Thermoplastic polyolefin waterproofing membrane and method of making same

Abstract

This invention discloses a thermoplastic polyolefin waterproof membrane and its preparation method, belonging to the field of polymer membrane materials. The thermoplastic polyolefin waterproof membrane includes a waterproof surface layer and a thermoplastic softening and permeating layer. The waterproof surface layer comprises the following components in parts by weight: 100 parts polyolefin elastomer, 25-28 parts polypropylene polyol, 8-9 parts toughening agent, 4-6 parts thermally conductive modifier, 0.8-1.5 parts antioxidant, and 1-1.2 parts light stabilizer. The thermoplastic softening and permeating layer comprises the following components in parts by weight. The composition comprises: 25-30 parts of a silane coupling agent containing isocyanate functional groups, 13-15 parts of epoxy polyurethane modified porous C5 petroleum resin microspheres, 0.15-0.25 parts of an organotin catalyst, and 10-12 parts of a photosensitizing reactant; wherein the photosensitizing reactant is a microcapsule formulation; the shell material of the microcapsule formulation includes hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer; the core material of the microcapsule formulation comprises the following components by weight fraction: 84-85 parts of the photosensitizing reactant and 4-6 parts of a photosensitizer. This application can be applied to the reinforcing sealing of welds in thermoplastic polyolefin waterproof membranes.

Description

Technical Field

[0001] This invention belongs to the field of polymer membrane materials and relates to a thermoplastic polyolefin waterproof membrane and its preparation method. Background Technology

[0002] Thermoplastic polyolefin (TPO) waterproof membrane is a new type of waterproof membrane made from thermoplastic polyolefin (TPO) synthetic resin as the base material, with the addition of antioxidants, anti-aging agents, softeners and other additives and auxiliaries. It has comprehensive characteristics such as high tensile strength, good puncture resistance, strong UV resistance, smooth surface, high reflectivity and stain resistance. It is easy to process, weldable and convenient to construct; it is currently a commonly used waterproof membrane for roofs and other applications.

[0003] Currently, the overlapping joints of adjacent thermoplastic polyolefin waterproof membranes are mainly sealed using hot air welding. Achieving a high level of seal during the welding process requires very high construction standards, making it difficult to ensure uniform and continuous welds, and increasing the risk of incomplete welds. Once an incomplete weld occurs, a weak point for penetration is created at the weld joint. Summary of the Invention

[0004] The purpose of this invention is to provide a thermoplastic polyolefin waterproof membrane and its preparation method, which solves the problem that the current method of forming a sealing layer by hot air welding at the overlap of adjacent thermoplastic polyolefin waterproof membranes has high construction requirements, makes it difficult to ensure uniform and continuous welds, and easily leads to missed welds. Once a missed weld occurs, a weak point for penetration is formed at the weld.

[0005] The technical solution adopted in this invention is as follows: A thermoplastic polyolefin waterproof membrane is used to reinforce and seal the weld seams of thermoplastic polyolefin waterproof membranes. The thermoplastic polyolefin waterproof membrane includes a waterproof surface layer and a thermoplastic softening and penetrating layer, wherein the thermoplastic softening and penetrating layer is uniformly and completely attached to one side of the waterproof surface layer. Calculated on a dry film basis, the thickness of the thermoplastic softening and penetrating layer is 1 / 2 to 2 / 3 of the thickness of the waterproof surface layer. Independently calculated, the waterproof surface layer comprises the following components in parts by weight: 100 parts polyolefin elastomer, 25-28 parts polypropylene polyol, 8-9 parts toughening agent, 4-6 parts thermally conductive modifier, 0.8-1.5 parts antioxidant, and 1-1.2 parts light stabilizer. Independently calculated, the thermoplastic softening and penetrating layer comprises the following components in parts by weight: 25-30 parts of a silane coupling agent containing isocyanate functional groups, 13-15 parts of epoxy polyurethane modified porous C5 petroleum resin microspheres, 0.15-0.25 parts of an organotin catalyst, and 10-12 parts of a photosensitizing reactant; the photosensitizing reactant is a microcapsule formulation; Independently calculated, the shell material of the microcapsule formulation comprises hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer; the core material of the microcapsule formulation comprises the following components by weight fraction: 84-85 parts photosensitizing reactant and 4-6 parts photosensitizer.

[0006] Furthermore, the epoxy polyurethane modified porous C5 petroleum resin microspheres were prepared by the following method, based on parts by weight: A. Add 50 parts of C5 petroleum resin, 30 parts of cyclohexane, 10 parts of n-heptane, 3 parts of polyvinyl alcohol, and 1 part of diethylene glycol dimethacrylate to a reaction vessel, heat to 80-85℃, and stir until homogeneous to form an oil phase; add 100 parts of deionized water and 1 part of sodium dodecylbenzenesulfonate to an emulsification vessel, and stir until homogeneous to form an aqueous phase; slowly add the aqueous phase dropwise to the oil phase, stir (300-400 r / min) and emulsify for 30-40 min to form an emulsion, heat to 60℃ and keep the reaction at that temperature for 3-4 hours, filter, wash, and dry to obtain porous C5 petroleum resin microspheres. B. Under dry nitrogen protection, polyether diol and toluene diisocyanate are reacted at 70-80℃ for 2-3 hours at a molar ratio of -NCO to -OH of 2:1 to obtain polyurethane prepolymer. Then, epoxy resin E-44 of 50% by mass of toluene diisocyanate is added and the reaction is continued at 80-90℃ for 1-2 hours to obtain epoxy polyurethane prepolymer. Porous C5 petroleum resin microspheres were immersed in anhydrous acetone solution containing epoxy polyurethane prepolymer and dibutyltin dilaurate. After being kept under vacuum for 40-50 minutes, the solution was filtered and dried to obtain epoxy polyurethane modified porous C5 petroleum resin microspheres. The mass ratio of porous C5 petroleum resin microspheres, epoxy polyurethane prepolymer, and dibutyltin dilaurate was 100:18:0.1.

