Flexible waterproof slurry and preparation method thereof

Abstract

The invention provides flexible waterproof slurry. The waterproof slurry comprises a solid raw material, a liquid raw material and a functional additive, the solid raw materials comprise Portland cement, quartz sand, hydroxypropyl methyl cellulose ether and a polycarboxylate superplasticizer; the liquid raw materials comprise an acrylic emulsion, a yttrium nitrate solution, a lanthanum chloride solution, a sodium lignin sulfonate solution, a dopamine hydrochloride solution and an acetic acid solution; the functional additive comprises a bio-based-rare earth composite modifier, a nano complexing agent and a self-repairing emulsion. Through combination of a bionic interface modification technology and a gradient cross-linked network, the elongation at break of the slurry is increased by 40% or above, and the slurry can tolerate 3mm deformation of a base layer without cracking; through the photocatalysis and antibacterial synergistic effect of the bio-based-rare earth composite modifier, self-decomposition of surface pollutants and the antibacterial rate of 99% or above are achieved, and meanwhile the cement consumption is reduced by 20%.

Description

Technical Field

[0001] The present invention relates to the technical field of waterproof slurries, and specifically relates to a flexible waterproof slurry and a preparation method thereof. Background Art

[0002] Waterproof mortar is currently widely used in the construction industry, mainly for waterproofing, anti-corrosion, anti-seepage, moisture-proofing and leakage repair projects of the interior and exterior walls of industrial and civil buildings, concrete, basements, water tanks, water towers, special-shaped roofs, tunnels, toilets, dams and other parts.

[0003] The existing waterproof slurries have poor bonding strength performance, poor flexibility performance, and it is difficult to coordinately improve the compressive strength performance with the bonding strength and flexibility. At the same time, the corrosion resistance and stability of the products are poor, which limits the use efficiency of the products. Summary of the Invention

[0004] Aiming at the defects of the existing technology, the purpose of the present invention is to provide a flexible waterproof slurry and a preparation method thereof to solve the problems raised in the above background art.

[0005] The present invention adopts the following technical solutions to solve the technical problems: The present invention provides a flexible waterproof slurry, and the waterproof slurry includes solid raw materials, liquid raw materials and functional additives; Among them, the solid raw materials include: portland cement, quartz sand, hydroxypropyl methylcellulose ether and polycarboxylate water reducer; The liquid raw materials include: acrylic emulsion, yttrium nitrate solution, lanthanum chloride solution, sodium lignosulfonate solution, hydrochloric acid dopamine solution and acetic acid solution; The functional additives include bio-based-rare earth composite modifiers, nano-composites and self-healing emulsions.

[0006] A preparation method of a flexible waterproof slurry for preparing the flexible waterproof slurry described in claim 1, the method includes the following steps: S01. Immerse the quartz sand in a sodium hydroxide solution, rinse it with deionized water after immersion, dry it in a vacuum drying oven after rinsing to obtain dried quartz sand, immerse the dried quartz sand in a hydrochloric acid dopamine solution for magnetic stirring, filter it after magnetic stirring, rinse it with ethanol after filtration, and perform vacuum drying after rinsing to obtain modified quartz sand; S02. Take cerium nitrate hexahydrate for solution preparation to obtain a cerium nitrate solution, take neodymium nitrate hexahydrate for solution preparation to obtain a neodymium nitrate solution, and mix the cerium nitrate solution and the neodymium nitrate solution to obtain a mixed solution of cerium nitrate and neodymium nitrate; Chitosan was added to acetic acid solution and stirred to dissolve. After dissolution, a mixed solution of cerium nitrate and neodymium nitrate was added dropwise and stirred at a constant temperature to obtain a reaction solution. The reaction solution was centrifuged by a centrifuge, and the precipitate was collected after centrifugation and freeze-dried. After freeze-drying, it was ball-milled by a ball mill to obtain a bio-based rare earth composite modifier; S03. Hydroxypropyl methyl cellulose ether and polycarboxylate superplasticizer were added to portland cement and modified quartz sand, and they were put into a mixer for mixing and stirring to obtain a premixed base material; S04. Polyurea-epoxy resin microcapsules were added to acrylic emulsion and stirred, and ultrasonic dispersion was carried out synchronously by an ultrasonic machine to obtain a dispersed solution. The dispersed solution was left standing to obtain a self-healing emulsion; S05. Tetraethyl orthosilicate, anhydrous ethanol and water were mixed according to the ratio to obtain a mixed solution. Ammonia water was added to the mixed solution and stirred at a constant temperature. After stirring, it was left standing for aging to obtain silica wet gel. The silica wet gel was washed with ethanol, and after washing, it was vacuum dried to obtain silica dry gel. The silica dry gel was ball-milled by a ball mill to obtain nano-silica. The nano-silica was dispersed in an ethanol solution of silane coupling agent and ultrasonic treatment was carried out to obtain a nano-silica suspension. The nano-silica suspension was vacuum filtered, washed with anhydrous ethanol after filtration, and then placed in a vacuum drying oven for drying to obtain dried modified nano-silica powder; Tetrabutyl titanate and ethanol were mixed according to the volume ratio. After mixing, an ethanol solution containing nitric acid was added dropwise and stirred to obtain a stirred product. The stirred product was transferred to a high-pressure reaction kettle, and urea was added for hydrothermal reaction to obtain a reacted product. The reacted product was centrifugally separated by a centrifuge, washed with ethanol after separation, and then dried to obtain dried powder. The dried powder was transferred to a muffle furnace for calcination to obtain anatase titanium dioxide. The anatase titanium dioxide was dispersed in an aqueous solution of polyethylene glycol and ultrasonic treatment was carried out. After ultrasonic treatment, a titanium dioxide suspension was obtained. The titanium dioxide suspension was centrifugally separated, and after centrifugal separation, it was vacuum dried to obtain dried modified nano-titanium dioxide powder; The dried modified nano-silica powder and the dried modified nano-titanium dioxide powder were weighed, and after weighing, they were added to ethanol and stirred, and ultrasonic treatment was carried out synchronously to obtain a treated suspension. The treated suspension was spray-dried to obtain a nano-composite agent; S06. The premixed base material and the self-healing emulsion were mixed, and a bio-based rare earth composite modifier and a nano-composite agent were added to obtain a composite product; The composite product was transferred to an electromagnetic field generator with a vertical magnetic field, and ultrasonic treatment was carried out synchronously to obtain a slurry treated in the first stage; Transfer the slurry processed in the first stage to an electromagnetic field generator with a parallel magnetic field and perform synchronous ultrasonic treatment to obtain a nano-enhanced slurry; S07. Mix a yttrium nitrate solution and a lanthanum chloride solution to obtain a mixed solution of yttrium nitrate and lanthanum chloride; Add the mixed solution of yttrium nitrate and lanthanum chloride to the nano-enhanced slurry and stir to react to obtain a slurry crosslinked in the first stage; Add a sodium lignosulfonate solution to the slurry crosslinked in the first stage and stir to react to obtain a slurry crosslinked in the second stage; Add a hydrochloric acid dopamine solution to the slurry crosslinked in the second stage and stir to react to obtain a slurry crosslinked in the third stage; S08. Place the slurry crosslinked in the third stage in a vacuum environment and stir to defoam to obtain a flexible waterproof slurry.

