Modified asphalt waterproof coiled material and preparation method thereof

Abstract

The invention relates to the technical field of waterproof coiled materials, in particular to a modified asphalt waterproof coiled material and a preparation method thereof. The waterproof coiled material prepared by the invention overcomes the problems of insufficient mechanical properties and poor adhesive force of asphalt coiled materials in the prior art. The modified asphalt waterproof coiled material is prepared by pre-soaking and rolling a composite matrix obtained by mixing and rolling the modified glass fiber and the matrix in the modified asphalt, and drying and curing. The use amount of diisocyanate and hydroxyl-terminated polydimethylsiloxane is controlled, so that the high-temperature resistance and low-temperature resistance of the waterproof coiled material are improved; the use amount of modified polyurethane is controlled, so that the mechanical property of the coiled material is improved; by changing the use amount of the modified asphalt and the composite base, the peel strength of the coiled material is improved, and the adhesive force of the coiled material is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of waterproof coiled materials, and specifically to a modified asphalt waterproof coiled material and a preparation method thereof. Background Art

[0002] A coiled material refers to a continuously coiled base material, which is mainly used for building walls, roofs, tunnels, roads, landfills, etc., and serves as a flexible building material product that can be coiled into a roll shape to resist the leakage of external rainwater and groundwater. As a leak-free connection between the engineering foundation and the building, it is the first barrier for the waterproofing of the entire project and plays a crucial role in the entire project.

[0003] Currently, there are mainly three types of domestic waterproof materials: asphalt-based waterproof coiled materials, polyurethane waterproof materials, and new polymer cement-based waterproof materials; according to the different carcasses, they are divided into non-carcass coiled materials, paper carcass coiled materials, fiberglass carcass coiled materials, glass cloth carcass coiled materials, and polyethylene carcass coiled materials. However, a large amount of waste gas is generated during the preparation of asphalt for asphalt-based waterproof coiled materials, causing serious environmental pollution, and accidents such as scalding and fires are likely to occur.

[0004] The modified asphalt waterproof coiled material is obtained by subjecting asphalt, softening oil, SBS, rubber powder, and additives, etc. to high-speed shearing and other processes under high-temperature conditions to obtain modified asphalt, and then using non-woven fabric, jute cloth, and fiberglass felt as the carcass, impregnating them in the modified asphalt, and compounding them with a plastic film as an isolation layer. The modified asphalt is prone to coagulation, and the rubber particles are not easily reacted completely, often leaving some fine particles or small lumps, resulting in insufficient modification of the asphalt, causing the prepared waterproof coiled material to be prone to cracking and having poor waterproof effect.

[0005] Patent CN114316803B reports a modified asphalt waterproof coiled material and a preparation method thereof. The waterproof coiled material modifies the asphalt by using styrene-butadiene rubber and modified phenolic resin in combination, which can improve the stability and mechanical properties of the final waterproof coiled material to a certain extent. However, while the branched borate ester increases the degree of branching, it reduces the high-temperature and low-temperature resistance of the waterproof coiled material, making it vulnerable to the environment.

[0006] Patent CN113914114B reports a modified asphalt waterproof coiled material and a preparation method thereof, including a modified asphalt layer, a carcass, a PET film, and mineral particles. The prepared modified asphalt waterproof coiled material has excellent waterproof performance, and its cold resistance and heat resistance are stable; however, the modified asphalt waterproof coiled material prepared by this invention has poor compatibility based on the modified asphalt layer, resulting in low adhesion and a decrease in peel strength.

[0007] Patent CN109456731B reports an SBS asphalt waterproofing coil and its preparation method. The coil includes an SBS coil body, a slow adhesion layer coated thereon, and a fast adhesion layer coated on the slow adhesion layer. The prepared waterproofing coil has strong adhesion, is not easy to peel off after adhesion, and has improved mechanical properties. However, the polymer used in the adhesion layer is easily affected by natural factors such as heat, oxygen, and ultraviolet light and undergoes aging. At the same time, the large introduction of SBS further reduces the anti-aging ability of the coil.

[0008] In summary, certain technical improvements have been made to asphalt waterproofing coils in the prior art, but there are still problems such as insufficient mechanical properties and poor bonding performance of the waterproofing coils, resulting in low adhesion, which in turn affects the overall service life of the coils.

[0009] Therefore, a modified asphalt waterproofing coil and its preparation method are proposed. Summary of the Invention

[0010] The purpose of the present invention is to provide a modified asphalt waterproofing coil and its preparation method. By polycondensing, chain-extending hexamethylene diisocyanate and hydroxyl-terminated polydimethylsiloxane, and capping with an antioxidant, epoxy resin is used to modify the polyurethane to modify the asphalt; glass fibers modified by an acrylic emulsion are mixed with the carcass and roll-pressed to obtain a composite carcass. The modified asphalt waterproofing coil is obtained by pre-impregnating and roll-pressing the composite carcass in the modified asphalt and drying and curing. By controlling the reaction conditions of the polyurethane, the high-temperature and low-temperature resistance of the waterproofing coil is improved; the polar groups of the epoxy resin are used to provide intermolecular forces to improve the mechanical properties of the modified asphalt waterproofing coil; a fluorine-containing compound is used as a functional monomer of the acrylic emulsion to improve the water resistance of the coil; the amounts of the composite carcass and the modified asphalt, and the curing reaction temperature are adjusted to improve the peel strength of the modified asphalt waterproofing coil and increase the adhesion; an antioxidant is grafted into the main chain of the coil and synergizes with titanium dioxide particles to improve the light shielding performance of the coil and enhance the anti-aging ability of the coil.