[0007] Furthermore, the photosensitizing reactants include epoxy acrylate and trimethylolpropane triacrylate in a mass ratio of 5:2; the photosensitizer is 2,2-dimethoxy-2-phenylacetophenone.

[0008] Furthermore, the hydroxyl-terminated polycaprolactone is OH-PCL-OH with a melting point of 60~63℃.

[0009] Further, the polyolefin elastomer is an ethylene-octene copolymer; the toughening agent is a styrene-ethylene-butene-styrene block copolymer; the antioxidant is a compound of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the light stabilizer is a hindered amine light stabilizer UV-770; and the organotin catalyst is dibutyltin dilaurate.

[0010] Further, the microcapsule formulation is prepared by the following method: hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer (melting point 75℃, molecular weight 114.14) in a mass ratio of 5:1 are blended and melted to obtain a mixed melt; while maintaining the melt state, the core material obtained by mixing the photosensitizer and photosensitizer is slowly added to the melt and stirred evenly to obtain a mixed system; 200 parts by weight of deionized water, 2 parts by weight of polyvinyl alcohol, and 0.5 parts by weight of sodium dodecyl sulfate are heated to (80-85℃) and mixed evenly to obtain an external phase; while maintaining 80-85℃, the mixed system is slowly added to the external phase, and emulsified using a high-speed dispersion homogenizer to form a uniform emulsion, then slowly cooled to 20-25℃ and allowed to stand, filtered, and dried to obtain the microcapsule formulation.

[0011] Furthermore, the polypropylene polyol is polypropylene glycol or polyoxypropylene triol.

[0012] Further, the thermally conductive modifier is prepared by the following method by weight fraction: 5 parts graphene and 8 parts boron nitride are added to 20 parts anhydrous ethanol, ultrasonically dispersed for 20-30 min, 0.5 parts silane coupling agent KH-550 are added, the temperature is raised to 50-55℃, and the mixture is stirred at a constant temperature for 2-3 h. After filtration and drying, the modified thermally conductive filler is obtained. The modified thermally conductive filler and 1.5 parts polyethylene wax are added to a high-speed mixer and mixed at 120℃ and 800-1000 r / min for 15-20 min. After cooling to room temperature, the mixture is pulverized to obtain the thermally conductive modifier.

[0013] Furthermore, the silane coupling agent containing isocyanate functional groups is 3-isocyanate-propyltrimethoxysilane.

[0014] The method for preparing a thermoplastic polyolefin waterproof membrane includes the following steps: S1. Preparation of the waterproof surface layer: Weigh each component of the waterproof surface layer according to the formula, add the polyolefin elastomer, polypropylene polyol, toughening agent, thermally conductive modifier, antioxidant, and light stabilizer to a high-speed mixer and mix evenly. Then, melt-blend and granulate the mixture using a twin-screw extruder to obtain the waterproof surface layer masterbatch. Shape the masterbatch using a casting machine or calender to obtain a waterproof surface layer film with a thickness of 0.5~0.8mm. S2. In a dry environment, the silane coupling agent containing isocyanate functional groups, epoxy polyurethane modified porous C5 petroleum resin microspheres, organotin catalysts and microcapsule formulations are placed in a dispersion device and mixed uniformly at room temperature to obtain a slurry with uniform viscosity. S3. The slurry obtained in step S2 is evenly coated on one side of the waterproof surface film obtained in step S1, and then dried in a circulating hot air environment at 50°C. The slurry forms a thermoplastic softening and penetrating layer with a thickness of 1 / 2 to 2 / 3 of the thickness of the waterproof surface layer on one side, thus obtaining the thermoplastic polyolefin waterproof film.

