Temperature gradient triggered microcapsule self-healing asphalt waterproofing membrane and preparation method thereof
Patent Information
- Application Number
- CN202610961878.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-30
- Publication Date
- 2026-10-23
Smart Images
Figure CN122956819A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of building materials and waterproofing materials, specifically relating to a temperature gradient triggered microcapsule self-healing bitumen waterproof membrane and its preparation method. Background Technology
[0002] Modified bitumen waterproof membranes are widely used in waterproofing projects for building roofs, basement floors, garage roofs, tunnels, and utility tunnels. However, uneven settlement stress in the building substrate and the membrane's own aging due to external environmental factors such as light, heat, and oxygen can lead to performance degradation and the appearance of micro-cracks on the surface or inside the membrane, subsequently causing leakage risks. Currently available self-healing bitumen membranes on the market still have the following problems that urgently need to be addressed: (1) The self-healing temperature range is limited and cannot be adapted to all seasons: Existing microcapsule self-healing systems are all triggered by a single temperature, and most can only heal themselves at high temperatures. They cannot repair cracks caused by low temperatures in winter or normal temperatures in spring and autumn, resulting in seasonal leakage blind spots. (2) The self-healing core material is uniform and lacks differentiation, resulting in poor temperature adaptability: Existing self-healing materials all use the same repair fluid, which cannot simultaneously achieve low-temperature fluidity, room-temperature uniformity, and high-temperature anti-flow properties, resulting in the inability to penetrate in low winter temperatures, the flow of repaired materials in high summer temperatures, and insufficient repair strength year-round. (3) The microcapsule wall structure is simple and lacks a hierarchical triggering mechanism: Existing microcapsule wall materials are universal and cannot achieve graded responses such as low-temperature brittleness, room-temperature stress triggering, and high-temperature thermal triggering. They are prone to problems such as premature capsule rupture, failure to trigger, and false triggering. (4) Heterogeneous repair, poor durability: Most self-healing core materials on the market are made of resin, PU, or epoxy, which are incompatible with asphalt substrates, leading to delamination at the repair interface and frequent secondary leaks. Summary of the Invention
[0003] To address the problems existing in the prior art, this invention provides a temperature gradient triggered microcapsule self-healing bitumen waterproof membrane and its preparation method. It employs a structural design combining three-temperature-zone gradient differential triggering and homogeneous adaptive bitumen self-healing core liquid, along with a low-temperature post-doping microcapsule preparation method. This results in a year-round self-healing modified bitumen waterproof membrane, achieving seamless self-healing in all seasons. It also maintains high flowability at low temperatures, high strength at room temperatures, and anti-flow properties at high temperatures, thereby improving the waterproof membrane's waterproofing effect and service life, making it more suitable for various building waterproofing projects.
[0004] To achieve the above objectives, the present invention adopts the following technical solution.
[0005] In a first aspect, the present invention provides a temperature gradient triggered microcapsule self-healing bitumen waterproof membrane, comprising, from top to bottom, an upper surface isolation layer, a surface layer, a substrate layer, a bottom layer, and a lower surface isolation layer; the surface layer and the bottom layer are prepared using a temperature gradient self-healing modified bitumen coating material; The temperature gradient self-healing modified asphalt coating is prepared from the following raw materials in parts by weight: 55-65 parts asphalt, 5-15 parts naphthenic oil, 8-12 parts SBS modifier, 3-5 parts rubber toughening agent, 1-2 parts compatibility stabilizer, 0.5-1 part high-temperature antioxidant, 10-15 parts inorganic filler, and 3-5 parts compounded temperature gradient triggered microcapsules; The compound temperature gradient triggered microcapsules are composed of low-temperature triggered microcapsules, room-temperature triggered microcapsules, and high-temperature triggered microcapsules; wherein... The triggering temperature range of the low-temperature triggered microcapsules is 0~15℃. The triggering temperature range of the room-temperature triggered microcapsules is 15~35℃. The triggering temperature range of the high-temperature triggered microcapsule is 35~65℃.
[0006] Optionally, the compound temperature gradient triggering microcapsule is composed of low-temperature triggering microcapsules, room-temperature triggering microcapsules, and high-temperature triggering microcapsules in a mass ratio of 3:(3.8~4.2):3 (for example, 3:4:3).
[0007] Preferably, in the compound temperature gradient triggered microcapsules, the particle size of the microcapsules is 100~200 micrometers.
[0008] Preferably, the upper surface insulating layer has a width of 1040~1060 mm, a thickness of 0.04~0.06 mm, and a basis weight of 8.5~11.5 g / m³. 2 Polyethylene film.
[0009] Preferably, the lower surface insulating layer has a width of 1040~1060mm, a thickness of 0.04~0.06mm, and a basis weight of 8.5~11.5g / m³. 2 Polyethylene film.
[0010] Preferably, the body layer is made of long-fiber polyester spunbond nonwoven fabric with a basis weight of 170~250 g / m². 2 Thickness is 0.95~1.3 mm, moisture content is ≤0.5%.
[0011] Preferably, the asphalt includes at least one of liquid petroleum asphalt and 90# asphalt.
[0012] Preferably, the low-temperature triggered microcapsule includes a capsule wall and a core fluid disposed inside the capsule wall, wherein the capsule wall is made of a urea-formaldehyde-nitrile rubber low-temperature brittle composite wall material.
[0013] Preferably, the room-temperature triggered microcapsule includes a capsule wall and a core fluid disposed inside the capsule wall, wherein the capsule wall is made of a silane crosslinked elastic urea-formaldehyde resin stress-sensitive wall material.
[0014] Preferably, the high-temperature triggered microcapsule includes a capsule wall and a core liquid disposed inside the capsule wall, wherein the capsule wall is prepared using a urea-formaldehyde-phase change paraffin thermosensitive composite wall material.
[0015] More preferably, the urea-formaldehyde-nitrile rubber low-temperature brittle composite wall material has an upper temperature resistance limit of 160℃, is extremely prone to brittleness under freeze-thaw stress at 0~15℃, and is completely stable and does not crack above 15℃.
[0016] More preferably, the upper limit of the temperature resistance of the silane crosslinked elastic urea-formaldehyde resin stress-sensitive wall material is 180°C, and crack tensile stress triggers the fracture.
[0017] More preferably, the urea-formaldehyde-phase change paraffin thermosensitive composite wall material has an upper temperature resistance limit of 180°C and uses high-temperature thermal expansion to trigger softening and cracking.
[0018] More preferably, in the low-temperature triggered microcapsule, the core fluid is a low-temperature homologous asphalt self-healing core fluid; the low-temperature homologous asphalt self-healing core fluid is made from the following raw materials in parts by weight: 54-56 parts liquid petroleum asphalt, 15-17 parts naphthenic oil, 10-12 parts SBS modifier, 7-9 parts polyisobutylene, 3-5 parts rubber toughening agent, 2-4 parts inorganic filler, 0.6-1.0 parts low-temperature antioxidant, and 0.5-0.9 parts low-temperature dispersant.
[0019] In this invention, the low-temperature homologous asphalt self-healing core fluid has high elasticity; specifically, the elongation at break of the low-temperature homologous asphalt self-healing core fluid is ≥950%. Polyisobutylene is beneficial in improving the low-temperature fluidity of the homologous asphalt self-healing core fluid and increasing its elongation.
[0020] Optionally, in the low-temperature homologous asphalt self-healing core liquid, the liquid petroleum asphalt can also be replaced with 90# asphalt, but the component ratio of 90# asphalt and naphthenic oil needs to be adjusted. Preferably, the liquid petroleum asphalt (200# asphalt) is obtained by blending 90# asphalt and naphthenic oil at a mass ratio of 6.5:3.5.
[0021] The present invention directly uses liquid petroleum asphalt (200#) in the low-temperature homologous asphalt self-healing core liquid, mainly because it is more conducive to obtaining excellent low-temperature crack resistance.
[0022] More preferably, in the room-temperature triggered microcapsule, the core fluid is a room-temperature homologous asphalt self-healing core fluid; the room-temperature homologous asphalt self-healing core fluid is made from the following raw materials in parts by weight: 57-59 parts of 90# asphalt, 13-15 parts of naphthenic oil, 8-10 parts of SBS modifier, 5-7 parts of polyisobutylene, 4-6 parts of rubber toughening agent, 3-5 parts of inorganic filler, 0.5-0.9 parts of high-temperature antioxidant, and 0.4-0.8 parts of general-purpose dispersant.