[0011] To achieve the above purpose, the present invention provides the following technical solutions: On the one hand, the present invention provides a preparation method of a modified asphalt waterproofing coil. The preparation of the modified asphalt waterproofing coil includes the following steps: Add asphalt to a reaction tank preheated to 150°C and melt it. After stirring for 15 minutes, raise the temperature to 170°C and stir for 20 minutes to obtain a mixture; add 20-50 parts of modified polyurethane and 10 parts of isoprene latex to the mixture, stir for 2 hours, then add 5 parts of graphene, raise the temperature to 200°C, and stir at 3500 rpm for 30 minutes to obtain a mixed material; add 3-8 parts of maleic anhydride to the mixed material and stir and react at 160°C for 1 hour to obtain modified asphalt.

[0012] Mix the modified glass fiber with the front and back sides of the base fabric at 160°C and roll them to obtain a composite base fabric; impregnate 30-60 parts of the composite base fabric with the modified asphalt to obtain an impregnated base fabric, coat 250-400 parts of the modified asphalt on the impregnated base fabric, roll and dry it, and the drying temperature is 160°C - 200°C to obtain a rolled material; laminate the surface of the rolled material with a polypropylene film, the lamination thickness is 2 mm, add 30 parts of mineral particles and 3-10 parts of titanium dioxide to the outermost layer, and cool and form to obtain the modified asphalt waterproof roll material; 60-90 parts of diisocyanate, 30-60 parts of hydroxyl-terminated polydimethylsiloxane, and 10 parts of butanediol are subjected to polycondensation and chain extension reactions to obtain a polyurethane prepolymer; add an antioxidant to the polyurethane prepolymer to cap it, and modify it with epoxy resin to obtain the modified polyurethane; Stir acrylonitrile, vinyl acetate, 2-hydroxyethyl acrylate, and 3-10 parts of a functional monomer to obtain a pre-emulsion; add a glass fiber precursor and ammonium persulfate to the pre-emulsion to obtain the modified glass fiber.

[0013] Preferably, the base fabric is selected from one of a polyester base fabric, a polyamide base fabric, and a glass fiber-reinforced polyester base fabric.

[0014] Preferably, the preparation of the polyurethane includes the following steps: Add 2-(2-chlorophenyl)-4,6-diphenyl-1,3,5-triazine, 4-hydroxybenzeneboronic acid, tetrakis(triphenylphosphine)palladium, and cesium carbonate to 1,4-dioxane, and react at 100°C for 6 h to obtain a reaction solution; cool the reaction solution, add water and ethyl acetate for dilution, extract and separate, distill under reduced pressure, and dry to obtain the antioxidant; Dry 60-90 parts of the diisocyanate and 30-60 parts of the hydroxyl-terminated polydimethylsiloxane in a vacuum drying oven at 80°C for 2 h to obtain a dry raw material; add the dry raw material to a four-necked flask and dissolve it with DMF to obtain a dissolution system; protect the dissolution system with nitrogen, heat it to 50°C, add dibutyltin dilaurate and react for 3 h to obtain a reaction system; add 10 parts of butanediol to the reaction system and carry out a chain extension reaction for 2 h to obtain a polyurethane prepolymer; Cool the polyurethane prepolymer to 40°C, add the antioxidant, and react at 60°C for 2 h to obtain an intermediate; cool the intermediate to room temperature, add triethylamine to neutralize the reaction system, and react for 30 min to obtain a neutralization system; add the epoxy resin to the neutralization system, add dibutyltin dilaurate, and react at 70°C for 3 h to obtain a reactant; cool the reactant and carry out vacuum degassing to obtain the modified polyurethane.

[0015] Preferably, the diisocyanate is selected from one of toluene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and p-phenylene diisocyanate.

[0016] Preferably, the epoxy resin is selected from one of E42, E44, E51, and E52; the ratio of the epoxy resin to the polyurethane prepolymer is 1:3 - 10 by parts.

[0017] Preferably, the preparation of the pre-emulsion includes the following steps: Add sodium dodecyl sulfate into a four-necked flask, add deionized water and stir for 15 min to obtain a mixed emulsion; add the acrylonitrile, the vinyl acetate, the 2-hydroxyethyl acrylate, and the functional monomer into the mixed emulsion, and stir for pre-emulsification for 30 min to obtain the pre-emulsion.

[0018] Preferably, the functional monomer is selected from one of perfluorooctylethyl acrylate, hexafluorobutyl methacrylate, methacrylic acid, and 2-(perfluorodecyl)ethyl methacrylate.

[0019] Preferably, the preparation of the modified glass fiber includes the following steps: Treat the glass fiber through steps such as dewaxing and alkali treatment to obtain the glass fiber precursor; add the ammonium persulfate and NaHCO3 into a four-necked flask, add deionized water and stir to dissolve, and stir at room temperature for 10 min to obtain a pre-reaction solution; heat the pre-reaction solution to 60 °C, add the glass fiber precursor, and stir for 10 min to obtain a stirred solution; dropwise add the pre-emulsion into the stirred solution, heat to 80 °C and react for 2 h to obtain a reaction solution; cool the reaction solution, wash with deionized water, extract with ethanol, and dry in vacuum at 60 °C to obtain the modified glass fiber.

