Self-repairing self-adhesive tireless polymer modified asphalt waterproofing membrane, weather-resistant modified asphalt waterproofing membrane and preparation method thereof

Abstract

The present invention discloses a type of self-repairing, self-adhesive, tireless polymer-modified asphalt waterproofing membrane, which uses asphalt, a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, an initiator, an SBS modifier, an SBR modifier, a compatibilizer, rubber powder, and a filler as main raw materials. The present invention first uses olefinic monomers and dihydrazide monomers to prepare a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends. This repair agent undergoes an addition reaction with the carbon-carbon double bonds in SBS and SBR, introducing a dynamic acylhydrazone bond between the SBS and SBR molecular chains to impart excellent self-repairing capabilities to the self-adhesive, tireless polymer-modified asphalt waterproofing membrane. The membrane can also effectively improve the high and low temperature performance and aging resistance of SBS and SBR elastomer-modified asphalt waterproofing membranes. Furthermore, a bentonite fluid is prepared and used to prepare a weather-resistant self-adhesive polymer-modified asphalt, which can further improve the waterproofing membrane's aging resistance, low-temperature flexibility, and seam peel strength.

Description

Technical Field

[0001] The present invention belongs to the technical field of building materials, and in particular relates to a self-repairing, self-adhesive, tireless polymer-modified asphalt waterproofing membrane, a weather-resistant modified asphalt waterproofing membrane and a preparation method thereof. Background Art

[0002] Self-adhesive polymer-modified asphalt waterproofing membranes not only offer excellent low-temperature flexibility but also enable direct bonding, eliminating the environmental pollution and fire risks associated with hot-melt construction. However, during construction and use, these membranes are susceptible to mechanical puncture, leading to leakage. Over time, they age and become brittle due to environmental factors such as heat, oxygen, and ultraviolet light, leading to cracking and leakage under external forces. Therefore, imparting self-healing cracks to self-adhesive polymer-modified asphalt waterproofing membranes and improving their aging resistance would be crucial for addressing building leakage and extending the service life of waterproofing projects.

[0003] Dynamic acylhydrazone bonds can break under external influences, but when the external stimulus is removed, the bonds can dynamically adjust and reorganize, thereby enabling the polymer to self-repair. Currently, there are two main methods for preparing polymers based on dynamic acylhydrazone self-repair. One method uses a compound containing a dynamic acylhydrazone bond (-CH=N-NH-) with hydroxyl groups (-OH) at both ends and a compound or prepolymer with isocyanate groups (-NCO) at both ends as reactive monomers. Dynamic acylhydrazone bonds are introduced into the polymer molecular chain through a condensation reaction to impart self-repairing properties to the polymer, as described in patent CN 106117486 B. The other method involves separately synthesizing macromolecular prepolymers containing hydrazide groups (-NHNH2) and aldehyde groups (-CHO), and then reacting the two macromolecular prepolymers to prepare a self-repairing polymer containing dynamic acylhydrazone bonds, as described in patent CN 110522948 B. However, the raw materials (asphalt, SBS, SBR) of self-adhesive polymer-modified asphalt waterproofing membranes do not contain -OH, -NCO, -NHNH2 or -CHO groups, and the above methods cannot be used to introduce dynamic acylhydrazone bonds into polymer-modified asphalt. In addition, the above schemes do not involve self-repair modification of the SBS and SBR polymers themselves; they cannot simultaneously improve the problems of insufficient high and low temperature resistance and aging resistance of SBS and SBR modified asphalt.

[0004] The unique layered structure of phyllosilicates gives them thermal insulation, oxygen barrier, and UV protection, and has been used to improve the aging resistance of asphalt. Because phyllosilicates are hydrophilic materials, they have poor compatibility with asphalt, making them prone to agglomeration in asphalt, seriously affecting the phyllosilicate's aging resistance and reducing the asphalt's low-temperature flexibility. To improve the compatibility of phyllosilicates with asphalt, phyllosilicates are often subjected to organic modification, such as utilizing the ion exchange properties of phyllosilicates to replace phyllosilicate interlayer cations (sodium ions, calcium ions, etc.) with organic cations to increase their lipophilicity. However, while existing organic modification methods can improve the dispersion of phyllosilicates in polymer-modified asphalt, organically modified phyllosilicates are inorganic powdery materials, which can reduce the low-temperature flexibility and seam peel strength of self-adhesive polymer-modified asphalt waterproofing membranes, seriously affecting the performance of the waterproofing membrane. Summary of the Invention

[0005] The purpose of the present invention is to address the problems and shortcomings of the prior art and provide a type of self-repairing, self-adhesive, tireless polymer-modified asphalt waterproofing membrane. A repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends is prepared using olefinic monomers and dihydrazide monomers. The carbon-carbon double bonds in the repair agent are used to undergo addition reaction with the carbon-carbon double bonds in SBS and SBR to introduce dynamic acylhydrazone bonds between the molecular chains of SBS and SBR for preparing self-adhesive polymer-modified asphalt, thereby giving the self-adhesive tireless polymer-modified asphalt waterproofing membrane excellent self-repairing properties, and simultaneously and effectively improving the high and low temperature properties and aging resistance of SBS and SBR elastomer-modified asphalt waterproofing membrane; further, natural bentonite, which is low-cost and widely available, is prepared into a fluid-like material and used to prepare weather-resistant self-adhesive polymer-modified asphalt, which can further improve the aging resistance of the waterproofing membrane, improve its low-temperature flexibility and joint peel strength, etc.

[0006] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is as follows:

[0007] A self-repairing, self-adhesive, tireless polymer-modified asphalt waterproofing membrane comprises the following components and their weight proportions: 100 parts of asphalt, 0.3-1 part of a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.03-0.06 part of an initiator, 15-20 parts of an SBS modifier, 8-13 parts of an SBR modifier, 30-50 parts of a compatibilizer, 30-40 parts of rubber powder, and 60-80 parts of a filler.

[0008] In the above solution, the asphalt is petroleum asphalt, the needle penetration of which at 25°C is 60 to 120 dmm and the softening point is greater than 45°C.

[0009] Furthermore, the asphalt is 70#, 90# and 110# petroleum asphalt.

[0010] In the above scheme, the repair agent containing an acylhydrazone bond and having carbon-carbon double bonds at both ends is prepared by condensation reaction of an aldehyde monomer and a dihydrazide monomer. The specific preparation method is:

[0011] 1) dissolving a dihydrazide monomer in glacial acetic acid and mixing uniformly to obtain a dihydrazide monomer solution;

[0012] 2) Adding an aldehyde monomer dropwise to the obtained dihydrazide monomer solution to react under heating and stirring, filtering under reduced pressure; washing and drying to obtain the repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends.

[0013] In the above scheme, the alkenal monomer is one of 10-undecenal, 9-undecenal, 8-undecenal, 10-hexadecenal, 8-nonenal, 4-pentenal, 7-octenal, 9-decenal, 8-undecenal, 4-hexenal, 5-octenal, 6-nonenal, acrolein or 3-phenylacrolein.

[0014] In the above scheme, the dihydrazide monomer is one of oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide or terephthalic acid dihydrazide.

[0015] In the above scheme, the molar ratio of the dihydrazide monomer to the aldehyde monomer is 1:2.0-2.1.

