Nanometer material for water stop of cavity of wall cable trench and preparation method of nanometer material

Abstract

The invention relates to the technical field of building materials, and particularly discloses a nanometer material for water stop of a cavity of a wall cable trench and a preparation method of the nanometer material. Comprising the following raw materials in parts by weight: 5-10 parts of sebacic acid, 50-70 parts of acrylic acid, 10-20 parts of olivine powder, 10-20 parts of magnesium aluminum silicate, 20-30 parts of calcium acrylate, 1-2 parts of an aluminate coupling agent, 1-2 parts of a curing agent, 1-2 parts of a coagulant, 1-2 parts of a water reducing agent, 1-2 parts of a performance additive, 30-40 parts of deionized water and 0.5-1 part of ammonium persulfate. The molecular structure of the modified additive contains phosphorus, silicon, fluorine and long-chain alkyl, and the modified additive and other raw materials have a synergistic effect to remarkably improve the flame retardance, compressive strength, chemical stability and waterproof performance of the nano material for wall cable trench cavity water stop. And meanwhile, the agglomeration phenomenon among the raw materials is also reduced by the modification additive, so that the nano material is ensured to have good strength and water plugging effect.

Description

Technical Field

[0001] The invention relates to the technical field of building materials, and in particular to a nano material for water-stopping a cavity of a wall cable trench and a preparation method thereof. Background Art

[0002] In recent years, with the changes in climate and geological conditions, power facilities such as cable trenches, cable wells, cable corridors and ring network cabinet foundations are facing increasingly serious safety hazards in specific areas (such as areas with rising water levels and sandy land areas). The environmental characteristics of these areas make it very easy for cavities to form in the foundations of power facilities, which in turn causes problems such as water accumulation, water seepage, foundation sinking, and collapse, which seriously threaten the safe and stable operation of power facilities and may even cause major safety accidents. Based on this, water-stopping materials that can effectively solve the above problems are increasingly valued by all parties, and the research and development and application of high-performance water-stopping materials have become key measures to ensure the safety of power facilities.

[0003] The patent application number CN201610206720.2 provides a fast-hardening early-strength nano-composite cement-based water plugging reinforcement material, the components of which include: ordinary silicate cement, sulphoaluminate cement, nano-SiO 2, lithium carbonate, sodium hydroxide and water reducer, and the rest is water. The fast-hardening and early-strengthening nano-composite cement-based water-blocking reinforcement material prepared by the invention has low admixture dosage, good initial fluidity, final setting time within 10 minutes, initial and final setting interval time not exceeding 3 minutes, and 24-hour compressive strength of more than 25MPa. It has broad application prospects in the fields of drilling wall protection, shotcrete, plugging and water stopping, dynamic water grouting, anti-seepage curtain and large crack reinforcement in complex formations. However, although the sulphoaluminate cement used in the invention has the advantages of fast hardening and early strength, its durability is poor, especially it is easy to decompose under high temperature conditions, resulting in a decrease in strength and expansion performance, affecting the use effect. The patent with application number CN202110546932.6 provides a polyurethane grouting material for foundation pit water stopping and its preparation method. The material is composed of the following components by mass: 20-40 parts of polyether polyol, 60-80 parts of isocyanate, 0.3-2 parts of catalyst, 4-8 parts of foam stabilizer, 10-20 parts of ethyl acetate, 0.5-1 parts of nano calcium carbonate, 0.5-1 parts of nano aluminum silicate and 0.5-1.5 parts of nano zirconium carbide. First, the polyether polyol is heated to 100-130°C and subjected to negative pressure dehydration and degassing treatment for 1.5-3.5 hours. After cooling to 20-40°C, isocyanate is added, and the reaction is carried out at 75-85°C for 2-3 hours to obtain a prepolymer reaction liquid. Then the temperature is lowered to 40-50°C, a foam stabilizer is added, and after mixing, ethyl acetate, catalyst and nanomaterials are added, and fully mixed to obtain a polyurethane grouting material. The polyurethane grouting material for foundation pit water stopping prepared by the invention has good strength and water blocking effect. The invention uses a variety of nanomaterials such as nano calcium carbonate, nano aluminum silicate, and nano zirconium carbide, but does not use a suitable dispersant. Due to intermolecular forces, electrostatic effects, etc., the nanomaterials will agglomerate to form aggregates, resulting in uneven dispersion in the polyurethane matrix, and the enhancement effects of the nanomaterials cannot be fully exerted, affecting the overall performance of the material.