[0020] Preferably, the average molecular weight of the hydroxyl-terminated polydimethylsiloxane is selected from 1600 - 2800.

[0021] Preferably, the linear velocity of the pre-impregnated roll before rolling is 25.5 - 35.5 m / min, the production speed is 30 - 40 m / min, and the linear velocity of the modified asphalt roll after rolling is 30.5 - 32.5 m / min.

[0022] On the other hand, the present invention provides a modified asphalt waterproof coil, which includes modified asphalt, a base fabric, modified glass fiber, mineral particles, and titanium dioxide; the modified asphalt waterproof coil is prepared by the method described in any one of the above.

[0023] Compared with the prior art, the beneficial effects of the present invention are: 1. The present invention obtains a modified polyurethane by polycondensation, chain extension of hexamethylene diisocyanate and hydroxyl-terminated polydimethylsiloxane, and end-capping with an antioxidant, and modifies the matrix asphalt with the modified polyurethane. The heat resistance of the coil material is increased by using the Si-O bond, and the low-temperature resistance of the coil material is effectively improved by the long-chain flexible structure. By controlling the amounts of diisocyanate and hydroxyl-terminated polydimethylsiloxane, the low-temperature flexibility of the prepared modified asphalt waterproof coil material is -42 °C, and the softening point is 153 °C.

[0024] 2. The present invention utilizes the increase in the crosslinking degree and hydrogen bond density between epoxy resin and polyurethane, so that a fuzzy interfacial layer is formed between the hard and soft segments of polyurethane, and a strong non-covalent bond attraction is formed between the hard and soft segments, thereby improving the tensile performance and elongation at break of the coil material. By controlling the amount of epoxy resin and the amount of modified polyurethane, the transverse tensile strength of the prepared modified asphalt waterproof coil material is 1315 N / mm, and the longitudinal tensile strength is 1228 N / mm, showing significantly improved mechanical properties.

[0025] 3. The present invention uses a pre-emulsion modified glass fiber prepared with perfluorooctylethyl acrylate as a functional monomer, mixes it with a base fabric and rolls them to obtain a composite base fabric, and pre-impregnates and rolls the composite base fabric in the modified asphalt, and dries and cures it to obtain the modified asphalt waterproof coil material. A dense protective film is formed on the surface of the waterproof coil material by fluorine atoms. The prepared modified asphalt waterproof coil material can achieve a water impermeability of 5.5 h under the condition of 0.3 MPa, showing significantly improved water resistance.

[0026] 4. The present invention improves the compatibility between the modified polyurethane and asphalt and the stability of the modified asphalt by adjusting the amount of maleic anhydride, and changes the crosslinking and curing temperature by adjusting the amounts of the composite base fabric and the modified asphalt, and improves the crosslinking degree between the modified polyurethane and the modified glass fiber in the modified asphalt. The formed crosslinked network structure improves the peel strength of the coil material. By changing the amounts of the modified asphalt and the composite base fabric and controlling the drying and curing temperature, the peel strength of the obtained modified asphalt waterproof coil material is 3.28 N / mm, showing significantly improved adhesion.

[0027] 5. The present invention uses an antioxidant as the end-capping agent of polyurethane, and an antioxidant is introduced into the main chain of the prepared modified asphalt, reducing the influence of free radical molecules on the intermolecular force of the modified asphalt molecules. At the same time, the addition of titanium dioxide particles further improves the aging resistance of the waterproof coil material. The strength retention rate of the prepared modified asphalt waterproof coil material irradiated at 80 °C for 800 h is 98.6%, and the low-temperature flexibility is -35 °C, showing significantly improved aging resistance. Description of the Drawings

[0028] Figure 1 It is a graph of the tensile strength and elongation at break results of Examples 15-18. Detailed Embodiments

[0029] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0030] For those not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. Reagents or instruments not specified by the manufacturer are all conventional products that can be obtained through commercial purchase.

[0031] Please refer to Figure 1 , the present invention provides a modified asphalt waterproof coiled material and its preparation method, and the technical solution is as follows: Example 1

[0032] 5 mmol of 2-(2-chlorophenyl)-4,6-diphenyl-1,3,5-triazine, 6 mmol of 4-hydroxybenzeneboronic acid, 0.02 mmol of tetrakis(triphenylphosphine)palladium, and 10 mmol of cesium carbonate were added to 5 ml of 1,4-dioxane, and reacted at 100 °C for 6 h to obtain a reaction solution; the reaction solution was cooled, diluted with water and ethyl acetate, extracted and separated, distilled under reduced pressure, and dried to obtain an antioxidant.

[0033] 80 parts of toluene diisocyanate and 50 parts of hydroxyl-terminated polydimethylsiloxane were dried in a vacuum drying oven at 80 °C for 2 h to obtain a dried raw material; the dried raw material was added to a four-necked flask and dissolved in 2 ml of DMF to obtain a dissolution system; the dissolution system was protected by nitrogen, heated to 50 °C, and 2 parts of dibutyltin dilaurate were added and reacted for 3 h to obtain a reaction system; 10 parts of butanediol were added to the reaction system, and the chain extension reaction was carried out at a constant temperature for 2 h to obtain a polyurethane prepolymer.