[0007] Compared with the prior art, the present invention has the following beneficial effects: Through the bionic interface modification technology combined with a gradient crosslinked network, the elongation at break of the slurry is increased by more than 40%, and it can withstand a deformation of 3 mm of the base layer without cracking; through the synergistic effect of photocatalysis and antibacterial of the bio-based-rare earth composite modifier, self-decomposition of surface pollutants and a bacteriostatic rate of more than 99% are achieved, while reducing the cement dosage by 20%; the magnetic field-oriented arrangement process of self-healing microcapsules and nano-composite agents enables the microcrack repair efficiency to reach more than 85%, and the impermeability is improved to less than 0.01 L / (m²·h); through multi-stage crosslinking and rare earth ion coordination strengthening, the flexural strength of the slurry reaches 12 MPa and the elastic modulus reaches 1.8 GPa, with both flexibility and compressive strength (a 35% strength increase); the anti-ultraviolet synergy of anatase TiO2 and rare earth ions enables the strength retention rate to exceed 90% after 1000 hours of outdoor exposure, and the mass loss ≤ 1.2%; through the vacuum defoaming and magnetic field-ultrasonic synergistic process, precise control of the slurry viscosity (8000 - 10000 mPa·s) and solid content (≥ 65%) is achieved, and the construction efficiency is increased by 30%. Description of the Drawings

[0008] Figure 1 It is a preparation flow chart of the preparation method of the flexible waterproof slurry of the present invention. Detailed Embodiments

[0009] The following combines specific embodiments to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

[0010] Example 1 A flexible waterproof slurry, the waterproof slurry comprising solid raw materials, liquid raw materials and functional additives; Among them, the solid raw materials include: portland cement, quartz sand, hydroxypropyl methyl cellulose ether and polycarboxylate water reducing agent; The liquid raw materials include: acrylic emulsion, yttrium nitrate solution, lanthanum chloride solution, sodium lignosulfonate solution, dopamine hydrochloride solution and acetic acid solution; The functional additives include bio-based rare earth composite modifiers, nano-composites and self-healing emulsions.

[0011] Example 2 This example provides a preparation method of a flexible waterproof slurry for preparing the above-mentioned flexible waterproof slurry, the method comprising the following steps: Step 1: Immerse 380 g of quartz sand in 550 mL of sodium hydroxide solution with a concentration of 0.1 mol / L for 25 min, rinse 3 times with deionized water after immersion, and then place it in a vacuum drying oven at 75 °C for 11 h of drying to obtain dried quartz sand. Immerse the dried quartz sand in 450 mL of dopamine hydrochloride solution with a concentration of 5 wt% and stir magnetically at 450 rpm. After magnetic stirring, filter, and then rinse 3 times with ethanol. After rinsing, perform vacuum drying at 55 °C for 7 h to obtain modified quartz sand, denoted as A1; Step 2: Prepare a solution of 90 mL of cerium nitrate hexahydrate with a concentration of 0.09 mol / L to obtain a cerium nitrate solution. Prepare a solution of 90 mL of neodymium nitrate hexahydrate with a concentration of 0.18 mol / L to obtain a neodymium nitrate solution. Mix the cerium nitrate solution and the neodymium nitrate solution in a 1:1 solution to obtain a mixed solution of cerium nitrate and neodymium nitrate, denoted as B1; Add 8 g of chitosan to 180 mL of acetic acid solution with a concentration of 1 wt% and stir to dissolve. After dissolution, add dropwise the mixed solution of cerium nitrate and neodymium nitrate in B1 and stir at a constant temperature of 60 °C for 4.5 h to obtain a reaction solution. Centrifuge the reaction solution at 5500 rpm for 3 h, collect the precipitate after centrifugation, perform freeze-drying at -50 °C for 23 h, and then perform ball milling at 300 rpm for 1 h to obtain a bio-based rare earth composite modifier, denoted as C1; Step 3: Take 380 g of portland cement, 360 g of the modified quartz sand in A1, add 4 g of hydroxypropyl methyl cellulose ether and 8 g of polycarboxylate water reducing agent, and put them into a mixer at 350 rpm for mixing and stirring for 13 min to obtain a premixed base material, denoted as D1; Step 4: Add 15 g of polyurea-epoxy resin microcapsules into 250 mL of acrylic emulsion with a concentration of 1.1 g / mL, and stir with a 350-rpm stirrer for 13 min. At the same time, use a 40-kHz ultrasonic machine to perform ultrasonic dispersion at 38 °C to obtain a dispersed solution. Let the dispersed solution stand to obtain a self-healing emulsion, denoted as E1; Step 5: Take 55 mL of tetraethyl orthosilicate, 220 mL of absolute ethanol, and 165 mL of water and mix them to obtain a mixed solution. Add 2 mL of ammonia water with a pH value of 8.5 to the mixed solution and stir with a 450-rpm stirrer at a constant temperature of 40 °C for 5.5 h. After stirring, let it stand for aging to obtain a silica wet gel. Wash the silica wet gel 3 times with ethanol, and then perform vacuum drying at 75 °C for 10 h to obtain a silica dry gel. Grind the silica dry gel with a 300-rpm ball mill for 2 h to obtain nano-silica. Disperse the nano-silica in a 1 wt% ethanol solution of silane coupling agent and perform ultrasonic treatment with a 40-kHz ultrasonic machine to obtain a nano-silica suspension. Perform vacuum filtration on the nano-silica suspension with a -0.08 MPa vacuum filter. After filtration, wash it with absolute ethanol, and then place it in a 55 °C vacuum drying oven for 8 h of drying to obtain a dried modified nano-silica powder, denoted as F1; Take 100 mL of tetrabutyl titanate and 500 mL of ethanol and mix them in a volume ratio of 1:5. After mixing, add 2.5 mL of ethanol solution containing nitric acid with a pH value of 2 and stir to obtain a stirred product. Transfer the stirred product to a 2.0-MPa autoclave, and add 4.5 g of urea for a hydrothermal reaction at 175 °C for 11.5 h to obtain a reacted product. Centrifuge the reacted product at 6000 rpm for 15 min, wash it with ethanol after separation, and then dry it to obtain a dried powder. Transfer the dried powder to a muffle furnace at 440 °C for 1.5 h of calcination to obtain anatase titanium dioxide. Disperse the anatase titanium dioxide in a 0.4 wt% aqueous solution of polyethylene glycol and perform ultrasonic treatment with a 40-kHz ultrasonic machine for 20 min. After ultrasonic treatment, obtain a titanium dioxide suspension. Centrifuge the titanium dioxide suspension at 5000 rpm for 15 min, and then perform vacuum drying at 60 °C for 1.7 h to obtain a dried modified nano-titanium dioxide powder, denoted as G1; Weigh 2.7 g of the dried modified nano-silica powder and 0.9 g of the dried modified nano-titanium dioxide powder. After weighing, add them to 150 mL of ethanol and stir using a 400 rpm blender. Simultaneously, perform ultrasonic treatment for 30 min using a 40 kHz ultrasonic machine to obtain the treated suspension. Feed the treated suspension to the inlet of a spray dryer at 180 °C at a rate of 5 mL / min for spray drying, and send it out from the outlet of the spray dryer at 80 °C to obtain a nano-composite agent, denoted as H1; Step 6: Mix 380 g of the premixed base material in D1 with 250 mL of the self-healing emulsion in E1, and add 8 g of the bio-based rare earth composite modifier in C1 and 3 g of the nano-composite agent in H1 to obtain a composite product; Transfer the composite product to a 450 W electromagnetic field generator with a 0.9 T vertical magnetic field, and simultaneously perform ultrasonic treatment for 11 min using a 40 kHz ultrasonic machine to obtain the slurry treated in the first stage; Transfer the slurry treated in the first stage to a 550 W electromagnetic field generator with a 0.7 T parallel magnetic field, and simultaneously perform ultrasonic treatment for 17 min using a 40 kHz ultrasonic machine to obtain a nano-enhanced slurry, denoted as J1; Step 7: Mix 20 mL of a yttrium nitrate solution with a concentration of 0.45 mol / L and 20 mL of a lanthanum chloride solution with a concentration of 0.45 mol / L to obtain a mixed solution of yttrium nitrate and lanthanum chloride; Add the mixed solution of yttrium nitrate and lanthanum chloride to the nano-enhanced slurry in J1 and perform a stirring reaction at a temperature of 23 °C for 11 min to obtain the slurry crosslinked in the first stage; Add 30 mL of a sodium lignosulfonate solution with a concentration of 7.5 wt% to the slurry crosslinked in the first stage and perform a stirring reaction at a temperature of 33 °C for 17 min to obtain the slurry crosslinked in the second stage; Add 20 mL of a hydrochloric acid dopamine solution with a concentration of 4.5 wt% to the slurry crosslinked in the second stage and perform a stirring reaction at a temperature of 23 °C for 24 min to obtain the slurry crosslinked in the third stage, denoted as K1; Step 8: Place the slurry crosslinked in the third stage in K1 in a vacuum environment and perform stirring and defoaming at a temperature of 49 °C and a speed of 100 rpm using a defoaming machine with a pressure of -0.08 MPa to obtain a flexible waterproof slurry, denoted as L1.