[0004] Therefore, in order to meet the growing demand for water-stopping materials in modern building and engineering construction, it is still necessary to develop a new nanomaterial for water-stopping of wall cable trench cavities. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a weather-resistant cable insulation material and a preparation method thereof. In order to ensure that the nanomaterial used for waterproofing the wall cable trench cavity can fully exert its waterproof performance, the agglomeration of inorganic raw materials must be reduced, and the nanomaterial must also maintain good use effects under harsh environments such as high temperature.

[0006] The technical solution adopted by the present invention to achieve the above-mentioned purpose is: A nano material for water-stopping a cavity of a cable trench in a wall, comprising the following raw materials in parts by weight: 5-10 parts of sebacic acid, 50-70 parts of acrylic acid, 10-20 parts of olivine powder, 10-20 parts of magnesium aluminum silicate, 20-30 parts of calcium acrylate, 1-2 parts of an aluminate coupling agent, 1-2 parts of a curing agent, 1-2 parts of a coagulant, 1-2 parts of a water reducing agent, 1-2 parts of a modifying agent, 30-40 parts of deionized water, and 0.5-1 parts of ammonium persulfate. The preparation method of the modifying agent is as follows: Step S1, adding 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine to anhydrous ethanol at 80-90° C. with stirring, reacting for 2-3 hours, cooling to room temperature, and purifying to obtain intermediate 1, the structural formula of intermediate 1 is: ; Step S2, adding intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid to toluene at 100-110° C. with stirring, reacting for 5.5-6.5 hours, cooling to room temperature, and purifying to obtain intermediate 2, the structural formula of intermediate 2 is: ; Step S3, at 50-60° C. and acidic conditions, add intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid to N,N-dimethylformamide, stir and react for 6-7 hours, cool to room temperature, purify, and obtain a modified auxiliary agent.

[0007] The synthetic route of intermediate 2 is as follows: ; .

[0008] Furthermore, in step S1, the molar ratio of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane, and triphenylphosphine is 1:0.9-1.1:0.01-0.02, and the amount of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid added to anhydrous ethanol is 0.06-0.08 g / mL.

[0009] Furthermore, in step S2, the molar ratio of the intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid is 1:0.9-1:0.01-0.02, and the amount of 2-aminododecanoic acid added to toluene is 0.04-0.05 g / mL.

[0010] Furthermore, in step S3, the molar ratio of the intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid is 3:0.85-1:6-6.5, and the amount of citric acid added to N,N-dimethylformamide is 0.05-0.06 g / mL.

[0011] Furthermore, the curing agent is selected from one or more of 2-methyl ethyl peroxide, m-phenylenediamine, and 4,4'-diaminodiphenyl sulfone.

[0012] Furthermore, the coagulant is water glass or aluminum sulfate.

[0013] Furthermore, the water reducer is a polycarboxylate water reducer.

[0014] Furthermore, the aluminate coupling agent is distearoyloxyisopropyl aluminate.

[0015] The present invention also provides a method for preparing a nano material for water-stopping a cavity of a wall cable trench, comprising the following steps: (1) grinding olivine powder, magnesium aluminum silicate and calcium acrylate by ball milling, adding part of deionized water and mixing evenly to obtain a mixture; (2) Adding sebacic acid, acrylic acid, aluminate coupling agent, curing agent, accelerator, water reducing agent, modification aid, ammonium persulfate and remaining deionized water to the mixture obtained in step (1) to react and obtain a nanomaterial for water-stopping the cavity of a wall cable trench.

[0016] The present invention has the following beneficial effects: The invention prepares a modified auxiliary agent by a chemical modification method. First, the carboxyl group of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid and the epoxy group of 5,6-epoxyhexyltriethoxysilane are subjected to a ring-opening reaction to obtain an intermediate 1. Then, the hydroxyl group of the intermediate 1 and the carboxyl group of 2-aminododecanoic acid are subjected to an esterification reaction to obtain an intermediate 2. Finally, the amino group of the intermediate 2 and the carboxyl group of citric acid are subjected to an amidation reaction to obtain the modified auxiliary agent. The modified auxiliary agent contains phosphorus, fluorine, silicon elements and long-chain alkyl groups in its molecular structure. The siloxyl group and the carboxyl group in the modified auxiliary agent can react with the active groups such as the hydroxyl group on the surface of materials such as magnesium aluminum silicate, thereby realizing connection with materials such as magnesium aluminum silicate, thereby making the components in the nano material system for water-stopping the wall cable trench cavity more tightly connected to form a whole. The introduction of inorganic substances such as magnesium aluminum silicate can form a three-dimensional network skeleton in the nanomaterials used for water-stopping in the wall cable trench cavity, resist external stress, reduce the risk of material shrinkage and cracking, and effectively enhance the compressive strength of the nanomaterials used for water-stopping in the wall cable trench cavity.

