Composite modified microfiber cloth, preparation method thereof, fiber-reinforced self-repairing permeable crystalline waterproofing membrane and application thereof

Abstract

The application relates to the field of building waterproofing, and discloses a composite modified microfiber cloth, a preparation method thereof, a fiber-reinforced self-repairing permeation crystallization waterproof roll material and application thereof. The method for preparing the composite modified microfiber cloth comprises the following steps: (1) stirring and mixing nylon 6, polyethylene and halloysite nanotubes at a proportion of 8-10:8-10:1 in weight ratio, melt blending and spinning to obtain fibers; after disorderly stacking treatment, the fibers are contacted with a polyurethane solution to perform soaking treatment, and a non-woven fabric is obtained; (2) the non-woven fabric is contacted and mixed with a coagulation solution to obtain a microfiber base cloth; (3) in the presence of an acid solution, the microfiber base cloth is subjected to acidification treatment to obtain an intermediate I; and (4) in the presence of a modification solution, the intermediate I is subjected to modification treatment to obtain the composite modified microfiber cloth. The fiber-reinforced self-repairing permeation crystallization waterproof roll material has excellent self-repairing and permeation crystallization functions.

Description

Technical Field

[0001] This invention relates to the field of building waterproofing, specifically to a composite modified microfiber fabric and its preparation method, a fiber-reinforced self-healing penetrating crystallizing waterproof membrane and its application. Background Technology

[0002] Traditional waterproof membranes are mainly made of materials such as asphalt and fiberglass cloth. During long-term use, the waterproof performance of the membrane will gradually decrease due to asphalt aging and fiberglass cloth damage, resulting in leakage and other problems. Furthermore, once the membrane cracks or is damaged, it cannot repair itself and requires manual repair, which is time-consuming and labor-intensive.

[0003] To address these issues, researchers have attempted to add various modified materials to waterproof membranes to improve their waterproofing performance and self-healing capabilities. For example, adding nanomaterials can improve the mechanical properties and aging resistance of waterproof membranes; adding self-healing materials can endow them with self-healing functions. However, existing waterproof membranes still struggle to fully achieve self-healing and penetration crystallization functions, thus failing to meet practical application requirements.

[0004] CN116640456A discloses a supported halloysite nanotube modified asphalt and its preparation method. This supported halloysite nanotube modified asphalt exhibits stable component content and, when applied to pavement structural layers, can delay asphalt aging and extend the service life of asphalt pavements. However, the preparation method for this prior art still requires further optimization.

[0005] CN116970354A discloses a polymer waterproof membrane and its preparation method. The waterproof membrane comprises, from top to bottom, an asphalt layer, a base layer, and an adhesive layer. By weight, the asphalt layer contains 120-150 parts asphalt base material, 10-20 parts modified plant fiber, 8-12 parts sodium silicate, 5-8 parts modified nano-silica, and 10-15 parts alumina powder. This polymer waterproof membrane exhibits good tensile and waterproof properties, with uniform and stable internal components, allowing for long-term effectiveness and suitability for harsh environments. However, this waterproof membrane lacks penetration crystallization and self-healing properties, and therefore cannot improve the impermeability and waterproof performance of subsequently poured concrete after construction.

[0006] Therefore, it is of great significance to develop a new type of waterproof membrane with a long service life, excellent waterproof performance, and the ability to self-heal and penetrate crystallize. Summary of the Invention

[0007] The purpose of this invention is to provide a waterproof membrane with excellent waterproof performance and self-healing and penetrating crystallization functions.

[0008] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a composite modified microfiber fabric, the method comprising:

[0009] (1) Nylon 6, polyethylene and halloysite nanotubes are stirred and mixed in a weight ratio of 8-10:8-10:1, and melt-blended and spun to obtain fibers; the fibers are then subjected to disordered stacking treatment and then contacted with polyurethane solution for immersion treatment to obtain nonwoven fabric.