[0016] In the above scheme, the heating and stirring reaction temperature is 50-70°C and the time is 0.5-1h.

[0017] In the above scheme, the initiator is a high-temperature initiator cumene hydroperoxide (half-life is 1 hour at 193° C.), and its usage accounts for 0.03 to 0.06% of the mass of the asphalt.

[0018] In the above scheme, the SBS modifier has a linear or star-shaped structure, a styrene content of 30-40%, and a molecular weight of 80,000-350,000.

[0019] In the above solution, the styrene content of the SBR modifier is 20-40%, and the molecular weight is 100,000-250,000.

[0020] In the above solution, the compatibilizer is one of aromatic oil, naphthenic oil and base oil.

[0021] In the above solution, the rubber powder is waste rubber powder with a fineness of 30 to 80 meshes.

[0022] In the above solution, the filler is one of talcum powder, limestone powder and fly ash, and has a fineness of 100 to 200 meshes.

[0023] The present invention also provides a weather-resistant, self-repairing, self-adhesive, tireless polymer-modified asphalt waterproof membrane, the components and their weight proportions including: 100 parts of asphalt, 0.3-1 parts of a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.03-0.06 parts of an initiator, 5-10 parts of a bentonite fluid, 15-20 parts of an SBS modifier, 8-13 parts of an SBR modifier, 30-50 parts of a compatibilizer, 30-40 parts of rubber powder, and 60-80 parts of a filler.

[0024] In the above scheme, the selection or preparation requirements of the asphalt, the repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, the initiator, the SBS modifier, the SBR modifier, the compatibilizer, the rubber powder, and the filler in the weather-resistant self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane are the same as above (corresponding requirements for self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane).

[0025] In the above scheme, the bentonite fluid is prepared by sequentially grafting surface hydroxylated bentonite with dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and sodium nonylphenol polyoxyethylene ether sulfate (NPES) (dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride also has a partial intercalation effect). The specific preparation method is as follows:

[0026] 1) adding bentonite to a hydrogen peroxide solution and stirring, filtering, washing, stirring in an alkaline solution, filtering, washing, and obtaining a surface-hydroxylated bentonite;

[0027] 2) The surface hydroxylated bentonite is uniformly dispersed in water, and then dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride is added dropwise for aging with intermittent shaking; sodium nonylphenol polyoxyethylene ether sulfate is then added, stirred for reaction, and allowed to stand. After the mixed solution separates, the supernatant is removed, and finally, the mixture is washed and dried to obtain a bentonite fluid.

[0028] In the above solution, the concentration of the hydrogen peroxide solution is 20-40 wt %; the mass ratio of bentonite to hydrogen peroxide solution is 1:5-15.

[0029] In the above scheme, the alkali solution is a sodium hydroxide solution with a pH value of 11 to 13; the mass ratio of bentonite to sodium hydroxide solution is 1:5 to 15.

[0030] In the above scheme, the stirring treatment time of the bentonite in the hydrogen peroxide solution is 1 to 3 hours; the stirring treatment time of the bentonite in the alkali solution is 3 to 5 hours.

[0031] In the above scheme, the mass ratio of the surface hydroxylated bentonite, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and sodium nonylphenol polyoxyethylene ether sulfate is 1:2-10:0.5-2.

[0032] In the above scheme, the aging time is 2 to 5 hours.

[0033] In the above scheme, the total shaking time of the intermittent shaking is not less than 5 minutes.

[0034] In the above scheme, the stirring reaction time is 3 to 6 hours; and the standing time is 1 to 2 hours.

[0035] In the above solution, the bentonite is sodium-based or calcium-based bentonite, the montmorillonite content is greater than 60wt%, and the fineness is 200 mesh.

[0036] The preparation method of the self-repairing self-adhesive polymer-modified asphalt waterproof membrane or the weather-resistant self-repairing self-adhesive polymer-modified asphalt waterproof membrane comprises the following steps:

[0037] 1) Heat the asphalt to 170-180°C, add the compatibilizer and bentonite fluid and mix evenly; the self-repairing self-adhesive non-tired polymer modified asphalt waterproof membrane does not require the addition of bentonite fluid;

[0038] 2) Add SBS modifier and SBR modifier, maintain the temperature at 170-180°C, and stir once;

[0039] 3) Raise the temperature to 180-190°C, add a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends and an initiator, and perform a secondary stirring treatment;

[0040] 4) Add rubber powder, maintain the temperature at 180-190°C, and stir three times;

[0041] 5) Add filler, maintain the temperature at 180-190° C., and stir for four times to obtain a self-repairing, self-adhesive, tireless polymer modified asphalt coating material;

[0042] 6) The obtained self-repairing self-adhesive tireless polymer modified asphalt coating material is made into a coating film with a thickness of 1.2 to 2 mm, and the upper and lower surfaces are respectively covered with a polyethylene isolation film and a silicone-coated isolation paper to obtain the self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane or the weather-resistant self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane.

[0043] In the above scheme, the first stirring process rate is 3000-5000 rpm, and the time is 10-30 min; the second stirring process rate is 3000-5000 rpm, and the time is 20-40 min; the third stirring process rate is 1000-4000 rpm, and the time is 20-40 min; the fourth stirring process rate is 1000-3000 rpm, and the time is 20-40 min.

[0044] The principle of the present invention is:

[0045] (1) The present invention uses olefinic monomers and dihydrazide monomers to synthesize a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends. Under the action of a high-temperature initiator, cumene hydroperoxide, the carbon-carbon double bonds in the repair agent react with the carbon-carbon double bonds in SBS and SBR to introduce an acylhydrazone bond between the molecular chains of SBS and SBR ( Figure 1 ) to form a dynamic reversible cross-linked network structure in the self-adhesive, tireless polymer-modified asphalt waterproofing membrane. When cracks appear in the self-adhesive, tireless polymer-modified asphalt waterproofing membrane, it can self-repair at room temperature through a reversible cleavage-rearrangement reaction of the acylhydrazone bond. This not only has high self-repair efficiency but also allows for repeated self-repair. Simultaneously, the present invention utilizes the C=C double bonds in the resulting repair agent to react with the C=C double bonds in SBS and SBR. This, on the one hand, forms cross-links between the SBS and / or SBR molecular chains, which is beneficial for improving the heat resistance and low-temperature flexibility of the elastomer-modified asphalt waterproofing membrane. On the other hand, it reduces the C=C double bond content in SBS and SBR, effectively preventing chain scission and degradation of SBS and SBR under the action of heat, ultraviolet rays, and oxygen, thereby significantly improving the anti-aging properties of the modified asphalt waterproofing membrane.

[0046] In addition, the addition of the repair agent makes the polymer network structure in the self-adhesive tireless polymer modified asphalt waterproof membrane more perfect, which can significantly improve the high-temperature anti-flow and low-temperature cracking resistance of the self-adhesive tireless polymer modified asphalt waterproof membrane. The repair agent containing acylhydrazone bonds contains more polar groups, which can form a large number of hydrogen bonds in the self-adhesive tireless polymer modified asphalt waterproof membrane, which is beneficial to improve the adhesion between the membranes and increase their joint peel strength.