[0017] The introduction of phosphorus in the molecular structure of the modified additive can improve the flame retardancy of the material. When heated, phosphorus-containing compounds will decompose to generate phosphoric acid, metaphosphoric acid and other substances. These substances have a strong dehydration effect and can form a carbonized layer on the surface of the material. The carbonized layer is a poor conductor of heat and can block heat transfer, thereby achieving flame retardancy, protecting the safety of cables and other equipment in the cable trench, and preventing the failure of water-stopping materials due to fire. The introduction of fluorine can improve the hydrophobicity and chemical stability of the material. Fluoride has a high chemical bond energy and is not easily destroyed by other chemicals, so that the material can maintain stable performance under different environmental conditions such as acid and alkaline environments, extending the service life of the material. In addition, the electronegativity of fluorine is extremely high. When it is introduced into the modified additive, the surface energy of the nanomaterial for water-stopping of the wall cable trench cavity prepared with the modified additive as raw material will be significantly reduced, and then it will have super hydrophobicity, which can significantly enhance the material's anti-penetration performance and reduce the risk of water penetrating into the cable trench. The introduction of silicon can significantly enhance the material's mechanical strength, chemical stability and flame retardancy. Silicon atoms exist in the modified additive in the form of silicon-oxygen bonds. The silicon-oxygen bonds are strong, providing a solid skeleton support for the nanomaterials used for water-stopping in the wall cable trench cavity. This structure enhances the hardness and compressive strength of the material, so that it can still maintain structural integrity and water-stopping effect when it is subjected to pressure and deformation of the wall cable trench. In addition, the silicon-oxygen bond also has high chemical stability and can resist the erosion of various chemical substances. When the nanomaterial contains silicon elements, the silicon-oxygen structure formed on its surface can serve as a barrier to prevent corrosive substances such as acids and alkalis from reacting with the internal components of the material. This allows the nanomaterials used for water-stopping to maintain stable performance and extend service life when facing acidic or alkaline substances that may exist in the cable trench. In addition, silicon elements can also promote the formation of a carbon layer when the material is burned. When heated, silicon atoms can interact with other atoms in the material, change the breaking mode and reaction path of the molecular chain, and allow more carbon elements to remain on the surface of the material to form a carbon layer. The carbon layer has good thermal insulation properties, which can further block heat transfer and slow down the thermal degradation rate of the material, thereby improving the flame retardant properties of the material. In addition, phosphorus and silicon elements can work together to improve the flame retardant properties of the material through synergistic effects, so that the material can maintain good performance in a high temperature environment. The introduction of long-chain alkyl groups can improve the dispersibility and hydrophobicity of the material. Due to its longer carbon chain structure, long-chain alkyl groups will form a "barrier" around the particles when connected to the surface of the particles. This steric hindrance effect increases the distance between the particles, thereby reducing the interaction and agglomeration tendency between the particles. This physical barrier effect helps to improve the dispersibility of the particles in the medium and prevent the agglomeration and sedimentation of the particles, thereby ensuring that the material performance is not affected. Moreover, the presence of long-chain alkyl groups will reduce the surface free energy of the material, increase the contact angle of water on the surface of the material, thereby achieving a hydrophobic effect and effectively preventing moisture from penetrating into the cable trench cavity.Therefore, the introduction of phosphorus, fluorine, silicon elements and long-chain alkyl groups can give the modified additives multifunctionality. Introducing modified additives into the nanomaterials for water-stopping in wall cable trench cavities can not only reduce the agglomeration and sedimentation of particles in the system, but also significantly enhance the flame retardancy, hydrophobicity, chemical stability and compressive strength of the nanomaterials.