[0010] (2) The nonwoven fabric is contacted and mixed with the coagulation liquid to obtain a microfiber base fabric; the volume fraction of the solute in the coagulation liquid is 30-40%, and the solute is selected from at least one of N,N-dimethylformamide, decahydronaphthalene and xylene;

[0011] (3) In the presence of an acidic solution, the microfiber base fabric is acidified to obtain intermediate I;

[0012] (4) In the presence of a modifying solution, the intermediate I is modified to obtain the composite modified microfiber fabric; the modifying solution contains a composite modifier with a concentration of 25-35 wt%, the composite modifier being a combination of silicate, phosphate, ethylenediaminetetraacetate and gluconate in a weight ratio of 7-9:5-7:4-6:1.

[0013] A second aspect of the present invention provides a composite modified microfiber fabric prepared by the method described in the first aspect above.

[0014] A third aspect of the present invention provides a fiber-reinforced self-healing penetrating crystalline waterproof membrane, the waterproof membrane comprising, from top to bottom, a composite modified microfiber cloth, a modified bitumen layer, a polyester base, a modified bitumen layer and a release membrane; wherein the composite modified microfiber cloth is the composite modified microfiber cloth described in the second aspect above.

[0015] The fourth aspect of this invention provides the application of the waterproof membrane described in the third aspect above in the field of building waterproofing.

[0016] Through the above technical solution, the present invention has at least the following beneficial technical effects:

[0017] (1) The composite modified microfiber fabric prepared by the method of preparing composite modified microfiber fabric provided by the present invention is applied to waterproof membrane, and the resulting waterproof membrane has excellent self-healing function and penetration crystallization function.

[0018] (2) The waterproof membrane provided by the present invention has excellent waterproof performance, can maintain good waterproof effect for a long time, effectively avoid leakage and other problems, and extend the service life of the waterproof membrane.

[0019] (3) In this invention, nylon 6, polyethylene and halloysite nanotubes are used to prepare composite microfiber cloth, which is then combined with modified bitumen and other materials to make the prepared waterproof membrane exhibit excellent comprehensive performance. Detailed Implementation

[0020] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] As previously stated, a first aspect of the present invention provides a method for preparing a composite modified microfiber fabric, the method comprising:

[0022] (1) Nylon 6, polyethylene and halloysite nanotubes are stirred and mixed in a weight ratio of 8-10:8-10:1, and melt-blended and spun to obtain fibers; the fibers are then subjected to disordered stacking treatment and then contacted with polyurethane solution for immersion treatment to obtain nonwoven fabric.

[0023] (2) The nonwoven fabric is contacted and mixed with the coagulation liquid to obtain a microfiber base fabric; the volume fraction of the solute in the coagulation liquid is 30-40%, and the solute is selected from at least one of N,N-dimethylformamide, decahydronaphthalene and xylene;

[0024] (3) In the presence of an acidic solution, the microfiber base fabric is acidified to obtain intermediate I;

[0025] (4) In the presence of a modifying solution, the intermediate I is modified to obtain the composite modified microfiber fabric; the modifying solution contains a composite modifier with a concentration of 25-35 wt%, the composite modifier being a combination of silicate, phosphate, ethylenediaminetetraacetate and gluconate in a weight ratio of 7-9:5-7:4-6:1.

[0026] According to a preferred embodiment, in step (1), the stirring and mixing temperature is 280-285°C, and the solid content of the polyurethane solution is 30%-65%.

[0027] According to a more preferred embodiment, in step (1), the soaking conditions include: a temperature of 40-50°C and a time of 0.5-2h.

[0028] Preferably, in step (1), the halloysite carbon nanotubes can be obtained by ultrasonic cleaning to remove surface impurities and then drying before use.

[0029] According to a preferred embodiment, in step (2), the contact mixing conditions include: a temperature of 40-55°C and a time of 0.5-2h.

[0030] According to a more preferred embodiment, in step (2), the solvent in the coagulation liquid is deionized water.

[0031] According to a preferred embodiment, in step (3), the H in the acidic solution + The concentration is 0.45-0.55 mol / L.