[0015] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. This invention discloses a thermoplastic polyolefin waterproof membrane with a waterproof surface layer as the base material. When reinforcing the weld seams of a waterproof membrane, it provides basic waterproof performance requirements at the weld seams, ensuring compatibility with the waterproof performance of the membrane. Based on this, a thermoplastic softening and penetrating layer is introduced. This layer uses epoxy polyurethane-modified porous C5 petroleum resin microspheres and photosensitive reactant microcapsules as core materials. The shell of the photosensitive reactant microcapsules primarily consists of hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer, with a melting point below 80°C. Below the soft spot of the waterproof surface layer, after heating the entire waterproof membrane to the melting point of the microcapsule formulation shell, the waterproof surface layer maintains structural stability and integrity. The microcapsule formulation releases the internal photosensitive reactant, which flows between the waterproof surface layer and the waterproof membrane (the surface of the waterproof membrane on both sides of the weld needs to be slightly polished to facilitate the penetration of the photosensitive reactant). While the photosensitive reactant penetrates into the membrane on both sides of the weld, it also penetrates into the pores of the softened epoxy polyurethane modified porous C5 petroleum resin microspheres and solidifies to form a tight bond with the microspheres. Furthermore, the epoxy polyurethane modified porous C5 petroleum resin microspheres soften when the photosensitive reactant microcapsules melt. After softening and expanding, they act as a barrier to the flow of the photosensitive reactant, preventing it from overflowing to the outside of the area where the thermoplastic polyolefin waterproof membrane is located, thus fully utilizing the photosensitive reactant. Under light irradiation, the photosensitive reactant cures, achieving a strong and sealed connection between the waterproof surface layer and the waterproof membrane. The cured layer formed by the photosensitive reactant at the weld seam further seals and strengthens the weld. The waterproof surface layer covers the weld seam, protecting it and further enhancing the sealing performance. 2. In this invention, epoxy polyurethane modifies porous C5 petroleum resin microspheres, improving their surface activity while retaining the soft point temperature of the porous C5 petroleum resin microspheres. This allows them to adhere tightly to the waterproof surface layer under the action of a silane coupling agent containing isocyanate functional groups. Attached Figure Description

[0016] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort, wherein: Figure 1 These are microscopic images of epoxy polyurethane modified porous C5 petroleum resin microspheres. Figure 2This is a flowchart illustrating the preparation method of the thermoplastic polyolefin waterproof membrane of the present invention. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments. The components of the embodiments of the invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0018] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0019] It should be noted that relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0020] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0021] This invention provides a thermoplastic polyolefin waterproof membrane for reinforcing and sealing welds in thermoplastic polyolefin waterproof membranes (during use, the membrane on both sides of the weld is lightly polished without damaging the membrane structure); the thermoplastic polyolefin waterproof membrane includes a waterproof surface layer and a thermoplastic softening and penetrating layer, the thermoplastic softening and penetrating layer being uniformly and completely attached to one side of the waterproof surface layer; calculated on a dry film basis, the thickness of the thermoplastic softening and penetrating layer is 1 / 2 to 2 / 3 of the thickness of the waterproof surface layer. Independently calculated, the waterproof surface layer comprises the following components in parts by weight: 100 parts polyolefin elastomer, 25-28 parts polypropylene polyol, 8-9 parts toughening agent, 4-6 parts thermally conductive modifier, 0.8-1.5 parts antioxidant, and 1-1.2 parts light stabilizer. Independently calculated, the thermoplastic softening and penetrating layer comprises the following components in parts by weight: 25-30 parts of a silane coupling agent containing isocyanate functional groups, 13-15 parts of epoxy polyurethane modified porous C5 petroleum resin microspheres (softening point 70℃), 0.15-0.25 parts of an organotin catalyst, and 10-12 parts of a photosensitizing reactant; the photosensitizing reactant is a microcapsule formulation. Independently calculated, the shell material of the microcapsule formulation comprises hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer; the core material of the microcapsule formulation comprises the following components by weight fraction: 84-85 parts photosensitizing reactant and 4-6 parts photosensitizer.

[0022] In the following embodiments, the epoxy polyurethane modified porous C5 petroleum resin microspheres were prepared by the following method, based on parts by weight: A. Add 50 parts of C5 petroleum resin, 30 parts of cyclohexane, 10 parts of n-heptane, 3 parts of polyvinyl alcohol, and 1 part of diethylene glycol dimethacrylate to a reaction vessel, heat to 80-85℃, and stir until homogeneous to form an oil phase; add 100 parts of deionized water and 1 part of sodium dodecylbenzenesulfonate to an emulsification vessel, and stir until homogeneous to form an aqueous phase; slowly add the aqueous phase dropwise to the oil phase, stir (300-400 r / min) and emulsify for 30-40 min to form an emulsion, heat to 60℃ and keep the reaction at that temperature for 3-4 hours, filter, wash, and dry to obtain porous C5 petroleum resin microspheres. B. Under dry nitrogen protection, polyether diol and toluene diisocyanate are reacted at 70-80℃ for 2-3 hours at a molar ratio of -NCO to -OH of 2:1 to obtain polyurethane prepolymer. Then, epoxy resin E-44 of 50% by mass of toluene diisocyanate is added and the reaction is continued at 80-90℃ for 1-2 hours to obtain epoxy polyurethane prepolymer. Porous C5 petroleum resin microspheres were immersed in anhydrous acetone solution containing epoxy polyurethane prepolymer and dibutyltin dilaurate. After maintaining the solution under vacuum for 40-50 minutes, the solution was filtered and dried to obtain epoxy polyurethane-modified porous C5 petroleum resin microspheres. The mass ratio of porous C5 petroleum resin microspheres, epoxy polyurethane prepolymer, and dibutyltin dilaurate was 100:18:0.1. SEM images of the epoxy polyurethane-modified porous C5 petroleum resin microspheres prepared by this method are shown below. Figure 1 As shown, there are obvious holes.