[0047] (2) Although traditional organic modification can improve the dispersion of layered silicates in polymer-modified asphalt, organically modified layered silicates are inorganic powder materials, which will reduce the low-temperature flexibility and joint peeling strength of self-adhesive polymer-modified asphalt waterproof membranes. The present invention selects natural bentonite with abundant sources, utilizes the hydroxyl groups on the surface of bentonite, and increases the hydroxyl content on the surface of bentonite by treating it with hydrogen peroxide and alkali solution. Then, the surface hydroxyl groups are reacted with dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to graft organic molecular chains on the surface of bentonite. Then, nonylphenol polyoxyethylene ether sodium sulfate (NPES) is anchored on the dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride molecules on the surface of bentonite through the action of ionic bonds, forming flexible long-chain organic macromolecules on the surface of bentonite (methyl, methylene, benzene ring and sulfate groups appear in the infrared spectrum of bentonite-like fluids), so that the bentonite exhibits fluid-like characteristics. Compared with traditional organic modified bentonite (such as CTAB intercalated bentonite), the contact angle of bentonite fluid is significantly increased ( Figure 2 ), exhibiting strong lipophilicity, significantly improving its dispersibility in polymer-modified asphalt. Furthermore, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, an organic cation, can also undergo ion exchange with cations (calcium and sodium ions) between bentonite interlayers. This means that some dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride molecules can intercalate into the bentonite interlayers, significantly expanding the interlayer spacing of the bentonite. This allows asphalt molecules to enter the bentonite interlayers during the polymer-modified asphalt preparation process, causing exfoliation. The bentonite is dispersed in the polymer-modified asphalt in the form of nanosheets, effectively enhancing the anti-aging properties of self-adhesive, tireless polymer-modified asphalt waterproofing membranes. Furthermore, the fluidization of bentonite transforms it from a rigid material into a flexible one. Its addition to polymer-modified asphalt not only does not reduce the low-temperature performance of the polymer-modified asphalt, but actually improves its low-temperature flexibility and joint peel strength.

[0048] (3) An acylhydrazone bond is introduced into the polymer (SBS and SBR) in the self-adhesive tireless polymer modified asphalt waterproof membrane to form a cross-linked network structure. After the bentonite fluid is added, the long organic macromolecular chains on the surface of the bentonite fluid are entangled with the polymer network, making the polymer network structure in the waterproof membrane more perfect, further improving the high and low temperature performance and self-repairing performance of the waterproof membrane. At the same time, due to the entanglement effect, the bentonite adheres to the polymer network, which can more effectively prevent the damage to the polymer network by heat, oxygen, and ultraviolet rays. The present invention can effectively improve the self-repairing function, high and low temperature performance and anti-aging performance of the self-adhesive tireless polymer modified asphalt waterproof membrane through the synergistic effect of the acylhydrazone bond introduced into the polymer molecular structure and the bentonite fluid.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] (1) By introducing a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends into the molecular chains of SBS and SBR, and utilizing the reversible breakage-rearrangement reaction of the acylhydrazone bond, the self-adhesive and tireless polymer modified asphalt waterproof membrane is endowed with excellent self-repairing ability; at the same time, the C=C double bonds in the repair agent react with the C=C double bonds in SBS and SBR to form a cross-linked network structure of SBS and SBR in the asphalt, reducing the C=C double bond content, and simultaneously improving the heat resistance, low-temperature flexibility and aging resistance of the polymer (SBS, SBR) modified asphalt waterproof membrane; in addition, the introduced acylhydrazone bond forms a large number of hydrogen bonds in the self-adhesive and tireless polymer modified asphalt waterproof membrane, which is beneficial to improve the adhesion between the membranes and increase the peel strength of the joints.

[0051] (2) The thermal insulation, oxygen barrier and UV protection capabilities of bentonite-like fluids can not only significantly improve the aging resistance of waterproof membranes, but also the fluidization of bentonite can transform it from a rigid material to a flexible material. Adding it to polymer-modified asphalt can effectively improve the low-temperature performance and joint peeling strength of polymer-modified asphalt waterproof membranes.

[0052] (3) The addition of a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends and a bentonite-like fluid can synergistically improve the high and low temperature performance, joint peeling strength and anti-aging performance of the self-adhesive tireless polymer modified asphalt waterproof membrane. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 The reaction mechanism of the repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends with the SBS modifier and the SBR modifier;

[0054] Figure 2 is the water contact angle of CTAB intercalated bentonite and bentonite-like fluid;

[0055] Figure 3 Infrared spectra of (a) a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, and (b) calcium bentonite and a calcium bentonite-like fluid;

[0056] Figure 4 These are photos of the weather-resistant, self-repairing, self-adhesive, tireless polymer-modified asphalt waterproofing membrane before (top) and after (bottom) repair of bending cracks. DETAILED DESCRIPTION

[0057] In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

[0058] The raw materials used in the following examples of the present invention are all commercially available. The preparation methods of the repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, the repair agent containing an acylhydrazone bond but not containing a carbon-carbon double bond, the bentonite fluid, and the CTAB intercalated bentonite are as follows:

[0059] Restorative agent A containing an acylhydrazone bond and carbon-carbon double bonds at both ends:

[0060] 60.00 g of glacial acetic acid was poured into a three-necked flask, 3.48 g of adipic acid dihydrazide was added and dissolved in the glacial acetic acid, and 6.74 g of 10-undecenal was then added dropwise to the three-necked flask. The mixture was stirred at 50°C for 60 min and filtered under reduced pressure. The resulting product was washed three times with ethanol and deionized water, respectively. The solid powder obtained by drying was the repair agent A containing an acylhydrazone bond and carbon-carbon double bonds at both ends.

[0061] Repair agent B containing an acylhydrazone bond and carbon-carbon double bonds at both ends:

[0062] 60.00 g of glacial acetic acid was poured into a three-necked flask, 3.88 g of terephthalic acid dihydrazide was added and dissolved in the glacial acetic acid, and 6.74 g of 10-undecenal was then added dropwise to the three-necked flask. The mixture was stirred and reacted at 60°C for 50 min, and filtered under reduced pressure. The resulting product was washed three times with ethanol and deionized water, respectively. The solid powder obtained by drying was the repair agent B containing an acylhydrazone bond and carbon-carbon double bonds at both ends.

[0063] Restorative agent C containing an acylhydrazone bond and carbon-carbon double bonds at both ends:

[0064] 60.00 g of glacial acetic acid was poured into a three-necked flask, 3.48 g of adipic acid dihydrazide was added and dissolved in the glacial acetic acid, and 5.29 g of 3-phenylpropenal was then added dropwise to the three-necked flask. The mixture was stirred and reacted at 70°C for 30 min, and filtered under reduced pressure. The resulting product was washed three times with ethanol and deionized water, respectively. The solid powder obtained by drying was the repair agent C containing an acylhydrazone bond and carbon-carbon double bonds at both ends.

[0065] Restorative agent D containing acylhydrazone bond but no carbon-carbon double bond:

[0066] 60.00 g of glacial acetic acid was poured into a three-necked flask, 3.48 g of adipic acid dihydrazide was added and dissolved in the glacial acetic acid, and 6.82 g of undecanal was then added dropwise to the three-necked flask. The mixture was stirred at 50°C for 60 min and filtered under reduced pressure. The resulting product was washed three times with ethanol and deionized water, respectively. The solid powder obtained by drying was the repair agent D containing an acylhydrazone bond but no carbon-carbon double bond.