[0034] 100 parts of the polyurethane prepolymer was cooled to 40 °C, acetone was added to reduce the viscosity, 15 parts of the antioxidant was added, and the reaction was carried out at 60 °C for 2 h to obtain an intermediate; the intermediate was cooled to room temperature, and triethylamine was added to neutralize the reaction system at 200 r / min for 30 min to obtain a neutralization system; 20 parts of epoxy resin was added to the neutralization system, and dibutyltin dilaurate was added at 200 r / min, and the reaction was carried out at 70 °C for 3 h to obtain a reaction product; the reaction product was cooled and degassed under vacuum to obtain a modified polyurethane.

[0035] By parts, 60 parts of 90# asphalt are added to a reaction tank preheated to 150 °C to facilitate its full melting. After stirring for 15 min, the temperature is raised to 170 °C, and stirred for 20 min to obtain a mixture; 40 parts of the modified polyurethane and 10 parts of isoprene latex are added to the mixture, stirred for 2 h, then 5 parts of graphene are added, and stirring continues for 30 min. The temperature is raised to 200 °C, and stirred at 3500 rpm for 30 min to obtain a mixed material; 5 parts of maleic anhydride are added to the mixed material, and stirred and reacted at 160 °C for 1 h to obtain modified asphalt.

[0036] 6 parts of sodium dodecyl sulfate are added to a four-necked flask, and 50 ml of deionized water is added and stirred and mixed for 15 min to obtain a mixed emulsion; 50 parts of acrylonitrile, 20 parts of vinyl acetate, 10 parts of 2-hydroxyethyl acrylate, and 8 parts of perfluoroalkyl ethyl acrylate are added to the mixed emulsion, stirred at 200 r / min, and pre-emulsified for 30 min to obtain a pre-emulsion.

[0037] The glass fiber is obtained through steps such as dewaxing and alkali treatment to get a glass fiber precursor; 3 parts of ammonium persulfate and the buffer NaHCO3 are added to a four-necked flask, 50 ml of deionized water is added and stirred until dissolved, and stirred at 200 rpm for 10 min at room temperature to obtain a pre-reaction solution; the pre-reaction solution is heated to 60 °C under an oil bath condition, the glass fiber precursor is added, and stirred at 200 rpm for 10 min to obtain a stirred solution; the pre-emulsion is slowly added dropwise to the stirred solution, heated to 80 °C and reacted for 2 h to obtain a reaction solution; the reaction solution is cooled, washed with deionized water, extracted with ethanol, and vacuum dried at 60 °C to obtain modified glass fiber.

[0038] The modified glass fiber is mixed with the front and back sides of the base fabric at 160 °C and roll-pressed to obtain a composite base fabric; 50 parts of the composite base fabric and the modified asphalt are pre-impregnated to obtain a pre-impregnated base fabric. 300 parts of the modified asphalt are coated on the pre-impregnated base fabric, roll-pressed and dried, and the drying temperature is 180 °C to obtain a roll-pressed material; a polypropylene film is laminated on the surface of the roll-pressed material, the lamination thickness is 2 mm, and 30 parts of mineral particles and 8 parts of titanium dioxide are added to the outermost layer, and cooled and formed to obtain a modified asphalt waterproof coil.

[0039] Examples 2 - 13 Refer to the preparation method and parameter conditions of Example 1, with the differences shown in Table 1.

[0040] Table 1 Changes in component dosages of Examples 1 - 13

[0041] Comparative Example 1 Refer to the preparation method and parameter conditions of Example 1, except that polyether diol is used to replace hydroxyl-terminated polydimethylsiloxane.

[0042] Example 14 Determination of high and low temperature resistance The low-temperature flexibility and softening point of the modified asphalt waterproof coiled materials prepared in Examples 1-13 and Comparative Example 1 were tested. The low-temperature flexibility and waterproofness were carried out in accordance with the standard GB18242-2008 "Elastomer Modified Asphalt Waterproof Coiled Materials"; the softening point was tested in accordance with the test method of GB / T 4507-2014 "Determination of Asphalt Softening Point - Ring and Ball Method". The test results are shown in Table 2.

[0043] Table 2 Determination of High and Low Temperature Resistance Performance of Examples 1-13 and Comparative Example 1