[0012] Example 3 This example provides a preparation method for a flexible waterproof slurry, which is used to prepare the above-mentioned flexible waterproof slurry. The method includes the following steps: Step 1: Immerse 400 g of quartz sand in 600 mL of sodium hydroxide solution with a concentration of 0.1 mol / L for 30 min. After immersion, rinse it 4 times with deionized water. Then place it in a vacuum drying oven at 80 °C for 12 h of drying to obtain the dried quartz sand. Immerse the dried quartz sand in 500 mL of hydrochloric acid dopamine solution with a concentration of 5 wt% and stir it magnetically at 500 rpm. After magnetic stirring, filter it, and then rinse it 3 times with ethanol. After the rinsing is completed, conduct vacuum drying at 60 °C for 8 h to obtain the modified quartz sand, denoted as A2; Step 2: Prepare a solution of 100 mL of cerium nitrate hexahydrate with a concentration of 0.1 mol / L to obtain a cerium nitrate solution. Prepare a solution of 100 mL of neodymium nitrate hexahydrate with a concentration of 0.2 mol / L to obtain a neodymium nitrate solution. Mix the cerium nitrate solution and the neodymium nitrate solution in a 1:1 solution ratio to obtain a mixed solution of cerium nitrate and neodymium nitrate, denoted as B2; Add 10 g of chitosan to 200 mL of acetic acid solution with a concentration of 1 wt% and stir to dissolve it. After dissolution, add dropwise the mixed solution of cerium nitrate and neodymium nitrate in B2 and conduct constant-temperature stirring at 60 °C for 5 h to obtain a reaction solution. Centrifuge the reaction solution at 6000 rpm for 4 h, collect the precipitate after centrifugation, conduct freeze-drying at -50 °C for 24 h, and then use a ball mill at 400 rpm for 2 h of ball milling to obtain a bio-based rare earth composite modifier, denoted as C2; Step 3: Take 400 g of Portland cement, 380 g of the modified quartz sand in A2, add 5 g of hydroxypropyl methylcellulose ether and 10 g of polycarboxylate water reducer, and put them into a mixer at 400 rpm for mixing and stirring for 15 min to obtain a premixed base material, denoted as D2; Step 4: Add 20 g of polyurea-epoxy resin microcapsules to 300 mL of acrylic emulsion with a concentration of 1.1 g / mL and stir it with a mixer at 400 rpm for 15 min. Synchronously use a 40 kHz ultrasonic machine to conduct ultrasonic dispersion under the condition of 40 °C to obtain a dispersed solution. Let the dispersed solution stand to obtain a self-healing emulsion, denoted as E2; Step 5: Take 60 mL of tetraethyl orthosilicate, 240 mL of absolute ethanol and 180 mL of water and mix them to obtain a mixed solution. Add 15 mL of ammonia water with a pH value of 9 to the mixed solution and stir it with a 500 rpm stirrer at a constant temperature of 40 °C for 6 h. After stirring, let it stand for aging to obtain a silica wet gel. Wash the silica wet gel 3 times with ethanol, and then carry out vacuum drying at 80 °C for 11 h to obtain a silica dry gel. Grind the silica dry gel with a 400 rpm ball mill for 3 h to obtain nano-silica. Disperse the nano-silica in a 1 wt% ethanol solution of silane coupling agent and carry out ultrasonic treatment with a 40 kHz ultrasonic machine to obtain a nano-silica suspension. Carry out vacuum filtration on the nano-silica suspension with a -0.09 MPa vacuum filter, wash it with absolute ethanol after filtration, and then place it in a 60 °C vacuum drying oven for drying for 9 h to obtain the dried modified nano-silica powder, denoted as F2; Take 100 mL of tetrabutyl titanate and 500 mL of ethanol and mix them according to a volume ratio of 1:5. After mixing, add 5 mL of ethanol solution containing nitric acid with a pH value of 2.5 and stir to obtain the stirred product. Transfer the stirred product to a 3.0 MPa autoclave, add 5 g of urea and carry out a hydrothermal reaction at 180 °C for 12 h to obtain the reacted product. Carry out centrifugal separation on the reacted product with a 7000 rpm centrifuge for 17.5 min, wash it with ethanol after separation, and then carry out drying to obtain the dried powder. Transfer the dried powder to a muffle furnace at 450 °C and calcine it for 2 h to obtain anatase titanium dioxide. Disperse the anatase titanium dioxide in a 0.5 wt% aqueous solution of polyethylene glycol and carry out ultrasonic treatment with a 40 kHz ultrasonic machine for 25 min. After ultrasonic treatment, obtain a titanium dioxide suspension. Carry out centrifugal separation on the titanium dioxide suspension with a 5500 rpm centrifuge for 17.5 min, and then carry out vacuum drying at 65 °C for 2 h to obtain the dried modified nano-titanium dioxide powder, denoted as G2; Weigh 3 g of the dried modified nano-silica powder and 1 g of the dried modified nano-titanium dioxide powder. After weighing, add them to 200 mL of ethanol and stir with a 500 rpm stirrer, and simultaneously carry out ultrasonic treatment with a 40 kHz ultrasonic machine for 35 min to obtain the treated suspension. Feed the treated suspension to the inlet of a spray dryer at 190 °C at a rate of 7.5 mL / min for spray drying, and send it out from the outlet of the spray dryer at 90 °C to obtain a nano-composite agent, denoted as H2; Step 6: Mix 400 g of the premixed base material in D2 with 300 mL of the self-healing emulsion in E2, and add 10 g of the bio-based rare earth composite modifier in C2 and 4 g of the nano-composite agent in H2 to obtain a composite product; Transfer the composite product to an electromagnetic field generator with a power of 500 W in a 1.0 T vertical magnetic field, and synchronously perform ultrasonic treatment for 12 min using a 40 kHz ultrasonic machine to obtain the slurry treated in the first stage; Transfer the slurry treated in the first stage to an electromagnetic field generator with a power of 600 W in a 0.8 T parallel magnetic field, and synchronously perform ultrasonic treatment for 18 min using a 40 kHz ultrasonic machine to obtain the nano-enhanced slurry, denoted as J2; Step 7: Take 20 mL of yttrium nitrate solution with a concentration of 0.5 mol / L and 20 mL of lanthanum chloride solution with a concentration of 0.5 mol / L and mix them to obtain a mixed solution of yttrium nitrate and lanthanum chloride; Add the mixed solution of yttrium nitrate and lanthanum chloride to the nano-enhanced slurry in J2 and carry out a stirring reaction at a temperature of 25 °C for 12 min to obtain the slurry crosslinked in the first stage; Add 40 mL of sodium lignosulfonate solution with a concentration of 8 wt% to the slurry crosslinked in the first stage and carry out a stirring reaction at a temperature of 35 °C for 18 min to obtain the slurry crosslinked in the second stage; Add 25 mL of hydrochloric acid dopamine solution with a concentration of 5 wt% to the slurry crosslinked in the second stage and carry out a stirring reaction at a temperature of 25 °C for 25 min to obtain the slurry crosslinked in the third stage, denoted as K2; Step 8: Take the slurry crosslinked in the third stage in K2 and place it in a vacuum environment. Use a defoaming machine with a pressure of -0.09 MPa to carry out stirring defoaming at a temperature of 50 °C and a speed of 150 rpm to obtain the flexible waterproof slurry, denoted as L2.