[0067] Sodium bentonite fluid:

[0068] 1) Weighing 10 parts by weight of sodium bentonite (montmorillonite content: 75 wt %, fineness: 200 mesh) into a beaker, adding 100 parts by weight of a hydrogen peroxide solution (concentration: 30 wt %), stirring at room temperature for 2 hours, filtering the solution with suction and washing it with deionized water, and then dispersing it in 100 parts by weight of a sodium hydroxide solution with a pH of 12. After stirring at room temperature for 4 hours, filtering the solution with suction and washing it with deionized water until neutral, thereby obtaining a surface hydroxylated bentonite;

[0069] 2) 10 parts by mass of surface hydroxylated bentonite was dispersed in 100 parts by mass of deionized water to prepare a dispersion, and 100 parts by mass of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride methanol solution (the concentration of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was 40 wt%) was slowly added dropwise to the dispersion and aged for 3 h with intermittent shaking; subsequently, 70 parts by mass of NPES aqueous solution (the concentration of NPES was 15 wt%) was added, stirred for 4 h and then allowed to stand, and the supernatant was removed after the mixed solution was separated; finally, the mixture was washed with deionized water and methanol in sequence to remove the unreacted NPES, and the obtained solid was placed in an oven at 105 ° C and dried for 6 h to obtain a sodium bentonite fluid.

[0070] Calcium-based bentonite fluid:

[0071] The preparation method of the calcium-based bentonite fluid is the same as that of the sodium-based bentonite fluid, except that the bentonite used is calcium-based bentonite with a montmorillonite content of 68 wt% and a fineness of 200 mesh.

[0072] CTAB intercalated sodium bentonite:

[0073] (1) Add 400 mL of deionized water, 20 g of sodium bentonite, and 6 g of concentrated hydrochloric acid to a three-necked flask and stir at 60°C at a speed of 500 r / min for 2 h.

[0074] (2) Add 10 g of CTAB, heat to 80 ° C and stir for 2 h, cool to room temperature, filter, wash the filter cake with deionized water, and then place the filter cake in an oven at 105 ° C to dry for 6 h. After grinding, pass through a 200 mesh sieve to obtain CTAB intercalated sodium bentonite.

[0075] CTAB intercalated calcium bentonite:

[0076] The preparation method of CTAB intercalated calcium bentonite is the same as that of CTAB intercalated sodium bentonite, except that the bentonite used is calcium bentonite with a montmorillonite content of 68 wt % and a fineness of 200 mesh.

[0077] Example 1

[0078] A self-repairing, self-adhesive, tireless polymer-modified asphalt waterproofing membrane comprises the following components and their weight proportions: 100 parts (by mass, the same below) of asphalt (softening point 49.3° C., needle penetration 71 dmm at 25° C.), 0.4 parts of a repair agent A containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.03 parts of cumene hydroperoxide, 16 parts of an SBS (linear structure, styrene content 30%, molecular weight 80,000-120,000) modifier, 9 parts of an SBR (styrene content 20%, molecular weight 100,000-150,000) modifier, 35 parts of a compatibilizer (aromatic oil), 32 parts of rubber powder (40 mesh), and 60 parts of a filler (talc, 200 mesh). The specific preparation process is as follows:

[0079] 1) Heat the asphalt to 180°C, add the compatibilizer and stir for 10 minutes to mix evenly;

[0080] 2) Add SBS modifier and SBR modifier, maintain the temperature at 180°C, and stir at 4000 rpm for 20 minutes;

[0081] 3) Raise the temperature to 190°C, add a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends and an initiator, and stir at 4000 rpm for 30 minutes;

[0082] 4) Add rubber powder, maintain the temperature at 190°C, and stir at 2000 rpm for 30 minutes;

[0083] 5) adding filler, maintaining the temperature at 190° C., and stirring at 2000 rpm for 30 minutes to obtain a self-repairing self-adhesive tireless polymer modified asphalt coating;

[0084] 6) The self-repairing self-adhesive non-tube polymer modified asphalt coating material is made into a 2 mm thick coating film, and the upper and lower surfaces are covered with a polyethylene release film and a silicone-coated release paper, respectively, to obtain a self-repairing self-adhesive non-tube polymer modified asphalt waterproof membrane.

[0085] Comparative Example 1

[0086] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 1, except that the following ingredients are used: 100 parts of asphalt (softening point 49.3° C., needle penetration 71 dmm at 25° C.), 0.4 parts of a repair agent D containing an acylhydrazone bond but not a carbon-carbon double bond, 0.03 parts of isopropylbenzene hydroperoxide, 16 parts of an SBS (linear structure, styrene content 30%, molecular weight 80,000-120,000) modifier, 9 parts of an SBR (styrene content 20%, molecular weight 100,000-150,000) modifier, 35 parts of a compatibilizer (aromatic oil), 32 parts of rubber powder (40 mesh), and 60 parts of a filler (talc, 200 mesh).

[0087] Comparative Example 2

[0088] A self-adhesive, tireless polymer-modified asphalt waterproofing membrane comprises the following components and their contents: 100 parts of asphalt (softening point 49.3° C., needle penetration 71 dmm at 25° C.), 16 parts of an SBS modifier (linear structure, 30% styrene content, molecular weight 80,000-120,000), 9 parts of an SBR modifier (20% styrene content, molecular weight 100,000-150,000), 35 parts of a compatibilizer (aromatic oil), 32 parts of rubber powder (40 mesh), and 60 parts of a filler (talc powder, 200 mesh). The specific preparation steps include the following:

[0089] 1) Heat the asphalt to 180°C, add the compatibilizer and stir for 10 minutes to mix evenly;

[0090] 2) Add SBS modifier and SBR modifier to asphalt, maintain the temperature at 180°C, and stir at 4000 rpm for 20 minutes;

[0091] 3) Heat to 190°C and stir at 4000 rpm for 30 min;

[0092] 4) Add rubber powder, maintain the temperature at 190°C, and stir at 2000 rpm for 30 minutes;

[0093] 5) Add filler, maintain the temperature at 190° C., and stir at 2000 rpm for 30 minutes to obtain a self-adhesive tireless polymer modified asphalt coating;

[0094] 6) The self-adhesive tireless polymer modified asphalt coating material is made into a coating film with a thickness of 2 mm, and the upper and lower surfaces are covered with a polyethylene release film and a silicone-coated release paper, respectively, to obtain a self-adhesive tireless polymer modified asphalt waterproof membrane.

[0095] The self-adhesive tireless polymer modified asphalt waterproof membranes obtained in Example 1 and Comparative Examples 1-2 were tested for high and low temperature performance, joint peel strength, anti-aging performance, and self-repairing performance, respectively. The specific methods are as follows:

[0096] High and low temperature performance and seam peel strength test:

[0097] The high and low temperature performance of the self-adhesive, tireless polymer-modified asphalt waterproof membrane prepared in Example 1 and Comparative Examples 1-2 were tested according to the "Bitumen Softening Point Determination - Ring and Ball Method" (GB / T 4507-2014) and the "Test Methods for Building Waterproofing Membranes: Part 14 - Low-Temperature Flexibility of Asphalt Waterproofing Membranes" (GB / T 328.14-2007), respectively; the joint peel strength was tested according to the "Test Methods for Building Waterproofing Membranes: Part 20 - Joint Peel Strength of Asphalt Waterproofing Membranes" (GB / T 328.20-2007).