[0044] It can be seen from the results in Table 2 that for the modified polyurethane prepared by using polyether diol to replace hydroxyl-terminated polydimethylsiloxane in Comparative Example 1, the low-temperature flexibility and softening point of the finally prepared modified asphalt waterproof coiled material showed a significant decrease compared with those in Examples 1-13, and the low-temperature resistance and high-temperature resistance of the coiled material decreased. Due to the introduction of polysiloxane, Si-O bonds with relatively high bond energy were introduced into the main chain of the polyurethane molecule, further increasing the heat resistance of the coiled material. At the same time, the silicon-oxygen bond has the flexibility of an ether bond, and silicon elements increase the use of the coiled material under low-temperature conditions, further improving the low-temperature resistance of the coiled material; it can be seen from the results of Examples 1-5 that with the change of the type of diisocyanate, the influence on the heat resistance of the coiled material is small. However, the introduction of aromatic or alicyclic rigid structures reduces the low-temperature performance of the coiled material, and the coiled material is prone to brittle fracture at lower temperatures, affecting its use. The long-chain flexible structure effectively improves the low-temperature resistance of the coiled material; it can be seen from the results of Examples 3, 6-8 that with the increase in the amount of diisocyanate, the high-temperature resistance and low-temperature resistance of the coiled material gradually increase. However, excessive isocyanate will introduce a branched structure into the main chain of the polyurethane, reducing the low-temperature resistance of the coiled material; it can be seen from the results of Examples 3, 9-11 that with the increase in the amount of hydroxyl-terminated polydimethylsiloxane, the high-temperature resistance gradually increases, and the low-temperature resistance shows a trend of increasing first and then decreasing; it can be obtained from the results of Examples 3, 12-13 that with the increase in the molecular weight of hydroxyl-terminated polydimethylsiloxane, the heat resistance gradually increases, and the low-temperature resistance shows a trend of increasing first and then decreasing. With the increase in the molecular weight of the chain segment, the unreacted siloxane accumulates in the polyurethane material, destroying the continuity of the macromolecular chain segments in the coiled material, further reducing the low-temperature resistance; it can be seen from the results in Table 2 that by changing the type of diisocyanate, the amounts of diisocyanate and hydroxyl-terminated polydimethylsiloxane, the low-temperature flexibility of the prepared modified asphalt waterproof coiled material is -42 °C, and the softening point is 153 °C, showing significantly improved high-temperature resistance and low-temperature resistance.

[0045] Examples 15-24 Refer to the preparation method and parameter conditions of Example 3, with the differences shown in Table 3.

[0046] Comparative Example 2 Referring to the preparation method and parameter conditions of Example 3, the difference is that modified polyurethane modified asphalt is not added.

[0047] Comparative Example 3 Referring to the preparation method and parameter conditions of Example 3, the difference is that epoxy resin is not added to the modified polyurethane.

[0048] Example 25 Tensile Strength Test The modified asphalt waterproof coiled materials prepared in Examples 15 - 24 and Comparative Examples 3 - 4 were subjected to tensile property tests. The tensile strength and elongation at break of the above waterproof coiled materials were tested according to the standard of GB18242 - 2008. During the tensile process, there was no asphalt cracking or separation from the carcass in the modified asphalt waterproof coiled materials. The test results of the transverse tensile strength and longitudinal tensile strength are shown in Table 3; the results of the transverse tensile strength and elongation at break of Examples 15 - 18 are as Figure 1 shown.

[0049] Table 3 Tensile Property Tests of Examples 15 - 24 and Comparative Examples 3 - 4

[0050] From the results in Table 3, it can be seen that the tensile strength of the waterproof coiled material prepared by adding modified polyurethane modified asphalt in Comparative Example 3 is significantly lower than that in Comparative Example 4 without epoxy - modified polyurethane, indicating that using epoxy resin to modify polyurethane, and at the same time using maleic anhydride can increase the compatibility between the modified polyurethane and asphalt. At the same time, polyurethane can form a three - dimensional network interpenetrating structure with epoxy resin, encapsulating the asphalt in the waterproof coiled material. Through curing with the curing agent in the composite carcass, the three - dimensional structure of the cured modified asphalt waterproof coiled material is more stable, further increasing the mechanical properties of the coiled material; from Figure 1From the results of Examples 15 - 18, it can be seen that as the epoxy degree of the epoxy resin increases, the transverse tensile strength of the coil can reach 1315 N / mm, and the longitudinal tensile strength can reach 1228 N / mm, showing significantly improved tensile properties. As the epoxy degree increases, a large number of hydrogen bonds can be formed between the epoxy resin and the hard and soft segments of the polyurethane. The increase in the crosslinking degree and hydrogen bond density between the epoxy resin and the polyurethane results in the formation of a fuzzy interfacial layer between the hard and soft segments of the polyurethane. As a transition layer between the soft and hard segments, the fuzzy interfacial layer can not only effectively separate the hard and soft segments but also form strong non-covalent bond attractions between the hard and soft segments, thereby improving the tensile properties and elongation at break of the coil. From the results of Examples 18 - 21, it can be seen that as the amount of epoxy resin increases, the tensile strength of the coil shows a gradually increasing and stabilizing trend. When the crosslinking degree reaches saturation, a stable network structure is formed under the polar action of the modified asphalt and the carcass, improving the tensile strength. From the results of Example 18 and Examples 22 - 24, it can be seen that as the content of the modified polyurethane increases, the tensile strength of the waterproof coil shows a trend of increasing first and then decreasing. The compatibility between the excessive modified polyurethane and the asphalt becomes poor, and some of the modified polyurethane fails to be successfully grafted onto the asphalt molecules. The generated urea groups will, to a certain extent, destroy the uniformity of the interpenetrating network and reduce the mechanical properties of the coil. Through Table 3, Figure 1 It can be seen that by controlling the type of epoxy resin and the ratio of the number of parts of the polyurethane prepolymer, and controlling the amount of the modified polyurethane, the transverse tensile strength of the modified asphalt waterproof coil prepared is 1315 N / mm, and the longitudinal tensile strength is 1228 N / mm, showing significantly improved mechanical properties.

[0051] Examples 26 - 37 Refer to the preparation method and parameter conditions of Example 18, with the differences shown in Table 4.