[0032] Preferably, in step (3), the acidic solution is selected from hydrochloric acid and / or sulfuric acid.

[0033] According to a more preferred embodiment, in step (3), the acidification treatment conditions include: a temperature of 20-30°C and a time of 2-4 hours.

[0034] According to a preferred embodiment, in step (3), the microfiber base fabric is further subjected to water washing and drying after acidification treatment to obtain the intermediate I.

[0035] According to a more preferred embodiment, in step (4), the solvent of the modified solution is deionized water.

[0036] Preferably, in step (4), the modification treatment conditions include: a pressure of 0.2-0.5 MPa, a temperature of 25-50°C, and a time of 1-1.5 h. The inventors of this invention have discovered that, under this preferred condition, the fiber-reinforced self-healing penetrating crystalline waterproof membrane prepared by this invention exhibits superior penetrating crystalline properties.

[0037] More preferably, in step (4), the silicate is selected from at least one of sodium silicate, potassium silicate and ammonium silicate; the phosphate is selected from at least one of sodium phosphate, potassium phosphate and ammonium phosphate; the ethylenediaminetetraacetic acid salt is disodium ethylenediaminetetraacetate and / or tetrasodium ethylenediaminetetraacetate; and the gluconate is selected from at least one of sodium gluconate, potassium gluconate and calcium gluconate.

[0038] In this invention, there are no special requirements for the volume of the coagulation liquid, the acidic solution, and the modified solution, as long as the nonwoven fabric, the microfiber base fabric, or the intermediate I is completely immersed.

[0039] Preferably, the method for preparing composite modified microfiber fabric further includes, in step (2), the material obtained by the contact mixing is sequentially subjected to water washing and drying treatment to obtain the microfiber base fabric.

[0040] Preferably, the conditions for the water washing treatment include: a temperature of 50-60℃ and a time of 1-5 hours.

[0041] Preferably, the drying conditions include a temperature of 120-150℃ and a time of 1-2 hours.

[0042] As previously stated, the second aspect of the present invention provides a composite modified microfiber fabric prepared by the method described in the first aspect.

[0043] Preferably, the basis weight of the composite modified microfiber fabric is 150-450 g / m². 2 .

[0044] As mentioned above, a third aspect of the present invention provides a fiber-reinforced self-healing penetrating crystalline waterproof membrane, characterized in that the waterproof membrane comprises, from top to bottom, a composite modified microfiber cloth, a modified bitumen layer, a polyester base, a modified bitumen layer, and a release membrane; wherein the composite modified microfiber cloth is the composite modified microfiber cloth described in the second aspect above.

[0045] Preferably, the modified asphalt layer is formed from modified asphalt layer raw materials, which contain base asphalt, oil, polymer modifier, tire rubber powder, penetrant and filler;

[0046] Based on the total weight of the modified asphalt layer raw materials, the content of the base asphalt is 40-60 wt%, the content of the oil is 1-10 wt%, the content of the polymer modifier is 3-10 wt%, the content of the tire rubber powder is 5-14 wt%, the content of the penetrant is 0.5-3 wt%, and the content of the filler is 25-45 wt%.

[0047] More preferably, the oil is selected from at least one of aromatic oil, anti-corrosion oil, and base oil.

[0048] More preferably, the polymer modifier is selected from at least one of butadiene-styrene-butadiene triblock copolymer (SBS), modified styrene-butadiene rubber (SSBR), butadiene-isoprene-butadiene triblock copolymer (SIS), and C5 hydrogenated resin.

[0049] Particularly preferably, the penetrant is selected from at least one of sodium silicate, sodium metasilicate, and calcium hydroxide.

[0050] Preferably, in the modified asphalt layer raw material, the base asphalt is selected from at least one of 70# asphalt, 90# asphalt and 200# asphalt.

[0051] More preferably, the average diameter of the tire rubber powder is 180-250 μm.

[0052] More preferably, the filler is selected from at least one of talc, heavy calcium carbonate, montmorillonite, kaolin, and metakaolin, and the average diameter of the filler is 15-80 μm.