[0018] The present invention compounds sebacic acid, acrylic acid, olivine powder, magnesium aluminum silicate, calcium acrylate, aluminate coupling agent, curing agent, coagulant, water reducer, modification aid and other raw materials to obtain a nano material for water stopping in a wall cable trench cavity. The modification aid has a synergistic effect with raw materials such as magnesium aluminum silicate, which can not only improve the compressive strength, flame retardant properties, hydrophobic properties and chemical stability of the material, but also ensure the reliability and long-term durability of the nano material for water stopping in complex environments, thereby effectively meeting the safety and service life requirements in practical applications. DETAILED DESCRIPTION

[0019] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0020] The raw materials used in the following examples are all common commercially available products. The olivine powder is forsterite powder with a MgO content of 57% and a SiO 2 The content is 43%, the particle size is 325 mesh, purchased from Erping Mineral Products Processing Plant in Lingshou County; the density of magnesium aluminum silicate is 2.3g / cm 3 , particle size is 325 mesh, purchased from Shijiazhuang Hualang Mineral Products Trading Co., Ltd.; calcium acrylate content ≥99.5%, moisture ≤0.5%, purchased from Hubei Xinghengye Technology Co., Ltd.; water glass effective ingredient content is 99%, density is 1.362g / mL, purchased from Jinan Huisheng Chemical Co., Ltd.; the measured value of water reduction rate of polycarboxylic acid water reducer is 31.2%, and the measured value of water bleeding rate is 52%, purchased from Jinan Yanglan New Material Technology Co., Ltd. Example 1

[0021] A nano material for water-stopping in a wall cable trench cavity, comprising the following raw materials in parts by weight: 5 parts of sebacic acid, 50 parts of acrylic acid, 10 parts of olivine powder, 10 parts of magnesium aluminum silicate, 20 parts of calcium acrylate, 1 part of aluminate coupling agent, 1 part of curing agent, 1 part of coagulant, 1 part of water reducing agent, 1 part of modification auxiliary agent, 30 parts of deionized water, and 0.5 parts of ammonium persulfate; The curing agent is 2-methyl ethyl peroxide, the coagulant is water glass, the water reducer is polycarboxylic acid water reducer, and the aluminate coupling agent is distearoyloxyisopropyl aluminate; The preparation method of the modified additive is as follows: Step S1, adding 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine to anhydrous ethanol at 80° C. with stirring, reacting for 3 hours, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at a temperature of 40° C. to remove anhydrous ethanol, to obtain intermediate 1, wherein the molar ratio of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine is 1:0.9:0.01, and the amount of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid added to anhydrous ethanol is 0.06 g / mL; Step S2, adding intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid to toluene at 100° C. with stirring, reacting for 6.5 hours, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at 60° C. to remove toluene to obtain intermediate 2, wherein the molar ratio of intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid is 1:0.9:0.01, and the amount of 2-aminododecanoic acid added to toluene is 0.04 g / mL; Step S3, at 50 ° C, add intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid to N,N-dimethylformamide, adjust the pH to 4.5-6 with 0.1 M HCl solution, stir and react for 7 hours, cool to room temperature, and then extract with deionized water of the same volume as N,N-dimethylformamide and ethyl acetate twice the volume of N,N-dimethylformamide in sequence, take the organic phase and distill under reduced pressure to obtain a modified auxiliary agent, wherein the molar ratio of intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid is 3:0.85:6, and the amount of citric acid added to N,N-dimethylformamide is 0.05 g / mL.

[0022] The synthetic route of intermediate 2 is as follows: ; .

[0023] The nuclear magnetic resonance results of intermediate 1 are: 1H NMR (300 MHz, acetone-d6) δ 5.37 (s, 1H), 4.08-4.36 (m, 7H), 3.79-3.88 (m, 6H), 1.20-1.41 (m, 21H), 0.51-0.60 (m, 2H).

[0024] The NMR results of intermediate 2 are: 1H NMR (300 MHz, acetone-d6) δ 8.76 (s, 2H), 5.16 (m, 1H), 4.16-4.42 (m, 6H), 3.76-3.85 (m, 6H), 3.36 (t, 1H), 1.88 (d, 2H), 1.49 (d, 2H), 1.21-1.36 (m, 35H), 0.88 (t, 3H), 0.56 (t, 2H).

