A high-hard-particle-coated glass fiber reinforced polyester base root-penetration-resistant self-protecting waterproof roll material

Abstract

The present application relates to waterproofing membrane technical field, and disclose a kind of high hard granule covering glass fiber reinforced polyester tire root penetration resistant self-protection type waterproofing membrane, the waterproofing membrane includes five layers structure of surface layer, upper adhesive layer, reinforcing layer, lower adhesive layer and isolation layer arranged in turn from top to bottom;The surface layer is high-hardness mineral particle covering layer, the upper adhesive layer is root penetration resistant modified asphalt glue, the reinforcing layer is glass fiber reinforced polyester composite tire base, the lower adhesive layer is high-pressure creep self-repairing elastic asphalt glue, and the isolation layer is PE film.The present application membrane has excellent root penetration resistance, high mechanical strength, surface self-protection function and damage self-repairing ability, effectively solve the technical problems that the existing waterproofing membrane is poor in root resistance reliability, easily subjected to ultraviolet aging and mechanical wear, microdamage accumulation leads to waterproofing failure, especially suitable for planting roof and exposed waterproofing engineering.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, specifically to a high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane. Background Technology

[0002] Waterproof membranes, as a core material in building waterproofing projects, are widely used for waterproofing and protection of basements, roofs, tunnels, bridges, and other projects. With the deepening of sponge city construction and green building concepts, green roof technology has developed rapidly in my country, placing higher demands on the root penetration resistance and durability of waterproof membranes.

[0003] Currently, root-penetration resistant waterproof membranes are mainly divided into two categories: physical root-barrier type and chemical root-barrier type. Physical root-barrier membranes are represented by copper foil composite-based or copper-based modified bitumen membranes. Their root-barrier principle utilizes the biotoxicity of copper ions to inhibit plant roots from growing into the membrane. However, copper, as a precious metal, significantly increases the raw material cost of the membrane, raising construction costs and hindering its widespread application in large-scale green roof projects. More importantly, during the long-term service of waterproof membranes, copper foil is highly susceptible to oxidation and corrosion due to changes in environmental humidity and temperature, as well as the acidic components in the bitumen. This leads to the formation of oxides such as verdigris on the surface, causing a decrease in the copper ion dissolution rate, a gradual decline in root-barrier function, and even complete loss of the membrane's waterproofing reliability, severely impacting its lifespan and waterproofing reliability.

[0004] Chemically-inhibited root-penetration resistant roofing membranes utilize chemical root-inhibiting substances added to modified bitumen to regulate the growth direction of plant roots and inhibit root penetration into the membrane. While this type of membrane reduces material costs to some extent, its base material is still primarily ordinary polyester felt. Existing ordinary polyester-based roofing membranes have limited tear and puncture resistance, while plant roots can generate puncture pressures as high as 1.5-2.0 MPa during growth. Furthermore, during the construction and maintenance of green roofs, the membrane is inevitably subjected to mechanical forces such as worker trampling, dropped tools, and rolling gravel, easily creating microscopic damage points on the membrane surface. These defects gradually expand under the combined effects of continuous root growth stress and environmental aging, ultimately leading to the penetration and failure of the waterproofing layer.

[0005] In summary, existing root-penetration resistant waterproof membranes still have significant shortcomings in terms of root resistance reliability, mechanical strength, surface protection, and long-term durability. There is an urgent need to develop a waterproof membrane that combines excellent root-penetration resistance, high mechanical strength, surface self-protection function, and long service life to meet the stringent requirements of modern green roof projects for the comprehensive performance of waterproof materials. Summary of the Invention

[0006] (a) Technical problems to be solved

[0007] To address the shortcomings of existing technologies, this invention provides a high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane. The prepared waterproof membrane exhibits excellent root-penetration resistance, self-healing properties, and mechanical properties.

[0008] (II) Technical Solution

[0009] A high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane, characterized in that the waterproof membrane comprises a five-layer structure, from top to bottom as follows: surface layer, upper adhesive layer, reinforcing layer, lower adhesive layer, and isolation layer;

[0010] The surface layer is a high-hardness mineral particle coating layer;

[0011] The upper adhesive layer is a root-penetration-resistant modified bitumen adhesive;

[0012] The reinforcing layer is a glass fiber reinforced polyester composite base;

[0013] The lower adhesive layer is a high-pressure creep self-healing elastic asphalt adhesive. The high pressure mentioned in this invention refers to the long-term pressure of ≥0.5MPa that the roll material can withstand during use.

