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CN-121991438-A - Chemical corrosion resistant flexible TPO waterproof coiled material and preparation process thereof

CN121991438ACN 121991438 ACN121991438 ACN 121991438ACN-121991438-A

Abstract

The invention relates to the technical field of waterproof coiled material preparation, in particular to a chemical corrosion resistant flexible TPO waterproof coiled material and a preparation process thereof. Comprises the following steps of preparing nano cage powder, preparing corrosion inhibition filler and preparing a chemical corrosion resistant flexible TPO waterproof coiled material. The corrosion inhibition filler prepared by the invention changes the corrosion inhibition performance of the filler from passive isolation to active protection through high-efficiency load and intelligent controlled release of the nano-cage to the 2-mercaptobenzothiazole, the high specific surface area and the multistage pore canal of the nano-cage can physically adsorb a large amount of 2-mercaptobenzothiazole molecules, and a finite field effect is provided to realize the chemical corrosion prevention effect, the magnesium-aluminum-cerium composite hydroxide of the nano-cage shell is sensitive to pH, and when the local microenvironment pH change is caused by the damage and corrosion of a waterproof layer, the accelerated release of the 2-mercaptobenzothiazole can be triggered, so that the intelligent corrosion response supplied according to needs is realized.

Inventors

  • WU JIN
  • CHENG LEI

Assignees

  • 扬州美邦工程材料有限公司

Dates

Publication Date
20260508
Application Date
20251231

Claims (10)

