30m / min to maintain the N2 atmosphere. 0.125mol of 11-hydroxyundecylphosphonic acid and 0.1mol of palmitic acid were added sequentially, along with 200mL of toluene as a solvent. After stirring and mixing until completely dissolved, 0.2wt% of p-toluenesulfonic acid (total mass of terminal hydroxyalkylphosphonic acid and palmitic acid) was added. The mixture was heated to 105℃ and stirred at a constant temperature for 5 hours to obtain a reaction solution. Methane was then removed by rotary evaporation under reduced pressure. 5wt% sodium bicarbonate solution was added, and the mixture was stirred to neutralize the solution. The pH was adjusted to 6.5-7. After standing and separating the layers, the mixture was extracted and washed. Residual water and trace amounts of solvent were removed by rotary evaporation under reduced pressure again. The mixture was then dried in a drying oven at a constant temperature to obtain the surface treatment agent.

[0049] S2: Mix basalt fiber and surface treatment agent at a mass ratio of 1:0.1 and add them to a grinding disc. Set the temperature to 90℃ and the rotation speed to 1600r / min and grind for 30min. The surface treatment agent will be evenly coated and anchored on the surface of the basalt fiber.

[0050] Preparation Example 3

[0051] The preparation method of modified basalt fiber includes the following steps:

[0052] S1: In a 500mL four-necked flask, N2 was continuously introduced to replace the air in the flask at a flow rate of 30m / min to maintain the N2 atmosphere. 0.115mol of 11-hydroxyundecylphosphonic acid and 0.1mol of palmitic acid were added sequentially, along with 200mL of toluene as a solvent. After stirring and mixing until completely dissolved, 0.2wt% of p-toluenesulfonic acid (total mass of terminal hydroxyalkylphosphonic acid and palmitic acid) was added. The mixture was heated to 105℃ and stirred at a constant temperature for 5 hours to obtain a reaction solution. Methane was then removed by rotary evaporation under reduced pressure. 5wt% sodium bicarbonate solution was added, and the mixture was stirred to neutralize the solution. The pH was adjusted to 6.5-7. After standing and separating the layers, the mixture was extracted and washed. Residual water and trace amounts of solvent were removed by rotary evaporation under reduced pressure again. The mixture was then dried in a drying oven at a constant temperature to obtain the surface treatment agent.

[0053] S2: Mix basalt fiber and surface treatment agent at a mass ratio of 1:0.12 and add them to a grinding disc. Set the temperature to 110℃ and the rotation speed to 1200r / min and grind for 30min. The surface treatment agent will be evenly coated and anchored on the surface of the basalt fiber.

[0054] Preparation Example 4

[0055] The preparation method of modified basalt fiber includes the following steps:

[0056] Basalt fiber and stearic acid are mixed at a mass ratio of 1:0.15 and added to a grinding disc. The temperature is set to 100℃ and the rotation speed is 1400r / min. Grinding is carried out for 30 minutes. The stearic acid is uniformly coated and anchored on the surface of the basalt fiber.

[0057] Preparation Example 5

[0058] The preparation method of modified basalt fiber includes the following steps:

[0059] Basalt fiber and undecylphosphonic acid are mixed at a mass ratio of 1:0.15 and added to a grinding disc. The temperature is set at 100℃ and the rotation speed is 1400r / min for 30min. Undecylphosphonic acid is uniformly coated and anchored on the surface of basalt fiber, thus obtaining the product.

[0060] Example

[0061] Example 1

[0062] A fiber-reinforced self-adhesive modified bitumen waterproof membrane includes a modified bitumen layer, a base material, a PET film, and mineral particles. By weight, the raw materials of the modified bitumen layer include 30.5 parts of 70# bitumen, 5-8 parts of naphthenic oil, 1.8 parts of modifier, 7.5 parts of modified basalt fiber, 8 parts of tire powder, 21 parts of fly ash, and 17 parts of stone powder. The modified basalt fiber is prepared by Preparation Example 1. The modifier includes SBR particles and SBS particles in a mass ratio of 2:3. The SBS particles include star-shaped SBS particles and linear SBS particles in a mass ratio of 1:1.

[0063] The preparation method of the above-mentioned fiber-reinforced self-adhesive modified bitumen waterproof membrane includes the following steps:

[0064] S1: Heat 70# asphalt to 130℃, then add modified basalt fiber, stir at 500r / min for 0.5h, then raise the temperature to 190℃, add modifier, continue stirring for 2h, then add naphthenic oil, tire powder, fly ash and stone powder, continue stirring for 5h to obtain modified asphalt coating.