[0023] In the following embodiments, the photosensitizing reactants include epoxy acrylate and trimethylolpropane triacrylate in a mass ratio of 5:2; the photosensitizer is 2,2-dimethoxy-2-phenylacetophenone.

[0024] In the following examples, the hydroxyl-terminated polycaprolactone is OH-PCL-OH with a melting point of 60~63℃.

[0025] In the following embodiments, the polyolefin elastomer is an ethylene-octene copolymer; the toughening agent is a styrene-ethylene-butene-styrene block copolymer; the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the light stabilizer is the hindered amine light stabilizer UV-770; and the organotin catalyst is dibutyltin dilaurate.

[0026] In the following embodiments, the microcapsule formulation was prepared by the following method: hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer (melting point 75°C, molecular weight 114.14) in a mass ratio of 5:1 were blended and melted to obtain a mixed melt; while maintaining the melt state, a core material obtained by mixing photosensitizer and photosensitizer was slowly added to the melt and stirred evenly to obtain a mixed system; 200 parts by weight of deionized water, 2 parts by weight of polyvinyl alcohol, and 0.5 parts by weight of sodium dodecyl sulfate were heated to (80-85°C) and mixed evenly to obtain an external phase; while maintaining 80-85°C, the mixed system was slowly added to the external phase, and emulsified using a high-speed dispersion homogenizer to form a uniform emulsion, then slowly cooled to 20-25°C and allowed to stand, filtered, and dried to obtain the microcapsule formulation.

[0027] In the following examples, the polypropylene polyol is polypropylene glycol or polyoxypropylene triol.

[0028] In the following embodiments, the thermally conductive modifier was prepared by the following method, by weight fraction: 5 parts graphene and 8 parts boron nitride were added to 20 parts anhydrous ethanol, ultrasonically dispersed for 20-30 min, 0.5 parts silane coupling agent KH-550 were added, the temperature was raised to 50-55℃, and the mixture was stirred at a constant temperature for 2-3 h. The mixture was then filtered and dried to obtain the modified thermally conductive filler. The modified thermally conductive filler was added to 1.5 parts polyethylene wax in a high-speed mixer and mixed at 120℃ and 800-1000 r / min for 15-20 min. The mixture was then cooled to room temperature and pulverized to obtain the thermally conductive modifier.

[0029] In the following embodiments, the silane coupling agent containing isocyanate functional groups is 3-isocyanate-propyltrimethoxysilane.

[0030] like Figure 2 As shown in the following embodiments, the method for preparing a thermoplastic polyolefin waterproof membrane includes the following steps: S1. Preparation of the waterproof surface layer: Weigh each component of the waterproof surface layer according to the formula, add the polyolefin elastomer, polypropylene polyol, toughening agent, thermally conductive modifier, antioxidant, and light stabilizer to a high-speed mixer and mix evenly. Then, melt-blend and granulate the mixture using a twin-screw extruder to obtain the waterproof surface layer masterbatch. Shape the masterbatch using a casting machine or calender to obtain a waterproof surface layer film with a thickness of 0.5~0.8mm. S2. In a dry environment, the silane coupling agent containing isocyanate functional groups, epoxy polyurethane modified porous C5 petroleum resin microspheres, organotin catalysts and microcapsule formulations are placed in a dispersion device and mixed uniformly at room temperature to obtain a slurry with uniform viscosity. S3. The slurry obtained in step S2 is evenly coated on one side of the waterproof surface film obtained in step S1, and then dried in a circulating hot air environment at 50°C. The slurry forms a thermoplastic softening and penetrating layer with a thickness of 1 / 2 to 2 / 3 of the thickness of the waterproof surface layer on one side, thus obtaining the thermoplastic polyolefin waterproof film.

[0031] Example 1

[0032] This invention provides a thermoplastic polyolefin waterproof membrane for reinforcing and sealing welds in thermoplastic polyolefin waterproof membranes (during use, the membrane on both sides of the weld is lightly polished without damaging the membrane structure); the thermoplastic polyolefin waterproof membrane includes a waterproof surface layer and a thermoplastic softening and penetrating layer, the thermoplastic softening and penetrating layer being uniformly and completely attached to one side of the waterproof surface layer; calculated on a dry film basis, the thickness of the thermoplastic softening and penetrating layer is 2 / 3 of the thickness of the waterproof surface layer. Independently calculated, the waterproof surface layer comprises the following components in parts by weight: 100 parts polyolefin elastomer, 25 parts polypropylene polyol (polyoxypropylene triol), 8 parts toughening agent, 4 parts thermally conductive modifier, 0.8 parts antioxidant, and 1 part light stabilizer. Independently calculated, the thermoplastic softening and penetrating layer comprises the following components in parts by weight: 25 parts of silane coupling agent containing isocyanate functional groups, 13 parts of epoxy polyurethane modified porous C5 petroleum resin microspheres, 0.15 parts of organotin catalyst, and 10 parts of photosensitizing reactant; the photosensitizing reactant is a microcapsule formulation. Independently calculated, the shell material of the microcapsule formulation comprises hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer in a mass ratio of 5:1; the core material of the microcapsule formulation comprises the following components in weight fractions: 84 parts photosensitizing reactant and 4 parts photosensitizer; the photosensitizing reactant comprises epoxy acrylate and trimethylolpropane triacrylate in a mass ratio of 5:2; the photosensitizer is 2,2-dimethoxy-2-phenylacetophenone.