[0052] Comparative Example 5 Refer to the preparation method and parameter conditions of Example 18, with the difference that no modified glass fiber is added.

[0053] Comparative Example 6 Refer to the preparation method and parameter conditions of Example 18, with the difference that unmodified glass fiber is added.

[0054] Example 38 Water resistance effect test Refer to GB 18242 - 2008 "Elastomer modified bitumen waterproof sheets" to conduct impermeability tests on the waterproof sheets prepared in Examples 26 - 37 and Comparative Examples 5 - 6. The test pressure is 0.3 MPa, and the water resistance effect of the coil is tested by the impermeability maintenance time. The test results are shown in Table 4.

[0055] Table 4 Water resistance effect test of Examples 26 - 37 and Comparative Examples 5 - 6

[0056] It can be seen from the results in Table 4 that in the modified asphalt waterproof coiled materials prepared in Comparative Examples 5-6, due to the absence of pre-emulsion modified glass fibers, the water impermeability performance decreased significantly; from the results of Examples 26-29, it can be seen that with the change of the functional monomer in the pre-emulsion, the water impermeability of the coiled material changed significantly. When using fluorine-containing functional monomers, during the film-forming process of the emulsion, fluorine atoms will migrate to the interface formed by the coiled material and air as the water volatilizes, and a dense protective film will be formed on the surface of the waterproof coiled material, improving the water resistance of the coiled material. When using methacrylic acid as the functional monomer, the increase in polar groups on the surface of the coiled material enhances the interaction between water molecules and the coiled material, reducing the water resistance effect; from the results of Examples 26, 30-32, it can be seen that with the increase in the amount of functional monomer, the fluorine atom content increases, a dense film structure is formed on the surface of the coiled material, reducing the influence of water molecules on the coiled material, and the water impermeability time of the waterproof coiled material gradually extends; from the results of Examples 26, 33-34, it can be seen that using a glass fiber-reinforced polyester base increases the compatibility with the modified glass fiber, and the polar groups in the modified glass fiber crosslink with the base, causing the non-polar fluorine-containing functional monomer to migrate to the interface formed by the coiled material and air, further increasing the water resistance effect of the coiled material; from the results of Examples 33, 35-37, it can be seen that with the increase in the amount of composite base, the water impermeability time of the coiled material gradually extends and tends to be constant. When the amount of composite base is low, the amount of the fluorine-containing protective film formed by the functional monomer migrating to the surface of the coiled material is small, and a dense film structure cannot be formed on the surface of the modified asphalt and air. Water molecules enter the interior of the coiled material through the polyurethane and epoxy resin systems of the modified asphalt layer, reducing the service life of the waterproof coiled material. It can be seen from the results in Table 4 that using the pre-emulsion prepared with perfluorooctylethyl acrylate as the functional monomer, controlling the type of base and the amount of composite base, the modified asphalt waterproof coiled material can achieve a water impermeability of 5.5 h under the condition of 0.3 MPa, showing a significantly improved water resistance effect.

[0057] Examples 39-50 Refer to the preparation method and parameter conditions of Example 33, with the differences shown in Table 5.

[0058] Comparative Example 7 Refer to the preparation method and parameter conditions of Example 33, with the difference that maleic anhydride is not added.

[0059] Comparative Example 8 Refer to the preparation method and parameter conditions of Example 33, with the difference that pre-emulsion modified glass fibers are not added.

[0060] Example 51 Peel performance test The modified asphalt waterproof coiled materials obtained in Examples 39-50 and Comparative Examples 7-8 were subjected to peel performance tests. According to the GB18242-2008 standard, the peel strength of the above waterproof coiled materials was tested, and the test results are shown in Table 5.

[0061] Table 5 Peel Performance Tests of Examples 39 - 50 and Comparative Examples 7 - 8

[0062] From the results in Table 5, it can be seen that for the modified asphalt prepared without adding maleic anhydride in Comparative Example 7, the peel strength of the waterproof coiled material prepared is significantly lower than that of Examples 39 - 50. Due to the addition of maleic anhydride, the compatibility between the modified asphalt and the modified polyurethane is increased, the binding force between the components in the modified asphalt is improved, and the agglomeration of graphene particles caused by the change in temperature during the drying process is avoided. At the same time, the addition of maleic anhydride improves the compatibility between the latex and the modified polyurethane, thereby improving the stability of the modified asphalt and avoiding the unevenness between the coiled material layers during the pre - impregnation with the composite base and the roller - press drying process, reducing the comprehensive performance of the coiled material; in Comparative Example 8, without adding the pre - emulsion, the peel strength of the coiled material is further improved. The addition of the acrylate pre - emulsion can combine with the polyurethane and epoxy resin in the modified asphalt and undergo a curing reaction during the drying process to cross - link and form a stable network structure, further improving the peel strength; from the results of Examples 39 - 42, it can be seen that as the amount of maleic anhydride increases, the peel strength of the waterproof coiled material gradually increases. However, an excessive amount of maleic anhydride will reduce the water - resistance effect of the fluorine monomer in the pre - emulsion and reduce the water - impermeability of the coiled material; from the results of Examples 39, 43 - 45, it can be seen that as the content of the modified asphalt increases, the peel strength of the coiled material shows a gradually increasing trend. When the amount of the modified asphalt reaches 300 parts, the increase in the peel strength gradually slows down, indicating that the cross - link between the modified asphalt and the composite base has reached a stable state with little change; from the results of Examples 39, 46 - 47, it can be seen that as the amount of the composite base increases, the peel strength of the coiled material shows a trend of first increasing and then decreasing. Due to the excessive composite base, the large amount of non - polar fluorine groups reduces the cross - link curing between the modified asphalt and the composite base, resulting in a decrease in the peel strength; from the results of Examples 39, 48 - 50, it can be seen that as the drying temperature increases, the peel strength gradually increases and tends to be constant. The increase in temperature is conducive to the cross - link curing of the acrylate pre - emulsion with the polyurethane - epoxy resin system in the modified asphalt to form a stable network structure; from the results in Table 5, by changing the amount of the modified asphalt and the composite base and controlling the drying and curing temperature, the peel strength of the modified asphalt waterproof coiled material is 3.28 N / mm, showing a significantly improved adhesion force.