[0013] Example 4 This example provides a preparation method of a flexible waterproof slurry for preparing the above-mentioned flexible waterproof slurry, and the method includes the following steps: Step 1: Immerse 420 g of quartz sand in 650 mL of sodium hydroxide solution with a concentration of 0.1 mol / L for 35 min. After immersion, rinse it 5 times with deionized water. After rinsing, place it in a vacuum drying oven at 85 °C for 13 h of drying to obtain the dried quartz sand. Immerse the dried quartz sand in 550 mL of hydrochloric acid dopamine solution with a concentration of 5 wt% and carry out magnetic stirring at 550 rpm. After magnetic stirring, filter it, and then rinse it 3 times with ethanol. After the rinsing is completed, carry out vacuum drying at 65 °C for 9 h to obtain the modified quartz sand, denoted as A3; Step 2: Prepare a solution of 110 mL of cerium nitrate hexahydrate with a concentration of 0.11 mol / L to obtain a cerium nitrate solution. Prepare a solution of 110 mL of neodymium nitrate hexahydrate with a concentration of 0.22 mol / L to obtain a neodymium nitrate solution. Mix the cerium nitrate solution and the neodymium nitrate solution in a 1:1 solution ratio to obtain a mixed solution of cerium nitrate and neodymium nitrate, denoted as B3; Add 12 g of chitosan to 220 mL of acetic acid solution with a concentration of 1 wt% and stir to dissolve. After dissolution, add the mixed solution of cerium nitrate and neodymium nitrate in B2 and stir at a constant temperature of 60 °C for 5.5 h to obtain a reaction solution. Centrifuge the reaction solution at 6500 rpm for 5 h, collect the precipitate after centrifugation, and freeze-dry it at -50 °C for 25 h. After freeze-drying, use a ball mill at 500 rpm to mill for 3 h to obtain a bio-based rare earth composite modifier, denoted as C3; Step 3: Take 420 g of portland cement, 400 g of modified quartz sand in A3, add 6 g of hydroxypropyl methylcellulose ether and 12 g of polycarboxylate superplasticizer, and put them into a mixer at 450 rpm for mixing and stirring for 17 min to obtain a premixed base material, denoted as D3; Step 4: Add 25 g of polyurea-epoxy resin microcapsules to 350 mL of acrylic emulsion with a concentration of 1.1 g / mL and stir with a mixer at 450 rpm for 17 min. At the same time, use a 40 kHz ultrasonic machine to perform ultrasonic dispersion under the condition of 42 °C to obtain a dispersed solution. Let the dispersed solution stand to obtain a self-healing emulsion, denoted as E3; Step 5: Mix 65 mL of tetraethyl orthosilicate, 260 mL of absolute ethanol and 195 mL of water to obtain a mixed solution. Add 25 mL of ammonia water with a pH value of 9.5 to the mixed solution and stir at a constant temperature of 40 °C with a mixer at 550 rpm for 6.5 h. After stirring, let it stand for aging to obtain silica wet gel. Wash the silica wet gel 3 times with ethanol, and then dry it in a vacuum at 85 °C for 12 h to obtain silica dry gel. Mill the silica dry gel with a ball mill at 500 rpm for 4 h to obtain nano-silica. Disperse the nano-silica in a 1 wt% ethanol solution of silane coupling agent and perform ultrasonic treatment with a 40 kHz ultrasonic machine to obtain a nano-silica suspension. Vacuum filter the nano-silica suspension with a -0.1 MPa vacuum filter, wash it with absolute ethanol after filtration, and then dry it in a 65 °C vacuum drying oven for 10 h to obtain dried modified nano-silica powder, denoted as F3; 100 mL of tetrabutyl titanate and 500 mL of ethanol were mixed at a volume ratio of 1:5. After mixing, 7.5 mL of an ethanol solution containing nitric acid with a pH of 3 was added dropwise and stirred to obtain a stirred product. The stirred product was transferred to a high-pressure reactor at 4.0 MPa, and 5.5 g of urea was added for a hydrothermal reaction at 185 °C for 12.5 h to obtain a reacted product. The reacted product was centrifuged at 8000 rpm for 20 min using a centrifuge, washed with ethanol after separation, and dried to obtain a dried powder. The dried powder was transferred to a muffle furnace at 460 °C and calcined for 2.5 h to obtain anatase-phase titanium dioxide. The anatase-phase titanium dioxide was dispersed in an aqueous solution of polyethylene glycol with a concentration of 0.6 wt% and ultrasonically treated using a 40 kHz ultrasonic machine for 30 min to obtain a titanium dioxide suspension. The titanium dioxide suspension was centrifuged at 6000 rpm for 20 min using a centrifuge, and then vacuum dried at 70 °C for 2.3 h to obtain a dried modified nano-titanium dioxide powder, denoted as G3; 3.3 g of the dried modified nano-silica powder and 1.1 g of the dried modified nano-titanium dioxide powder were weighed. After weighing, they were added to 250 mL of ethanol and stirred using a 600 rpm stirrer, and simultaneously ultrasonically treated using a 40 kHz ultrasonic machine for 40 min to obtain a treated suspension. The treated suspension was fed to the inlet of a spray dryer at 200 °C at a rate of 10 mL / min for spray drying and sent out from the outlet of the spray dryer at 100 °C to obtain a nano-composite agent, denoted as H3; Step 6: 420 g of the premixed base material in D3 was mixed with 350 mL of the self-healing emulsion in E3, and 12 g of the bio-based rare-earth composite modifier in C3 and 5 g of the nano-composite agent in H3 were added to obtain a composite product; The composite product was transferred to an electromagnetic field generator with a power of 550 W under a 1.1 T vertical magnetic field, and ultrasonically treated using a 40 kHz ultrasonic machine for 13 min simultaneously to obtain a slurry treated in the first stage; The slurry treated in the first stage was transferred to an electromagnetic field generator with a power of 650 W under a 0.9 T parallel magnetic field, and ultrasonically treated using a 40 kHz ultrasonic machine for 19 min simultaneously to obtain a nano-enhanced slurry, denoted as J3; Step 7: 20 mL of a yttrium nitrate solution with a concentration of 0.55 mol / L and 20 mL of a lanthanum chloride solution with a concentration of 0.55 mol / L were mixed to obtain a mixed solution of yttrium nitrate and lanthanum chloride; The nano-enhanced slurry in J3 was added with the mixed solution of yttrium nitrate and lanthanum chloride and stirred and reacted at 27 °C for 13 min to obtain a slurry crosslinked in the first stage; To the slurry after the first-stage crosslinking, 50 mL of sodium lignosulfonate solution with a concentration of 8.5 wt% was added, and a stirring reaction was carried out at a temperature of 37 °C for 19 min to obtain the slurry after the second-stage crosslinking; To the slurry after the second-stage crosslinking, 30 mL of hydrochloric acid dopamine solution with a concentration of 5.5 wt% was added, and a stirring reaction was carried out at a temperature of 27 °C for 26 min to obtain the slurry after the third-stage crosslinking, denoted as K3; Step 8: Take the slurry after the third-stage crosslinking in K3 and place it in a vacuum environment. Use a defoaming machine with a pressure of -0.1 MPa to carry out stirring defoaming at a temperature of 51 °C at 200 rpm to obtain a flexible waterproof slurry, denoted as L3.