[0033] The application method of the thermoplastic polyolefin waterproof membrane is as follows: The surface of the waterproof membrane on both sides of the weld is lightly polished (without damaging the structure of the waterproof membrane). Then, the side containing the thermoplastic softening and penetrating layer of this application is pressed and pre-attached to the area where the weld is located. The entire waterproof membrane fully covers the weld (the coverage area of ​​the waterproof membrane needs to extend 50mm beyond each side of the weld, and the coverage area of ​​the waterproof membrane matches the polished area of ​​the membrane). The waterproof membrane is then heated to 80℃, causing the microcapsule shell to melt and the microspheres to soften. The membrane is pressed until it adheres tightly and a uniform, visible layer is formed between the waterproof surface and the membrane. Heating is then stopped (the pressure and time applied by the construction personnel are adjusted according to the actual situation). Finally, ultraviolet light (365nm wavelength, 1000mW / cm²) is applied for 40-50 seconds to complete the sealing and reinforcement of the weld.

[0034] Example 2

[0035] Based on Example 1, this embodiment of the invention provides a thermoplastic polyolefin waterproof membrane for reinforcing and sealing weld seams of thermoplastic polyolefin waterproof membranes (during use, the membrane on both sides of the weld seam is lightly polished without damaging the membrane structure); the thermoplastic polyolefin waterproof membrane includes a waterproof surface layer and a thermoplastic softening and penetrating layer, the thermoplastic softening and penetrating layer being uniformly and completely attached to one side of the waterproof surface layer; calculated on a dry film basis, the thickness of the thermoplastic softening and penetrating layer is 2 / 3 of the thickness of the waterproof surface layer. Independently calculated, the waterproof surface layer comprises the following components in parts by weight: 100 parts polyolefin elastomer, 27 parts polypropylene polyol, 8.5 parts toughening agent, 5 parts thermally conductive modifier, 1.2 parts antioxidant, and 1.1 parts light stabilizer. Independently calculated, the thermoplastic softening and penetrating layer comprises the following components in parts by weight: 28 parts of silane coupling agent containing isocyanate functional groups, 14 parts of epoxy polyurethane modified porous C5 petroleum resin microspheres, 0.2 parts of organotin catalyst, and 11 parts of photosensitizing reactant; the photosensitizing reactant is a microcapsule formulation. Independently calculated, the shell material of the microcapsule formulation comprises hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer; the core material of the microcapsule formulation comprises the following components by weight fraction: 85 parts photosensitizer and 5 parts photosensitizer.

[0036] Example 3

[0037] Based on Example 1, this embodiment of the invention provides a thermoplastic polyolefin waterproof membrane for reinforcing and sealing weld seams of thermoplastic polyolefin waterproof membranes (during use, the membrane on both sides of the weld seam is lightly polished without damaging the membrane structure); the thermoplastic polyolefin waterproof membrane includes a waterproof surface layer and a thermoplastic softening and penetrating layer, the thermoplastic softening and penetrating layer being uniformly and completely attached to one side of the waterproof surface layer; calculated on a dry film basis, the thickness of the thermoplastic softening and penetrating layer is 2 / 3 of the thickness of the waterproof surface layer. Independently calculated, the waterproof surface layer comprises the following components in parts by weight: 100 parts polyolefin elastomer, 28 parts polypropylene polyol, 9 parts toughening agent, 6 parts thermally conductive modifier, 1.5 parts antioxidant, and 1.2 parts light stabilizer. Independently calculated, the thermoplastic softening and penetrating layer comprises the following components in parts by weight: 30 parts of silane coupling agent containing isocyanate functional groups, 15 parts of epoxy polyurethane modified porous C5 petroleum resin microspheres, 0.25 parts of organotin catalyst, and 12 parts of photosensitizing reactant; the photosensitizing reactant is a microcapsule formulation. Independently calculated, the shell material of the microcapsule formulation comprises hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer; the core material of the microcapsule formulation comprises the following components by weight fraction: 85 parts photosensitizing reactant and 6 parts photosensitizer.

[0038] Example 4

[0039] Based on Example 2, the difference is that in this example, the thickness of the thermoplastic softening and penetrating layer is half the thickness of the waterproof surface layer. All other parts are the same.

[0040] Comparative Example 1 This comparative example provides a thermoplastic polyolefin waterproof membrane, excluding a thermoplastic softening and penetrating layer and a thermally conductive modifier, comprising the following components in parts by weight: 100 parts polyolefin elastomer, 27 parts polypropylene polyol, 8.5 parts toughening agent, 1.2 parts antioxidant, and 1.1 parts light stabilizer. The polyolefin elastomer is an ethylene-octene copolymer; the toughening agent is a styrene-ethylene-butene-styrene block copolymer; the antioxidant is a compound of antioxidant 1010 and antioxidant 168 in a 1:1 mass ratio; and the light stabilizer is a hindered amine light stabilizer, UV-770. The preparation method is the same as the preparation method for the waterproof surface layer described above.