[0014] The isolation layer is a PE film.

[0015] Preferably, the high-hardness mineral particle covering layer is one or more of black granite particles and black basalt particles.

[0016] Preferably, the root penetration resistant modified asphalt adhesive is composed of SBS, asphalt, and a root inhibitor, and its preparation method includes the following steps:

[0017] Heat the asphalt to 160-170℃, add SBS for shear dispersion for 1-2 hours, then add root inhibitor and stir for 20-40 minutes to obtain root penetration resistant modified asphalt adhesive.

[0018] Preferably, the mass ratio of the asphalt, SBS, and root inhibitor is 100:5-10:3-7.

[0019] Preferably, the root inhibitor is methyl 2-(4-chloro-2-methylphenoxy)propionate, which can interfere with root development, inhibit plant root growth, and prevent roots from penetrating the waterproof layer.

[0020] Preferably, the glass fiber reinforced polyester composite has a basis weight ≥ 240 g / m², and its preparation method includes the following steps:

[0021] (1) Polyester web formation: PET chips are melt-spun and air-blown to form an upper polyester fiber web and a lower polyester fiber web, respectively;

[0022] (2) Directional reinforcement: The lower layer of polyester fiber web is continuously conveyed forward, and continuous alkali-free glass fiber rovings are evenly laid on the surface of the fiber web at equal intervals along the longitudinal direction of the material flow, and the tension of the glass fiber rovings is controlled to keep it straight and without bending.

[0023] (3) Laying the mesh: Cover the upper layer of polyester fiber mesh on top of the laid glass fiber yarn to form a three-layer laminated blank of "upper polyester fiber mesh - longitudinal glass fiber yarn - lower polyester fiber mesh";

[0024] (4) Needle-punching consolidation: The preform is needle-punched on both sides using a high-speed needle-punching process. The polyester fibers interweave and bind together, locking the glass fiber roving inside the fiber web to initially form a composite fabric.

[0025] (5) Hot pressing and shaping: The composite fabric is fed into a hot rolling mill and hot-pressed at 180-220℃ and 0.3-1.0MPa pressure. The surface polyester fiber melts and bonds, strengthens the interface, and prevents the glass fiber from slipping under stress.

[0026] (6) Post-treatment: The sizing is carried out by impregnation with styrene-acrylic emulsion, and after drying, it is wound up to obtain glass fiber reinforced polyester composite base.

[0027] Preferably, the preparation method of the high-pressure creep self-healing elastic asphalt adhesive includes the following steps:

[0028] After mixing asphalt, SBS, and styrene-butadiene rubber evenly, the temperature is controlled at 180-190℃. Then, naphthenic oil, sulfur, and antioxidant are added and stirred for 2-3 hours. Modified talc powder is then added and stirred for 1-2 hours to obtain high-pressure creep self-healing elastic asphalt adhesive.

[0029] Preferably, the mass ratio of the asphalt, SBS, styrene-butadiene rubber, naphthenic oil, sulfur, antioxidant, and modified talc is 100:5-8:3-7:6-10:1-3:0.2-0.5:10-15.

[0030] Preferably, the preparation method of the modified talc powder includes the following steps:

[0031] (1) Vanillin and furfural were dispersed in ethanol solvent, stirred and dispersed, nitrogen gas was introduced, and stirred for 2-3 h. The temperature was raised to 70-80℃ and the reaction was carried out for 16-20 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with ethanol, and dried to obtain the intermediate. The reaction synthesis route is as follows:

[0032] ;

[0033] (2) The intermediate and N-propyltriethoxysilane maleimide were dispersed in toluene solvent, stirred and mixed evenly, and then heated to 90℃ and reacted for 18-20 h. After the reaction was completed, the mixture was filtered, washed and dried to obtain vanillin-based silane. The reaction synthesis route is as follows:

[0034] ;

[0035] (3) Disperse vanillin-based silane in a 90% ethanol aqueous solution and stir for 20-30 min. Then add talc powder and stir for 1-2 h. After the reaction is complete, filter, wash with ethanol, and dry to obtain modified talc powder.