[0053] According to one specific embodiment, the steps for preparing the fiber-reinforced self-healing penetrating crystalline waterproof membrane include:

[0054] S1: Add the base asphalt and oil to a reactor preheated to 130-150℃, stir and react for 20-30 minutes to obtain mixture I;

[0055] S2: At 170-190℃, the polymer modifier and the mixture I are mixed, and then tire rubber powder and penetrant are added. The mixture is stirred and reacted for 2.5-3.5 hours to obtain mixture II.

[0056] S3: Keeping the temperature constant, stir the filler and the mixture II for 1-1.5 hours to obtain modified asphalt;

[0057] S4: The modified bitumen is extruded and formed on a polyester base, and then composite modified microfiber cloth and a release film are attached to the upper and lower surfaces. The thickness of the roll is controlled at 3.0±0.2mm to obtain the fiber-reinforced self-healing penetrating crystalline waterproof roll.

[0058] According to a preferred embodiment, the polyester base material is pretreated by impregnation with the matrix bitumen, and the basis weight of the polyester base material is 130-310 g / m³. 2 .

[0059] According to a more preferred embodiment, the release film is a PET release film and / or a PE release film.

[0060] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all instruments and raw materials used are commercially available products.

[0061] The following examples include some of the raw materials used and their sources:

[0062] Nylon 6: Grade J2700, purchased from Juheshun Company;

[0063] Polyethylene: Grade 4000D, purchased from Zhejiang Qianxilong Fiber Co., Ltd.;

[0064] Halloysite nanotubes: grade JN-4, purchased from Guangdong Jina Company;

[0065] Aromatic oil: Grade R9, purchased from Guangzhou Dagang Company;

[0066] 70# asphalt: purchased from Jingbo Petrochemical Company;

[0067] 90# asphalt: purchased from Jingbo Petrochemical Company;

[0068] Base oil: Grade 61#, purchased from Guangdong Geyang Company;

[0069] Reduced-line oil: purchased from Hualu Petrochemical Company;

[0070] Butadiene-styrene-butadiene triblock copolymer (SBS): Grade 411#, purchased from LG Corporation;

[0071] Modified styrene-butadiene rubber (SSBR): Grade 1901H, purchased from Yueyang Petrochemical Company;

[0072] Butadiene-isoprene-butadiene triblock copolymer (SIS): grade 1105, purchased from Yueyang Petrochemical Company;

[0073] Polyurethane solution: solid content 35%, purchased from Yantai Wanhua Company;

[0074] C5 hydrogenated resin: molecular weight 1400, purchased from Guangzhou Tiankai Chemical Co., Ltd.

[0075] Tire rubber powder: average diameter 250μm, purchased from Hunan Zhongyu Company;

[0076] Trihydrate: average diameter 75μm, purchased from Qixia Rongguan Company;

[0077] Metakaolin: with an average diameter of 45 μm, purchased from Jiaozuo Yukun Mining Company;

[0078] Polyester base material: purchased from Hubei Youbu Company;

[0079] PET release film and PE release film: purchased from Shanghai Youpusi Company.

[0080] Preparation Example 1

[0081] This preparation example illustrates the preparation of the composite modified microfiber fabric provided by the present invention, including the following steps:

[0082] (1) The halloysite nanotubes were ultrasonically cleaned for 60 min, centrifuged and dried to obtain halloysite nanotubes.

[0083] (2) Weigh 10 kg of halloysite nanotubes, mix nylon 6, polyethylene and halloysite nanotubes in a weight ratio of nylon 6: polyethylene: halloysite nanotubes = 10: 9: 1, stir and heat to 280°C to melt it, then extrude it through a screw extruder and spray it out from the spinneret through a metering pump to form fibers.

[0084] (3) The fibers are randomly stacked and then immersed in a polyurethane solution at 40°C for 30 minutes to obtain the nonwoven fabric required by the present invention.