[0098] Anti-aging performance test:

[0099] The self-adhesive tireless polymer modified asphalt waterproof membranes prepared in Example 1 and Comparative Examples 1-2 were heat aged at 80°C for 10 days, and then the softening point, low-temperature flexibility and joint peel strength of the waterproof membranes after aging were tested respectively. The softening point increment, low-temperature flexibility change and joint peel strength change before and after aging were calculated according to Formula (1), Formula (2) and Formula (3). The smaller the softening point increment, low-temperature flexibility change and joint peel strength change, the better the aging resistance of the waterproof membrane.

[0100] Softening point increment = softening point after aging - softening point before aging (1)

[0101] Change in low-temperature flexibility = low-temperature flexibility after aging - low-temperature flexibility before aging (2)

[0102] Change in seam peel strength = seam peel strength after aging - seam peel strength before aging (3)

[0103] Self-repair performance test:

[0104] A: The self-adhesive non-tired polymer modified asphalt waterproof membrane prepared in Example 1 and Comparative Examples 1-2 was made into dumbbell-shaped tensile specimens with a length of 115 mm, a width of 25 mm, and a narrow parallel portion with a width of 6 mm in the middle. The specimens were then kept at -40°C for half an hour, bent until cracks appeared on the surface, and finally the tensile specimens with cracks on the surface were placed at 25°C for 12 hours before being subjected to a tensile test. The tensile rate was 500 mm / min and the gauge length was 10 mm. The self-repairing performance was measured by the recovery rate at break (R ε ) indicates that R ε Calculate according to formula (4):

[0105]

[0106] Among them, ε0 and ε1 are the elongation at break of the self-adhesive tireless polymer modified asphalt waterproof membrane before breaking and after self-repair, respectively.

[0107] B: The self-adhesive, tireless polymer-modified asphalt waterproof membranes prepared in Example 1 and Comparative Examples 1-2 were made into circular specimens with a diameter of 130 mm. The circular specimens were pierced with a blade 5.5 mm long and 0.5 mm thick. After being placed at 25°C for 12 hours, their impermeability was tested in accordance with the "Test Methods for Building Waterproofing Membranes: Part 10: Waterproofness of Asphalt and Polymer Waterproofing Membranes" (GB / T 328.10-2007).

[0108] Table 1 Performance test results of Example 1 and Comparative Examples 1-2

[0109]

[0110]

[0111] As can be seen from Table 1, compared with Comparative Example 1 and Comparative Example 2, the self-repairing, self-adhesive, tireless polymer modified asphalt waterproof membrane prepared in Example 1 has a higher softening point and lower low-temperature flexibility, and the softening point increment and low-temperature flexibility change after thermal aging are both smaller, indicating that it has better high and low temperature performance and anti-aging performance. At the same time, cracks are artificially created in the waterproof membrane, and after self-repair at 25°C for 12 hours, the elongation at break recovery rate of the self-adhesive, tireless polymer modified asphalt waterproof membrane prepared in Example 1 is much higher than that of Comparative Example 1 and Comparative Example 2. After the prefabricated cracks in the waterproof membrane prepared in Example 1 are self-repaired, they are impermeable under a water pressure of 0.15 MPa, while the prefabricated cracks in the waterproof membrane prepared in Comparative Example 1 and Comparative Example 2 are permeable under a water pressure of 0.1 MPa after self-repair. This shows that the self-adhesive, tireless polymer modified asphalt waterproof membrane prepared in Example 1 has excellent self-repairing ability.

[0112] Example 2

[0113] A self-repairing, self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 1, except that the raw materials and their amounts are: 100 parts of asphalt (softening point 47.2°C, needle penetration 92 dmm at 25°C), 0.7 parts of a repair agent B containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.05 parts of isopropylbenzene hydroperoxide, 18 parts of an SBS (star-shaped structure, styrene content of 40%, molecular weight of 250,000-320,000) modifier, 10 parts of an SBR (styrene content of 30%, molecular weight of 130,000-180,000) modifier, 42 parts of a compatibilizer (naphthenic oil), 34 parts of rubber powder (60 mesh), and 70 parts of a filler (limestone powder, 100 mesh).

[0114] Comparative Example 3

[0115] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is roughly the same as that of Comparative Example 2, except that the raw materials and their amounts are: 100 parts of asphalt (softening point 47.2°C, needle penetration 92 dmm at 25°C), 18 parts of SBS (star structure, styrene content 40%, molecular weight 250,000-320,000) modifier, 10 parts of SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 42 parts of compatibilizer (naphthenic oil), 34 parts of rubber powder (60 mesh) and 70 parts of filler (limestone powder, 100 mesh).

[0116] The self-adhesive tireless polymer modified asphalt waterproof membranes prepared in Example 2 and Comparative Example 3 were tested for high and low temperature performance, joint peel strength, aging resistance and self-repairing performance (same as Example 1 and Comparative Examples 1-2). The test results are shown in Table 2.

[0117] Table 2 Performance test results of Example 2 and Comparative Example 3

[0118]

[0119]

[0120] As can be seen from Table 2, the high and low temperature performance, aging resistance and self-repair performance of the self-repairing and self-adhesive polymer modified asphalt waterproof membrane prepared in Example 2 are significantly higher than those of the self-adhesive polymer modified asphalt waterproof membrane prepared in Comparative Example 3, indicating that the self-adhesive polymer modified asphalt waterproof membrane prepared in Example 2 has excellent high and low temperature, aging resistance and self-repair capabilities.

[0121] Example 3

[0122] A self-repairing, self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 1, except that the raw materials and their amounts are: 100 parts of asphalt (softening point 45.9°C, needle penetration 116 dmm at 25°C), 1 part of a repair agent C containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.05 part of isopropylbenzene hydroperoxide, 18 parts of an SBS (star structure, styrene content of 30%, molecular weight of 300,000-350,000) modifier, 12 parts of an SBR (styrene content of 30%, molecular weight of 130,000-180,000) modifier, 47 parts of a compatibilizer (base oil), 35 parts of rubber powder (80 mesh), and 80 parts of a filler (fly ash, 150 mesh).

[0123] Comparative Example 4

[0124] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is roughly the same as that of Comparative Example 2, except that the raw materials and their amounts are: 100 parts of asphalt (softening point 45.9°C, needle penetration 116 dmm at 25°C), 18 parts of SBS (star structure, styrene content 30%, molecular weight 300,000-350,000) modifier, 12 parts of SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 47 parts of compatibilizer (base oil), 35 parts of rubber powder (80 mesh) and 80 parts of filler (fly ash, 150 mesh).

[0125] The self-adhesive tireless polymer modified asphalt waterproof membranes prepared in Example 3 and Comparative Example 4 were tested for high and low temperature performance, joint peel strength, aging resistance and self-repairing performance (same as Example 1 and Comparative Examples 1-2). The test results are shown in Table 3.