[0036] Preferably, in (1), the mass ratio of vanillin to furfurylamine is 1.5-2:1; in (2), the mass ratio of intermediate to N-propyltriethoxysilane maleimide is 1:1.4-1.8; and in (3), the amount of vanillin-silane used is 2-5% of the mass of talc.

[0037] This invention involves a Schiff base reaction between vanillin and furfurylamine to generate an intermediate containing dynamic imine bonds. This intermediate is then reacted with N-propyltriethoxysilane maleimide via a Diels-Alder cycloaddition reaction to prepare vanillin-based silane. This vanillin-based silane is then grafted onto the surface of talc powder, resulting in modified talc powder containing both dynamic imine bonds and thermally reversible DA bonds. The imine bonds, under normal service conditions, can achieve rapid chemical "stitching" of microcrack interfaces through reversible condensation reactions, responding sensitively to minor damage during transportation, construction, and use. The DA bonds, under micro-temperature rise conditions caused by localized stress concentration in the crack, trigger a reverse DA reaction, temporarily dissociating the cross-linked network and enhancing the local fluidity of the material to fill the crack. After the temperature returns to normal, a forward DA reaction occurs, covalently re-bonding the molecular chains on both sides of the crack, completing a high-quality repair. The complementary repair temperature ranges of the two dynamic bonds enable the roll material to possess self-healing capabilities across the entire service temperature range, from room temperature to elevated temperatures.

[0038] (iii) Beneficial technical effects

[0039] The upper adhesive layer of the waterproof membrane of this invention uses a root-penetration-resistant modified bitumen adhesive composed of SBS, bitumen, and a root inhibitor. The root inhibitor is methyl 2-(4-chloro-2-methylphenoxy)propionate, which effectively regulates the growth direction of plant roots and inhibits root penetration into the membrane. Compared with existing copper-based physical root-blocking membranes, this invention uses a chemical root-blocking method, avoiding the inherent defect of copper foil oxidation failure leading to a decline in root-blocking function. The root-blocking effect is more durable and stable. Furthermore, compared with ordinary polyester-based chemical root-blocking membranes, this invention significantly improves the membrane's resistance to root penetration pressure through the synergistic reinforcement of the glass fiber-reinforced polyester composite base. The double-layer modified bitumen structure of the upper and lower adhesive layers together constitutes a dense waterproof root-blocking barrier, ensuring that the membrane maintains its waterproof function for a long time under the long-term stress of plant root growth.

[0040] This invention employs a glass fiber reinforced polyester composite base as the reinforcing layer. This base utilizes a three-layer composite structure design: an upper polyester fiber web, longitudinal glass fiber yarn, and a lower polyester fiber web. Combined with a high-speed needle-punching process, the polyester fibers interweave and bind together, firmly locking the glass fiber roving within the fiber web. Hot-pressing at 180-220℃ then melts and bonds the surface polyester fibers, forming a three-dimensional network reinforcement structure. This structure fully leverages the synergistic reinforcement effect of the excellent elongation properties of polyester fibers and the high tensile strength of glass fibers, effectively solving the problems of relative slippage and interlayer delamination that often occur between the glass fiber layer and the polyester layer in existing glass fiber reinforcement methods. The base design, with a roll weight ≥240g / m², ensures excellent tensile strength, tear strength, and puncture resistance, effectively resisting root penetration stress and mechanical damage such as trampling and gravel breakage during construction.

[0041] The lower adhesive layer of this invention is a high-pressure creep self-healing elastic asphalt adhesive, which is compounded from asphalt, SBS, styrene-butadiene rubber, naphthenic oil, sulfur, antioxidants, and modified talc. The synergistic toughening effect of SBS and styrene-butadiene rubber endows the asphalt adhesive with excellent elastic recovery and creep characteristics. When the roll material is damaged, the vanillin-silane structure on the surface of the modified talc contains dual dynamic covalent bonds of imine and DA bonds, which, together with the creep flow properties of the asphalt adhesive itself, enable the damaged area to self-heal and close under pressure, preventing micro-damage from expanding into through-hole defects, and significantly improving the service reliability and service life of the roll material.

[0042] The surface layer of this invention is a high-hardness mineral particle covering layer, using one or more of black granite particles or black basalt particles as the covering material. These high-hardness mineral particles have a high Mohs hardness and excellent wear resistance, forming a permanent protective layer on the surface of the roll material. This protective layer effectively shields against solar ultraviolet radiation, preventing the underlying root-penetration-resistant modified asphalt adhesive from undergoing photo-oxidative aging and embrittlement; it also resists physical wear such as wind, sand, gravel, and friction from construction machinery.