[0063] Examples 52 - 61 Refer to the preparation method and parameter conditions of Example 39, with the differences shown in Table 6.

[0064] Comparative Example 9 Refer to the preparation method and parameter conditions of Example 39, with the difference that no antioxidant is added and 35 parts of epoxy resin are added.

[0065] Comparative Example 10 Referring to the preparation method and parameter conditions of Example 39, the difference is that titanium dioxide is not added.

[0066] Example 62 Aging Resistance Performance Test Samples of the modified asphalt waterproof coiled materials prepared in Examples 52 - 61 and Comparative Examples 9 - 10 were taken, with dimensions of 180×25 mm. According to the low temperature flexibility tested in Example 14 and the elongation at break measured in Example 25, the specimens were placed in an ultraviolet aging test chamber for ultraviolet aging acceleration experiment. The test temperature was 80°C, the light source was an 800W high-pressure mercury lamp, the distance between the specimen and the light source was 20 mm, and the irradiation time was 800 h. The tensile strength of the composite material before and after irradiation was tested, and the strength retention rate was calculated. The low temperature flexibility was recorded. The test results are shown in Table 6.

[0067] Table 6 Aging Resistance Performance Test of Examples 52 - 61 and Comparative Examples 9 - 10

[0068] As can be seen from the results in Table 6, the aging resistance of the modified asphalt waterproofing membrane prepared in Example 9 without adding an antioxidant as the end-capping agent of polyurethane is significantly reduced compared with Examples 52-61; the anti-aging performance of the waterproofing membrane prepared in Comparative Example 10 without adding titanium dioxide is significantly improved compared with Comparative Example 9, but the strength retention rate is only 80.2%, still showing poor aging resistance. The addition of titanium dioxide provides ultraviolet shielding performance for the waterproofing membrane, which can reduce the damage of ultraviolet rays to the membrane. From the results of Examples 52-55, it can be seen that with the increase of the antioxidant dosage, the anti-aging performance of the waterproofing membrane shows a trend of increasing first and then decreasing. The addition of the antioxidant introduces an ultraviolet light shielding agent into the main chain structure of the modified asphalt, reducing the influence of free radical molecules on the intermolecular force of the modified asphalt molecules, thereby reducing the aging resistance of the waterproofing membrane. However, the addition of an excessive amount of antioxidant introduces more non-polar groups into the membrane, and a stable cross-linked structure cannot be formed during the curing process. Under the long-term action of ultraviolet light, the polar groups inside the material are oxidized by ultraviolet light, resulting in a decrease in the strength retention rate. From the results of Examples 52, 56-58, it can be seen that with the increase of the modified polyurethane dosage, the anti-aging performance of the waterproofing membrane gradually improves. However, the addition of an excessive amount of modified polyurethane leads to poor compatibility with asphalt, and some modified polyurethanes fail to be successfully grafted onto the asphalt molecules, and the generated urea groups will, to a certain extent, destroy the uniformity of the interpenetrating network and reduce the mechanical properties of the membrane. From the results of Examples 52, 59-61, it can be seen that with the increase of the titanium dioxide dosage, the anti-aging performance of the waterproofing membrane gradually improves, manifested as the strength retention rate gradually increases and tends to be constant. However, the addition of an excessive amount of titanium dioxide particles increases the possibility of agglomeration of titanium dioxide particles and mineral particles, further affecting the comprehensive performance of the membrane during use. As can be seen from the results in Table 6, the modified asphalt waterproofing membrane prepared by using antioxidant-capped modified polyurethane modified asphalt and adding titanium dioxide synergistically has a strength retention rate of 98.6% after being irradiated at 80 °C for 800 h and a low temperature flexibility of -35 °C, showing significantly improved aging resistance.

[0069] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a modified asphalt waterproofing membrane, characterized in that: The preparation method comprises the following steps: The modified glass fiber is mixed with the front and back sides of the tire base and rolled to obtain a composite tire base; the composite tire base is pre-impregnated with modified asphalt to obtain a pre-impregnated tire base; the modified asphalt is coated on the pre-impregnated tire base, and the roller is dried to obtain a roller material; the surface of the roller material is coated with a polypropylene film, mineral particles and titanium dioxide are added to the outermost layer in sequence, and the modified asphalt waterproof membrane is obtained by cooling and molding; The modified asphalt is prepared by stirring and heating 90# asphalt, adding modified polyurethane and isoprene latex, stirring and adding graphene and maleic anhydride, and stirring for reaction; The modified polyurethane is prepared by polycondensation and chain extension of diisocyanate, terminal hydroxyl polydimethylsiloxane and butanediol, end-capping with an antioxidant, and modification with an epoxy resin; The modified glass fiber is obtained by stirring and reacting acrylonitrile, vinyl acetate, hydroxyethyl acrylate and functional monomers as a glass fiber precursor; The functional monomer is selected from one of perfluorooctyl ethyl acrylate, hexafluorobutyl methacrylate, methacrylic acid, and 2-(perfluorodecyl)ethyl methacrylate.