[0023] In this invention, the elongation of the room-temperature homologous asphalt self-healing core liquid is ≥850%.
[0024] Optionally, in the room-temperature homogeneous asphalt self-healing core liquid, 90# asphalt can also be replaced by liquid petroleum asphalt, but the component ratio of liquid petroleum asphalt and naphthenic oil needs to be adjusted. Preferably, the liquid petroleum asphalt (200# asphalt) is obtained by blending 90# asphalt and naphthenic oil at a mass ratio of 6.5:3.5.
[0025] In this invention, 90# asphalt is directly used in the self-healing core liquid of the same source asphalt at room temperature, mainly because it is beneficial to obtain excellent anti-flow and heat resistance performance under both room temperature and high temperature environments.
[0026] More preferably, in the high-temperature triggered microcapsule, the core fluid is a high-temperature homologous asphalt self-healing core fluid; the high-temperature homologous asphalt self-healing core fluid is made from the following raw materials in parts by weight: 59-61 parts of 90# asphalt, 11-13 parts of naphthenic oil, 7-9 parts of SBS modifier, 4-6 parts of polyisobutylene, 5-7 parts of rubber toughening agent, 4-6 parts of inorganic filler, 0.8-1.2 parts of high-temperature antioxidant, and 0.1-0.5 parts of high-temperature dispersant.
[0027] In this invention, the high-temperature homologous asphalt self-healing core liquid has high-temperature stability with heat resistance, high temperature resistance and non-flow, and is a high-temperature stable homologous asphalt self-healing core liquid with a fracture elongation ≥800%.
[0028] In this invention, the low-temperature homologous asphalt self-healing core liquid, the room-temperature homologous asphalt self-healing core liquid, and the high-temperature homologous asphalt self-healing core liquid refer to the main components other than additives, such as asphalt, naphthenic oil, and SBS modifier, which are the same as those in the temperature gradient self-healing modified asphalt functional material.
[0029] More preferably, the low-temperature homologous asphalt self-healing core liquid is made from the following raw materials in parts by weight: 55 parts liquid petroleum asphalt, 16 parts naphthenic oil, 11 parts SBS modifier, 8 parts polyisobutylene, 4 parts rubber toughening agent, 3 parts inorganic filler, 0.8 parts low-temperature antioxidant, and 0.7 parts low-temperature dispersant.
[0030] More preferably, the room-temperature homologous asphalt self-healing core liquid is made from the following raw materials in parts by weight: 58 parts 90# asphalt, 14 parts naphthenic oil, 9 parts SBS modifier, 6 parts polyisobutylene, 5 parts rubber toughening agent, 4 parts inorganic filler, 0.7 parts high-temperature antioxidant, and 0.6 parts general-purpose dispersant.
[0031] More preferably, the high-temperature homologous asphalt self-healing core liquid is made from the following raw materials in parts by weight: 60 parts of 90# asphalt, 12 parts of naphthenic oil, 8 parts of SBS modifier, 5 parts of polyisobutylene, 6 parts of rubber toughening agent, 5 parts of inorganic filler, 1.0 part of high-temperature antioxidant, and 0.3 parts of high-temperature dispersant.
[0032] Preferably, the low-temperature homologous asphalt self-healing core liquid has a ring and ball softening point of 55~57℃ and an elongation of ≥950%; it does not solidify at -20℃ and has excellent fluidity.
[0033] Preferably, the softening point of the room-temperature homologous asphalt self-healing core liquid using the ring and ball method is 57~59℃, and the elongation is ≥850%.
[0034] Preferably, the high-temperature homologous asphalt self-healing core liquid has a ring and ball softening point of 59~60℃, an elongation of ≥800%, and does not flow at 65℃.
[0035] In this invention, low-temperature triggered microcapsule contact, room-temperature triggered microcapsule contact, and high-temperature triggered microcapsule contact are three sets of self-healing repair systems that combine differentiated homologous asphalt core fluid with capsule walls corresponding to triggering conditions, and are respectively suitable for repairing micro-damage in the corresponding temperature range.
[0036] Preferably, the liquid petroleum asphalt is 200# asphalt, with an asphalt softening point of 17~26℃ and a 0.1 mm penetration of 180~220.
[0037] Preferably, the 90# asphalt is heavy-duty road petroleum asphalt with an asphalt softening point of 40~55℃ and a 0.1mm penetration of 80~100.
[0038] Preferably, the naphthenic oil has a flash point >210°C and a kinematic viscosity of 19~27 mm at 40°C. 2 / s, freezing point is -25℃.
[0039] Preferably, the polyisobutylene is a medium molecular weight, highly reactive polyisobutylene with a molecular weight of 800-1200 and a flash point >210℃.
[0040] Preferably, the SBS modifier is a linear SBS with a styrene to butadiene block ratio of 40:60 (for example, the SBS modifier brand is YH792 / 1401).
[0041] Preferably, the rubber toughening agent comprises C5 resin or oil-extended SBR styrene-butadiene rubber powder.
[0042] More preferably, the oil-extended SBR styrene-butadiene rubber powder has a particle size of 80~120 mesh, an ash content of ≤1.5%, and a Tg (glass transition temperature) of -49~-55℃; the C5 resin is a hydrogenated petroleum resin with a softening point of 85~110℃.
[0043] Preferably, the compatibility stabilizer includes an SBS modified asphalt compatibility stabilizer (e.g., grade LF-618), with an effective component of ≥98%, and is thermally stable at 180°C without decomposition.
[0044] Preferably, the low-temperature antioxidant includes a low-temperature-specific hindered phenolic antioxidant (Yingkou Tianyuan T5024), with a melting point of 65~75℃ and a flash point >220℃; it does not crystallize or precipitate at -20℃ and is stable for a long time at 160℃.
[0045] Preferably, the high-temperature antioxidant comprises a complex of antioxidant 1010 (pentaerythritol ester) and antioxidant 168 (triphosphite), wherein the mass ratio of antioxidant 1010 to antioxidant 168 is 2:1, the melting point is 110~125℃, the flash point is >230℃; it is stable for a long time at 65℃, and thermally stable at 190℃ without decomposition, thus inhibiting thermal flow aging.
[0046] Preferably, the low-temperature dispersant includes a low-temperature compatible dispersant for asphalt (e.g., Dow 4170), which does not stratify at -20°C and has a miscibility of ≥98%.
[0047] Preferably, the universal dispersant comprises a polymeric interfacial active modified powder (e.g., Dongying Runfeng HMD-1) with an effective component ≥98%, thermally stable at 180℃ without decomposition, and a flash point >230℃.
[0048] Preferably, the high-temperature dispersant includes a high-temperature cross-linking polymeric stabilizer (e.g., RL-9689), which does not degrade at 160~200℃, inhibits high-temperature flow, and has a flash point >250℃.
[0049] Preferably, the inorganic filler includes at least one of wollastonite powder, talc powder, calcium carbonate and kaolin, with an oil absorption value of 22~28 g / 100 g and a fineness of 600~800 mesh.
[0050] The self-healing principle of the temperature gradient triggered microcapsule self-healing bitumen waterproof membrane provided by this invention is as follows: When microcracks, pinholes, or minor fissures appear in asphalt waterproof membranes, the microcapsules within the corresponding temperature range rupture precisely under the dual effects of crack stress compression and temperature changes. The homologous asphalt self-healing core liquid inside the microcapsules automatically flows out, self-leveling and filling the cracks and pinholes. The repair core liquid and the original modified asphalt material creep and fuse over time, solidifying at room temperature, and the damaged area reforms into an integrated waterproof structure. The tensile, water resistance, and aging resistance of the repaired area are consistent with the membrane itself, achieving a good self-healing repair effect.
[0051] Secondly, the present invention provides a method for preparing any of the above-mentioned temperature gradient triggered microcapsule self-healing bitumen waterproof membranes, comprising the following steps: Step 1: Prepare temperature gradient self-healing modified bitumen coating, including the following steps: The asphalt and naphthenic oil are stirred and mixed evenly, and the temperature is raised to 150~160℃; then, at 150~160℃, SBS modifier, rubber toughening agent and compatibility stabilizer are added and stirred and mixed, and the temperature is maintained at 160~170℃ for softening and swelling to obtain a mixture. The mixture is ground and homogenized (to modify the asphalt); a high-temperature antioxidant is added and stirred (preferably, the high-temperature antioxidant is added after the SBS modifier in the mixture is completely dissolved), inorganic filler is added, and the mixture is stirred and stirred under a constant temperature of 160~170℃. Then the temperature is lowered to 125~135℃, and compound temperature gradient triggered microcapsules are added and stirred and mixed under a constant temperature of 125~135℃ to obtain the temperature gradient self-healing modified asphalt coating material. Step 2: Apply the temperature gradient self-healing modified bitumen coating material prepared in Step 1 to the upper and lower surfaces of the prepreg layer to form a top layer and a bottom layer. Then, apply an isolation layer to the surface of the top layer and the bottom layer to form an upper surface isolation layer and a lower surface isolation layer. After cooling and shaping, cut and roll up to obtain a temperature gradient triggered microcapsule self-healing bitumen waterproof membrane.