[0043] In summary, this invention constructs a high-performance waterproof membrane system integrating root inhibition, reinforcement, self-healing, and self-protection through a five-layer synergistic design: the upper bonding layer uses SBS modified bitumen adhesive containing chemical root inhibitors, achieving a more durable and stable chemical root inhibition effect than copper-based membranes, avoiding the inherent defects of metal oxidation failure; the reinforcement layer uses a glass fiber reinforced polyester composite base prepared by needle punching and hot pressing, utilizing the three-dimensional network entanglement structure of polyester fibers and longitudinal glass fiber yarns, significantly improving the tensile strength, tear strength, and burst resistance of the membrane, effectively solving the problems of insufficient mechanical properties of ordinary polyester-based membranes and easy peeling between multi-layer composite base layers. The invention addresses several challenges. The high-pressure creep self-healing elastic asphalt adhesive in the lower bonding layer contains talc powder modified with vanillin-based silane. The dynamic imine and DA bonds on the surface of this modified talc powder can undergo reversible fracture and recombination at microcracks. This, combined with the creep flow properties of the asphalt adhesive itself, endows the membrane with an intelligent function of actively repairing micro-damage, preventing minor defects from expanding into through-cracks. The high-hardness black granite or black basalt mineral particle surface layer forms a permanent protective barrier throughout the membrane's lifespan, effectively shielding it from ultraviolet radiation and resisting wind and sand abrasion. This overcomes the drawbacks of existing membranes, such as surface aging after the release liner is removed and the weak adhesion and easy detachment of fine sand surface layers. The synergistic effect of these functional layers gives the invention excellent root penetration resistance, outstanding mechanical strength, significant self-healing ability, and durable surface protection. The overall technical effect is significantly superior to existing similar products, fully meeting the application needs of green roofs and exposed waterproofing projects for high-performance, long-life waterproofing materials. Detailed Implementation

[0044] Unless otherwise specified, all materials and reagents used in the following examples are commercially available. Experimental methods not specifically described in the examples are generally performed under standard conditions or as recommended by the manufacturer.

[0045] The preparation method of N-propyltriethoxysilane maleimide includes the following steps: Under nitrogen protection, 10.38 g of maleic anhydride and 23.4 g of aminopropyltriethoxysilane are dispersed in toluene and stirred for 2 h. Then, 14.4 g of zinc chloride is added, the temperature is raised to 80 °C, and then a toluene solution containing 17 g of hexamethyldisilazane is added. The reaction is carried out for 5 h. After the reaction is completed, the mixture is filtered and rotary evaporated to obtain N-propyltriethoxysilane maleimide.

[0046] Root inhibitor chemical formula: C 11 H 13 ClO3 (methyl 2-(4-chloro-2-methylphenoxy)propionate), purchased from Shanghai Maideshengli Chemical Co., Ltd.

[0047] Preparation Example 1

[0048] This embodiment provides a method for preparing a glass fiber reinforced polyester matrix composite, comprising the following steps:

[0049] (1) Polyester web formation: PET chips are melt-spun and air-blown to form an upper polyester fiber web and a lower polyester fiber web, respectively;

[0050] (2) Directional reinforcement: The lower layer of polyester fiber web is continuously conveyed forward, and continuous alkali-free glass fiber rovings are evenly laid on the surface of the fiber web at equal intervals along the longitudinal direction of the material flow, and the tension of the glass fiber rovings is controlled to keep it straight and without bending.

[0051] (3) Laying the mesh: Cover the upper layer of polyester fiber mesh on top of the laid glass fiber yarn to form a three-layer laminated blank of "upper polyester fiber mesh - longitudinal glass fiber yarn - lower polyester fiber mesh";

[0052] (4) Needle-punching consolidation: The preform is needle-punched on both sides using a high-speed needle-punching process. The polyester fibers interweave and bind together, locking the glass fiber roving inside the fiber web to initially form a composite fabric.

[0053] (5) Hot pressing and shaping: The composite fabric is fed into the hot rolling mill and hot pressed at 200℃ and 1.0MPa pressure. The surface polyester fiber melts and bonds, strengthens the interface, and prevents the glass fiber from slipping under stress.