[0085] (4) The nonwoven fabric is contacted and mixed with an aqueous solution of N,N-dimethylformamide (DMF) with a concentration of 35% by volume for 1 hour, and the temperature of the aqueous solution of N,N-dimethylformamide (DMF) is 40°C. The product obtained above is washed with water at 50°C for 1 hour, and then dried at 130°C for 1 hour to obtain the microfiber base fabric.

[0086] (5) The microfiber base fabric is immersed in a hydrochloric acid solution with a concentration of 0.5 mol / L, stirred at 25°C for 3 h, and then washed with deionized water until it is neutral. After drying, intermediate I is obtained.

[0087] (6) The intermediate I was immersed in a 30wt% modification solution with a mass ratio of sodium silicate:sodium phosphate:EDTA-tetrasodium:sodium gluconate = 8:6:5:1 for modification treatment. The modification treatment conditions were: pressure 0.2MPa, temperature 45℃, and time 1h. The modified product was dried at 110℃ for 2h to obtain composite modified microfiber fabric-A1, the basis weight of which was 250g / m². 2 .

[0088] Preparation Example 2

[0089] (1) The halloysite nanotubes were ultrasonically cleaned for 60 min, centrifuged and dried to obtain halloysite nanotubes.

[0090] (2) Weigh 10 kg of halloysite nanotubes, mix nylon 6, polyethylene and halloysite nanotubes in a weight ratio of nylon 6: polyethylene: halloysite nanotubes = 8:10:1, stir and heat to 285°C to melt it, and then extrude it through a screw extruder and spray it out from the spinneret through a metering pump to form fibers.

[0091] (3) The fibers are randomly stacked and then immersed in a polyurethane solution at 50°C for 60 minutes to obtain the nonwoven fabric required by the present invention.

[0092] (4) The nonwoven fabric is contacted and mixed with a xylene aqueous solution with a concentration of 40% by volume for 1 hour, and the temperature of the xylene aqueous solution is 45°C. The product obtained above is washed with water at 60°C for 2 hours, and then dried at 150°C for 1 hour to obtain the microfiber base fabric.

[0093] (5) The microfiber base fabric is immersed in a sulfuric acid solution with a concentration of 0.25 mol / L, stirred at 25°C for 3 h, and then washed with deionized water until it is neutral. After drying, intermediate I is obtained.

[0094] (6) The intermediate I was immersed in a 30wt% modification solution with a mass ratio of potassium silicate:potassium phosphate:disodium EDTA:potassium gluconate = 9:7:6:1 for modification treatment. The modification conditions were: pressure 0.3MPa, temperature 45℃, and time 1.5h. The modified product was dried at 110℃ for 2h to obtain composite modified microfiber fabric-A2, with a basis weight of 300g / m². 2 .

[0095] Preparation Example 3

[0096] This preparation example uses a method similar to that of Preparation Example 1, except that in step (6), the conditions for modifying intermediate I are adjusted to: pressure of 0.1 MPa, temperature of 45°C, and time of 1 h. A composite modified microfiber fabric-A3 is thus prepared, with a basis weight of 250 g / m³. 2 .

[0097] Comparative Preparation Example 1

[0098] This comparative preparation example uses a method similar to that of Preparation Example 1. The difference is that the obtained microfiber base fabric is not subjected to the acidification treatment in step (5), but is directly subjected to the modification treatment in step (6) of Preparation Example 1 to obtain the composite modified microfiber fabric-DA1. The basis weight of the composite modified microfiber fabric-DA1 is 260 g / m². 2 .

[0099] Comparative Preparation Example 2

[0100] This comparative preparation example was prepared using a method similar to that of Preparation Example 1. The difference was that the modification treatment in step (6) was not performed. The microfiber base fabric obtained in step (4) was acidified using the same method as in step (5) of Preparation Example 1, resulting in a basis weight of 240 g / m². 2 Composite microfiber fabric - DA2.

[0101] Comparative preparation example 3

[0102] This comparative preparation example was carried out using a method similar to that of Preparation Example 1. The difference was that in step (6), the modified solution in Preparation Example 1 was replaced with a 30wt% sodium silicate aqueous solution. The remaining operations were the same as in Preparation Example 1, resulting in a yield of 250 g / m³. 2 Composite modified microfiber fabric - DA3.