[0041] Comparative Example 2 Based on Example 2, the difference from Example 2 is that the polypropylene polyol in the waterproof surface layer of this comparative example is replaced with polypropylene, while the rest are the same.

[0042] Comparative Example 3 Based on Example 2, the difference from Example 2 is that the waterproof surface layer in this comparative example does not contain a thermally conductive modifier, but all other aspects are the same, with adaptive modifications made to the preparation method.

[0043] Comparative Example 4 Based on Example 2, the difference from Example 2 is that the thermoplastic softening and penetrating layer in this comparative example does not contain epoxy polyurethane modified porous C5 petroleum resin microspheres, while the rest are the same, and the preparation method has been adapted.

[0044] Comparative Example 5 Based on Example 2, the difference from Example 2 is that the thermoplastic softening and permeating layer in this comparative example does not contain microcapsule formulations (does not contain photosensitizing reactants), while all other aspects are the same, with adaptive modifications made to the preparation method.

[0045] Comparative Example 6 Based on Example 2, the difference from Example 2 is that the core material of the thermoplastic softening and permeating layer in this comparative example is not prepared as a capsule formulation and does not contain a capsule shell layer. The photosensitizer and photosensitizer are directly added to the thermoplastic softening and permeating layer in proportion. Everything else is the same, and the preparation method has been adapted.

[0046] Comparative Example 7 Based on Example 2, the difference from Example 2 is that the shell material of the capsule formulation in the thermoplastic softening and permeating layer of this comparative example does not include hydroxyl-terminated polycaprolactone, while the rest are the same, and the preparation method has been adapted.

[0047] Comparative Example 8 Based on Example 2, the difference from Example 2 is that the shell material of the capsule formulation in the thermoplastic softening and permeating layer of this comparative example does not include ethylene-vinyl acetate copolymer, while the rest are the same, and the preparation method has been adapted.

[0048] Comparative Example 9 Based on Example 2, the difference from Example 2 is that the porous C5 petroleum resin microspheres in this comparative example are used directly without epoxy polyurethane modification, while the rest are the same, with adaptive modifications made to the preparation method.

[0049] Experimental Example 1 The macroscopic forming characteristics of the thermoplastic polyolefin waterproof membranes prepared in Examples 1-4 and Comparative Examples 1-9 of this application were tested, as well as the macroscopic adhesion of the membranes to the weld area (welds formed by hot air heating welding according to the prior art, with incomplete welding) of the waterproof membrane (commercially available TPO waterproof membrane, 1.5 mm thick, conforming to GB / T27789-2011 standard) after being used according to the above method; the results are shown in Table 1. Table 1. Macroscopic view of the self-forming of thermoplastic polyolefin waterproof membrane and its adhesion to waterproof membrane. The macroscopic forming characteristics of thermoplastic polyolefin waterproof membranes Macroscopic adhesion between thermoplastic polyolefin waterproof membrane and waterproof roll material Example 1 No defects The adhesive is tight and there are no gaps, curling edges, bubbles or other abnormalities. Example 2 No defects The adhesive is tight and there are no gaps, curling edges, bubbles or other abnormalities. Example 3 No defects The adhesive is tight and there are no gaps, curling edges, bubbles or other abnormalities. Example 4 No defects The adhesive is tight and there are no gaps, curling edges, bubbles or other abnormalities. Comparative Example 1 No defects Unable to bond, delaminates instantly, does not meet usage requirements. Comparative Example 2 A gap appears between the waterproof top layer and the thermoplastic softening and penetrating layer. The adhesion is weak, the interface is cracked, and it does not meet the usage requirements. Comparative Example 3 No defects The interface contains a large number of bubbles. Comparative Example 4 No defects The adhesive layer has an uneven appearance, with visible photosensitive reactants overflowing to the outside of the waterproof membrane-covered area, resulting in blurred edges. Comparative Example 5 No defects The adhesion is weak, and the thermoplastic polyolefin waterproof membrane is easily peeled off. Comparative Example 6 The thermoplastic softening and permeation layer showed obvious wrinkles, and during storage, it partially hardened and clumped. The adhesive layer is characterized by point-like adhesion and numerous voids, making it fragile and prone to cracking in multiple places. Comparative Example 7 Localized peeling and uneven coating of thermoplastic softening and penetrating layer Extensive curling at the edges, a few air bubbles, and poor adhesion were observed. Comparative Example 8 The thermoplastic softening permeation layer exhibits unevenly distributed protrusions, resulting in inconsistent film thickness. Consequently, the thermoplastic softening permeation layer lacks sufficient strength during storage, making it prone to premature release of the core material. Uneven adhesion, excessive adhesion in some areas, and localized gaps and bubbles appearing. Comparative Example 9 Bubbles and uneven protrusions Adhesive layer bubbles and cracks Experimental Example 2 Based on Example 1, further tests were conducted on the impermeability, room temperature peel strength, low temperature bending performance, and firmness (whether the weld area is leaking after aging) of thermoplastic polyolefin waterproof membranes (Examples 1-4) that were applied to TPO waterproof membranes (containing leaking welds) after weld sealing reinforcement, with no obvious defects in the thermoplastic polyolefin waterproof membrane itself and no obvious defects after bonding with the weld seams of the waterproof membrane (where there are leaking welds at the overlap of the membranes after hot air heating). The results are shown in Table 2. Blank control group 1 was a spliced ​​waterproof membrane (commercially available TPO waterproof membrane) with leaking welds (gaps) formed at the overlap of the waterproof membranes after hot air heating, and which did not use the waterproof membrane prepared in the examples or comparative examples of this application. Blank control group 2 was a spliced ​​waterproof membrane (commercially available TPO waterproof membrane) with qualified weld seams formed at the overlap of the waterproof membranes after hot air heating, and which did not use the waterproof membrane prepared in the examples or comparative examples of this application. Impermeability: The impermeability of the weld area of ​​the waterproof membrane is tested according to the national standard GB 27789-2011 "Thermoplastic Polyolefin (TPO) Waterproof Membrane". The test result is 0.3MPa, 2h. If it is impermeable, it is considered qualified. Peel strength at room temperature: The sample was cut into peel strips of 100mm×25mm. The peel strength between the waterproof membrane and TPO roll (Examples 1-4) or between TPO rolls (blank control groups 1 and 2) was tested at a peel speed of 50mm / min using a 180° peel method. The unit is N / 25mm. Low-temperature bending performance: The low-temperature bending performance of the weld area of ​​the waterproof membrane is tested according to the national standard GB 27789-2011 "Thermoplastic Polyolefin (TPO) Waterproof Membrane". If there are no cracks at -40℃, it meets the standard. For robustness: referring to GB / T 18244-2000, the sample was placed in a 40℃ ultraviolet aging chamber (UVB-313 ultraviolet lamp, irradiation intensity 0.71W / (m²・nm)) and aged for 1000h. After removal, the impermeability of the weld area was tested to see if it was qualified.