[0025] The present invention also provides a method for preparing a nano material for water-stopping a cavity of a wall cable trench, comprising the following steps: (1) ball-milling olivine powder, magnesium aluminum silicate and calcium acrylate, and then adding 20 parts of deionized water to mix evenly to obtain a mixture, wherein the ball-to-material ratio during ball milling is 15:1, the rotation speed is 600 r / min, the ball milling time is 10 h, and zirconium oxide balls are selected, the small ball diameter is 1 mm, the medium ball diameter is 3 mm, the large ball diameter is 5 mm, and the ratio of large, medium and small balls is 4:4:2; (2) Adding sebacic acid, acrylic acid, aluminate coupling agent, curing agent, coagulant, water reducing agent, modification aid, ammonium persulfate and remaining deionized water to the mixture obtained in step (1), adjusting the pH value to 3.5-4.5 with 0.1 M HCl solution, and carrying out stirring polymerization reaction at a temperature of 60° C. for 2 h to obtain a nanomaterial for waterproofing the cavity of a wall cable trench. The average particle size of the nanomaterial for waterproofing the cavity of a wall cable trench is measured by a laser particle size analyzer to be 82.6 nm. Example 2

[0026] A nano material for water-stopping a cavity in a cable trench of a wall, comprising the following raw materials in parts by weight: 10 parts of sebacic acid, 70 parts of acrylic acid, 20 parts of olivine powder, 20 parts of magnesium aluminum silicate, 30 parts of calcium acrylate, 2 parts of aluminate coupling agent, 2 parts of curing agent, 2 parts of coagulant, 2 parts of water reducing agent, 2 parts of modification auxiliary agent, 40 parts of deionized water, and 1 part of ammonium persulfate; The curing agent is m-phenylenediamine, the coagulant is aluminum sulfate, the water reducer is polycarboxylic acid water reducer, and the aluminate coupling agent is distearoyloxyisopropylaluminate; The preparation method of the modified additive is as follows: Step S1, adding 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine to anhydrous ethanol at 90° C. with stirring, reacting for 2 hours, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at a temperature of 40° C. to remove anhydrous ethanol, to obtain intermediate 1, wherein the molar ratio of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine is 1:1.1:0.02, and the amount of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid added to anhydrous ethanol is 0.08 g / mL; Step S2, adding intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid to toluene at 110° C. with stirring, reacting for 5.5 hours, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at 60° C. to remove toluene to obtain intermediate 2, wherein the molar ratio of intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid is 1:1:0.02, and the amount of 2-aminododecanoic acid added to toluene is 0.05 g / mL; Step S3, at 60 ° C, add intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid to N,N-dimethylformamide, adjust the pH to 4.5-6 with 0.1 M HCl solution, stir and react for 6 hours, cool to room temperature, and then extract with deionized water of the same volume as N,N-dimethylformamide and ethyl acetate twice the volume of N,N-dimethylformamide in sequence, take the organic phase and distill under reduced pressure to obtain a modified auxiliary agent, wherein the molar ratio of intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid is 3:1:6.5, and the amount of citric acid added to N,N-dimethylformamide is 0.06 g / mL.

[0027] The present invention also provides a method for preparing a nano material for water-stopping a cavity of a wall cable trench, comprising the following steps: (1) ball-milling olivine powder, magnesium aluminum silicate and calcium acrylate, and then adding 25 parts of deionized water to mix evenly to obtain a mixture, wherein the ball-to-material ratio during ball milling is 15:1, the rotation speed is 600 r / min, the ball milling time is 10 h, and zirconium oxide balls are selected, the small ball diameter is 1 mm, the medium ball diameter is 3 mm, the large ball diameter is 5 mm, and the ratio of large, medium and small balls is 4:4:2; (2) Adding sebacic acid, acrylic acid, aluminate coupling agent, curing agent, coagulant, water reducing agent, modification aid, ammonium persulfate and remaining deionized water to the mixture obtained in step (1), adjusting the pH value to 3.5-4.5 with 0.1 M HCl solution, and carrying out stirring polymerization reaction at a temperature of 60° C. for 3 h to obtain a nanomaterial for waterproofing the cavity of a wall cable trench. The average particle size of the nanomaterial for waterproofing the cavity of a wall cable trench is measured by a laser particle size analyzer to be 87.1 nm. Example 3