[0103] Comparative preparation example 4

[0104] This comparative preparation example was carried out using a method similar to that of Preparation Example 1. The difference was that in step (6), the modified solution in Preparation Example 1 was replaced with a 30 wt% sodium phosphate aqueous solution. The remaining operations were the same as in Preparation Example 1, resulting in a yield of 250 g / m³. 2 Composite modified microfiber fabric - DA4.

[0105] Comparative preparation example 5

[0106] This comparative preparation example was carried out using a method similar to that of Preparation Example 1. The difference was that in step (6), the modified solution in Preparation Example 1 was replaced with a 30wt% EDTA-tetrasodium aqueous solution. The remaining operations were the same as in Preparation Example 1, resulting in a yield of 250 g / m³. 2 Composite modified microfiber fabric - DA5.

[0107] Comparative preparation example 6

[0108] This comparative preparation example was carried out using a method similar to that of Preparation Example 1. The difference was that in step (6), the modified solution in Preparation Example 1 was replaced with a 30wt% sodium gluconate aqueous solution. The remaining operations were the same as in Preparation Example 1, resulting in a yield of 250 g / m³. 2 Composite modified microfiber fabric - DA6.

[0109] The embodiments of the present invention are used to prepare fiber-reinforced self-healing penetrating crystalline waterproof membranes. Unless otherwise specified, the amounts of raw materials used in the following examples are parts by weight, and each part by weight represents 100g.

[0110] Example 1

[0111] S1: Add 45 parts by weight of 70# asphalt and 7 parts by weight of oil (the oil is a combination of aromatic oil and linear oil with a mass ratio of 2:5) to a reactor preheated to 140°C, stir and react for 30 minutes to obtain mixture I;

[0112] S2: At 180°C, 6 parts by weight of polymer modifier with a mass ratio of SBS:SSBR = 4:6 are mixed with the mixture I, and then 10 parts by weight of tire rubber powder and 2 parts by weight of sodium metasilicate are added. The mixture is stirred and reacted for 3 hours to obtain mixture II.

[0113] S3: Keeping the temperature constant at 180°C, mix 30 parts by weight of heavy calcium carbonate with the mixture II for 1.5 hours to obtain modified asphalt;

[0114] S4: The modified asphalt is subjected to a weight of 200 g / m³. 2The material is formed on a polyester base, and the upper and lower surfaces are covered with composite modified microfiber cloth-A1 and PE release film. The thickness of the roll is controlled at 3.0±0.2mm to obtain fiber-reinforced self-healing penetrating crystalline waterproof roll-B1.

[0115] Example 2

[0116] S1: Add 50 parts by weight of 90# asphalt and 2 parts by weight of base oil to a reactor preheated to 150°C, stir and react for 30 minutes to obtain mixture I;

[0117] S2: At 170°C, 8 parts by weight of polymer modifier with a mass ratio of SBS:SSBR:SIS = 3:3:2 are mixed with the mixture I, and then 7 parts by weight of tire rubber powder and 1 part by weight of calcium hydroxide are added. The mixture is stirred and reacted for 3.5 hours to obtain mixture II.

[0118] S3: Keeping the temperature constant at 170°C, mix 32 parts by weight of metakaolin with the mixture II for 1 hour to obtain modified asphalt;

[0119] S4: The modified asphalt is subjected to a weight of 200 g / m³. 2 The material is formed on a polyester base, and the upper and lower surfaces are covered with composite modified microfiber cloth-A2 and PET release film. The thickness of the roll is controlled at 3.0±0.2mm to obtain fiber-reinforced self-healing penetrating crystalline waterproof roll-B2.

[0120] Example 3

[0121] This embodiment is carried out with reference to the method of Embodiment 1. The difference is that in step S2, this embodiment uses an equal part by weight of C5 hydrogenated resin to replace the polymer modifier in Embodiment 1 to obtain fiber-reinforced self-healing penetrating crystalline waterproof membrane-B3.