  1. 1. The flexible TPO waterproof coiled material is characterized by comprising a corrosion inhibition functional layer, a bio-based adhesive layer and a polyolefin waterproof layer, wherein the corrosion inhibition functional layer, the bio-based adhesive layer and the polyolefin waterproof layer are sequentially arranged from top to bottom.
  2. 2. A process for preparing a chemical corrosion resistant flexible TPO waterproof roll according to claim 1, comprising the steps of: S1, preparing nano cage powder Dispersing Zn-Co-ZIF powder in deionized water, ultrasonically forming a uniform suspension, pouring the uniform suspension into a hydrothermal kettle, dissolving magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and cerium nitrate hexahydrate in the deionized water together to obtain a mixed salt solution, dissolving urea in the deionized water to obtain a urea solution, sequentially and slowly dropwise adding the mixed salt solution and the urea solution into the hydrothermal kettle filled with the suspension formed by Zn-Co-ZIF, and performing hydrothermal reaction to obtain nano cage primary powder; s2, preparing corrosion inhibition filler Adding 2-mercaptobenzothiazole into water, magnetically stirring until the 2-mercaptobenzothiazole is completely dissolved to obtain a corrosion inhibitor solution, adding nano cage powder into the corrosion inhibitor solution, magnetically stirring, centrifuging, separating to obtain a solid product, washing the solid product, and vacuum drying to obtain a corrosion inhibition filler; S3, preparing chemical corrosion resistant flexible TPO waterproof coiled material Adding ethylene propylene diene monomer, polypropylene, additives, zinc oxide and stearic acid into a double-screw extruder for blending, extruding the mixed materials into polyolefin sheets through the extruder to obtain a polyolefin waterproof layer, carrying out plasma treatment on the surface of the polyolefin waterproof layer, then coating a bio-based adhesive layer coating liquid on the surface by using a scraper, drying, reheating and solidifying, cooling to room temperature to form a bio-based adhesive layer, adding a corrosion inhibition filler into methanol to obtain a precursor solution, soaking the polyolefin waterproof layer with the bio-based adhesive layer into the precursor solution, then taking out, cleaning, drying in vacuum to form a corrosion inhibition functional layer, and obtaining sheets of which the corrosion inhibition functional layer, the bio-based adhesive layer and the polyolefin waterproof layer are sequentially arranged, and rolling to obtain the chemical corrosion resistant flexible TPO waterproof coiled material.
  3. 3. The chemical corrosion resistant flexible TPO waterproof coiled material according to claim 2, wherein the step S1 is to prepare nano cage powder, and specifically comprises the following steps: Dispersing 0.5-0.7 part by mass of Zn-Co-ZIF powder in 70-80 parts by mass of deionized water, performing ultrasonic treatment for 10-20 minutes to form uniform suspension, and pouring the uniform suspension into a hydrothermal kettle; 1.2 to 1.4 parts by mass of magnesium nitrate hexahydrate, 0.3 to 0.5 part by mass of aluminum nitrate nonahydrate and 0.08 to 0.1 part by mass of cerium nitrate hexahydrate are jointly dissolved in 20 to 25 parts by mass of deionized water to obtain a mixed salt solution; Dissolving 1-1.2 parts by mass of urea in 10-12 parts by mass of deionized water to obtain urea solution; Under the continuous magnetic stirring of 200-300r/min, the mixed salt solution and the urea solution are slowly dripped into a hydrothermal kettle filled with a suspension formed by Zn-Co-ZIF in sequence, the hydrothermal kettle is sealed and placed into a blast drying box for hydrothermal reaction, the temperature is raised to 130-140 ℃ from room temperature at the speed of 2 ℃ per minute, then the constant temperature is kept for 20-22h at 130-140 ℃, then the temperature is naturally cooled to 23-25 ℃ at room temperature, solids are centrifugally collected, deionized water and absolute ethyl alcohol are used for alternately washing for 3 times, and the freezing drying is carried out for 24-26h, so that the nano cage primary powder is obtained; Dispersing 0.2-0.4 part by mass of nano cage primary powder in 100-110 parts by mass of NaOH solution with the concentration of 0.3M, placing in a 70-75 ℃ water bath, magnetically stirring for 4-5 hours at the rotating speed of 200-300r/min, centrifugally washing for 10-15 minutes by using deionized water, and freeze-drying for 24-26 hours again to obtain nano cage powder.
  4. 4. The chemical corrosion resistant flexible TPO waterproof coiled material according to claim 3, wherein the step S2 is to prepare a corrosion inhibition filler, and specifically comprises the following steps: Adding 2-mercaptobenzothiazole into water, regulating the pH to 9-10 by using a NaOH solution, magnetically stirring until the solution is completely dissolved, and regulating the concentration to 0.1-0.2mol/L to obtain a corrosion inhibitor solution; Adding nano cage powder into a corrosion inhibitor solution according to the feed liquid ratio of (1-2) g to 100mL, placing the solution at the room temperature of 23-25 ℃ and keeping out of the sun, and continuously magnetically stirring the solution for 24-26 hours at the rotating speed of 200-300 r/min; Centrifuging for 10-15min at a rotation speed of 11000-12000r/min after the reaction is finished, separating to obtain a solid product, washing the solid product with alkaline water with pH=9 for 1-2 times, and vacuum drying at 50-60 ℃ to obtain the corrosion inhibition filler.