[0065] S2: Select a weight of 200g / m 2The polyester base is 1.2mm thick. After the base is unrolled and dried, it is immersed in a pre-impregnation oil bath. The temperature of the pre-impregnation oil bath is maintained at 190℃. After the dried base is pre-impregnated, the excess oil is squeezed out and then immersed in an oil coating bath. Modified asphalt coating is applied to both sides of the base. After the modified asphalt layer is formed on both sides, it is fixed in thickness by a thickness fixing device. The coating temperature is maintained at 180℃.

[0066] S3: At 50℃, PET film is applied to the surface of the modified asphalt layer on both sides, and the final film thickness on one side is 0.02mm. Then, mineral particles are sprinkled at 70℃, cooled, embossed, and cooled a second time to obtain the finished product with a thickness of (1.55±0.2)mm.

[0067] Example 2

[0068] A fiber-reinforced self-adhesive modified bitumen waterproof membrane includes a modified bitumen layer, a base material, a PET film, and mineral particles. By weight, the raw materials of the modified bitumen layer include 25 parts of 70# bitumen, 5 parts of naphthenic oil, 1.5 parts of modifier, 5 parts of modified basalt fiber, 6 parts of tire powder, 15 parts of fly ash, and 25 parts of stone powder. The modified basalt fiber is prepared by Preparation Example 1. The modifier includes SBR particles and SBS particles in a mass ratio of 3:4. The SBS particles include star-shaped SBS particles and linear SBS particles in a mass ratio of 2:1.

[0069] The preparation method of the above-mentioned fiber-reinforced self-adhesive modified bitumen waterproof membrane includes the following steps:

[0070] S1: Heat 70# asphalt to 135℃, then add modified basalt fiber, stir at 300r / min for 1h, then raise the temperature to 200℃, add modifier, continue stirring for 1h, then add naphthenic oil, tire powder, fly ash and stone powder, continue stirring for 3h to obtain modified asphalt coating.

[0071] S2: Select a weight of 200g / m 2 The polyester base material has a thickness of 1.2mm. After the base material is unrolled and dried, it is immersed in a pre-impregnation oil bath. The temperature of the pre-impregnation oil bath is maintained at 200℃. After the dried base material is pre-impregnated, the excess oil is squeezed out and then immersed in an oil coating bath. Modified asphalt coating is applied to both sides of the base material. After the modified asphalt layer is formed on both sides, it is fixed in thickness by a thickness fixing device. The coating temperature is maintained at 200℃.

[0072] S3: At 70℃, PET film is applied to the surface of the modified asphalt layer on both sides, and the final film thickness on one side is 0.02mm. Then, mineral particles are sprinkled at 90℃, cooled, embossed, and cooled a second time to obtain the finished product with a thickness of (1.55±0.2)mm.

[0073] Example 3

[0074] A fiber-reinforced self-adhesive modified bitumen waterproof membrane includes a modified bitumen layer, a base material, a PET film, and mineral particles. By weight, the raw materials of the modified bitumen layer include 35 parts of 70# bitumen, 8 parts of naphthenic oil, 2 parts of modifier, 9 parts of modified basalt fiber, 10 parts of tire powder, 25 parts of fly ash, and 15 parts of stone powder. The modified basalt fiber is prepared by Preparation Example 1. The modifier includes SBR particles and SBS particles in a mass ratio of 2:4. The SBS particles include star-shaped SBS particles and linear SBS particles in a mass ratio of 1.5:1.

[0075] The preparation method of the above-mentioned fiber-reinforced self-adhesive modified bitumen waterproof membrane includes the following steps:

[0076] S1: Heat 70# asphalt to 130℃, then add modified basalt fiber, stir at 400r / min for 0.8h, then raise the temperature to 190℃, add modifier, continue stirring for 1.5h, then add naphthenic oil, tire powder, fly ash and stone powder, continue stirring for 4h to obtain modified asphalt coating;

[0077] S2: Select a weight of 200g / m 2 The polyester base is 1.2mm thick. After the base is unrolled and dried, it is immersed in a pre-impregnation oil bath. The temperature of the pre-impregnation oil bath is maintained at 190℃. After the dried base is pre-impregnated, the excess oil is squeezed out and then immersed in an oil coating bath. Modified asphalt coating is applied to both sides of the base layer. After the modified asphalt layer is formed on both sides, it is fixed in thickness by a thickness fixing device. The coating temperature is maintained at 200℃.