[0122] Example 4

[0123] This embodiment follows the method of Embodiment 1, except that in step S4, this embodiment uses composite modified microfiber cloth-A3 instead of composite modified microfiber cloth-A1 in Embodiment 1 to obtain fiber-reinforced self-healing penetrating crystalline waterproof membrane-B4.

[0124] Comparative Example 1

[0125] This comparative example is carried out in accordance with the method of Example 1. The difference is that in step S4, this comparative example uses composite modified microfiber cloth-DA1 instead of composite modified microfiber cloth-A1 in Example 1 to obtain fiber reinforced self-healing penetrating crystallizing waterproof membrane-DB1.

[0126] Comparative Example 2

[0127] This comparative example is carried out according to the method of Example 1. The difference is that in step S4, this comparative example uses composite microfiber cloth-DA2 instead of composite modified microfiber cloth-A1 in Example 1 to obtain fiber-reinforced self-healing penetrating crystalline waterproof membrane-DB2.

[0128] Comparative Example 3

[0129] This comparative example is carried out according to the method of Example 1. The difference is that in step S4, this comparative example uses composite modified microfiber cloth-DA3 instead of composite modified microfiber cloth-A1 in Example 1 to obtain fiber-reinforced self-healing penetrating crystallizing waterproof membrane-DB3.

[0130] Comparative Example 4

[0131] This comparative example is carried out according to the method of Example 1. The difference is that in step S4, this comparative example uses composite modified microfiber cloth-DA4 instead of composite modified microfiber cloth-A1 in Example 1 to obtain fiber-reinforced self-healing penetrating crystallizing waterproof membrane-DB4.

[0132] Comparative Example 5

[0133] This comparative example is carried out according to the method of Example 1. The difference is that in step S4, this comparative example uses composite modified microfiber cloth-DA5 instead of composite modified microfiber cloth-A1 in Example 1 to obtain fiber-reinforced self-healing penetrating crystallizing waterproof membrane-DB5.

[0134] Comparative Example 6

[0135] This comparative example is carried out according to the method of Example 1. The difference is that in step S4, this comparative example uses composite modified microfiber cloth-DA6 instead of composite modified microfiber cloth-A1 in Example 1 to obtain fiber-reinforced self-healing penetrating crystallizing waterproof membrane-DB6.

[0136] Comparative Example 7

[0137] This comparative example was conducted using the same method as in Example 1, except that in step S4, this comparative example used a weight of 250 g / m³. 2 The polyester base was replaced with the composite modified microfiber fabric-A1 in Example 1 to obtain fiber-reinforced self-healing penetrating crystalline waterproof membrane-DB7.

[0138] Test case

[0139] Referring to the standard T / CECS1634-2024 for self-healing penetrating crystalline composite waterproof membranes, the fiber-reinforced self-healing penetrating crystalline waterproof membranes prepared in the above examples were subjected to a permeability pressure test on coated concrete and a second permeability pressure test on coated concrete after water permeation. The permeation pressure was recorded, and the test results are shown in Table 1.

[0140] Table 1

[0141]

[0142] As can be seen from the results in Table 1, the fiber-reinforced self-healing penetrating crystalline waterproof membrane prepared by the present invention has better penetrating crystalline effect and self-healing effect on concrete after curing, meeting the standard requirements of T / CECS1634-2024 for self-healing penetrating crystalline composite waterproof membrane.