[0014] Comparative Example 1 The difference from Example 3 is that the bio-based rare earth composite modifier was not added.

[0015] Comparative Example 2. The difference from Example 3 is that the self-healing emulsion was not added.

[0016] Comparative Example 3. The difference from Example 3 is that the quartz sand was not modified.

[0017] Comparative Example 4. The difference from Example 3 is that the nano-composite agent was not added.

[0018] To verify the effectiveness of the present invention, the conventional performance tests of Examples 2-4 and Comparative Examples 1-4 were carried out, and they were placed under the condition of 2% sodium hydroxide alkali mist for 24 h to test the alkali corrosion resistance stability of the products. The test results of the compressive strength performance, bond strength, and flexibility are shown in Table 1 below.

[0019] Table 1:

[0020] As can be seen from Table 1 above, the compressive strength (35.6 MPa) and flexibility (5.8 mm) of Example 2 are close to those of Example 3, indicating that the performance is balanced under the intermediate ratio, and the performance decline is small under the alkali corrosion resistance condition (the compressive strength only drops by 0.3 MPa), verifying the anti-corrosion effect of the bio-based rare earth composite modifier.

[0021] Example 3 has the best comprehensive performance (compressive strength 35.8 MPa, flexibility 5.9 mm, bond strength 3.9 MPa), reflecting the synergistic effect of the gradient crosslinking network and functional additives. The retention rate of the alkali corrosion resistance performance exceeds 99% (the compressive strength only drops by 0.2 MPa), attributed to the photocatalytic self-cleaning ability of rare earth ions.

[0022] The compressive strength of Example 4 (35.4 MPa) is slightly lower than that of Example 3, possibly due to local stress concentration caused by excessive nano-composite agent. The flexibility (5.4 mm) and bonding strength (3.6 MPa) are still better than those of the comparative example, indicating a relatively high formula tolerance.

[0023] In Comparative Example 1, the compressive strength (30.2 MPa) and alkali corrosion resistance (18.5 MPa) decreased significantly, proving that rare earth complexes play a key role in strength and corrosion resistance. The bonding strength (2.8 MPa) is insufficient due to the lack of the strengthening effect of the interface modifier.