[0052] Preferably, in step 1, the softening and swelling time is 10-20 min (e.g., 13 min, 15 min or 18 min).
[0053] Preferably, in step 1, the grinding and homogenization temperature is 175~185℃ (e.g., 178℃, 180℃ or 182℃), and the time is 60~90 min (e.g., 70 min, 75 min, 80 min or 85 min).
[0054] Preferably, in step 1, after adding the high-temperature antioxidant and continuing to stir and mix for 15-25 minutes (e.g., 18 minutes, 20 minutes or 22 minutes), the inorganic filler is added.
[0055] Preferably, in step 1, the compound temperature zone gradient triggered microcapsules are added and stirred under a constant temperature of 125~135℃, wherein the stirring rate is 1000~1500 r / min and the stirring time is 15~20 min to ensure uniform mixing.
[0056] In this invention, in step 1, the mixture generally needs to be ground for 60 to 90 minutes, and samples are taken for observation. If the modifier is completely dissolved, the colloid mill is stopped, a high-temperature antioxidant is added, and stirring is continued for 15 to 25 minutes before proceeding to the next step, namely, adding inorganic fillers and compound temperature gradient triggered microcapsules.
[0057] Preferably, in step 1, inorganic filler is added and stirred and mixed under a constant temperature of 160~170℃ for 25~35 min (e.g., 30 min).
[0058] In this invention, in steps 1-3, the compound temperature gradient triggering microcapsules are added and stirred under constant temperature conditions of 125~135℃. This is a low-temperature constant temperature incorporation process to avoid premature rupture and failure of the microcapsules under high temperature shear conditions, and to ensure that the microcapsules only trigger self-healing repair under the corresponding temperature conditions when cracks appear in the roll material construction application.
[0059] Preferably, in step 2, the temperature gradient self-healing modified asphalt coating material prepared in step 1 is applied to the upper and lower surfaces of the pre-impregnation layer using an oil coating thickness-fixing process to form a top layer and a bottom layer.
[0060] Preferably, the preparation method of the compound temperature gradient triggered microcapsules includes the following steps: (1) Prepare self-healing core liquids of three temperature zones using homogeneous asphalt according to the formula (i.e., low temperature homogeneous asphalt self-healing core liquid, normal temperature homogeneous asphalt self-healing core liquid, and high temperature homogeneous asphalt self-healing core liquid): The asphalt is heated to 140-150℃, and naphthenic oil and polyisobutylene are added and premixed (e.g., for 10 min). Then, SBS modifier is added and stirred under heat preservation conditions (e.g., low-speed stirring, preferably at 1000-1500 r / min) until fully swollen. Next, rubber toughening agent, inorganic filler, and additives are added sequentially and stirred (e.g., stirring and mixing for 20 min to obtain a homogeneous system). The temperature is then lowered to 110-120℃ and kept at this temperature (to remove air bubbles, eliminate internal stress in the components, and ensure uniform fluidity and no impurities in the core liquid), resulting in low-temperature homologous asphalt self-healing core liquid, room-temperature homologous asphalt self-healing core liquid, and high-temperature homologous asphalt self-healing core liquid. The additives include antioxidants and dispersants. Antioxidants include any one of low-temperature antioxidants and high-temperature antioxidants. Dispersants include any one of low-temperature dispersants, general-purpose dispersants, and high-temperature dispersants. Emulsification and dispersion preparation of core liquid: Using water (e.g., deionized water) as the main medium, add an anionic dispersion stabilizer and stir to dissolve; adjust the pH to 4.5~5.0, preheat to 52~56℃ and keep warm, add the above-prepared low-temperature homologous asphalt self-healing core liquid, room-temperature homologous asphalt self-healing core liquid and high-temperature homologous asphalt self-healing core liquid to the aqueous phase system for shearing, preferably at a shearing rate of 2800~3000 r / min for 20~30 min (e.g., 25 min), to form an oil / water emulsion, that is, to form low-temperature homologous asphalt self-healing core liquid, room-temperature homologous asphalt self-healing core liquid and high-temperature homologous asphalt self-healing core liquid; (2) Preparation of three-temperature zone microcapsules, specifically including the following steps: Preparation of low-temperature triggered microcapsules: The low-temperature homologous asphalt self-healing core liquid prepared by emulsification and dispersion is stirred at a constant temperature of 52~55℃, and modified urea-formaldehyde resin prepolymer is added to react (preferably for 30~35 min) to form a primary wall layer; then, nitrile rubber modified emulsion is incorporated to perform interfacial graft copolymerization to construct a composite capsule wall layer; then, the reaction system is kept at a constant temperature (preferably 55~60℃, for example, 58℃) for crosslinking and curing (preferably for 55~60 min) to form a low-temperature triggered composite capsule wall, and a low-temperature triggered coating liquid is obtained; the low-temperature triggered coating liquid is cooled to 28~32℃, allowed to stand for 90~100 min, washed with water, filtered, dried, and subjected to particle size sieving to obtain low-temperature triggered microcapsules with a particle size of 100~200 micrometers; Preparation of room temperature triggered microcapsules: The room-temperature triggered microcapsules prepared by emulsification and dispersion were stirred at a constant temperature of 52-55°C, and silane crosslinked modified urea-formaldehyde resin prepolymer was added for interfacial polymerization at a constant temperature (preferably 40-45 min) to form a wall layer; then the temperature was raised to 60-65°C (e.g., 62°C) for constant temperature crosslinking and curing (preferably 55-60 min) to form a capsule wall layer (e.g., a capsule wall layer with moderate softness and high mechanical stress sensitivity); a room-temperature triggered coating solution was obtained; the room-temperature triggered coating solution was cooled to 28-32°C, allowed to stand for 90-100 min, washed with water, filtered, dried, and sieved to obtain room-temperature triggered microcapsules with a particle size of 100-200 micrometers; Preparation of high-temperature triggered microcapsules: The high-temperature triggered microcapsules prepared by emulsification and dispersion were stirred at a constant temperature of 58-60℃, and a highly cross-linked high-temperature resistant urea-formaldehyde resin was added for prepolymerization (preferably 45-50 min). Then, a phase change paraffin thermosensitive modification component was added to complete the thermosensitive modification of the capsule wall. Finally, the reaction system was heated to 68-70℃ for cross-linking and curing (preferably 65-70 min) to form a capsule wall layer (i.e., a high-temperature resistant capsule wall layer) to obtain a high-temperature triggered coating liquid. The high-temperature triggered coating liquid was cooled to 28-32℃, allowed to stand for 90-100 min, washed, filtered, dried, and sieved to obtain high-temperature triggered microcapsules with a particle size of 100-200 micrometers. (3) Preparation of compound temperature gradient triggered microcapsules: Low-temperature triggered microcapsules, room-temperature triggered microcapsules, and high-temperature triggered microcapsules are mixed (or compounded) at a mass ratio of 3:(3.8~4.2):3 (preferably 3:4:3) to obtain compound temperature gradient triggered microcapsules.
[0061] The waterproof membrane provided by this invention comprises, in sequence, an upper surface isolation layer, a temperature-gradient self-healing modified bitumen functional surface layer, a matrix layer, a temperature-gradient self-healing modified bitumen functional underlayer, and a lower surface isolation layer. Its core component is the addition of specific mass ratios of low-temperature, room-temperature, and high-temperature gradient microcapsules to the temperature-gradient self-healing modified bitumen functional underlayer and surface layer. The temperature-gradient self-healing modified bitumen coating in the underlayer and surface layer features differentiated capsule wall triggering structures and a dedicated homologous asphalt self-healing core liquid designed for different temperature zones. This enables precise, graded self-healing across the entire temperature range of 0-65℃, overcoming the shortcomings of traditional self-healing membranes, such as single temperature zone compatibility, poor repair effect, and easy delamination and leakage. Simultaneously, a low-temperature post-admixing preparation process at 125-135℃ is used to prevent premature microcapsule rupture during production. This achieves year-round, blind-zone-free self-healing repair of the membrane, while also maintaining high flowability at low temperatures, high strength at room temperatures, and anti-flow properties at high temperatures. This improves the waterproof membrane's waterproofing effect and service life, making it more suitable for various building waterproofing projects.