  5. 5. The chemical corrosion resistant flexible TPO waterproof roll according to claim 4, wherein the step S3 is to prepare the chemical corrosion resistant flexible TPO waterproof roll, and specifically comprises the following steps: Adding 20-30 parts by mass of ethylene propylene diene monomer, 10-12 parts by mass of polypropylene, 2-3 parts by mass of zinc oxide and 1-2 parts by mass of stearic acid into a double-screw extruder for blending, melting at 190 ℃ for 2min, adding sulfur as a vulcanizing agent, mixing for 3min, adding 20-25 parts by mass of ethylene propylene diene monomer and 7-9 parts by mass of polypropylene, mixing for 5min, extruding the mixed materials into polyolefin sheets through the extruder to obtain a polyolefin waterproof layer; Carrying out plasma treatment on the surface of the polyolefin waterproof layer, then coating a bio-based adhesive layer coating liquid on the surface with a scraper, wherein the thickness is 2-4mm, performing preliminary drying for 5-10min at 50-60 ℃, performing heat curing for 10-15min at 90-100 ℃, and cooling to the room temperature of 23-25 ℃ to form a bio-based adhesive layer; Adding 2-3 parts by mass of corrosion inhibition filler into 100 parts by mass of methanol to obtain a precursor solution, soaking a polyolefin waterproof layer with a bio-based adhesive layer in the precursor solution, heating in a water bath to 40-50 ℃, soaking for 3-4 hours, then taking out, washing with methanol for 2-3 times, drying in a vacuum drying oven at 60-80 ℃ for 6-12 hours to form a corrosion inhibition functional layer, obtaining sheets with the corrosion inhibition functional layer, the bio-based adhesive layer and the polyolefin waterproof layer arranged in sequence, and winding to obtain the chemical corrosion resistant flexible TPO waterproof coiled material.
  6. 6. The chemical corrosion resistant flexible TPO waterproof coiled material according to claim 3, wherein the Zn-Co-ZIF powder in the step S1 is prepared by the following specific preparation method: 1.4 to 1.6 parts by mass of zinc nitrate hexahydrate and 1.4 to 1.6 parts by mass of cobalt nitrate hexahydrate are dissolved in 100 to 110 parts by mass of methanol to obtain solution A; dissolving 6.5-6.7 parts by mass of 2-methylimidazole in 100-102 parts by mass of methanol to obtain solution B; Rapidly mixing the solution A and the solution B at room temperature of 23-25 ℃, stirring for 10-15 minutes at a rotating speed of 300-500r/min by using a magnetic stirrer, standing and aging for 24-26 hours, filtering and separating precipitate after the completion, centrifugally washing the precipitate with methanol for 5-8 minutes, washing 3 times, and drying the washed precipitate in a vacuum drying oven at 60-70 ℃ for 12-14 hours to obtain Zn-Co-ZIF powder.
  7. 7. The flexible TPO waterproof coiled material resistant to chemical corrosion according to claim 5, wherein the preparation method comprises the steps of placing 130-150 parts by mass of acrylate copolymer emulsion in a glue mixing kettle, stirring at a rotating speed of 300-400r/min, heating to 60-65 ℃, adding 80-90 parts by mass of bio-based hot melt adhesive, continuously stirring for 1-1.5h, heating to 120-130 ℃, stirring for 10-20min, reducing the system temperature to 30-40 ℃, adding 0.5-1 part by mass of cross-linking agent and 0.5-1 part by mass of wetting leveling agent, and stirring for 30-40min to obtain the coating liquid of the bio-based adhesive layer.
  8. 8. The flexible TPO waterproof coiled material with chemical resistance according to claim 7, wherein the acrylic ester copolymer emulsion is prepared by mixing, emulsifying and copolymerizing 70-80 parts by mass of isooctyl acrylate, 3-5 parts by mass of acrylic acid, 27-30 parts by mass of vinyl acetate, 1.5-2 parts by mass of sodium dodecyl sulfate, 0.4-0.6 part by mass of initiator ammonium persulfate and 95-100 parts by mass of deionized water, and enabling the solid content of the copolymer to be 50% and the pH value to be 6.5-7.
  9. 9. The chemical corrosion resistant flexible TPO waterproof coiled material according to claim 7, wherein the specific preparation method of the bio-based hot melt adhesive comprises the following steps: adding 2-3 parts by mass of glutinous rice starch into 0.4-0.8 part by mass of plasticizer glycerol, mixing for 10-20min at a rotating speed of 3000-3500r/min, standing for 24-26h, heating to 120-130 ℃ to form a molten state, extruding, and granulating to obtain thermoplastic particles; Heating rosin to 180-200 ℃, sequentially adding pentaerythritol, zinc oxide and an antioxidant, keeping the temperature at 240-260 ℃ for reaction for 8-9 hours, then cooling to 140-160 ℃, adding thermoplastic particles, wherein the mass ratio of the rosin to the pentaerythritol to the zinc oxide to the antioxidant to the thermoplastic particles is 1 (0.3-0.5): 0.04:0.005 (1-2), and mixing for 10-30 minutes to obtain the bio-based hot melt adhesive.
  10. 10. The flexible TPO waterproof roll resistant to chemical corrosion according to claim 2, wherein the inner liner of the hydrothermal kettle in step S1 is polytetrafluoroethylene.