[0028] A nano material for water-stopping a cavity in a cable trench of a wall, comprising the following raw materials in parts by weight: 8 parts of sebacic acid, 60 parts of acrylic acid, 15 parts of olivine powder, 15 parts of magnesium aluminum silicate, 25 parts of calcium acrylate, 1.5 parts of aluminate coupling agent, 1.5 parts of curing agent, 1.5 parts of coagulant, 1.5 parts of water reducing agent, 1.5 parts of modification aid, 35 parts of deionized water, and 0.8 parts of ammonium persulfate; The curing agent is 4,4'-diaminodiphenyl sulfone, the coagulant is aluminum sulfate, the water reducer is polycarboxylic acid water reducer, and the aluminate coupling agent is distearoyloxyisopropyl aluminate; The preparation method of the modified additive is as follows: Step S1, adding 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine to anhydrous ethanol at 85° C. with stirring, reacting for 2.5 hours, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at a temperature of 40° C. to remove anhydrous ethanol, to obtain intermediate 1, wherein the molar ratio of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine is 1:1:0.015, and the amount of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid added to anhydrous ethanol is 0.07 g / mL; Step S2, adding intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid to toluene at 105° C. with stirring, reacting for 6 hours, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at 60° C. to remove toluene to obtain intermediate 2, wherein the molar ratio of intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid is 1:0.95:0.015, and the amount of 2-aminododecanoic acid added to toluene is 0.045 g / mL; Step S3, at 55 ° C, add intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid to N,N-dimethylformamide, adjust the pH to 4.5-6 with 0.1 M HCl solution, stir the reaction for 6.5 hours, cool to room temperature, and then extract with deionized water of the same volume as N,N-dimethylformamide and ethyl acetate twice the volume of N,N-dimethylformamide in sequence, take the organic phase and distill under reduced pressure to obtain a modified auxiliary agent, wherein the molar ratio of intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid is 3:0.9:6.2, and the amount of citric acid added to N,N-dimethylformamide is 0.055 g / mL.

[0029] The present invention also provides a method for preparing a nano material for water-stopping a cavity of a wall cable trench, comprising the following steps: (1) ball-milling olivine powder, magnesium aluminum silicate and calcium acrylate, and then adding 23 parts of deionized water and mixing evenly to obtain a mixture, wherein the ball-to-material ratio during ball milling is 15:1, the rotation speed is 600 r / min, the ball milling time is 10 h, and zirconium oxide balls are selected, the small ball diameter is 1 mm, the medium ball diameter is 3 mm, the large ball diameter is 5 mm, and the ratio of large, medium and small balls is 4:4:2; (2) Adding sebacic acid, acrylic acid, aluminate coupling agent, curing agent, coagulant, water reducing agent, modification aid, ammonium persulfate and remaining deionized water to the mixture obtained in step (1), adjusting the pH value to 3.5-4.5 with 0.1 M HCl solution, and carrying out stirring polymerization reaction at a temperature of 60° C. for 2.5 h to obtain a nanomaterial for waterproofing the cavity of a wall cable trench. The average particle size of the nanomaterial for waterproofing the cavity of a wall cable trench is measured by a laser particle size analyzer to be 81.9 nm. Comparative Example 1

[0030] A nano material for water-stopping in a wall cable trench cavity, comprising the following raw materials in parts by weight: 8 parts of sebacic acid, 40 parts of acrylic acid, 10 parts of olivine powder, 10 parts of magnesium aluminum silicate, 10 parts of calcium acrylate, 0.5 parts of aluminate coupling agent, 1.5 parts of curing agent, 1.5 parts of coagulant, 0.5 parts of water reducing agent, 0.5 parts of modification auxiliary agent, 35 parts of deionized water, and 0.8 parts of ammonium persulfate; The curing agent is 4,4'-diaminodiphenyl sulfone, the coagulant is aluminum sulfate, the water reducer is polycarboxylic acid water reducer, and the aluminate coupling agent is distearoyloxyisopropyl aluminate; The preparation method of the modified additive is as follows: Step S1, adding 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine to anhydrous ethanol at 70° C. with stirring, reacting for 1 hour, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at a temperature of 40° C. to remove anhydrous ethanol, to obtain intermediate 1, wherein the molar ratio of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine is 1:0.5:0.005, and the amount of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid added to anhydrous ethanol is 0.07 g / mL; Step S2, adding intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid to toluene at 80° C. with stirring, reacting for 6 hours, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at 60° C. to remove toluene to obtain intermediate 2, wherein the molar ratio of intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid is 1:0.8:0.015, and the amount of 2-aminododecanoic acid added to toluene is 0.045 g / mL; Step S3, at 55 ° C, add intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid to N,N-dimethylformamide, adjust the pH to 4.5-6 with 0.1 M HCl solution, stir and react for 6.5 hours, cool to room temperature, and then extract with deionized water of the same volume as N,N-dimethylformamide and ethyl acetate twice the volume of N,N-dimethylformamide in sequence, take the organic phase and distill under reduced pressure to obtain a modified auxiliary agent, wherein the molar ratio of intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid is 1:0.9:2, and the amount of citric acid added to N,N-dimethylformamide is 0.055 g / mL.