[0062] In this invention, the above-mentioned technical features can be freely combined to form new technical solutions, provided they do not conflict with each other.
[0063] Compared with the prior art, the above-mentioned technical solution provided by the present invention has the following beneficial technical effects: (1) The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane provided by the present invention uses three gradient temperature triggered microcapsules of low temperature, normal temperature and high temperature to accurately compound and obtain compound temperature zone gradient triggered microcapsules. The triggering temperature range is 0~15℃, 15~35℃ and 35~65℃, which is suitable for seasonal temperature changes throughout the year. They do not interfere with each other and act in separate zones to achieve self-healing of bitumen waterproof membrane throughout the year. (2) The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane provided by the present invention adopts a differentiated capsule wall material design. The low temperature triggered microcapsule adopts low temperature brittle wall material cold stress triggering, the room temperature triggered microcapsule adopts stress elastic wall material deformation tensile triggering, and the high temperature triggered microcapsule adopts thermosensitive phase change wall material high temperature softening triggering. The differentiated capsule wall material ensures that the microcapsule rupture is triggered in intervals under seasonal temperature changes throughout the year, so that the bitumen waterproof membrane can self-heal at different temperatures. (3) The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane provided by the present invention, wherein the gradient exclusive homologous bitumen self-healing core liquid is designed for three temperature ranges, and three sets of bitumen self-healing core liquids with different ratios, different softness and hardness, elongation and fluidity are designed respectively to achieve temperature zone repair; in addition, the gradient exclusive homologous adaptive bitumen self-healing core liquid, all core liquids are bitumen matrix, which are homologously integrated with the modified bitumen material of the membrane body to avoid incompatibility and secondary leakage caused by layering; (4) The method for preparing temperature gradient triggered microcapsule self-healing bitumen waterproof membrane provided by the present invention adopts a low-temperature post-mixing preparation method, adding compound temperature gradient triggered microcapsules in the temperature range of 125~135℃, ensuring that the microcapsules do not damage the capsule wall in advance during the production process and are accurately triggered during the construction and application stage, thereby improving the effectiveness of the self-healing of bitumen waterproof membrane. Attached Figure Description
[0064] Figure 1 This is a schematic diagram of the structure of the temperature gradient triggered microcapsule self-healing bitumen waterproof membrane of the present invention. Detailed Implementation
[0065] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0066] Unless otherwise specified, the terminology used herein should be understood as having the meaning commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the event of any conflict, this specification shall prevail.
[0067] In the following embodiments, the specific information of each raw material is as follows: The liquid petroleum asphalt is 200# asphalt, with an asphalt softening point of 17~26℃ and a 0.1 mm penetration of 180~220. 90# asphalt is heavy-duty road petroleum asphalt with an asphalt softening point of 40~55℃ and a 0.1 mm penetration of 80~100. Naphthenic oils have a flash point >210℃ and a kinematic viscosity of 19~27 mm at 40℃. 2 / s, freezing point is -25℃; Polyisobutylene is a medium molecular weight, highly reactive polyisobutylene with a molecular weight of 800~1200 and a flash point >210℃; The SBS modifier is a linear SBS with a styrene to butadiene block ratio of 40:60, and the grade is YH792 / 1401. Oil-extended SBR styrene-butadiene rubber powder, with a particle size of 80~120 mesh, ash content ≤1.5%, and Tg of -49~-55℃; C5 resin is a hydrogenated petroleum resin with a softening point of 85~110℃; The compatibility stabilizer is an SBS modified asphalt compatibility stabilizer, brand name LF-618, with an effective component of ≥98%, and is thermally stable at 180℃ without decomposition; The low-temperature antioxidant is a low-temperature-specific hindered phenolic antioxidant, sourced from Yingkou Tianyuan, brand name T5024, with a melting point of 65~75℃ and a flash point >220℃; it does not crystallize or precipitate at -20℃ and is long-term stable at 160℃. The high-temperature antioxidant is a complex of antioxidant 1010 (pentaerythritol ester) and antioxidant 168 (triphosphite ester) in a mass ratio of 2:1. It has a melting point of 110~125℃ and a flash point of >230℃. It is stable at 65℃ for a long time and thermally stable at 190℃ without decomposition, thus inhibiting thermal flow aging. The low-temperature dispersant is a low-temperature compatible dispersant specifically for asphalt, using Dow 4170, which does not stratify at -20℃ and has a miscibility of ≥98%. The general-purpose dispersant is a polymeric interfacial modified powder, derived from Dongying Runfeng HMD-1; the effective ingredient content is ≥98%, it is thermally stable at 180℃ without decomposition, and the flash point is >230℃. The high-temperature dispersant is a high-temperature cross-linking polymeric stabilizer, brand name RL-9689; it does not degrade at 160~200℃, inhibits high-temperature flow, and has a flash point >250℃. The inorganic filler is made of wollastonite powder, with an oil absorption value of 22~28 g / 100 g and a fineness of 600~800 mesh.
[0068] Example 1 A temperature gradient triggered microcapsule self-healing bitumen waterproof membrane, such as Figure 1 As shown, the coating comprises, from top to bottom, an upper surface isolation layer, a top layer, a carcass layer (i.e., polyester carcass), a bottom layer, and a lower surface isolation layer; the top layer and the bottom layer are prepared using a temperature gradient self-healing modified asphalt coating material; wherein, the temperature gradient self-healing modified asphalt coating material is prepared from the following raw materials in parts by weight: 55 parts of 90# asphalt, 5 parts of naphthenic oil, 8 parts of SBS modifier, 3 parts of oil-extended SBR styrene-butadiene rubber powder (rubber toughening agent), 1 part of compatibility stabilizer, 0.5 parts of high-temperature antioxidant, 10 parts of inorganic filler, and 3 parts of compound temperature gradient triggered microcapsules.
[0069] Specifically, the compound temperature gradient triggering microcapsules are prepared by mixing low-temperature triggering microcapsules, room-temperature triggering microcapsules, and high-temperature triggering microcapsules in a mass ratio of 3:4:3. The low-temperature triggering microcapsules include a low-temperature triggering composite capsule wall and an internal low-temperature homologous asphalt self-healing core liquid, with a triggering temperature range of 0~15℃. The room-temperature triggering microcapsules include a room-temperature triggering composite capsule wall and an internal room-temperature homologous asphalt self-healing core liquid, with a triggering temperature range of 15~35℃. The high-temperature triggering microcapsules include a high-temperature triggering composite capsule wall and an internal high-temperature homologous asphalt self-healing core liquid, with a triggering temperature range of 35~65℃.
[0070] Specifically, the low-temperature homologous asphalt self-healing core liquid is composed of the following raw materials by weight: 55 parts liquid petroleum asphalt (i.e., 200# asphalt), 16 parts naphthenic oil, 11 parts SBS modifier, 8 parts polyisobutylene, 4 parts C5 resin, 3 parts inorganic filler, 0.8 parts low-temperature antioxidant, and 0.7 parts low-temperature dispersant.
[0071] The room temperature homogeneous asphalt self-healing core liquid is composed of the following raw materials by weight: 58 parts 90# asphalt, 14 parts naphthenic oil, 9 parts SBS modifier, 6 parts polyisobutylene, 5 parts C5 resin, 4 parts inorganic filler, 0.7 parts high temperature antioxidant, and 0.6 parts general dispersant.
[0072] The high-temperature homologous asphalt self-healing core liquid is composed of the following raw materials by weight: 60 parts 90# asphalt, 12 parts naphthenic oil, 8 parts SBS modifier, 5 parts polyisobutylene, 6 parts C5 resin, 5 parts inorganic filler, 1.0 part high-temperature antioxidant, and 0.3 parts high-temperature dispersant.
