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CN-121974594-A - Metal-organic framework doped waterproof master batch, cement-based waterproof material, and preparation and application thereof

CN121974594ACN 121974594 ACN121974594 ACN 121974594ACN-121974594-A

Abstract

The invention discloses a metal organic framework doped waterproof master batch which comprises MIL-68 (Al), sodium carbonate, sodium silicate and glycine, wherein the waterproof master batch is doped into a cement-based waterproof material and is used for improving the cracking resistance and the self-repairing efficiency of a concrete structure, and the MIL-68 (Al) is prepared by carrying out hydrothermal reaction on reaction raw materials of aluminum chloride and terephthalic acid in a reaction solvent of N, N-dimethylformamide according to a molar ratio of 1:1-2 at 120-150 ℃. The cement-based waterproof material prepared from the waterproof master batch has the dual advantages of flexible regulation and rigidity enhancement, has the advantages of strong crack inhibition capability, high MOFs decomposition controllability, good long-term waterproof stability, high microstructure compactness, tight combination with a concrete substrate and self-repairing, and is suitable for the waterproof engineering of concrete structures of easily-cracked base layers such as building roofs, basements, tunnels and the like.

Inventors

  • WANG SHUO
  • ZHANG ZHILIANG

Assignees

  • 石家庄固盾防水保护材料有限公司

Dates

Publication Date
20260505
Application Date
20260210

Claims (10)

  1. 1. A metal organic framework doped waterproof master batch is characterized by comprising MIL-68 (Al), sodium carbonate, sodium silicate and glycine, wherein the waterproof master batch is doped into a cement-based waterproof material and is used for improving the cracking resistance and the self-repairing efficiency of a concrete structure; the MIL-68 (Al) is prepared by hydrothermal reaction of reaction raw materials of aluminum chloride and terephthalic acid in a molar ratio of 1:1-2 in a reaction solvent of N, N-dimethylformamide at 120-150 ℃.
  2. 2. The metal-organic framework doped waterproof masterbatch according to claim 1, characterized in that the MILs-68 (Al) is prepared under the following conditions: Dissolving aluminum chloride and terephthalic acid in N, N-dimethylformamide solution, carrying out ultrasonic dispersion, transferring to a hydrothermal reaction kettle, reacting for 12-24 hours at 120-150 ℃, cooling to room temperature after the reaction is finished, carrying out centrifugal separation to obtain precipitate, washing the precipitate, and carrying out vacuum drying to obtain powdery MIL-68 (Al), wherein the preferable volume ratio of N, N-dimethylformamide to water in the N, N-dimethylformamide solution is 3-5:1, and the ultrasonic dispersion time is 30-60 min.
  3. 3. The metal-organic framework doped waterproof master batch according to claim 2, wherein the precipitate is washed sequentially with N, N-dimethylformamide and methanol, and then dried in vacuum at 80-100 ℃ for 6-8 hours.
  4. 4. The metal-organic framework doped waterproof master batch for concrete according to claim 2, wherein the purity of MIL-68 (Al) is more than or equal to 98%, the particle size is 100-500 nm, and the specific surface area is more than or equal to 1000 m 2 /g.
  5. 5. The metal-organic framework doped waterproof master batch of claim 1, wherein each 100 parts by mass of the cement-based waterproof material comprises 5-10 parts of MIL-68 (Al), 1-10 parts of sodium carbonate, 1-5 parts of sodium silicate and 1-3 parts of glycine.
  6. 6. A cement-based waterproof material, which is characterized by comprising a base material, the waterproof master batch according to any one of claims 1-5 and an auxiliary agent; Preferably, the base material comprises Portland cement and quartz sand, and/or the auxiliary agent comprises anhydrous gypsum, volcanic ash, bentonite, a water reducing agent and hydroxypropyl methyl cellulose.
  7. 7. The cement-based waterproof material according to claim 6, wherein each 100 parts by mass of the cement-based waterproof material comprises 20-40 parts of quartz sand, 5-10 parts of MIL-68 (Al), 1-10 parts of sodium carbonate, 1-5 parts of sodium silicate, 1-3 parts of glycine, 1-10 parts of anhydrous gypsum, 1-5 parts of volcanic ash, 1-5 parts of organic bentonite, 0.1-1 part of sodium polycarboxylate water reducer, 0.1-1 part of hydroxypropyl methyl cellulose and up to 100 parts of portland cement.
  8. 8. The cement-based waterproof material according to claim 7, wherein the silicate cement has a strength grade of not less than 42.5, the quartz sand has a grading sand of 50-300 meshes, the volcanic ash has a fineness of not less than 800 meshes, the sodium silicate, the anhydrite, the hydroxypropyl methylcellulose and the glycine have a fineness of not less than 40 meshes, and the organic bentonite has a fineness of not less than 400 meshes.
  9. 9. The method for preparing the cement-based waterproof material according to any one of claims 6 to 8, wherein the cement-based waterproof material product is obtained by placing the accurately measured raw materials of each component into a mixer, continuously stirring, uniformly mixing, and sealing and packaging.
  10. 10. The method of using the cement-based waterproof material according to any one of claims 6 to 8, wherein the cement-based waterproof material is added to cement mortar or concrete material to form a waterproof self-repairing concrete structure, and preferably the cement-based waterproof material is added in an amount of 1 to 5wt%.