[0031] The present invention also provides a method for preparing a nano material for water-stopping a cavity of a wall cable trench, comprising the following steps: (1) ball-milling olivine powder, magnesium aluminum silicate and calcium acrylate, and then adding 25 parts of deionized water to mix evenly to obtain a mixture, wherein the ball-to-material ratio during ball milling is 15:1, the rotation speed is 600 r / min, the ball milling time is 7 h, and zirconium oxide balls are selected, the small ball diameter is 1 mm, the medium ball diameter is 3 mm, the large ball diameter is 5 mm, and the ratio of large, medium and small balls is 4:4:2; (2) Adding sebacic acid, acrylic acid, aluminate coupling agent, curing agent, coagulant, water reducing agent, modification aid, ammonium persulfate and remaining deionized water to the mixture obtained in step (1), adjusting the pH value to 3.5-4.5 with 0.1 M HCl solution, and carrying out stirring polymerization reaction at a temperature of 60° C. for 2.5 h to obtain a nanomaterial for waterproofing the cavity of a wall cable trench. The average particle size of the nanomaterial for waterproofing the cavity of a wall cable trench is measured by a laser particle size analyzer to be 101.5 nm. Comparative Example 2

[0032] A nano material for water-stopping a cavity in a cable trench of a wall, comprising the following raw materials in parts by weight: 8 parts of sebacic acid, 60 parts of acrylic acid, 15 parts of olivine powder, 15 parts of magnesium aluminum silicate, 25 parts of calcium acrylate, 1.5 parts of aluminate coupling agent, 1.5 parts of curing agent, 1.5 parts of coagulant, 1.5 parts of water reducing agent, 1.5 parts of modification aid, 35 parts of deionized water, and 0.8 parts of ammonium persulfate; The curing agent is 4,4'-diaminodiphenyl sulfone, the coagulant is aluminum sulfate, the water reducer is polycarboxylic acid water reducer, and the aluminate coupling agent is distearoyloxyisopropyl aluminate; The preparation method of the modified additive is as follows: Step S1, adding 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane, and triphenylphosphine to anhydrous ethanol at 85° C. with stirring, reacting for 2.5 hours, cooling to room temperature, and filtering to obtain a filtrate, then rotary evaporating the filtrate at a temperature of 40° C. to remove anhydrous ethanol to obtain an intermediate, wherein the molar ratio of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane, and triphenylphosphine is 1:1:0.015, and the amount of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid added to the anhydrous ethanol is 0.07 g / mL; Step S2, at 105 ° C, under stirring conditions, adding the intermediate, 2-aminododecanoic acid and p-toluenesulfonic acid to toluene, reacting for 6 hours, cooling to room temperature and filtering to obtain a filtrate, then rotary evaporating the filtrate at a temperature of 60 ° C to remove toluene to obtain a modified auxiliary agent, wherein the molar ratio of the intermediate, 2-aminododecanoic acid and p-toluenesulfonic acid is 1:0.95:0.015, and the amount of 2-aminododecanoic acid added to toluene is 0.045 g / mL.

[0033] The present invention also provides a method for preparing a nano material for water-stopping a cavity of a wall cable trench, comprising the following steps: (1) ball-milling olivine powder, magnesium aluminum silicate and calcium acrylate, and then adding 25 parts of deionized water to mix evenly to obtain a mixture, wherein the ball-to-material ratio during ball milling is 15:1, the rotation speed is 600 r / min, the ball milling time is 7 h, and zirconium oxide balls are selected, the small ball diameter is 1 mm, the medium ball diameter is 3 mm, the large ball diameter is 5 mm, and the ratio of large, medium and small balls is 4:4:2; (2) Adding sebacic acid, acrylic acid, aluminate coupling agent, curing agent, coagulant, water reducing agent, modification aid, ammonium persulfate and remaining deionized water to the mixture obtained in step (1), adjusting the pH value to 3.5-4.5 with 0.1 M HCl solution, and carrying out stirring polymerization reaction at a temperature of 60° C. for 2.5 h to obtain a nanomaterial for waterproofing the cavity of a wall cable trench. The average particle size of the nanomaterial for waterproofing the cavity of a wall cable trench is measured by a laser particle size analyzer to be 110.7 nm. Comparative Example 3