[0073] The preparation method of the above-mentioned temperature gradient triggered microcapsule self-healing bitumen waterproof membrane includes the following steps: Step S1: Preparation of composite temperature-zone gradient-triggered microcapsules Step S1-1: Pre-preparing the three-temperature-zone homogeneous asphalt self-healing core liquid, namely, low-temperature homogeneous asphalt self-healing core liquid, normal-temperature homogeneous asphalt self-healing core liquid, and high-temperature homogeneous asphalt self-healing core liquid; the pre-preparation of the three-temperature-zone homogeneous asphalt self-healing core liquid is carried out according to the following order of addition of raw materials: The asphalt is heated to 140-150℃, naphthenic oil and polyisobutylene are added and premixed for 10 min, then SBS modifier is added. Under heat preservation, the mixture is stirred at low speed (1000-1500 r / min) for 30 min until fully swollen. Then, C5 resin, inorganic filler, and additives (antioxidant, dispersant) are added sequentially and stirred for 20 min until homogeneous. The mixture is then cooled to 110-120℃. Finally, under heat preservation conditions, air bubbles are removed and internal stresses of the components are eliminated to ensure uniform fluidity and absence of impurities in the core liquid, resulting in a pre-formed three-temperature-zone homogeneous asphalt self-healing core liquid. The additives include antioxidants and dispersants. Antioxidants include any one of low-temperature and high-temperature antioxidants; dispersants include any one of low-temperature, general-purpose, and high-temperature dispersants. The specific selection is based on the actual composition of the three-temperature-zone homogeneous asphalt self-healing core liquid. For example, in preparing low-temperature homologous asphalt self-healing core liquid, the antioxidant is a low-temperature antioxidant and the dispersant is a low-temperature dispersant; in preparing room-temperature homologous asphalt self-healing core liquid, the antioxidant is a high-temperature antioxidant and the dispersant is a general-purpose dispersant.
[0074] Step S1-2: The pre-prepared three-temperature-zone homogeneous asphalt self-healing core liquid is emulsified and dispersed to prepare the core liquid, specifically including the following steps: Using deionized water as the main medium, an anionic dispersion stabilizer (sodium lignosulfonate, brand name SQ-1, from Shandong Shengquan New Material Co., Ltd.) was added and stirred to dissolve it. Then, the pH value was adjusted to 4.5~5.0, and the mixture was preheated to 52~56℃ and kept at that temperature. The pre-prepared three-temperature zone homologous asphalt self-healing core liquid was added to the aqueous phase system at a uniform rate and sheared at a high speed of 2800~3000 r / min for 25 min to form a uniform oil / water emulsion, thus obtaining low-temperature homologous asphalt self-healing core liquid, room-temperature homologous asphalt self-healing core liquid, and high-temperature homologous asphalt self-healing core liquid, respectively.
[0075] Steps S1-3: Low-temperature triggered composite capsule walls, room-temperature triggered composite capsule walls, and high-temperature triggered composite capsule walls are synthesized using the encapsulation method to obtain low-temperature triggered microcapsules, room-temperature triggered microcapsules, and high-temperature triggered microcapsules; the specific steps are as follows.
[0076] S1-3-1. Coating Synthesis of Low-Temperature Triggered Composite Encapsulation Wall: The low-temperature homologous asphalt self-healing core liquid prepared in step S1-2 was stirred at a constant temperature and low speed at 52~55℃. Then, modified urea-formaldehyde resin prepolymer (UF-M01 low-temperature nitrile-modified urea-formaldehyde prepolymer, purchased from Zibo Huasen) was added dropwise, and the reaction was carried out for 30~35 min to form a primary wall layer. Then, nitrile rubber modified emulsion (Lanxess KRYNAC3345C carboxylated nitrile rubber emulsion, with an AN content of 33%) was slowly incorporated to construct a composite encapsulation wall layer through interfacial graft copolymerization. Then, the above reaction system was cross-linked and cured at a constant temperature of 58℃ for 55~60 min to enhance the low-temperature brittleness characteristics and maintain stable toughness at room temperature, forming a low-temperature triggered composite encapsulation wall, and obtaining a low-temperature triggered coating liquid. The modified urea-formaldehyde resin prepolymer is a urea + formaldehyde low-temperature condensation UF prepolymer with a urea / formaldehyde molar ratio of 1:1.5. It is an aqueous liquid prepolymer with a solid content of 50±2% and a pH value of 4.5~5.5.
[0077] S1-3-2, Room Temperature Triggered Composite Capsule Wall Coating Synthesis: The room temperature homogeneous asphalt self-healing core liquid prepared in step S1-2 was stirred at a constant temperature and low speed at 55℃. A silane crosslinked modified urea-formaldehyde resin prepolymer (SM-UF-SiO2 silane crosslinked microcapsule-specific urea-formaldehyde prepolymer, from Jiangsu Sanmu) was added dropwise. Interfacial polymerization was carried out under heat preservation conditions for 40-45 min to form a wall layer. Then, the system was heated to 62℃ for constant temperature crosslinking and curing for 55-60 min to form a moderately soft and hard, mechanically stress-sensitive capsule wall layer, i.e., a room temperature triggered composite capsule wall, resulting in a room temperature triggered coating liquid. The silane crosslinked modified urea-formaldehyde resin prepolymer is a silane flexible crosslinked modified urea-formaldehyde resin prepolymer formed by dehydration and graft copolymerization of aminosilane coupling agent KH550 (accounting for 2%-4% of the total prepolymer mass) and (urea + formaldehyde low-temperature condensation) UF prepolymer.
[0078] S1-3-3, High-Temperature Triggered Composite Capsule Wall Coating Synthesis: The high-temperature homologous asphalt self-healing core liquid prepared in step S1-2 is stirred at a controlled temperature and low speed at 58~60℃. Highly cross-linked high-temperature resistant urea-formaldehyde resin (UF-M03 paraffin thermosensitive modified urea-formaldehyde prepolymer, from Zibo Huasen) is added dropwise for a prepolymerization reaction of 45~50 min. Then, phase change paraffin thermosensitive modification components are slowly and uniformly incorporated to complete the thermosensitive modification composite of the capsule wall. The system is heated to 68~70℃ for cross-linking and curing for 65~70 min to form a high-temperature resistant capsule wall layer, i.e., the high-temperature triggered composite capsule wall, resulting in the high-temperature triggered coating liquid. The highly cross-linked high-temperature resistant urea-formaldehyde resin is a highly cross-linked UF prepolymer (F / U ratio = 1:1.7) resistant to high temperatures up to 180℃. 52# phase change paraffin emulsion (phase change temperature 52-58℃) is uniformly dispersed within the urea-formaldehyde skeleton during the polymerization stage.
[0079] Step S1-4, Microcapsule Curing and Shaping: The low-temperature triggering coating solution, room-temperature triggering coating solution, and high-temperature triggering coating solution prepared in steps S1-3-1 to S1-3-3 are slowly cooled to 28-32℃, allowed to stand for 90-100 min, washed and filtered with water, dried at 40℃ with forced air, and then sieved to obtain three types of temperature-zone triggering microcapsules with a particle size of 100-200 micrometers. The three types of temperature-zone triggering microcapsules are uniformly mixed at a mass ratio of 3:4:3 (low-temperature triggering microcapsules, room-temperature triggering microcapsules, and high-temperature triggering microcapsules) to obtain composite temperature-zone gradient triggering microcapsules.
[0080] Step S2: Preparation of temperature gradient self-healing modified bitumen coating The preparation method of the temperature gradient self-healing modified asphalt coating using the above-mentioned compounded temperature gradient triggered microcapsules includes the following steps: Mix 55 parts by weight of 90# asphalt with 5 parts by weight of naphthenic oil and heat to 150°C. Add 8 parts by weight of SBS modifier, 3 parts by weight of rubber toughening agent, and 1 part by weight of compatibility stabilizer. Keep the mixture at 160°C for 15 min to swell and obtain a mixture. Grind and homogenize the mixture using a colloid mill. Specifically, grind at 175°C for 60 min until the SBS modifier is completely dissolved. Then add 0.5 parts by weight of high-temperature antioxidant and stir for 20 min. Add 10 parts by weight of inorganic filler and stir at 160°C for 30 min. Then cool to 125°C and add 3 parts by weight of the above-mentioned compounded temperature gradient triggered microcapsules. Stir at a stirring rate of 1000 r / min for 15 min to obtain temperature gradient self-healing modified asphalt coating.
[0081] Step S3: Molding of compound temperature zone gradient triggered microcapsule self-healing modified bitumen rolls The above-mentioned temperature gradient self-healing modified bitumen coating is applied to both sides of the prepreg polyester substrate, covered with a polyethylene release film, cooled and shaped, cut and rolled to obtain the roll material.