[0143] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A fiber-reinforced self-healing, penetrating, crystalline waterproof membrane, characterized in that, The waterproof membrane comprises, from top to bottom, a composite modified microfiber fabric, a modified bitumen layer, a polyester base, a modified bitumen layer, and a release membrane; The composite modified microfiber fabric is prepared by a method including the following steps: (1) Nylon 6, polyethylene and halloysite nanotubes are stirred and mixed in a weight ratio of 8-10:8-10:1, and melt-blended and spun to obtain fibers; The fibers are randomly stacked and then immersed in a polyurethane solution to obtain a nonwoven fabric. (2) The nonwoven fabric is contacted and mixed with the coagulation liquid to obtain a microfiber base fabric; the volume fraction of the solute in the coagulation liquid is 30-40%, and the solute is selected from at least one of N,N-dimethylformamide, decahydronaphthalene and xylene; (3) In the presence of an acidic solution, the microfiber base fabric is acidified to obtain intermediate I; (4) In the presence of a modified solution, the intermediate I is modified to obtain the composite modified microfiber fabric; The modified solution contains a composite modifier at a concentration of 25-35 wt%, which is a combination of silicate, phosphate, ethylenediaminetetraacetate and gluconate in a weight ratio of 7-9:5-7:4-6:

1.

2. The waterproof membrane according to claim 1, wherein, In step (1), the stirring and mixing temperature is 280-285℃, and the solid content of the polyurethane solution is 30%-65%.

3. The waterproof membrane according to claim 1, wherein, In step (2), the conditions for contact mixing include: a temperature of 40-55°C and a time of 0.5-2h.

4. The waterproof membrane according to claim 1, wherein, In step (3), the acidic solution contains H + The concentration is 0.45-0.55 mol / L.

5. The waterproof membrane according to claim 1, wherein, In step (3), the acidification treatment conditions include: a temperature of 20-30℃ and a time of 2-4h.

6. The waterproof membrane according to claim 1, wherein, In step (4), the conditions for the modification treatment include: pressure of 0.2-0.5 MPa, temperature of 25-50℃, and time of 1-1.5 h.

7. The waterproof membrane according to claim 1, wherein, In step (4), the silicate is selected from at least one of sodium silicate, potassium silicate and ammonium silicate; the phosphate is selected from at least one of sodium phosphate, potassium phosphate and ammonium phosphate; the ethylenediaminetetraacetic acid salt is disodium ethylenediaminetetraacetate and / or tetrasodium ethylenediaminetetraacetate; and the gluconate is selected from at least one of sodium gluconate, potassium gluconate and calcium gluconate.

8. The waterproof membrane according to claim 1, wherein, The method further includes: in step (2), the material obtained by the contact mixing is sequentially subjected to water washing and drying treatment to obtain the microfiber base fabric.

9. The waterproof membrane according to claim 1, wherein, The modified asphalt layer is formed from modified asphalt layer raw materials, which contain base asphalt, oil, polymer modifier, tire rubber powder, penetrant and filler; Based on the total weight of the modified asphalt layer raw materials, the content of the base asphalt is 40-60 wt%, the content of the oil is 1-10 wt%, the content of the polymer modifier is 3-10 wt%, the content of the tire rubber powder is 5-14 wt%, the content of the penetrant is 0.5-3 wt%, and the content of the filler is 25-45 wt%.

10. The waterproof membrane according to claim 9, wherein, The oil is selected from at least one of aromatic oil, anti-corrosion oil, and base oil.

11. The waterproof membrane according to claim 9, wherein, The polymer modifier is selected from at least one of styrene-butadiene-styrene triblock copolymer, modified styrene-butadiene rubber, styrene-isoprene-styrene triblock copolymer, and C5 hydrogenated resin.

12. The waterproof membrane according to claim 9, wherein, The penetrant is selected from at least one of sodium silicate, sodium metasilicate, and calcium hydroxide.

13. The waterproof membrane according to claim 9, wherein, In the modified asphalt layer raw material, the base asphalt is selected from at least one of 70# asphalt, 90# asphalt and 200# asphalt.

14. The waterproof membrane according to claim 9, wherein, The average diameter of the tire rubber powder is 180-250 μm.

15. The waterproof membrane according to claim 9, wherein, The filler is selected from at least one of talc, heavy calcium carbonate, montmorillonite, kaolin, and metakaolin, and the average diameter of the filler is 15-80 μm.

16. The application of the waterproof membrane according to any one of claims 1-15 in the field of building waterproofing.

Images