[0126] Table 3 Performance test results of Example 3 and Comparative Example 4

[0127]

[0128]

[0129] As can be seen from Table 3, the high and low temperature performance, aging resistance and self-repair performance of the self-repairing and self-adhesive polymer modified asphalt waterproof membrane prepared in Example 3 are significantly higher than those of the self-adhesive polymer modified asphalt waterproof membrane prepared in Comparative Example 4, indicating that the self-adhesive polymer modified asphalt waterproof membrane prepared in Example 3 has excellent high and low temperature, aging resistance and self-repair capabilities.

[0130] Example 4

[0131] A weather-resistant, self-repairing, self-adhesive, non-tired polymer-modified asphalt waterproofing membrane, comprising the following components and their weight proportions: 100 parts (by mass, the same below) of asphalt (softening point 49.3° C., needle penetration 71 dmm at 25° C.), 0.5 parts of a repair agent A containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.04 parts of cumene hydroperoxide, 5 parts of a sodium bentonite fluid, 15 parts of an SBS (linear structure, styrene content 30%, molecular weight 80,000-120,000) modifier, 8 parts of an SBR (styrene content 20%, molecular weight 100,000-150,000) modifier, 30 parts of a compatibilizer (aromatic oil), 30 parts of rubber powder (40 mesh), and 60 parts of a filler (talc, 200 mesh). The specific preparation process is as follows:

[0132] 1) Heat the asphalt to 180°C, add the compatibilizer and bentonite fluid and stir for 10 minutes to mix evenly;

[0133] 2) Add SBS modifier and SBR modifier to asphalt, maintain the temperature at 180°C, and stir at 4000 rpm for 20 minutes;

[0134] 3) Raise the temperature to 190°C, add a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends and an initiator, and stir at 4000 rpm for 30 minutes;

[0135] 4) Add rubber powder, maintain the temperature at 190°C, and stir at 2000 rpm for 30 minutes;

[0136] 5) Add filler, maintain the temperature at 190° C., and stir at 2000 rpm for 30 minutes to obtain a weather-resistant self-repairing self-adhesive tireless polymer modified asphalt coating;

[0137] 6) The weather-resistant self-repairing self-adhesive tireless polymer modified asphalt coating is made into a 2 mm thick coating film, and the upper and lower surfaces are covered with a polyethylene release film and a silicone-coated release paper, respectively, to obtain a weather-resistant self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane.

[0138] Comparative Example 5

[0139] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 1, except that the components and their contents are: 100 parts of asphalt (softening point 49.3° C., needle penetration 71 dmm at 25° C.), 0.5 parts of a repair agent A containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.04 parts of isopropylbenzene hydroperoxide, 15 parts of an SBS (linear structure, styrene content 30%, molecular weight 80,000-120,000) modifier, 8 parts of an SBR (styrene content 20%, molecular weight 100,000-150,000) modifier, 30 parts of a compatibilizer (aromatic oil), 30 parts of rubber powder (40 mesh), and 60 parts of a filler (talc, 200 mesh).

[0140] Comparative Example 6

[0141] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 1, except that the components and their contents are: 100 parts of asphalt (softening point 49.3° C., needle penetration 71 dmm at 25° C.), 0.5 parts of a repair agent D containing an acylhydrazone bond but no carbon-carbon double bond, 0.04 parts of isopropylbenzene hydroperoxide, 15 parts of an SBS (linear structure, styrene content 30%, molecular weight 80,000-120,000) modifier, 8 parts of an SBR (styrene content 20%, molecular weight 100,000-150,000) modifier, 30 parts of a compatibilizer (aromatic oil), 30 parts of rubber powder (40 mesh), and 60 parts of a filler (talc, 200 mesh).

[0142] Comparative Example 7

[0143] A self-adhesive, tireless polymer-modified asphalt waterproofing membrane comprises the following components and their contents: 100 parts of asphalt (softening point 49.3° C., needle penetration 71 dmm at 25° C.), 5 parts of sodium bentonite fluid, 15 parts of SBS (linear structure, styrene content 30%, molecular weight 80,000-120,000) modifier, 8 parts of SBR (styrene content 20%, molecular weight 100,000-150,000) modifier, 30 parts of a compatibilizer (aromatic oil), 30 parts of rubber powder (40 mesh), and 60 parts of a filler (talc powder, 200 mesh). The specific preparation steps include the following:

[0144] 1) Heat the asphalt to 180°C, add the compatibilizer and bentonite fluid and stir for 10 minutes;

[0145] 2) Add SBS modifier and SBR modifier to asphalt, maintain the temperature at 180°C, and stir at 4000 rpm for 20 minutes;

[0146] 3) Heat to 190°C and stir at 4000 rpm for 30 min;

[0147] 4) Add rubber powder, maintain the temperature at 190°C, and stir at 2000 rpm for 30 minutes;

[0148] 5) Add filler, maintain the temperature at 190° C., and stir at 2000 rpm for 30 minutes to obtain a self-adhesive tireless polymer modified asphalt coating;

[0149] 6) The self-adhesive tireless polymer modified asphalt coating material is made into a coating film with a thickness of 2 mm, and the upper and lower surfaces are covered with a polyethylene release film and a silicone-coated release paper, respectively, to obtain a self-adhesive tireless polymer modified asphalt waterproof membrane.

[0150] Comparative Example 8

[0151] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Comparative Example 7, except that the components and their amounts are: 100 parts of asphalt (softening point 49.3° C., needle penetration 71 dmm at 25° C.), 5 parts of CATB intercalated sodium bentonite, 15 parts of SBS (linear structure, styrene content 30%, molecular weight 80,000-120,000) modifier, 8 parts of SBR (styrene content 20%, molecular weight 100,000-150,000) modifier, 30 parts of a compatibilizer (aromatic oil), 30 parts of rubber powder (40 mesh), and 60 parts of a filler (talc, 200 mesh).

[0152] Comparative Example 9

[0153] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is roughly the same as that of Comparative Example 2, except that the components and their amounts are: 100 parts of asphalt (softening point 49.3°C, needle penetration 71 dmm at 25°C), 15 parts of SBS (linear structure, styrene content 30%, molecular weight 80,000-120,000) modifier, 8 parts of SBR (styrene content 20%, molecular weight 100,000-150,000) modifier, 30 parts of compatibilizer (aromatic oil), 30 parts of rubber powder (40 mesh) and 60 parts of filler (talc, 200 mesh).

[0154] The self-adhesive tireless polymer modified asphalt waterproof membranes prepared in Example 4 and Comparative Examples 5-9 were tested for high and low temperature performance, joint peel strength, aging resistance and self-repairing performance (same as Example 1 and Comparative Examples 1-2). The test results are shown in Table 4.