[0082] Example 2 A compound temperature gradient triggered microcapsule self-healing modified bitumen roll material differs from Example 1 only in the composition and dosage of the temperature gradient self-healing modified bitumen coating, as detailed below: Temperature gradient self-healing modified bitumen coating is made from the following raw materials in parts by weight: 60 parts of 90# asphalt, 10 parts of naphthenic oil, 10 parts of SBS modifier, 4 parts of rubber toughening agent, 1.5 parts of compatibility stabilizer, 0.8 parts of high-temperature antioxidant, 12 parts of inorganic filler, and 4 parts of compound temperature gradient triggered microcapsules.
[0083] The composite temperature gradient triggering microcapsule is prepared by mixing low-temperature triggering microcapsules, room-temperature triggering microcapsules and high-temperature triggering microcapsules in a mass ratio of 3:4:3, which is the same as the composite temperature gradient triggering microcapsule and its preparation method in Example 1.
[0084] The preparation method of the above-mentioned compound temperature zone gradient triggered microcapsule self-healing modified bitumen roll material differs from the preparation method in Example 1 as follows: Step S2: Preparation of temperature gradient self-healing modified bitumen coating Mix 60 parts by weight of 90# asphalt with 10 parts by weight of naphthenic oil and heat to 155℃. Add 10 parts by weight of SBS modifier, 4 parts by weight of rubber toughening agent, and 1.5 parts by weight of compatibility stabilizer. Keep the mixture at 165℃ for 15 min to swell and obtain a mixture. Grind the mixture using a colloid mill to homogenize it. Specifically, grind at 180℃ for 75 min until the SBS modifier is completely dissolved. Then add 0.8 parts by weight of high-temperature antioxidant and stir for 20 min. Add 12 parts by weight of inorganic filler and stir at 165℃ for 30 min. Then cool down to 130℃, add compound temperature gradient triggered microcapsules, and stir at a stirring rate of 1200 r / min for 18 min to obtain temperature gradient self-healing modified asphalt coating.
[0085] Example 3 A compound temperature gradient triggered microcapsule self-healing modified bitumen roll material differs from Example 1 only in the composition and dosage of the temperature gradient self-healing modified bitumen coating, as detailed below: Temperature gradient self-healing modified bitumen coating is made from the following raw materials in parts by weight: 65 parts of 90# asphalt, 15 parts of naphthenic oil, 12 parts of SBS modifier, 5 parts of rubber toughening agent, 2 parts of compatibility stabilizer, 1 part of high-temperature antioxidant, 15 parts of inorganic filler, and 5 parts of compound temperature gradient triggered microcapsules.
[0086] The composite temperature gradient triggering microcapsule is prepared by mixing low-temperature triggering microcapsules, room-temperature triggering microcapsules and high-temperature triggering microcapsules in a mass ratio of 3:4:3, which is the same as the composite temperature gradient triggering microcapsule and its preparation method in Example 1.
[0087] The preparation method of the above-mentioned compound temperature zone gradient triggered microcapsule self-healing modified bitumen roll material differs from the preparation method in Example 1 as follows: Step S2: Preparation of temperature gradient self-healing modified bitumen coating Mix 90# asphalt with naphthenic oil according to the weight ratio, and heat to 160℃; add SBS modifier, rubber toughening agent, and compatibility stabilizer, and keep at 170℃ for 15 min to obtain a mixture. Use a colloid mill to grind and homogenize the mixture, specifically, grind at 185℃ for 90 min until the SBS modifier is completely dissolved; then add high-temperature antioxidant and stir for 20 min, add inorganic filler, and stir at 170℃ for 30 min; then cool to 135℃, add compound temperature gradient triggered microcapsules, and stir at a stirring rate of 1500 r / min for 20 min to obtain temperature gradient self-healing modified asphalt coating.
[0088] Comparative Example 1 A temperature-triggered microcapsule self-healing modified bitumen roll material includes, from top to bottom, an upper surface isolation layer, a surface layer, a substrate layer, a bottom layer, and a lower surface isolation layer; the surface layer and the bottom layer are prepared using a temperature-healing modified bitumen coating material; the difference between this and Example 2 is that this comparative example uses a temperature-healing modified bitumen coating material instead of the temperature gradient self-healing modified bitumen coating material in Example 1.
[0089] Specifically, the temperature-self-healing modified bitumen coating is prepared from the following raw materials in parts by weight: The mixture consists of 60 parts of 90# asphalt, 10 parts of naphthenic oil, 10 parts of SBS modifier, 4 parts of rubber toughening agent, 1.5 parts of compatibility stabilizer, 0.8 parts of high-temperature antioxidant, 12 parts of inorganic filler, and 4 parts of high-temperature triggered epoxy resin core microcapsules. The high-temperature triggered epoxy resin core microcapsules include a phase change paraffin capsule wall and a high-temperature triggered epoxy resin core liquid located inside the capsule wall, without any built-in homologous asphalt core liquid.
[0090] That is, the difference between this comparative example and Example 2 is that a high-temperature triggered epoxy resin core microcapsule is used instead of the compound temperature gradient triggered microcapsule in Example 2, so as to obtain a temperature self-healing modified asphalt coating material with only a single microcapsule, no temperature gradation, no homologous asphalt core liquid, and no gradient ratio.
[0091] The preparation method of the above-mentioned temperature-triggered microcapsule self-healing modified bitumen roll material includes the following steps: Step S1: Preparation of temperature-self-healing modified asphalt coating Mix 90# asphalt with naphthenic oil according to the weight ratio, and heat to 150℃; add SBS modifier, oil-extended SBR styrene-butadiene rubber powder (rubber toughening agent), and compatibility stabilizer, and keep at 160℃ for 15 min to obtain a mixture. Use a colloid mill to grind and homogenize the mixture, specifically, grind at 175℃ for 60 min until the SBS modifier is completely dissolved; then add antioxidant and stir for 20 min, add inorganic filler and stir to mix, stir at 160℃ and directly incorporate high-temperature triggered epoxy resin core microcapsules, stir and mix at a stirring rate of 1000 r / min to obtain temperature self-healing modified asphalt coating material.
[0092] Step S2: Temperature-triggered microcapsule self-healing modified bitumen roll molding 5-10 minutes before the molding process of the temperature-self-healing modified bitumen coating, add 1.9-2.6 parts of a latent amine curing agent (Guangzhou Taiji New Materials, Tai luck-D97) to the coating and disperse it evenly in the coating. Apply the temperature-self-healing modified bitumen coating with the latent amine curing agent to both sides of a pre-impregnated polyester substrate, cover with a polyethylene release film, cool and set, slit and roll to obtain the roll material.
[0093] In this comparative example, the principle of high-temperature triggered self-healing of the temperature-triggered microcapsule-modified asphalt membrane is as follows: High temperature triggers epoxy resin as the core fluid. When the material is heated to above 35°C, the phase change paraffin wax in the capsule wall absorbs heat and melts, expanding and generating internal pressure that causes the capsule wall to crack. As the temperature rises, the viscosity of the core fluid epoxy resin in the capsule wall decreases and its fluidity increases. It seeps into the capillary channels of the cracks in the roll material and fills the microcracks and pinholes. At the same time, the pre-dispersed curing agent in the roll material (dispersed in the temperature self-healing modified bitumen coating) is activated at high temperatures of 35-65°C, cross-links and polymerizes with the epoxy resin to form a rigid epoxy solid that seals the cracks and blocks the water seepage channels.
[0094] Comparative Example 2 A method for preparing a self-healing modified bitumen roll with compound temperature zone gradient-triggered microcapsules is disclosed. The only difference between this method and Example 2 is the temperature at which the compound temperature zone gradient-triggered microcapsules are incorporated; all other technical aspects remain the same. Details are as follows: Step S2: Preparation of temperature gradient self-healing modified bitumen coating Mix 60 parts by weight of 90# asphalt with 10 parts by weight of naphthenic oil and heat to 155℃. Add 10 parts by weight of SBS modifier, 4 parts by weight of rubber toughening agent and 1.5 parts by weight of compatibility stabilizer, and keep at 165℃ for 15 min to obtain a mixture. Use a colloid mill to grind and homogenize the mixture, specifically, grind at 180℃ for 75 min until the SBS modifier is completely dissolved. Then add 0.8 parts by weight of high temperature antioxidant and stir for 20 min. Add 12 parts by weight of inorganic filler and stir at 165℃ for 30 min. Then add compound temperature gradient triggered microcapsules and stir at a stirring rate of 1200 r / min for 18 min to obtain temperature gradient self-healing modified asphalt coating.