[0078] S3: At 60℃, PET film is applied to the surface of the modified asphalt layer on both sides, and the final film thickness on one side is 0.02mm. Then, mineral particles are sprinkled at 80℃, cooled, embossed, and cooled a second time to obtain the finished product with a thickness of (1.55±0.2)mm.

[0079] Example 4

[0080] A fiber-reinforced self-adhesive modified bitumen waterproof membrane differs from Example 1 only in that the modified basalt fiber in the modified bitumen layer raw material is prepared in Example 2.

[0081] Example 5

[0082] A fiber-reinforced self-adhesive modified bitumen waterproof membrane differs from Example 1 only in that the modified basalt fiber in the modified bitumen layer raw material is prepared by Example 3.

[0083] Example 6

[0084] A fiber-reinforced self-adhesive modified bitumen waterproof membrane differs from Example 1 only in that the SBS particles in the modified bitumen layer raw material are only star-shaped SBS particles.

[0085] Example 7

[0086] A fiber-reinforced self-adhesive modified bitumen waterproof membrane differs from Example 1 only in that the SBS particles in the modified bitumen layer raw material are only linear SBS particles.

[0087] Comparative Example

[0088] Comparative Example 1

[0089] A fiber-reinforced self-adhesive modified bitumen waterproof membrane differs from Example 1 only in that the modified basalt fiber in the modified bitumen layer raw material is prepared by Example 4.

[0090] Comparative Example 2

[0091] A fiber-reinforced self-adhesive modified bitumen waterproof membrane differs from Example 1 only in that the modified basalt fiber in the modified bitumen layer raw material is prepared by Example 5.

[0092] Comparative Example 3

[0093] A fiber-reinforced self-adhesive modified bitumen waterproof membrane differs from Example 1 only in that modified basalt fiber is not added to the modified bitumen layer raw material.

[0094] Performance testing

[0095] According to the requirements of GB / T 35467-2017 and GB / T55030-2022, the fiber-reinforced self-adhesive modified bitumen waterproof membranes prepared in Examples 1-7 and Comparative Examples 1-3 were subjected to performance tests for tensile strength, heat resistance, low-temperature flexibility and joint peel strength. Each group of tests was performed 3 times, and the average value of the 3 test results was taken as the final result and recorded in Table 1.

[0096] Table 1

[0097]

[0098] According to the performance test results of Examples 1-5 and Comparative Example 3 in Table 1, Examples 1-5 use terminal hydroxyl alkylphosphonic acid and palmitate esterification products as surface treatment agents to modify basalt fibers, forming a skeleton in the asphalt matrix. This works synergistically with the composite modifiers formed by SBR / star-shaped and linear SBS to form an interpenetrating network structure. On the one hand, this endows the modified asphalt layer with excellent mechanical properties, with the joint peel strength remaining stable at 1.8-1.9 N / mm. This is due to the oleophilic modification of the fibers, which enhances the cohesion of the modified asphalt layer without reducing adhesion, thus achieving a balance between cohesion and peel strength. On the other hand, it effectively constrains the viscous flow of asphalt at high temperatures, preventing flow deformation, and effectively toughens the material at low temperatures, inhibiting the propagation of microcracks, significantly improving the durability of the waterproof membrane under extreme temperature conditions.

[0099] Based on the performance test results of Examples 1 and 6-7, it can be seen that in Example 6, only star-shaped SBS was used as the modifier, resulting in a significant decrease in tensile strength. In Example 7, only linear SBS was used, leading to a decrease in tensile strength and a deterioration in low-temperature flexibility. It can be seen that although star-shaped SBS has high cohesive strength and high crosslinking density, it has poor toughness and self-adhesion. On the other hand, although linear SBS has better processing performance and compatibility, it has poor cohesive support strength. When the two are compounded in a reasonable ratio, a balance between strength and toughness can be effectively achieved.