[0024] In Comparative Example 2, the flexibility (4.4 mm) and impermeability decreased (bonding strength 3.0 MPa), indicating that self-healing microcapsules are crucial for crack repair. The alkali corrosion-resistant bonding strength (1.9 MPa) is relatively low because a gradient cross-linked protective layer was not formed.

[0025] In Comparative Example 3, the compressive strength (33.4 MPa) and flexibility (4.8 mm) are between those of the examples and the comparative examples, indicating that the modification of quartz sand can improve the interfacial bonding force. The alkali corrosion resistance (26.3 MPa) is still better than that of Comparative Examples 1-2 because other functional additives partially compensate for the defects.

[0026] In Comparative Example 4, the compressive strength (31.5 MPa) and bonding strength (2.9 MPa) decreased significantly, indicating that the strengthening effect of nano-particles on mechanical properties is indispensable. The flexibility (4.3 mm) decreased because of the lack of the toughening effect of nano-materials.

[0027] Please refer to Figure 1 , Figure 1 , which is the flow chart of the steps for the preparation method of the flexible waterproof slurry of the present invention.

[0028] The environmental performance tests of Examples 2-4 and Comparative Examples 1-4 were carried out, and the test results are shown in Table 2 below.

[0029] Table 2:

[0030] As can be seen from Table 2 above, in Example 2, the bio-based rare earth composite modifier reduced the cement consumption by 20%, and the photocatalytic effect reduced the cleaning requirement to 2 times / year.

[0031] Under the optimal formula of Example 3, the material life was extended to 16 years and the waste was reduced by 60%, reflecting the synergistic effect of rare earth and self-healing.

[0032] In Example 4, the excessive nano-composite agent led to a slight increase in the cleaning requirement (3 times / year), but it is still better than the prior art.

[0033] In Comparative Example 1, no rare earth composite agent was added, the cement consumption was not reduced, the service life was only 8 years, and the waste volume was high.

[0034] In Comparative Example 2, there was no self-healing emulsion, and the poor impermeability led to an increase in the cleaning requirement to 5 times / year.

[0035] In Comparative Example 3, the interfacial bonding of the unmodified quartz sand was weak, and the material service life was only 10 years.

[0036] In Comparative Example 4, there was no nano composite agent, and the poor mechanical properties led to a relatively high waste volume.

[0037] The technical effects of Examples 2-4 and Comparative Examples 1-4 were tested, and the test results are shown in Table 3 below.

[0038] Table 3:

[0039] As can be seen from Table 3 above, in Example 2: The gradient cross-linked network increased the compressive strength to 35.6 MPa, and the self-healing efficiency was 85%.

[0040] In Example 3: The coordination of rare earth ions strengthened the alkali corrosion resistance with a retention rate of 99%, and the self-healing efficiency reached 90%.

[0041] In Example 4: The excessive nano composite agent led to a slight decrease in flexibility (5.4 mm), but the compressive strength was still better than the prior art.

[0042] In Comparative Example 1: Without the rare earth composite agent, the compressive strength dropped sharply to 30.2 MPa, and the alkali corrosion resistance retention rate was only 60%.

[0043] In Comparative Example 2: Without the self-healing emulsion, the microcracks could not be repaired, and the self-healing efficiency was only 30%.

[0044] In Comparative Example 3: The interfacial bonding of the unmodified quartz sand was poor, and the flexibility was only 4.8 mm.

[0045] In Comparative Example 4: Without the nano composite agent, the compressive strength was as low as 31.5 MPa, and the self-healing efficiency was 20%.

[0046] The cost tests of Examples 2-4 and Comparative Examples 1-4 were carried out, and the test results are shown in Table 4 below.

[0047] Table 4:

[0048] As can be seen from Table 4 above, in Example 2: The raw material cost increased by 25%, but the maintenance cost decreased by 60%, and the total cost was saved by 40%.

[0049] In Example 3: The high raw material input (+29%) was offset by the extremely low maintenance cost (-70%), and the total cost was the lowest.

[0050] Example 4: The redundant formulation leads to slightly higher maintenance costs, but the total cost is still lower than the prior art.

[0051] Comparative Example 1: Frequent maintenance is required without the rare earth compound.

[0052] Comparative Example 2: High maintenance costs are caused by the absence of the self-healing emulsion.

[0053] Comparative Example 3: Additional repairs are needed for the unmodified quartz sand.

[0054] Comparative Example 4: Poor crack resistance and high maintenance costs are caused by the absence of the nano-compound.

[0055] Example 2 was compared with a commercially available flexible waterproof slurry, and the comparison results are shown in Table 5 below.

[0056] Table 5:

[0057] As can be seen from Table 5 above, the compressive strength of Example 2 reaches 35.6 MPa, which is 27.1% higher than that of the commercially available product (28.0 MPa), attributed to the mechanical enhancement of the gradient cross-linked network and the nano-compound.

[0058] The flexibility of Example 2 is 5.8 mm (4.0 mm for the commercially available product), an increase of 45%, thanks to the crack closure ability of the self-healing emulsion and the interfacial toughness modified by rare earth.

[0059] The commercially available product has no self-healing function, and the self-healing efficiency of Example 2 reaches 85%, which can repair micro-cracks (≤0.1 mm), significantly extending the service life of the material.

[0060] The compressive retention rate of Example 2 under 2% sodium hydroxide alkali mist condition is 97% (60% for the commercially available product), reflecting the photocatalytic anti-corrosion ability of the bio-based rare earth composite modifier.

[0061] The service life of Example 2 is extended to 15 years (10 years for the commercially available product), and the total cost is reduced by 40.3%. The saved maintenance costs cover the increased raw material costs.

[0062] In summary, through bionic interface modification, multi-stage cross-linking and self-healing technology, the present invention realizes the multi-functional synergy of high strength, high flexibility, corrosion resistance and self-healing of the waterproof slurry, while reducing the life cycle cost, providing an innovative solution for the building waterproofing field and having broad market application prospects.

[0063] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, in any aspect, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be embraced within the present invention.

[0064] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative manner of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A flexible waterproof slurry, characterized in that, The waterproof slurry includes solid raw materials, liquid raw materials and functional additives; Among them, the solid raw materials include: portland cement, quartz sand, hydroxypropyl methylcellulose ether and polycarboxylate water reducer; The liquid raw materials include: acrylic emulsion, yttrium nitrate solution, lanthanum chloride solution, sodium lignosulfonate solution, dopamine hydrochloride solution and acetic acid solution; The functional additives include bio-based rare earth composite modifier, nano-composite agent and self-healing emulsion.