[0095] Performance evaluation of self-healing modified bitumen rolls 1) Self-healing rate across the entire temperature range: A standard through-crack of 0.2 mm was created on the surface of the roll material. The cracks were kept at 0~15℃, 15~35℃, and 35~65℃ for 2 hours respectively. The crack repair and filling status was observed, the crack width was measured, and the self-healing rate was calculated. Self-healing rate = (original crack width - remaining crack width after self-healing) / original crack width * 100%; 2) Elongation at break of asphalt: The elongation rate of the asphalt layer when there are pores and cracks is tested according to the method in standard GB / T 328.9-2007.
[0096] 3) Low temperature flexibility: Bend at -20℃ according to the method in standard GB / T 328.14-2007 and observe whether there are cracks.
[0097] 4) Heat resistance: Refer to Method B in standard GB / T 328.11-2007, place vertically at 65℃ for 4 hours, and observe the flow.
[0098] 5) Microcapsule integrity rate before construction and use: Microscopic observation was used to count the percentage of intact capsules; where, integrity rate = number of intact and undamaged capsules / total number of sample capsules * 100%.
[0099] 6) Performance retention rate of self-healing roll material in normal temperature environment: Calculate the ratio of the tensile properties of the self-healing roll material to that of the virgin roll material; specifically, retention rate = tensile properties of self-healing roll material / tensile properties of virgin roll material * 100%.
[0100] 7) Water resistance: Immerse in water at 23±2℃ for 3 hours and observe whether there is delamination, peeling, or blistering at the repair interface.
[0101] Table 1 shows the performance test evaluation of the self-healing modified bitumen rolls prepared in each embodiment and comparative example.
[0102] Table 1 Performance test evaluation data of self-healing modified bitumen rolls
[0103] As shown in Table 1, compared with Comparative Example 1, Examples 1, 2, and 3, the composite temperature gradient triggered microcapsules in the roll material all achieved good self-healing performance for microcracks in the temperature range of 0~65℃. In particular, they were significantly better than traditional self-healing roll materials (i.e., the roll material in Comparative Example 1) in the medium and low temperature range. Traditional self-healing roll materials only provide limited repair in summer and cannot meet the self-healing needs of roll materials in the low temperature environment of autumn and winter.
[0104] By comparing the retention rate of self-healing elongation performance and the delamination, it can be seen that the roll material with compound temperature zone gradient triggered microcapsules has a higher retention rate of elongation performance after microcrack repair and no delamination. This indicates that the homologous asphalt self-healing core liquid in the compound temperature zone gradient triggered microcapsules of the present invention has been well integrated with the asphalt coating of the original roll material, with no incompatibility, while maintaining good physical elongation performance.
[0105] By comparing Example 2 and Comparative Example 2, under the same raw material ratio and using a low-temperature constant temperature incorporation process of 125~135℃, the microcapsule integrity rate is better than that of conventional addition processes. This avoids the premature rupture and failure of microcapsules due to high-temperature shearing, and the retention of self-healing effective components inside the finished roll material is far superior to that of conventional high-temperature addition processes.
[0106] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.
Claims
1. A temperature gradient triggered microcapsule self-healing bitumen waterproof membrane, characterized in that... It includes, from top to bottom, an upper surface isolation layer, a surface layer, a body layer, a bottom layer, and a lower surface isolation layer; the surface layer and the bottom layer are prepared using a temperature gradient self-healing modified asphalt coating material; The temperature gradient self-healing modified asphalt coating is prepared from the following raw materials in parts by weight: 55-65 parts asphalt, 5-15 parts naphthenic oil, 8-12 parts SBS modifier, 3-5 parts rubber toughening agent, 1-2 parts compatibility stabilizer, 0.5-1 part high-temperature antioxidant, 10-15 parts inorganic filler, and 3-5 parts compounded temperature gradient triggered microcapsules; The compound temperature gradient triggered microcapsules are composed of low-temperature triggered microcapsules, room-temperature triggered microcapsules, and high-temperature triggered microcapsules; wherein... The triggering temperature range of the low-temperature triggered microcapsules is 0~15℃. The triggering temperature range of the room-temperature triggered microcapsules is 15~35℃. The triggering temperature range of the high-temperature triggered microcapsule is 35~65℃.
2. The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to claim 1, characterized in that... , The compound temperature gradient triggered microcapsules are composed of low-temperature triggered microcapsules, room-temperature triggered microcapsules, and high-temperature triggered microcapsules in a mass ratio of 3:(3.8~4.2):
3.
3. The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to claim 1, characterized in that... , In the compound temperature gradient triggered microcapsules, the particle size of the microcapsules is 100~200 micrometers; The upper surface insulating layer has a width of 1040~1060 mm, a thickness of 0.04~0.06 mm, and a basis weight of 8.5~11.5 g / m². 2 polyethylene film; The lower surface isolation layer has a width of 1040~1060mm, a thickness of 0.04~0.06mm, and a basis weight of 8.5~11.5 g / m². 2 polyethylene film; The body layer is made of long-fiber polyester spunbond nonwoven fabric with a basis weight of 170~250 g / m². 2 Thickness: 0.95~1.3 mm; Moisture content: ≤0.5%; The asphalt includes at least one of liquid petroleum asphalt and 90# asphalt.
4. The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to claim 2, characterized in that... , The low-temperature triggered microcapsule includes a capsule wall and a core fluid disposed inside the capsule wall. The capsule wall is made of a urea-formaldehyde-nitrile rubber low-temperature brittle composite wall material. The room temperature triggered microcapsule includes a capsule wall and a core fluid disposed inside the capsule wall. The capsule wall is made of a silane cross-linked elastic urea-formaldehyde resin stress-sensitive wall material. The high-temperature triggered microcapsule includes a capsule wall and a core liquid disposed inside the capsule wall. The capsule wall is made of urea-formaldehyde-phase change paraffin thermosensitive composite wall material.
5. The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to claim 4, characterized in that... , The urea-formaldehyde-nitrile rubber low-temperature brittle composite wall material has an upper temperature resistance limit of 160℃. It is extremely prone to brittle cracking under freeze-thaw stress at 0~15℃, but is completely stable and does not crack above 15℃. The silane crosslinked elastic urea-formaldehyde resin stress-sensitive wall material has a maximum temperature resistance of 180℃ and is fracture-triggered by crack tensile stress. The urea-formaldehyde-phase change paraffin thermosensitive composite wall material has a maximum temperature resistance of 180℃ and uses high-temperature thermal expansion to trigger softening and cracking.
6. The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to claim 4, characterized in that... , In the low-temperature triggered microcapsule, the core fluid is a low-temperature homologous asphalt self-healing core fluid; the low-temperature homologous asphalt self-healing core fluid is made from the following raw materials in parts by weight: 54-56 parts liquid petroleum asphalt, 15-17 parts naphthenic oil, 10-12 parts SBS modifier, 7-9 parts polyisobutylene, 3-5 parts rubber toughening agent, 2-4 parts inorganic filler, 0.6-1.0 parts low-temperature antioxidant, and 0.5-0.9 parts low-temperature dispersant; preferably, the low-temperature homologous asphalt self-healing core fluid has a ring and ball softening point of 55-57℃, an elongation of ≥950%, and does not solidify at -20℃; In the room-temperature triggered microcapsule, the core fluid is a room-temperature homologous asphalt self-healing core fluid; the room-temperature homologous asphalt self-healing core fluid is made from the following raw materials in parts by weight: 57-59 parts of 90# asphalt, 13-15 parts of naphthenic oil, 8-10 parts of SBS modifier, 5-7 parts of polyisobutylene, 4-6 parts of rubber toughening agent, 3-5 parts of inorganic filler, 0.5-0.9 parts of high-temperature antioxidant, and 0.4-0.8 parts of general-purpose dispersant; preferably, the room-temperature homologous asphalt self-healing core fluid has a ring and ball softening point of 57-59℃ and an elongation of ≥850%; In the high-temperature triggered microcapsule, the core fluid is a high-temperature homologous asphalt self-healing core fluid; the high-temperature homologous asphalt self-healing core fluid is made from the following raw materials in parts by weight: 59-61 parts of 90# asphalt, 11-13 parts of naphthenic oil, 7-9 parts of SBS modifier, 4-6 parts of polyisobutylene, 5-7 parts of rubber toughening agent, 4-6 parts of inorganic filler, 0.8-1.2 parts of high-temperature antioxidant, and 0.1-0.5 parts of high-temperature dispersant; preferably, the high-temperature homologous asphalt self-healing core fluid has a ring and ball softening point of 59-60℃, an elongation of ≥800%, and does not flow at 65℃.