[0155] Table 4 Performance test results of Example 4 and Comparative Examples 5-9

[0156]

[0157] It can be seen from Table 4 that compared with Comparative Examples 5-9, the self-adhesive tireless polymer modified asphalt waterproof membrane prepared in Example 4 has the highest softening point and joint peel strength, the lowest low-temperature flexibility, the smallest softening point increment, low-temperature flexibility change and joint peel strength change after aging, the largest recovery rate of elongation at break, and the watertightness after self-repair reaches 0.15 MPa. It has the best high and low temperature performance, joint peel performance, anti-aging performance and self-repair performance. Compared with Comparative Example 9, Comparative Example 5 is mixed with a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, but no bentonite fluid is added. The prepared self-adhesive tireless polymer modified asphalt waterproof membrane has excellent self-repairing performance, and the high and low temperature performance, joint peeling strength and aging resistance are also improved; Comparative Example 6 is mixed with a repair agent containing an acylhydrazone bond but not carbon-carbon double bonds, and the self-repairing performance, high and low temperature performance, joint peeling strength and aging resistance of the prepared self-adhesive tireless polymer modified asphalt waterproof membrane have no obvious changes; Comparative Example 7 is mixed with a bentonite fluid, but Without the addition of a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, the prepared self-adhesive, tireless polymer-modified asphalt waterproofing membrane had excellent anti-aging properties and good high- and low-temperature performance, but its elongation at break recovery rate was low, and after self-repair of the cracks, it was water-permeable at a water pressure of 0.1 MPa, indicating very weak self-repairing ability. In Comparative Example 8, without the addition of a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, but with the addition of CTAB-intercalated sodium bentonite, the prepared self-adhesive, tireless polymer-modified asphalt waterproofing membrane had some improvement in anti-aging properties, but poor low-temperature flexibility and seam peel strength. As can be seen from Example 4, Comparative Example 5, and Comparative Example 7, the addition of a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends significantly improved the self-repairing properties of the self-adhesive, tireless polymer-modified asphalt waterproofing membrane, and the synergistic effect of the repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends and the bentonite fluid further improved the self-repairing properties, high- and low-temperature performance, and anti-aging properties of the waterproofing membrane. The performance test results of Comparative Examples 7, 8 and 9 show that making bentonite into a fluid-like material not only effectively improves the anti-aging performance of the waterproof membrane, but also significantly improves its high and low temperature performance and seam peeling strength.

[0158] Example 5

[0159] A weather-resistant, self-repairing, self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 4, except that the components and their weight proportions are: 100 parts of asphalt (softening point 47.2°C, needle penetration 92 dmm at 25°C), 0.6 parts of a repair agent B containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.05 parts of isopropyl benzene hydroperoxide, 7 parts of a calcium-based bentonite fluid, 20 parts of an SBS (star-shaped structure, styrene content of 40%, molecular weight of 250,000-320,000) modifier, 8 parts of an SBR (styrene content of 30%, molecular weight of 130,000-180,000) modifier, 40 parts of a compatibilizer (naphthenic oil), 35 parts of rubber powder (60 mesh), and 70 parts of a filler (limestone powder, 100 mesh).

[0160] Comparative Example 10

[0161] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 5, except that the components and their contents are: 100 parts of asphalt (softening point 47.2° C., needle penetration 92 dmm at 25° C.), 0.6 parts of a repair agent B containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.05 parts of isopropylbenzene hydroperoxide, 20 parts of an SBS (star-shaped structure, styrene content 40%, molecular weight 250,000-320,000) modifier, 8 parts of an SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 40 parts of a compatibilizer (naphthenic oil), 35 parts of rubber powder (60 mesh), and 70 parts of a filler (limestone powder, 100 mesh).

[0162] Comparative Example 11

[0163] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is roughly the same as that of Comparative Example 7, except that the components and their contents are: 100 parts of asphalt (softening point 47.2°C, needle penetration 92 dmm at 25°C), 7 parts of calcium-based bentonite fluid, 20 parts of SBS (star structure, styrene content 40%, molecular weight 250,000-320,000) modifier, 8 parts of SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 40 parts of compatibilizer (naphthenic oil), 35 parts of rubber powder (60 mesh) and 70 parts of filler (limestone powder, 100 mesh).

[0164] Comparative Example 12

[0165] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Comparative Example 7, except that the components and their contents are: 100 parts of asphalt (softening point 47.2°C, needle penetration 92 dmm at 25°C), 7 parts of CTAB intercalated calcium-based bentonite, 20 parts of SBS (star-shaped structure, styrene content 40%, molecular weight 250,000-320,000) modifier, 8 parts of SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 40 parts of a compatibilizer (naphthenic oil), 35 parts of rubber powder (60 mesh) and 70 parts of a filler (limestone powder, 100 mesh).

[0166] Comparative Example 13

[0167] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is roughly the same as that of Comparative Example 2, except that the components and their contents are: 100 parts of asphalt (softening point 47.2°C, needle penetration 92 dmm at 25°C), 20 parts of SBS (star structure, styrene content 40%, molecular weight 250,000-320,000) modifier, 8 parts of SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 40 parts of compatibilizer (naphthenic oil), 35 parts of rubber powder (60 mesh) and 70 parts of filler (limestone powder, 100 mesh).

[0168] The self-adhesive tireless polymer modified asphalt waterproof membranes prepared in Example 5 and Comparative Examples 10-13 were tested for high and low temperature performance, joint peel strength, aging resistance and self-repairing performance (same as Example 1 and Comparative Examples 1-2). The test results are shown in Table 5.

[0169] Table 5 Performance test results of Example 5 and Comparative Examples 10-13

[0170]

[0171] As can be seen from Table 5, Example 5 simultaneously adds a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends and a bentonite fluid, and the prepared self-adhesive tireless polymer modified asphalt waterproof membrane has excellent high and low temperature performance, joint peeling performance, anti-aging performance and self-repairing performance; Comparative Example 10 adds a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, and the prepared self-adhesive tireless polymer modified asphalt waterproof membrane has excellent self-repairing performance; compared with Comparative Example 13, the anti-aging performance of the self-adhesive tireless polymer modified asphalt waterproof membranes prepared by Comparative Example 11 and Comparative Example 12, which are respectively added with bentonite fluid and CTAB intercalated calcium-based bentonite, are improved, but the waterproof membrane prepared in Comparative Example 11 with the addition of bentonite fluid not only effectively improves the anti-aging performance of the waterproof membrane, but also significantly improves its high and low temperature performance and joint peeling strength.

[0172] Example 6

[0173] A weather-resistant, self-repairing, self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 4, except that the components and their weight proportions are: 100 parts of asphalt (softening point 45.9°C, needle penetration 116 dmm at 25°C), 0.8 parts of a repair agent C containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.05 parts of isopropyl benzene hydroperoxide, 9 parts of a calcium-based bentonite fluid, 16 parts of an SBS (star-shaped structure, styrene content of 30%, molecular weight of 300,000-350,000) modifier, 12 parts of an SBR (styrene content of 30%, molecular weight of 130,000-180,000) modifier, 45 parts of a compatibilizer (base oil), 38 parts of rubber powder (80 mesh), and 75 parts of a filler (fly ash, 150 mesh).

[0174] Comparative Example 14

[0175] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Example 1, except that the components and their contents are: 100 parts of asphalt (softening point 45.9° C., needle penetration 116 dmm at 25° C.), 0.8 parts of a repair agent C containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.05 parts of isopropylbenzene hydroperoxide, 16 parts of an SBS (star-shaped structure, styrene content 30%, molecular weight 300,000-350,000) modifier, 12 parts of an SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 45 parts of a compatibilizer (base oil), 38 parts of rubber powder (80 mesh), and 75 parts of a filler (fly ash, 150 mesh).

[0176] Comparative Example 15

[0177] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is roughly the same as that of Comparative Example 7, except that the components and their contents are: 100 parts of asphalt (softening point 45.9°C, needle penetration 116 dmm at 25°C), 9 parts of calcium-based bentonite fluid, 16 parts of SBS (star structure, styrene content 30%, molecular weight 300,000-350,000) modifier, 12 parts of SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 45 parts of compatibilizer (base oil), 38 parts of rubber powder (80 mesh) and 75 parts of filler (fly ash, 150 mesh).