2. A flexible waterproof slurry according to claim 1, characterized in that, The solid content of the acrylic emulsion is 50-55%; the silicon dioxide content of the quartz sand is ≥97%; the viscosity of the hydroxypropyl methylcellulose ether is 35000-45000 mPa·s; the solid content of the polycarboxylate water reducer is 40%.

3. A preparation method of a flexible waterproof slurry for preparing the flexible waterproof slurry according to claim 1, characterized in that, The method includes the following steps: S01. Immerse the quartz sand in sodium hydroxide solution, rinse it with deionized water after immersion, dry it in a vacuum drying oven after rinsing to obtain dried quartz sand, immerse the dried quartz sand in dopamine hydrochloride solution for magnetic stirring, filter it after magnetic stirring, rinse it with ethanol after filtration, and perform vacuum drying after rinsing to obtain modified quartz sand; S02. Take cerium(III) nitrate hexahydrate for solution preparation to obtain cerium nitrate solution, take neodymium(III) nitrate hexahydrate for solution preparation to obtain neodymium nitrate solution, and mix the cerium nitrate solution and neodymium nitrate solution to obtain a mixed solution of cerium nitrate and neodymium nitrate; Add chitosan to acetic acid solution for stirring and dissolving, dropwise add the mixed solution of cerium nitrate and neodymium nitrate after dissolution for constant temperature stirring to obtain a reaction solution, centrifuge the reaction solution by a centrifuge, collect the precipitate after centrifugation for freeze-drying, and perform ball milling on the freeze-dried product by a ball mill to obtain a bio-based rare earth composite modifier; S03. Add portland cement and modified quartz sand to hydroxypropyl methylcellulose ether and polycarboxylate water reducer, and put them into a mixer for mixing and stirring to obtain a premixed base material; S04. Add polyurea-epoxy resin microcapsules to acrylic emulsion for stirring, and simultaneously perform ultrasonic dispersion with an ultrasonic machine to obtain a dispersed solution, and let the dispersed solution stand to obtain a self-healing emulsion; S05. Mix tetraethyl orthosilicate, absolute ethanol and water to obtain a mixed solution, add ammonia water to the mixed solution for constant temperature stirring, let it stand for aging after stirring to obtain silica wet gel, wash the silica wet gel with ethanol, perform vacuum drying after washing to obtain silica dry gel, perform ball milling on the silica dry gel by a ball mill to obtain nano-silica, disperse the nano-silica in a silane coupling agent ethanol solution for ultrasonic treatment to obtain a nano-silica suspension, perform vacuum filtration on the nano-silica suspension, wash it with absolute ethanol after filtration, and dry it in a vacuum drying oven after washing to obtain a dried modified nano-silica powder; Mix tetrabutyl titanate and ethanol in a volume ratio. After mixing, add an ethanol solution containing nitric acid dropwise and stir to obtain a stirred product. Transfer the stirred product to a high-pressure reactor, add urea and conduct a hydrothermal reaction to obtain a reacted product. Centrifuge and separate the reacted product using a centrifuge, wash it with ethanol after separation, and dry it after washing to obtain a dried powder. Transfer the dried powder to a muffle furnace for calcination to obtain anatase-phase titanium dioxide. Disperse the anatase-phase titanium dioxide in an aqueous polyethylene glycol solution and perform ultrasonic treatment. After ultrasonic treatment, obtain a titanium dioxide suspension. Centrifuge and separate the titanium dioxide suspension, and perform vacuum drying after centrifugation to obtain a dried modified nano-titanium dioxide powder; Weigh the dried modified nano-silica powder and the dried modified nano-titanium dioxide powder. After weighing, add them to ethanol and stir while simultaneously performing ultrasonic treatment to obtain a treated suspension. Spray-dry the treated suspension to obtain a nano-composite agent; S06. Mix the premixed base material and the self-healing emulsion, and add a bio-based-rare earth composite modifier and a nano-composite agent to obtain a composite product; Transfer the composite product to an electromagnetic field generator with a vertical magnetic field and simultaneously perform ultrasonic treatment to obtain a slurry treated in the first stage; Transfer the slurry treated in the first stage to an electromagnetic field generator with a parallel magnetic field and simultaneously perform ultrasonic treatment to obtain a nano-enhanced slurry; S07. Mix a yttrium nitrate solution and a lanthanum chloride solution to obtain a mixed solution of yttrium nitrate and lanthanum chloride; Add the mixed solution of yttrium nitrate and lanthanum chloride to the nano-enhanced slurry and stir to react to obtain a slurry crosslinked in the first stage; Add a sodium lignosulfonate solution to the slurry crosslinked in the first stage and stir to react to obtain a slurry crosslinked in the second stage; Add a hydrochloric acid dopamine solution to the slurry crosslinked in the second stage and stir to react to obtain a slurry crosslinked in the third stage; S08. Place the slurry crosslinked in the third stage in a vacuum environment and stir to remove bubbles to obtain a flexible waterproof slurry.

4. The preparation method of a flexible waterproof slurry according to claim 3, characterized in that, During the process of obtaining the modified quartz sand in step S01, the mass of the quartz sand is 380 - 420 g, the concentration of the sodium hydroxide solution is 0.1 mol / L, the volume of the sodium hydroxide solution is 550 - 650 mL, the soaking time is 25 - 35 min, the number of rinses with deionized water is 3 - 5 times, the drying temperature of the vacuum drying oven is 75 - 85 °C, the drying time is 11 - 13 h, the concentration of the hydrochloric acid dopamine solution is 5 wt%, the volume of the hydrochloric acid dopamine solution is 450 - 550 mL, the magnetic stirring speed is 450 - 550 rpm, the number of rinses with ethanol is 3 times, and the vacuum drying temperature after rinsing is 55 - 65 °C, and the vacuum drying time is 7 - 9 h.

5. The preparation method of a flexible waterproof slurry according to claim 4, characterized in that, In the process of obtaining the bio-based rare earth composite modifier in step S02, the concentration of the cerium nitrate solution is 0.09 - 0.11 mol / L, the volume of the cerium nitrate solution is 90 - 110 mL, the concentration of the neodymium nitrate solution is 0.18 - 0.22 mol / L, the volume of the neodymium nitrate solution is 90 - 110 mL. The volume ratio of the cerium nitrate solution to the neodymium nitrate solution in the mixed solution of cerium nitrate and neodymium nitrate is 1:

1. The mass of chitosan is 8 - 12 g, the concentration of the acetic acid solution is 1 wt%, the volume of the acetic acid solution is 180 - 220 mL, the constant temperature stirring temperature is 60 °C, the constant temperature stirring time is 4.5 - 5.5 h, the centrifuge speed is 5500 - 6500 rpm, the centrifugation time is 3 - 5 h, the freeze-drying temperature is -50 °C, the freeze-drying time is 23 - 25 h, the speed of the ball mill is 300 - 500 rpm, and the ball milling time is 1 - 3 h; In the process of obtaining the premixed base material in step S03, the mass of the portland cement is 380 - 420 g, the mass of the modified quartz sand is 360 - 400 g, the mass of the hydroxypropyl methyl cellulose ether is 4 - 6 g, the mass of the polycarboxylate superplasticizer is 8 - 12 g, the mixing and stirring speed is 350 - 450 rpm, and the mixing and stirring time is 13 - 17 min.