Description

Chemical corrosion resistant flexible TPO waterproof coiled material and preparation process thereof Technical Field The invention relates to the technical field of waterproof coiled material preparation, in particular to a chemical corrosion resistant flexible TPO waterproof coiled material and a preparation process thereof. Background TPO waterproof coiled material, which is totally called as thermoplastic polyolefin waterproof coiled material, is a synthetic high molecular waterproof material prepared by taking olefin polymers such as ethylene, propylene and the like as basic resins, blending and modifying the basic resins, and adding additives such as antioxidants, light stabilizers and the like. Because the TPO coiled material combines the flexibility of rubber and the weldability of plastic, has excellent weather resistance, ageing resistance, high reflectivity and recoverable environment-friendly characteristics, the TPO coiled material has become one of the first-choice waterproof materials in the fields of modern building roofs, underground engineering, bridge tunnels, planted roofs and the like, and is particularly suitable for large public buildings and industrial facilities with strict requirements on durability and environmental protection. However, TPO waterproofing rolls present serious chemical corrosion challenges in long-term complex service environments, especially in chemical parks, coastal salt fog areas, acid rain frequent areas, or where corrosive elements such as snow solvents, stray currents, and the like are present. The traditional TPO waterproof coiled material realizes water resistance by relying on physical barrier effect, and the chemical anti-corrosion function is usually realized by adding corrosion inhibition filler, but the existing corrosion inhibition filler is often uncontrollable in release and single in action mechanism, and long-acting and intelligent protection are difficult to realize. In particular, once corrosion occurs after localized breakage, the general filler is unable to respond to environmental changes to accelerate the release of corrosion inhibiting components, which can lead to continued expansion of the corrosion. In addition, the coiled material is adhered to the base surface by adopting common pressure-sensitive adhesive or hot melt adhesive, creep, aging or stripping easily occurs under the actions of temperature change, damp heat and chemical medium, and lasting and effective adhesive strength is difficult to maintain in a complex environment, so that the long-acting application of the TPO waterproof coiled material in a severe chemical corrosion environment is limited. Therefore, the invention provides a chemical corrosion resistant flexible TPO waterproof coiled material and a preparation process thereof, so as to solve the problems in the prior art. Disclosure of Invention Aiming at the defects existing in the prior art, the invention aims to provide a chemical corrosion resistant flexible TPO waterproof coiled material and a preparation process thereof. A chemical corrosion resistant flexible TPO waterproof coiled material comprises a corrosion inhibition functional layer, a bio-based adhesive layer and a polyolefin waterproof layer, wherein the corrosion inhibition functional layer, the bio-based adhesive layer and the polyolefin waterproof layer are sequentially arranged from top to bottom. A preparation process of a chemical corrosion resistant flexible TPO waterproof coiled material comprises the following steps: S1, preparing nano cage powder Dispersing Zn-Co-ZIF powder in deionized water, ultrasonically forming a uniform suspension, pouring the uniform suspension into a hydrothermal kettle, dissolving magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and cerium nitrate hexahydrate in the deionized water together to obtain a mixed salt solution, dissolving urea in the deionized water to obtain a urea solution, sequentially and slowly dropwise adding the mixed salt solution and the urea solution into the hydrothermal kettle filled with the suspension formed by Zn-Co-ZIF, and performing hydrothermal reaction to obtain nano cage primary powder; s2, preparing corrosion inhibition filler Adding 2-mercaptobenzothiazole into water, magnetically stirring until the 2-mercaptobenzothiazole is completely dissolved to obtain a corrosion inhibitor solution, adding nano cage powder into the corrosion inhibitor solution, magnetically stirring, centrifuging, separating to obtain a solid product, washing the solid product, and vacuum drying to obtain a corrosion inhibition filler; S3, preparing chemical corrosion resistant flexible TPO waterproof coiled material Adding ethylene propylene diene monomer, polypropylene, additives, zinc oxide and stearic acid into a double-screw extruder for blending, extruding the mixed materials into polyolefin sheets through the extruder to obtain a polyolefin waterproof layer, carrying out plasma treatment on the