[0054] (6) Post-treatment: The sizing was carried out by impregnation with styrene-acrylic emulsion, dried and then wound up with a basis weight of 240 g / m² to obtain glass fiber reinforced polyester composite base.

[0055] Preparation Example 2

[0056] This embodiment provides a method for preparing a glass fiber reinforced polyester matrix composite, comprising the following steps:

[0057] (1) Polyester web formation: PET chips are melt-spun and air-blown to form an upper polyester fiber web and a lower polyester fiber web, respectively;

[0058] (2) Directional reinforcement: The lower layer of polyester fiber web is continuously conveyed forward, and continuous alkali-free glass fiber rovings are evenly laid on the surface of the fiber web at equal intervals along the longitudinal direction of the material flow, and the tension of the glass fiber rovings is controlled to keep it straight and without bending.

[0059] (3) Laying the mesh: Cover the upper layer of polyester fiber mesh on top of the laid glass fiber yarn to form a three-layer laminated blank of "upper polyester fiber mesh - longitudinal glass fiber yarn - lower polyester fiber mesh";

[0060] (4) Needle-punching consolidation: The preform is needle-punched on both sides using a high-speed needle-punching process. The polyester fibers interweave and bind together, locking the glass fiber roving inside the fiber web to initially form a composite fabric.

[0061] (5) Hot pressing and shaping: The composite fabric is fed into the hot rolling mill and hot pressed at 220℃ and 0.3MPa pressure. The surface polyester fiber melts and bonds, strengthens the interface, and prevents the glass fiber from slipping under stress.

[0062] (6) Post-treatment: The sizing was carried out by impregnation with styrene-acrylic emulsion, dried and then wound up with a basis weight of 240 g / m² to obtain glass fiber reinforced polyester composite base.

[0063] Preparation Example 3

[0064] This embodiment provides a method for preparing root penetration resistant modified asphalt adhesive, including the following steps:

[0065] By weight, 100 parts of asphalt are heated to 165°C, 5 parts of SBS are added and sheared and dispersed for 2 hours, and then 3 parts of methyl 2-(4-chloro-2-methylphenoxy)propionate root inhibitor are added and stirred for 20 minutes to obtain root penetration resistant modified asphalt adhesive.

[0066] Preparation Example 4

[0067] This embodiment provides a method for preparing root penetration resistant modified asphalt adhesive, including the following steps:

[0068] By weight, 100 parts of asphalt are heated to 160°C, 8 parts of SBS are added and sheared and dispersed for 1 hour, and then 5 parts of methyl 2-(4-chloro-2-methylphenoxy)propionate root inhibitor are added and stirred for 30 minutes to obtain root penetration resistant modified asphalt adhesive.

[0069] Preparation Example 5

[0070] This embodiment provides a method for preparing root penetration resistant modified asphalt adhesive, including the following steps:

[0071] By weight, 100 parts of asphalt are heated to 170°C, 10 parts of SBS are added and sheared and dispersed for 2 hours, and then 7 parts of methyl 2-(4-chloro-2-methylphenoxy)propionate root inhibitor are added and stirred for 40 minutes to obtain root penetration resistant modified asphalt adhesive.

[0072] Preparation Example 6

[0073] This embodiment provides a method for preparing high-pressure creep self-healing elastic asphalt adhesive, including the following steps:

[0074] By weight, 100 parts asphalt, 5 parts SBS, and 3 parts styrene-butadiene rubber are mixed evenly, and the temperature is controlled at 180℃. Then, 6 parts naphthenic oil, 1 part sulfur, and 0.2 parts antioxidant 1010 are added and stirred for 2 hours. Then, 10 parts modified talc powder are added and stirred for 1 hour to obtain high-pressure creep self-healing elastic asphalt adhesive.

[0075] The preparation method of the modified talc powder includes the following steps:

[0076] (1) Disperse 10g of vanillin and 5g of furfural in ethanol solvent, stir and disperse, introduce nitrogen gas, stir for 3h, heat to 70℃, react for 20h, after the reaction is completed, cool to room temperature, filter, wash with ethanol, dry, and obtain intermediate.

[0077] (2) 5g of intermediate and 9g of N-propyltriethoxysilane maleimide were dispersed in toluene solvent, stirred and mixed evenly, and then heated to 90℃ and reacted for 19h. After the reaction was completed, the mixture was filtered, washed and dried to obtain vanillin silane.