[0100] Based on the performance test results of Example 1 and Comparative Examples 1-2, it can be seen that this application uses terminal hydroxyl alkyl phosphonic acid and palmitate esterification products as surface treatment agents. After mixing with basalt fibers and grinding, the surface of basalt fibers is modified. The phosphonic acid groups form a chemical anchor with the surface of basalt fibers, and the long-chain alkyl groups endow the fibers with excellent hydrophobic and oleophilic properties, so that the basalt fibers are uniformly dispersed in the asphalt and spontaneously form a continuous three-dimensional skeleton network, which effectively constrains the slippage of the asphalt molecular chains and efficiently transfers the external load to the high-strength fibers, significantly improving the cohesion and tensile strength of the modified asphalt layer. Stearic acid, on the other hand, is only a physical coating of single-chain fatty acids and only weakly binds to the fiber surface. It has no chemical anchor and is prone to debonding under stress. It cannot effectively build a stable skeleton network and has limited effect on improving the cohesion of asphalt. It cannot achieve a balance between cohesion and peel strength. In Comparative Example 2, there is no palmitic acid structure, so a double long-chain oleophilic structure cannot be formed. The interface anchoring and compatibility are insufficient, and it is also impossible to achieve a balance between cohesion and peel strength.

[0101] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A fiber-reinforced self-adhesive modified bitumen waterproof membrane, comprising a modified bitumen layer, a base material, a PET film, and mineral granules, characterized in that, The modified asphalt layer comprises, by weight, 25-35 parts of 70# asphalt, 5-8 parts of base oil, 1.5-2 parts of modifier, 5-9 parts of modified basalt fiber and 6-10 parts of tire powder. The modified basalt fiber is obtained by surface modification of the esterification reaction product of terminal hydroxyalkylphosphonic acid and palmitic acid.

2. The fiber-reinforced self-adhesive modified bitumen waterproof membrane according to claim 1, characterized in that, The method for preparing the modified basalt fiber includes the following steps: S1: In an inert atmosphere, terminal hydroxyl alkylphosphonic acid, palmitic acid and catalyst are added to an organic solvent and stirred and mixed. The reaction is heated to obtain a reaction solution. The organic solvent is removed by rotary evaporation under reduced pressure. Then sodium bicarbonate solution is added, stirred and neutralized, and after standing, the mixture is extracted by separation. The solvent is removed again by rotary evaporation under reduced pressure and then placed in a drying oven for constant temperature drying to obtain a surface treatment agent. S2: Mix basalt fiber and surface treatment agent, then add to a grinding disc and grind to obtain the desired product.

3. The fiber-reinforced self-adhesive modified bitumen waterproof membrane according to claim 2, characterized in that, In step S2, the grinding conditions for basalt fiber and surface treatment agent are 90-110℃ and 1200-1600r / min.

4. The fiber-reinforced self-adhesive modified bitumen waterproof membrane according to claim 2, characterized in that, The terminal hydroxyalkylphosphonic acid is selected from any one of 11-hydroxyundecylphosphonic acid, 12-hydroxydodecylphosphonic acid, 13-hydroxytetrazylphosphonic acid, 14-hydroxytetradecylphosphonic acid, 15-hydroxypentadecanylphosphonic acid, and 16-hydroxyhexadecylphosphonic acid.

5. The fiber-reinforced self-adhesive modified bitumen waterproof membrane according to claim 1, characterized in that, The modifier comprises SBR particles and SBS particles in a mass ratio of (2-3):(3-4).

6. The fiber-reinforced self-adhesive modified bitumen waterproof membrane according to claim 5, characterized in that, The SBS particles include star-shaped SBS particles and linear SBS particles with a mass ratio of (1-2):

1.

7. The method for preparing the fiber-reinforced self-adhesive modified bitumen waterproof membrane according to any one of claims 1-6, characterized in that, Includes the following steps: S1: Heat 70# asphalt to 130-135℃, then add modified basalt fiber, stir at 300-500r / min for 0.5-1h, then raise the temperature to 190-200℃, add modifier, continue stirring for 1-2h, then add base oil and tire powder, continue stirring for 3-5h to obtain modified asphalt coating; S2: After uncoiling and drying the base material, immerse it in the oiling tank and apply modified asphalt coating to both sides of the base material to form a modified asphalt layer on both sides. S3: Cover the modified asphalt layers on both sides with PET film, sprinkle mineral granules, cool, emboss, and cool a second time to obtain the final product.

8. The method for preparing the fiber-reinforced self-adhesive modified bitumen waterproof membrane according to claim 7, characterized in that, In step S3, the temperature for coating with PET film is 50-70℃, and the temperature for sprinkling mineral granules is 70-90℃.

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