[0050] Table 2 Performance Testing of Sealing Reinforcement for Thermoplastic Polyolefin Waterproof Membranes Permeability room temperature peel strength Low temperature bending performance Stability Example 1 qualified 100±1 No cracks at -40℃ qualified Example 2 qualified 105±1 No cracks at -40℃ qualified Example 3 qualified 102±1 No cracks at -40℃ qualified Example 4 qualified 100±2 No cracks at -40℃ qualified Blank control group 1 Unqualified ＜50 Non-compliant with standards Unqualified (severe water leakage) Blank control group 2 qualified 90±2 No cracks at -40℃ qualified This application is primarily used to improve the sealing performance of waterproof membranes with incomplete welds and gaps. The reinforced waterproof membrane exhibits stronger sealing performance, achieving the sealing performance of a qualified weld. Furthermore, for waterproof membranes with qualified welds, this application can also reinforce the sealing of those welds, providing protection for the welds.

[0051] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A thermoplastic polyolefin waterproof membrane, characterized in that: It is used to reinforce and seal the weld seams of thermoplastic polyolefin waterproof membranes; the thermoplastic polyolefin waterproof membrane includes a waterproof surface layer and a thermoplastic softening and penetrating layer, the thermoplastic softening and penetrating layer being uniformly and fully attached to one side of the waterproof surface layer. Based on dry film calculations, the thickness of the thermoplastic softening and penetrating layer is 1 / 2 to 2 / 3 of the thickness of the waterproof surface layer; Independently calculated, the waterproof surface layer comprises the following components in parts by weight: 100 parts polyolefin elastomer, 25-28 parts polypropylene polyol, 8-9 parts toughening agent, 4-6 parts thermally conductive modifier, 0.8-1.5 parts antioxidant, and 1-1.2 parts light stabilizer. Independently calculated, the thermoplastic softening and penetrating layer comprises the following components in parts by weight: 25-30 parts of a silane coupling agent containing isocyanate functional groups, 13-15 parts of epoxy polyurethane modified porous C5 petroleum resin microspheres, 0.15-0.25 parts of an organotin catalyst, and 10-12 parts of a photosensitizing reactant; the photosensitizing reactant is a microcapsule formulation; Independently calculated, the shell material of the microcapsule formulation comprises hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer; the core material of the microcapsule formulation comprises the following components by weight fraction: 84-85 parts photosensitizing reactant and 4-6 parts photosensitizer.