[0178] Comparative Example 16

[0179] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is substantially the same as that of Comparative Example 7, except that the components and their contents are: 100 parts of asphalt (softening point 45.9°C, needle penetration 116 dmm at 25°C), 9 parts of CTAB intercalated calcium-based bentonite, 16 parts of SBS (star structure, styrene content 30%, molecular weight 300,000-350,000) modifier, 12 parts of SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 45 parts of a compatibilizer (base oil), 38 parts of rubber powder (80 mesh) and 75 parts of a filler (fly ash, 150 mesh).

[0180] Comparative Example 17

[0181] A self-adhesive, tireless polymer-modified asphalt waterproof membrane, the preparation method of which is roughly the same as that of Comparative Example 2, except that the components and their contents are: 100 parts of asphalt (softening point 45.9°C, needle penetration 116 dmm at 25°C), 16 parts of SBS (star structure, styrene content 30%, molecular weight 300,000-350,000) modifier, 12 parts of SBR (styrene content 30%, molecular weight 130,000-180,000) modifier, 45 parts of compatibilizer (base oil), 38 parts of rubber powder (80 mesh) and 75 parts of filler (fly ash, 150 mesh).

[0182] The self-adhesive tireless polymer modified asphalt waterproof membranes prepared in Example 6 and Comparative Examples 14-17 were tested for high and low temperature performance, joint peel strength, aging resistance and self-repairing performance (same as Example 1 and Comparative Examples 1-2). The test results are shown in Table 6.

[0183] Table 6 Performance test results of Example 6 and Comparative Examples 14-17

[0184]

[0185] As can be seen from Table 6, Example 6 simultaneously adds a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends and a bentonite fluid, and the prepared self-adhesive tireless polymer modified asphalt waterproof membrane has excellent high and low temperature performance, joint peeling performance, anti-aging performance and self-repairing performance; Comparative Example 14 adds a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, and the prepared self-adhesive tireless polymer modified asphalt waterproof membrane has excellent self-repairing performance; compared with Comparative Example 17, the anti-aging performance of the self-adhesive tireless polymer modified asphalt waterproof membranes prepared by Comparative Example 15 and Comparative Example 16, which are respectively added with bentonite fluid and CTAB intercalated calcium-based bentonite, are improved, but the waterproof membrane prepared in Comparative Example 15 with the addition of bentonite fluid not only effectively improves the anti-aging performance of the waterproof membrane, but also significantly improves its high and low temperature performance and joint peeling strength.

[0186] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalences, replacements and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A self-repairing, self-adhesive, tireless polymer modified asphalt waterproof membrane, characterized in that: The components and their weight proportions include: 100 parts of asphalt, 0.3-1 parts of a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.03-0.06 parts of an initiator, 15-20 parts of an SBS modifier, 8-13 parts of an SBR modifier, 30-50 parts of a compatibilizer, 30-40 parts of rubber powder, and 60-80 parts of a filler; The repair agent containing an acylhydrazone bond and having carbon-carbon double bonds at both ends is prepared by condensation reaction of an aldehyde monomer and a dihydrazide monomer.

2. A weather-resistant self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane, characterized in that: The components and their weight proportions include: 100 parts of asphalt, 0.3-1 parts of a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends, 0.03-0.06 parts of an initiator, 5-10 parts of a bentonite fluid, 15-20 parts of an SBS modifier, 8-13 parts of an SBR modifier, 30-50 parts of a compatibilizer, 30-40 parts of rubber powder, and 60-80 parts of a filler; The repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends is prepared by condensation reaction of an aldehyde monomer and a dihydrazide monomer; The bentonite fluid is prepared by sequentially grafting surface hydroxylated bentonite with dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and sodium nonylphenol polyoxyethylene ether sulfate.

3. The weather-resistant self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane according to claim 2, characterized in that: The mass ratio of the surface hydroxylated bentonite, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and sodium nonylphenol polyoxyethylene ether sulfate is 1:2-10:0.5-2.

4. The self-repairing self-adhesive polymer modified asphalt waterproof membrane according to claim 1 or the weather-resistant self-repairing self-adhesive polymer modified asphalt waterproof membrane according to claim 2, characterized in that: The asphalt is petroleum asphalt, and its needle penetration at 25°C is 60-120 dmm and its softening point is greater than 45°C.

5. The self-repairing self-adhesive polymer modified asphalt waterproof membrane according to claim 1 or the weather-resistant self-repairing self-adhesive polymer modified asphalt waterproof membrane according to claim 2, characterized in that: The alkenal monomer is one of 10-undecenal, 9-undecenal, 8-undecenal, 10-hexadecenal, 8-nonenal, 4-pentenal, 7-octenal, 9-decenal, 4-hexenal, 5-octenal, 6-nonenal, acrolein or 3-phenylacrolein; and the dihydrazide monomer is one of oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide or terephthalic acid dihydrazide.

6. The self-repairing self-adhesive polymer modified asphalt waterproof membrane according to claim 1 or the weather-resistant self-repairing self-adhesive polymer modified asphalt waterproof membrane according to claim 2, characterized in that: The SBS modifier has a linear or star-shaped structure, a styrene content of 30-40%, and a molecular weight of 80,000-350,000; the SBR modifier has a styrene content of 20-40%, and a molecular weight of 100,000-250,000.

7. The self-repairing self-adhesive polymer modified asphalt waterproof membrane according to claim 1 or the weather-resistant self-repairing self-adhesive polymer modified asphalt waterproof membrane according to claim 2, characterized in that: The compatibilizer is one of aromatic oil, naphthenic oil and base oil; the rubber powder is waste rubber powder with a fineness of 30-80 meshes; the filler is one of talcum powder, limestone powder and fly ash with a fineness of 100-200 meshes.

8. A method for preparing the self-repairing self-adhesive non-tube polymer modified asphalt waterproofing membrane according to claim 1 or the weather-resistant self-repairing self-adhesive non-tube polymer modified asphalt waterproofing membrane according to claim 2, characterized in that: The following steps are involved: 1) Heat the asphalt to 170-180°C, add the compatibilizer and bentonite fluid and mix evenly; the self-repairing, self-adhesive, non-tired polymer modified asphalt waterproof membrane does not require the addition of bentonite fluid; 2) Add SBS modifier and SBR modifier, maintain the temperature at 170-180°C, and stir once; 3) Raise the temperature to 180-190°C, add a repair agent containing an acylhydrazone bond and carbon-carbon double bonds at both ends and an initiator for secondary stirring; 4) Add rubber powder, maintain the temperature at 180-190°C, and stir three times; 5) Add filler, maintain the temperature at 180-190°C, and stir four times to obtain a self-repairing, self-adhesive, tireless polymer modified asphalt coating material; 6) The obtained self-repairing self-adhesive tireless polymer modified asphalt coating is formed into a coating film with a thickness of 1.2 to 2 mm, and the upper and lower surfaces are covered with a polyethylene release film and a silicone-coated release paper, respectively, to obtain the self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane or the weather-resistant self-repairing self-adhesive tireless polymer modified asphalt waterproof membrane.

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