[0078] (3) Disperse 0.2g of vanillin silane in a 90% ethanol aqueous solution and stir for 20min. Then add 10g of talc powder and stir for 2h. After the stirring is completed, filter, wash with ethanol, and dry to obtain modified talc powder.

[0079] Preparation Example 7

[0080] This embodiment provides a method for preparing high-pressure creep self-healing elastic asphalt adhesive, including the following steps:

[0081] By weight, 100 parts asphalt, 6 parts SBS, and 5 parts styrene-butadiene rubber are mixed evenly, and the temperature is controlled at 185℃. Then, 8 parts naphthenic oil, 2 parts sulfur, and 0.4 parts antioxidant 1010 are added and stirred for 3 hours. Then, 13 parts modified talc powder are added and stirred for 2 hours to obtain high-pressure creep self-healing elastic asphalt adhesive.

[0082] The preparation method of the modified talc powder includes the following steps:

[0083] (1) Disperse 8g of vanillin and 5g of furfural in ethanol solvent, stir and disperse, introduce nitrogen gas, stir for 2h, heat to 80℃, react for 16h, after the reaction is completed, cool to room temperature, filter, wash with ethanol, dry, and obtain intermediate.

[0084] (2) 5g of intermediate and 8g of N-propyltriethoxysilane maleimide were dispersed in toluene solvent, stirred and mixed evenly, and then heated to 90℃ and reacted for 18h. After the reaction was completed, the mixture was filtered, washed and dried to obtain vanillin silane.

[0085] (3) Disperse 0.4g of vanillin-based silane in a 90% ethanol aqueous solution, stir for 30min, then add 10g of talc powder, stir for 1h, filter, wash with ethanol, and dry to obtain modified talc powder.

[0086] Preparation Example 8

[0087] This embodiment provides a method for preparing high-pressure creep self-healing elastic asphalt adhesive, including the following steps:

[0088] By weight, 100 parts asphalt, 8 parts SBS, and 7 parts styrene-butadiene rubber are mixed evenly, and the temperature is controlled at 190℃. Then, 10 parts naphthenic oil, 3 parts sulfur, and 0.5 parts antioxidant 1010 are added and stirred for 3 hours. Then, 15 parts modified talc powder are added and stirred for 2 hours to obtain high-pressure creep self-healing elastic asphalt adhesive.

[0089] The preparation method of the modified talc powder includes the following steps:

[0090] (1) Disperse 7.2g of vanillin and 5g of furfural in ethanol solvent, stir and disperse, introduce nitrogen gas, stir for 3h, heat to 75℃, react for 18h, after the reaction is completed, cool to room temperature, filter, wash with ethanol, dry, and obtain intermediate;

[0091] (2) 5g of intermediate and 7g of N-propyltriethoxysilane maleimide were dispersed in toluene solvent, stirred and mixed evenly, and then heated to 90℃ and reacted for 20h. After the reaction was completed, the mixture was filtered, washed and dried to obtain vanillin silane.

[0092] (3) Disperse 0.5g of vanillin-based silane in a 90% ethanol aqueous solution, stir for 25min, then add 10g of talc powder, stir for 2h, filter, wash with ethanol, and dry to obtain modified talc powder.

[0093] A high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane is provided. The waterproof membrane comprises a five-layer structure, from top to bottom: surface layer, upper adhesive layer, reinforcing layer, lower adhesive layer, and isolation layer. Each layer is pressurized by double rollers and cooled to form the waterproof membrane.

[0094] Table 1:

[0095] surface layer upper adhesive layer Enhancement layer lower adhesive layer isolation layer Example A Black granite particles Preparation Example 3: Root Penetration-Resistant Modified Asphalt Adhesive Preparation Example 1: Glass fiber reinforced polyester composite matrix prepared Preparation Example 6: High-pressure creep self-healing elastic asphalt adhesive PE film Example B Black basalt particles Preparation Example 4: Root Penetration-Resistant Modified Asphalt Adhesive Preparation Example 1: Glass fiber reinforced polyester composite matrix prepared Preparation Example 7: High-pressure creep self-healing elastic asphalt adhesive PE film Example C Black granite particles Preparation Example 5: Root Penetration-Resistant Modified Asphalt Adhesive Preparation Example 2: Glass fiber reinforced polyester composite matrix prepared Preparation Example 8: High-pressure creep self-healing elastic asphalt adhesive PE film

[0096] Comparative Example A

[0097] The difference between this comparative example and Example A is that the upper adhesive layer does not contain methyl 2-(4-chloro-2-methylphenoxy)propionate root inhibitor.