6. The preparation method of a flexible waterproof slurry according to claim 5, characterized in that, In the process of obtaining the self-healing emulsion in step S04, the mass of the polyurea-epoxy resin microcapsule is 15 - 25 g, the concentration of the acrylic emulsion is 1.1 g / mL, the volume of the acrylic emulsion is 250 - 350 mL, the stirring rate is 350 - 450 rpm, the stirring time is 13 - 17 min. Synchronously, the frequency of the ultrasonic machine is 40 kHz, and the dispersion condition temperature is 38 - 42 °C.

7. The preparation method of a flexible waterproof slurry according to claim 6, characterized in that, In the process of obtaining the nano-composite agent in step S05, the volume of tetraethyl orthosilicate is 55 - 65 mL, the volume of absolute ethanol is 220 - 260 mL, the volume of water is 165 - 195 mL. The pH value of the added ammonia water is 8.5 - 9.5, the ammonia water addition amount is 2 - 25 mL, the constant temperature stirring temperature is 40 °C, the constant temperature stirring rate is 450 - 550 rpm, the constant temperature stirring time is 5.5 - 6.5 h, the number of times of washing with ethanol is 3 - 5 times, the temperature of vacuum drying after washing is 75 - 85 °C, the time of vacuum drying after washing is 10 - 12 h, the speed of the ball mill is 300 - 500 rpm, the ball milling time is 2 - 4 h, the concentration of the ethanol solution of the silane coupling agent is 1 wt%, the frequency of the ultrasonic machine is 40 kHz, the ultrasonic treatment time is 30 - 40 min, the vacuum filtration pressure is -0.08 to -0.1 MPa, the drying temperature in the vacuum drying oven is 55 - 65 °C, and the drying time is 8 - 10 h; The volume ratio of tetrabutyl titanate to ethanol is 1:5, the volume of tetrabutyl titanate is 100 mL, the volume of ethanol is 500 mL, the pH value of the ethanol solution containing nitric acid is 2 - 3, the addition amount of the ethanol solution containing nitric acid is 2.5 - 7.5 mL, the pressure of the autoclave is 2.0 - 4.0 MPa, the added urea is 4.5 - 5.5 g, the hydrothermal temperature of the autoclave is 175 - 185 °C, the hydrothermal reaction time of the autoclave is 11.5 - 12.5 h, the rotation speed of the centrifuge is 6000 - 8000 rpm, the centrifugation time is 15 - 20 min, the calcination temperature in the muffle furnace is 440 - 460 °C, the calcination time in the muffle furnace is 1.5 - 2.5 h, the concentration of the polyethylene glycol aqueous solution is 0.4 - 0.6 wt%, the frequency of the ultrasonic machine is 40 kHz, the treatment time of the ultrasonic machine is 20 - 30 min, the centrifugation separation rate of the titanium dioxide suspension is 5000 - 6000 rpm, the centrifugation time is 15 - 20 min, the temperature for vacuum drying after centrifugation separation is 60 - 70 °C, and the time for vacuum drying after centrifugation separation is 1.7 - 2.3 h; Take the mass of the dried modified nano - silica powder as 2.7 - 3.3 g, take the mass of the dried modified nano - titanium dioxide powder as 0.9 - 1.1 g, add 150 - 250 mL of ethanol, the stirring rate is 400 - 600 rpm, simultaneously perform ultrasonic treatment with a frequency of 40 kHz, simultaneously perform ultrasonic treatment for 30 - 40 min, the inlet temperature of spray drying is 180 - 200 °C, the outlet temperature of spray drying is 80 - 90 °C, and the feeding rate of spray drying is 5 - 10 mL / min.

8. The preparation method of a flexible waterproof slurry according to claim 7, characterized in that, During the process of obtaining the nano - enhanced slurry in step S06, the mass of the premixed base material is 380 - 420 g, the volume of the self - healing emulsion is 250 - 350 mL, the added mass of the bio - based rare - earth composite modifier is 8 - 12 g, the added mass of the nano - composite agent is 3 - 5 g, the magnetic field intensity of the electromagnetic field generator of the vertical magnetic field is 0.9 - 1.1 T, the ultrasonic treatment power of the vertical magnetic field is 450 W - 550 W, the ultrasonic treatment frequency of the vertical magnetic field is 40 kHz, the ultrasonic treatment time of the vertical magnetic field is 11 - 13 min, the magnetic field intensity of the electromagnetic field generator of the parallel magnetic field is 0.7 - 0.9 T, the ultrasonic treatment power of the parallel magnetic field is 550 W - 650 W, the ultrasonic treatment frequency of the parallel magnetic field is 40 kHz, and the ultrasonic treatment time of the parallel magnetic field is 17 - 19 min.

9. The preparation method of a flexible waterproof slurry according to claim 8, characterized in that, During the process of obtaining the third - stage cross - linked slurry in step S07, the concentration of the yttrium nitrate solution is 0.45 - 0.55 mol / L, the volume of the yttrium nitrate solution is 20 mL, the concentration of the lanthanum chloride solution is 0.45 - 0.55 mol / L, the volume of the lanthanum chloride solution is 20 mL, the temperature for stirring is 23 - 27 °C, and the stirring time is 11 - 13 min; The concentration of the sodium lignosulfonate solution is 7.5 - 8.5 wt%, the volume of the sodium lignosulfonate solution is 30 - 50 mL, the temperature for stirring with the addition of the sodium lignosulfonate solution is 33 - 37 °C, and the stirring time with the addition of the sodium lignosulfonate solution is 17 - 19 min; The concentration of the dopamine hydrochloride solution added is 4.5 - 5.5 wt%, the volume of the dopamine hydrochloride solution added is 20 - 30 mL, the temperature for stirring with the addition of the dopamine hydrochloride solution is 23 - 27 °C, and the stirring time with the addition of the dopamine hydrochloride solution is 24 - 26 min.

10. The preparation method of a flexible waterproof slurry according to claim 9, characterized in that, In the process of obtaining the flexible waterproof slurry in step S08, the defoaming strength is -0.08 to -0.1 MPa, the defoaming temperature is 49 - 51 °C, and the stirring rate is 100 - 200 rpm.

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