7. The temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to claim 6, characterized in that... , The liquid petroleum asphalt is 200# asphalt, with an asphalt softening point of 17~26℃ and a 0.1 mm penetration of 180~220. The 90# asphalt is heavy-duty road petroleum asphalt with an asphalt softening point of 40~55℃ and a 0.1 mm penetration of 80~100. The naphthenic oil has a flash point >210℃ and a kinematic viscosity of 19~27 mm at 40℃. 2 / s, freezing point is -25℃; The polyisobutylene is a medium molecular weight, high-activity polyisobutylene with a molecular weight of 800-1200 and a flash point >210℃. The SBS modifier is a linear SBS with a styrene to butadiene block ratio of 40:60; The rubber toughening agent includes C5 resin or oil-extended SBR styrene-butadiene rubber powder. The oil-extended SBR styrene-butadiene rubber powder has a particle size of 80~120 mesh, an ash content of ≤1.5%, and a Tg of -49~-55℃. The C5 resin is a hydrogenated petroleum resin with a softening point of 85~110℃. The compatibility stabilizer includes SBS modified asphalt compatibility stabilizer with an effective component of ≥98% and thermal stability at 180℃ without decomposition. The low-temperature antioxidant includes a low-temperature-specific hindered phenolic antioxidant with a melting point of 65~75℃ and a flash point >220℃; it does not crystallize and / or precipitate at -20℃ and is stable at 160℃ for a long time. The high-temperature antioxidant comprises a complex of antioxidant 1010 and antioxidant 168, wherein the mass ratio of antioxidant 1010 to antioxidant 168 is 2:
1. The low-temperature dispersant includes a low-temperature compatible dispersant specifically for asphalt. The general-purpose dispersant comprises a polymeric interfacial active modified powder with an effective component of ≥98%, which is thermally stable at 180℃ and does not decompose. The high-temperature dispersant includes a high-temperature cross-linking polymeric stabilizer, and the high-temperature dispersant does not degrade at 160~200℃; The inorganic filler includes at least one of wollastonite powder, talc powder, calcium carbonate and kaolin, with a fineness of 600-800 mesh.
8. A method for preparing a temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: Step 1: Prepare temperature gradient self-healing modified asphalt coating, including the following steps: The asphalt and naphthenic oil are stirred and mixed evenly, and the temperature is raised to 150~160℃; then, at 150~160℃, SBS modifier, rubber toughening agent and compatibility stabilizer are added and stirred and mixed, and the temperature is maintained at 160~170℃ for softening and swelling to obtain a mixture. The mixture is ground and homogenized, a high-temperature antioxidant is added and stirred, then an inorganic filler is added and stirred at a constant temperature of 160-170°C. The mixture is then cooled to 125-135°C and stirred at a constant temperature of 125-135°C to obtain the temperature gradient self-healing modified asphalt coating material, which is used as a topcoat and a basecoat. Step 2: Apply the temperature gradient self-healing modified bitumen coating material prepared in Step 1 to the upper and lower surfaces of the prepreg layer to form a top layer and a bottom layer. Then, apply an isolation layer to the surface of the top layer and the bottom layer to form an upper surface isolation layer and a lower surface isolation layer. After cooling and shaping, cut and roll up to obtain a temperature gradient triggered microcapsule self-healing bitumen waterproof membrane.
9. The method for preparing temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to claim 8, characterized in that, The preparation method of the compound temperature gradient triggered microcapsules includes the following steps: (1) Pre-prepare low-temperature homogeneous asphalt self-healing core liquid, normal-temperature homogeneous asphalt self-healing core liquid, and high-temperature homogeneous asphalt self-healing core liquid according to the formula: Asphalt is heated to 140-150℃, naphthenic oil and polyisobutylene are added and premixed, then SBS modifier is added. Under heat preservation conditions, the mixture is stirred until fully swollen. Next, rubber toughening agent, inorganic filler, and additives are added sequentially and stirred until homogeneous for 20 minutes. The mixture is then cooled to 110-120℃ and kept at that temperature to obtain pre-made low-temperature homologous asphalt self-healing core liquid, room-temperature homologous asphalt self-healing core liquid, and high-temperature homologous asphalt self-healing core liquid. The additives include antioxidants and dispersants; the antioxidants include any one of low-temperature antioxidants and high-temperature antioxidants; the dispersants include any one of low-temperature dispersants, general-purpose dispersants, and high-temperature dispersants. Emulsification and dispersion preparation of core fluid: Water is used as the main medium, an anionic dispersion stabilizer is added and stirred to dissolve; pH is adjusted to 4.5~5.0, preheated to 52~56℃ and kept at that temperature, the above-prepared low-temperature homologous asphalt self-healing core fluid, room-temperature homologous asphalt self-healing core fluid and high-temperature homologous asphalt self-healing core fluid are respectively added to the aqueous phase system for shearing to form oil / water emulsion, that is, low-temperature homologous asphalt self-healing core fluid, room-temperature homologous asphalt self-healing core fluid and high-temperature homologous asphalt self-healing core fluid are formed; (2) Preparation of three-temperature zone microcapsules, specifically including the following steps: Preparation of low-temperature triggered microcapsules: The low-temperature homologous asphalt self-healing core liquid prepared by emulsification and dispersion was stirred at a constant temperature of 52~55℃, and modified urea-formaldehyde resin prepolymer was added to react and form a primary wall layer; then, nitrile rubber modified emulsion was incorporated and interface graft copolymerization was carried out to construct a composite capsule wall layer; then, the reaction system was cross-linked and cured at a constant temperature to form a low-temperature triggered composite capsule wall, and a low-temperature triggered coating liquid was obtained; the low-temperature triggered coating liquid was cooled to 28~32℃, allowed to stand for 90~100 min, washed with water, filtered, dried, and sieved to obtain low-temperature triggered microcapsules with a particle size of 100~200 micrometers; Preparation of room temperature triggered microcapsules: The room-temperature triggered microcapsules prepared by emulsification and dispersion were stirred at a constant temperature of 52-55℃, and silane crosslinked modified urea-formaldehyde resin prepolymer was added for interfacial polymerization under heat preservation to form a wall layer; then the temperature was raised to 60-65℃ for crosslinking and curing to form a capsule wall layer, thus obtaining a room-temperature triggered coating liquid; the room-temperature triggered coating liquid was cooled to 28-32℃, allowed to stand for 90-100 min, washed with water, filtered, dried, and sieved to obtain room-temperature triggered microcapsules with a particle size of 100-200 micrometers; Preparation of high-temperature triggered microcapsules: The high-temperature triggered microcapsules prepared by emulsification and dispersion were stirred at a constant temperature of 58-60℃, and a highly cross-linked high-temperature resistant urea-formaldehyde resin was added for prepolymerization. Then, a phase change paraffin thermosensitive modification component was added to complete the thermosensitive modification of the capsule wall. Finally, the reaction system was heated to 68-70℃ for cross-linking and curing to form a capsule wall layer, resulting in a high-temperature triggered coating liquid. The high-temperature triggered coating liquid was cooled to 28-32℃, allowed to stand for 90-100 min, washed, filtered, dried, and sieved to obtain high-temperature triggered microcapsules with a particle size of 100-200 micrometers. (3) Preparation of compound temperature gradient triggered microcapsules: Low-temperature triggered microcapsules, room-temperature triggered microcapsules, and high-temperature triggered microcapsules were mixed at a mass ratio of 3:(3.8~4.2):3 to obtain composite temperature gradient triggered microcapsules.
10. The method for preparing the temperature gradient triggered microcapsule self-healing bitumen waterproof membrane according to claim 8, characterized in that, In step 1, the softening and swelling time is 10-20 minutes; or In step 1, the grinding and homogenization temperature is 175~185℃; or Preferably, in step 1, after adding the high-temperature antioxidant and continuing to stir and mix for 15-25 minutes, the inorganic filler is added; or In step 1, the composite temperature-zone gradient-triggered microcapsules are added and stirred under a constant temperature of 125~135℃, wherein the stirring rate is 1000~1500 r / min and the stirring time is 15~20 min; or In step 1, inorganic filler is added and stirred at a constant temperature of 160-170℃ for 25-35 minutes; or In step 2, the temperature gradient self-healing modified asphalt coating material prepared in step 1 is applied to the upper and lower surfaces of the pre-impregnation layer using an oil coating thickness-fixing process to form a surface layer and a bottom layer.