Description

Metal-organic framework doped waterproof master batch, cement-based waterproof material, and preparation and application thereof Technical Field The invention relates to the technical field of modification and optimization of cement-based waterproof materials, in particular to a metal-organic framework doped waterproof master batch, a self-repairing cement-based waterproof material added with the waterproof master batch, and a preparation method and application thereof. Background The concrete structure is a core structural form of modern civil engineering, is one of the most widely applied structural types in the fields of building, bridge, tunnel, water conservancy and the like, has waterproof performance, is a key for guaranteeing the long-term service life, and has decisive effects on maintaining the stable internal environment of the building and guaranteeing the normal exertion of the using function. To realize high-efficiency and durable waterproof effect, a dual protection system of 'impervious concrete body and additional waterproof of key parts' needs to be constructed, on one hand, the self-waterproof line of a firm structure is built by relying on the compactness and crack resistance of waterproof concrete, and on the other hand, a waterproof barrier with omnibearing and no dead angle is formed by arranging the corresponding additional waterproof layers through waterproof materials in a matching way aiming at high-leakage nodes such as structural foundations, construction joints, basement facades, roofs, kitchen and toilet spaces and the like. The cement-based waterproof materials widely used at present are mainly divided into organic and inorganic. The inorganic waterproof material is favored in practice because of being compatible with chemical components of a concrete base material (belonging to silicate systems), strong in binding power and good in durability, and an interface treatment agent is not needed, but the inorganic material is usually insufficient in flexibility, and an ideal waterproof system often requires crack resistance with both the durability of rigid protection and flexibility adaptation, so that the advantage complementation is attempted to be realized through organic-inorganic composite, but the binding strength of the organic material and a cement base is limited, so that a stable and efficient synergistic waterproof system is difficult to form by the organic material and the cement base, and the integral waterproof effect is influenced. In the prior art, although the Na 2CO3@SiO2 microcapsule is utilized to solve the problems of reduced application effect, waste of master batch and the like caused by the reaction of the high-activity master batch and cement, the waterproof performance of the concrete is improved, the existence of NaOH is unfavorable for the preservation of raw materials due to the fact that the alkalinity is large, and the limitation exists in practical application, so that the inherent defect that an inorganic waterproof material is cracked and failed along with a base layer due to the fact that the rigidity is large and the deformability is poor is solved, and the waterproof material which meets application requirements is developed, and is still one of the technical focusing directions. Disclosure of Invention Aiming at the inherent defects of cracking and waterproof failure along with a base layer caused by high rigidity and poor deformability of an inorganic waterproof material, the invention provides a MIL-68 (Al) -based metal-organic framework doped waterproof master batch which is doped into a cement-based waterproof material and can obviously improve the mechanical property and waterproof property of a concrete structure. In order to achieve the above purpose, the metal-organic framework doped waterproof master batch provided by the invention comprises MIL-68 (Al), sodium carbonate, sodium silicate and glycine, and the waterproof master batch is doped into a cement-based waterproof material for improving the cracking resistance and the self-repairing efficiency of a concrete structure; the MIL-68 (Al) is prepared by hydrothermal reaction of reaction raw materials of aluminum chloride and terephthalic acid in a molar ratio of 1:1-2 in a reaction solvent of N, N-dimethylformamide at 120-150 ℃. With the research and development of new material technology, metal Organic Frameworks (MOFs) become breakthrough materials with the characteristics of high specific surface area, regular nano pore channels, adjustable chemical composition, structure and the like, and gradually show excellent performance in the fields of gas adsorption, catalysis, sensors and the like. According to the invention, the chemical properties, the diversity of the sizes, the controllability and the like of MOFs materials are utilized to modify cement hydration and product structures, the MIL-68 (Al) is used as a specific MOFs material to prepare the core waterproof master batch o