2. The thermoplastic polyolefin waterproof membrane according to claim 1, characterized in that: The epoxy polyurethane modified porous C5 petroleum resin microspheres were prepared by the following method, based on parts by weight: A. Add 50 parts of C5 petroleum resin, 30 parts of cyclohexane, 10 parts of n-heptane, 3 parts of polyvinyl alcohol, and 1 part of diethylene glycol dimethacrylate to a reaction vessel, heat to 80-85℃, and stir until homogeneous to form an oil phase; add 100 parts of deionized water and 1 part of sodium dodecylbenzenesulfonate to an emulsification vessel, and stir until homogeneous to form an aqueous phase; slowly add the aqueous phase dropwise to the oil phase, stir and emulsify for 30-40 minutes to form an emulsion, heat to 60℃ and keep the reaction at that temperature for 3-4 hours, filter, wash, and dry after the reaction to obtain porous C5 petroleum resin microspheres. B. Under dry nitrogen protection, polyether diol and toluene diisocyanate are reacted at 70-80℃ for 2-3 hours at a molar ratio of -NCO to -OH of 2:1 to obtain polyurethane prepolymer. Then, epoxy resin E-44 of 50% by mass of toluene diisocyanate is added and the reaction is continued at 80-90℃ for 1-2 hours to obtain epoxy polyurethane prepolymer. Porous C5 petroleum resin microspheres were immersed in anhydrous acetone solution containing epoxy polyurethane prepolymer and dibutyltin dilaurate. After being kept under vacuum for 40-50 minutes, the solution was filtered and dried to obtain epoxy polyurethane modified porous C5 petroleum resin microspheres. The mass ratio of porous C5 petroleum resin microspheres, epoxy polyurethane prepolymer, and dibutyltin dilaurate was 100:18:0.

1.

3. The thermoplastic polyolefin waterproof membrane according to claim 1, characterized in that: The photosensitizing reactants include epoxy acrylate and trimethylolpropane triacrylate in a mass ratio of 5:2; the photosensitizer is 2,2-dimethoxy-2-phenylacetophenone.

4. The thermoplastic polyolefin waterproof membrane according to claim 1, characterized in that: Hydroxyl-terminated polycaprolactone is OH-PCL-OH with a melting point of 60~63℃.

5. The thermoplastic polyolefin waterproof membrane according to claim 1, characterized in that: The polyolefin elastomer is an ethylene-octene copolymer; the toughening agent is a styrene-ethylene-butene-styrene block copolymer; the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the light stabilizer is a hindered amine light stabilizer UV-770; and the organotin catalyst is dibutyltin dilaurate.

6. The thermoplastic polyolefin waterproof membrane according to claim 1, characterized in that: The microcapsule formulation is prepared by the following method: hydroxyl-terminated polycaprolactone and ethylene-vinyl acetate copolymer in a mass ratio of 5:1 are blended and melted to obtain a mixed melt; while maintaining the melt state, a core material obtained by mixing photosensitizer and photosensitizer is slowly added to the melt and stirred evenly to obtain a mixed system; 200 parts by weight of deionized water, 2 parts by weight of polyvinyl alcohol, and 0.5 parts by weight of sodium dodecyl sulfate are heated to 80-85°C and mixed evenly to obtain an external phase; while maintaining 80-85°C, the mixed system is slowly added to the external phase, and emulsified using a high-speed dispersion homogenizer to form a uniform emulsion, then slowly cooled to 20-25°C and allowed to stand, filtered, and dried to obtain the microcapsule formulation.

7. The thermoplastic polyolefin waterproof membrane according to claim 1, characterized in that: The polypropylene polyol is either polypropylene glycol or polyoxypropylene triol.

8. The thermoplastic polyolefin waterproof membrane according to claim 1, characterized in that: The thermally conductive modifier is prepared by the following method by weight fraction: 5 parts graphene and 8 parts boron nitride are added to 20 parts anhydrous ethanol, ultrasonically dispersed for 20-30 min, 0.5 parts silane coupling agent KH-550 are added, the temperature is raised to 50-55℃, and the mixture is stirred at a constant temperature for 2-3 h. After filtration and drying, the modified thermally conductive filler is obtained. Add the modified thermally conductive filler and 1.5 parts of polyethylene wax to a high-speed mixer and mix for 15-20 minutes at 120℃ and 800-1000 r / min. Cool to room temperature and pulverize to obtain the thermally conductive modifier.

9. The thermoplastic polyolefin waterproof membrane according to claim 1, characterized in that: The isocyanate-functionalized silane coupling agent is 3-isocyanate-propyltrimethoxysilane.

10. A method for preparing a thermoplastic polyolefin waterproof membrane according to any one of claims 1-9, characterized in that: Includes the following steps: S1. Preparation of the waterproof surface layer: Weigh each component of the waterproof surface layer according to the formula, add the polyolefin elastomer, polypropylene polyol, toughening agent, thermally conductive modifier, antioxidant, and light stabilizer to a high-speed mixer and mix evenly. Then, melt-blend and granulate the mixture using a twin-screw extruder to obtain the waterproof surface layer masterbatch. Shape the masterbatch using a casting machine or calender to obtain a waterproof surface layer film with a thickness of 0.5~0.8mm. S2. In a dry environment, the silane coupling agent containing isocyanate functional groups, epoxy polyurethane modified porous C5 petroleum resin microspheres, organotin catalysts and microcapsule formulations are placed in a dispersion device and mixed uniformly at room temperature to obtain a slurry with uniform viscosity. S3. The slurry obtained in step S2 is evenly coated on one side of the waterproof surface film obtained in step S1, and then dried in a circulating hot air environment at 50°C. The slurry forms a thermoplastic softening and penetrating layer with a thickness of 1 / 2 to 2 / 3 of the thickness of the waterproof surface layer on one side, thus obtaining the thermoplastic polyolefin waterproof film.

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