2. The method for preparing a modified asphalt waterproofing membrane according to claim 1, characterized in that: The tire base is selected from one of a polyester tire base, a polyamide tire base, and a glass fiber reinforced polyester tire base.

3. The method for preparing a modified asphalt waterproofing membrane according to claim 1, characterized in that: The preparation of the modified polyurethane comprises the following steps: Add 2-(2-chlorophenyl)-4,6-diphenyl-1,3,5-triazine, 4-hydroxyphenylboric acid, tetrakistriphenylphosphine palladium and cesium carbonate to 1,4-dioxane, and react at 100° C. for 6 hours to obtain a reaction system; cool the reaction system, add water and ethyl acetate to dilute, extract and separate, perform vacuum distillation, and dry to obtain the antioxidant; Dry 60-90 parts of the diisocyanate and 30-60 parts of the terminal hydroxyl polydimethylsiloxane in a vacuum drying oven at 80° C. for 2 hours to obtain a dry raw material; add the dry raw material into a four-necked flask and dissolve it in DMF to obtain a dissolving system; protect the dissolving system with nitrogen, heat it to 50° C., add dibutyltin dilaurate and react for 3 hours to obtain a reaction system; add 10 parts of butanediol to the reaction system, and carry out a chain extension reaction for 2 hours to obtain a polyurethane prepolymer; The polyurethane prepolymer is cooled to 40°C, 8-18 parts of the antioxidant is added, and the mixture is reacted at 60°C for 2 hours to obtain an intermediate; the intermediate is cooled to room temperature, triethylamine is added to neutralize the reaction system, and the mixture is reacted for 30 minutes to obtain a neutralization system; the epoxy resin and dibutyltin dilaurate are added to the neutralization system, and the mixture is reacted at 70°C for 3 hours to obtain a reactant; the reactant is cooled, and vacuum degassing is performed to obtain the modified polyurethane.

4. The method for preparing a modified asphalt waterproofing membrane according to claim 1, characterized in that: The preparation of the modified asphalt comprises the following steps: The 90# asphalt is added into a reaction tank preheated at 150°C to melt, and the mixture is obtained by stirring and heating; 20-50 parts of the modified polyurethane and 10 parts of the isoprene latex are added into the mixture, and the mixture is stirred for 2 hours, and then 5 parts of the graphene are added, the temperature is raised to 200°C, and the mixture is stirred at 3500rpm for 30 minutes to obtain a mixed material; 3-8 parts of maleic anhydride are added into the mixture, and the mixture is stirred for reaction to obtain modified asphalt.

5. The method for preparing a modified asphalt waterproofing membrane according to claim 3, characterized in that: The diisocyanate is selected from toluene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and p-xylylene diisocyanate; and the average molecular weight of the hydroxy-terminated polydimethylsiloxane is 1600-2800.

6. The method for preparing a modified asphalt waterproofing membrane according to claim 3, characterized in that: The epoxy resin is selected from one of E42, E44, E51 and E52; the ratio of the epoxy resin to the polyurethane prepolymer is 1:3-10.

7. The method for preparing a modified asphalt waterproofing membrane according to claim 1, characterized in that: The preparation of the modified glass fiber comprises the following steps: The glass fiber is subjected to the steps of dewaxing and alkali treatment to obtain the glass fiber precursor; ammonium persulfate and NaHCO3 are added into a four-necked flask, added into deionized water, stirred to dissolve, and stirred for 10 minutes at room temperature to obtain a pre-reaction liquid; the pre-reaction liquid is heated, the glass fiber precursor is added, and stirred to obtain a stirred liquid; the pre-emulsion is dripped into the stirred liquid, and the temperature is increased for reaction to obtain a reaction liquid; the reaction liquid is cooled, washed with deionized water, extracted with ethanol, and vacuum dried to obtain the modified glass fiber.

8. The method for preparing a modified asphalt waterproofing membrane according to claim 7, characterized in that: The preparation of the pre-emulsion comprises the following steps: Sodium dodecyl sulfate is added into a four-necked flask, and then added into deionized water and stirred for 15 minutes to obtain a mixed emulsion; 50 parts of acrylonitrile, 20 parts of vinyl acetate, 10 parts of hydroxyethyl acrylate, and 3-10 parts of functional monomer are added into the mixed emulsion, and stirred for pre-emulsification for 30 minutes to obtain the pre-emulsion.

9. A modified asphalt waterproofing membrane, characterized in that: The modified asphalt waterproofing roll material comprises 250-400 parts of modified asphalt, 30-60 parts of composite base, 30 parts of mineral particles and 3-10 parts of titanium dioxide; The modified asphalt waterproofing membrane is prepared by the method as described in any one of claims 1-8.

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