[0098] Comparative Example B

[0099] The difference between this comparative example and Example A is that talc powder is used instead of modified talc powder in the lower adhesive layer.

[0100] Comparative Example C

[0101] The difference between this comparative example and Example A is that it does not contain an upper adhesive layer.

[0102] Comparative Example D

[0103] The difference between this comparative example and Example A is that it does not contain a lower adhesive layer.

[0104] Comparative Example E

[0105] The difference between this comparative example and Example A is that it does not contain a reinforcing layer.

[0106] Comparative Example F

[0107] The difference between this comparative example and Example A is that N-propyltriethoxysilane maleimide is used instead of vanillin silane in the lower adhesive layer, while the remaining steps are the same as in Example A.

[0108] Root resistance performance was tested in accordance with GB / T35468-2017.

[0109] Tensile properties were tested in accordance with GB / T328.8-2007.

[0110] Table 2:

[0111] Root penetration resistance <![CDATA[Maximum tensile force / N·mm -1 > Example A No root system, no penetration point 1468 Example B No root system, no penetration point 1571 Example C No root system, no penetration point 1604 Comparative Example A With few roots, penetration points appeared. 1417 Comparative Example B Root system with numerous penetration points 1267 Comparative Example C The root system is dense and has large areas of penetration points. 1176 Comparative Example D The root system is dense and has large areas of penetration points. 1087 Comparative Example E The root system is dense and has large areas of penetration points. 895 Comparative Example F With few roots, penetration points appeared. 1340

[0112] As can be seen from the table, the waterproof membrane prepared in this application has excellent root barrier properties and mechanical properties, and the three-layer structure of upper adhesive layer, lower adhesive layer and reinforcing layer is indispensable.

[0113] The waterproof membrane was prepared into dumbbell-shaped tensile specimens with a length of 115 mm, a width of 25 mm, and a narrow parallel section in the middle with a width of 6 mm. The elongation at break (A) was tested. Then, the specimens were kept at -40℃ for half an hour, bent until cracks appeared on the surface, and then placed at room temperature for 24 hours. Finally, they were placed in a drying oven at 60℃ for 12 hours. After the drying, the elongation at break (B) was tested. The self-healing performance was expressed as the elongation at break recovery rate (R), where R (%) = B / A × 100%.

[0114] The waterproof membrane was made into a circular specimen with a diameter of 130 mm. The circular specimen was pierced with a blade with a length of 5.5 mm and a thickness of 0.5 mm. It was placed at 25°C for 24 hours and the water impermeability was tested in accordance with GB / T328.8-2007.

[0115] Table 3:

[0116] R（%） Waterproofing after crack self-healing Example A 90.3 Pressure held at 0.5 MPa for 30 minutes, watertight. Example B 94.6 Pressure held at 0.5 MPa for 30 minutes, watertight. Example C 97.1 Pressure held at 0.5 MPa for 30 minutes, watertight. Comparative Example A 86.6 Pressure held at 0.5 MPa for 30 minutes, watertight. Comparative Example B 61.0 Pressure held at 0.5 MPa for 30 minutes, water permeable. Comparative Example C 80.3 Hold pressure at 0.1 MPa for 10 minutes, then allow water to pass through. Comparative Example D - Hold pressure at 0.1 MPa for 10 minutes, then allow water to pass through. Comparative Example E 88.0 Hold pressure at 0.1 MPa for 10 minutes, then allow water to pass through. Comparative Example F 70.6 Hold pressure at 0.1 MPa for 10 minutes, then allow water to pass through.

[0117] As shown in the table, the waterproof membrane prepared in this application has excellent self-healing and waterproof properties.

[0118] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane, characterized in that, The waterproof membrane comprises a five-layer structure, from top to bottom: surface layer, upper adhesive layer, reinforcing layer, lower adhesive layer, and isolation layer; The surface layer is a high-hardness mineral particle coating layer; The upper adhesive layer is a root-penetration-resistant modified bitumen adhesive; The reinforcing layer is a glass fiber reinforced polyester composite base; The lower adhesive layer is a high-pressure creep self-healing elastic asphalt adhesive; The isolation layer is a PE film.

2. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 1, characterized in that, The high-hardness mineral particle covering layer is one or more of black granite particles and black basalt particles.

3. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 1, characterized in that, The root penetration resistant modified asphalt adhesive is composed of SBS, asphalt, and a root inhibitor, and its preparation method includes the following steps: Heat the asphalt to 160-170℃, add SBS for shear dispersion for 1-2 hours, then add root inhibitor and stir for 20-40 minutes to obtain root penetration resistant modified asphalt adhesive.

4. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 3, characterized in that, The mass ratio of the asphalt, SBS, and root inhibitor is 100:5-10:3-7.

5. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 1, characterized in that, The root inhibitor is methyl 2-(4-chloro-2-methylphenoxy)propionate.

6. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 1, characterized in that, The glass fiber reinforced polyester base composite has a basis weight ≥240g / m², and its preparation method includes the following steps: (1) Polyester web formation: PET chips are melt-spun and air-blown to form an upper polyester fiber web and a lower polyester fiber web, respectively; (2) Directional reinforcement: The lower layer of polyester fiber web is continuously conveyed forward, and continuous alkali-free glass fiber rovings are evenly laid on the surface of the fiber web at equal intervals along the longitudinal direction of the material flow, and the tension of the glass fiber rovings is controlled to keep it straight and without bending. (3) Laying the mesh: Cover the upper layer of polyester fiber mesh on top of the laid glass fiber yarn to form a three-layer laminated blank of "upper polyester fiber mesh - longitudinal glass fiber yarn - lower polyester fiber mesh"; (4) Needle-punching consolidation: The preform is needle-punched on both sides using a high-speed needle-punching process. The polyester fibers interweave and bind together, locking the glass fiber roving inside the fiber web to initially form a composite fabric. (5) Hot pressing and shaping: The composite fabric is fed into a hot rolling mill and hot-pressed at 180-220℃ and 0.3-1.0MPa pressure. The surface polyester fiber melts and bonds, strengthens the interface, and prevents the glass fiber from slipping under stress. (6) Post-treatment: The sizing is carried out by impregnation with styrene-acrylic emulsion, and after drying, it is wound up to obtain glass fiber reinforced polyester composite base.

7. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 1, characterized in that, The preparation method of the high-pressure creep self-healing elastic asphalt adhesive includes the following steps: After mixing asphalt, SBS, and styrene-butadiene rubber evenly, the temperature is controlled at 180-190℃. Then, naphthenic oil, sulfur, and antioxidant are added and stirred for 2-3 hours. Modified talc powder is then added and stirred for 1-2 hours to obtain high-pressure creep self-healing elastic asphalt adhesive.

8. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 7, characterized in that, The mass ratio of the asphalt, SBS, styrene-butadiene rubber, naphthenic oil, sulfur, antioxidant, and modified talc is 100:5-8:3-7:6-10:1-3:0.2-0.5:10-15.

9. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 7, characterized in that, The preparation method of the modified talc powder includes the following steps: (1) Vanillin and furfural were dispersed in ethanol solvent, stirred and dispersed, nitrogen gas was introduced, and stirred for 2-3 hours. The temperature was raised to 70-80℃ and the reaction was carried out for 16-20 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with ethanol, and dried to obtain the intermediate. (2) The intermediate and N-propyltriethoxysilane maleimide were dispersed in toluene solvent, stirred and mixed evenly, and then heated to 90°C and reacted for 18-20 h. After the reaction was completed, the mixture was filtered, washed and dried to obtain vanillin silane. (3) Disperse vanillin-based silane in a 90% ethanol aqueous solution and stir for 20-30 min. Then add talc powder and stir for 1-2 h. After the reaction is complete, filter, wash with ethanol, and dry to obtain modified talc powder.

10. The high-hardness particle-coated glass fiber reinforced polyester-based root-penetration resistant self-protective waterproof membrane according to claim 9, characterized in that, In (1), the mass ratio of vanillin to furfurylamine is 1.5-2:1; in (2), the mass ratio of intermediate to N-propyltriethoxysilane maleimide is 1:1.4-1.8; in (3), the amount of vanillin-based silane used is 2-5% of the mass of talc.