[0034] A nano material for water-stopping a cavity in a cable trench of a wall, comprising the following raw materials in parts by weight: 8 parts of sebacic acid, 60 parts of acrylic acid, 15 parts of olivine powder, 15 parts of magnesium aluminum silicate, 25 parts of calcium acrylate, 1.5 parts of aluminate coupling agent, 1.5 parts of curing agent, 1.5 parts of coagulant, 1.5 parts of water reducing agent, 35 parts of deionized water, and 0.8 parts of ammonium persulfate; The curing agent is 4,4'-diaminodiphenyl sulfone, the coagulant is aluminum sulfate, the water reducer is polycarboxylic acid water reducer, and the aluminate coupling agent is distearoyloxyisopropyl aluminate; The present invention also provides a method for preparing a nano material for water-stopping a cavity of a wall cable trench, comprising the following steps: (1) ball-milling olivine powder, magnesium aluminum silicate and calcium acrylate, and then adding 25 parts of deionized water to mix evenly to obtain a mixture, wherein the ball-to-material ratio during ball milling is 15:1, the rotation speed is 600 r / min, the ball milling time is 7 h, and zirconium oxide balls are selected, the small ball diameter is 1 mm, the medium ball diameter is 3 mm, the large ball diameter is 5 mm, and the ratio of large, medium and small balls is 4:4:2; (2) Adding sebacic acid, acrylic acid, aluminate coupling agent, curing agent, coagulant, water reducing agent, ammonium persulfate and remaining deionized water to the mixture obtained in step (1), adjusting the pH value to 3.5-4.5 with 0.1 M HCl solution, and carrying out stirring polymerization reaction at a temperature of 60° C. for 2.5 hours to obtain a nanomaterial for waterproofing the cavity of a wall cable trench. The average particle size of the nanomaterial for waterproofing the cavity of a wall cable trench is measured by a laser particle size analyzer to be 111.2 nm.

[0035] Compressive strength test: The nanomaterial used for waterproofing the cavity of the cable trench in the wall is made into a cylindrical specimen with a diameter of 40mm and a height of 100mm, and the test is carried out according to the compressive strength test method of the sand consolidation body in JC / T 2037-2010 "Acrylate Grouting Materials".

[0036] Permeability coefficient test: According to the requirements for permeability coefficient in JC / T 2037-2010 "Acrylate Grouting Materials", the penetration test method in GB / T 50123-1999 "Civil Test Method Standard" is used for testing. The permeability coefficient test is for six specimens per group. Pour the prepared nanomaterial slurry for wall cable trench cavity water stop into the ring cutter, so that the slurry forms a solid in the ring cutter and stands for 1 day, then install the ring cutter with the solid into the penetration container and conduct the penetration test according to the variable head penetration test method. Before conducting the penetration test, the ring cutter with the solid should be wrapped with plastic wrap to prevent the solid from drying and shrinking.

[0037] Flame retardancy test: According to the requirements for combustion performance test in GB 8624-2012 "Combustion performance classification of building materials and products", GB / T 5464-2010 "Test method for non-combustibility of building materials", GB / T 14402-2007 "Combustion performance of building materials and products - Determination of calorific value of combustion" and GB / T 20284-2006 "Single combustion test of building materials or products" are used to evaluate the combustion performance level of the test piece.

[0038] Durability test: First, the wall cable trench cavity water stop is made into a cube with a side length of 40mm using nanomaterials, and then the test piece is left to stand for 1 day to obtain the test piece, and each test piece is immersed in 10% sodium hydroxide solution and 1% hydrochloric acid solution for 72 hours. Then take out the test piece, observe whether there is powdering or cracking on its surface, and record it.

[0039] The specific test data can be seen from Table 1.

[0040] Table 1 Performance test results:

[0041] According to the data in Table 1, the nanomaterials for water-stopping the cavity of the wall cable trench prepared in Examples 1-3 are superior to the materials of Comparative Examples 1-3 in terms of compressive strength and permeability coefficient. This shows that by adjusting the ratio of each raw material and introducing a modifying agent, the compressive resistance and water resistance of the material can be significantly improved, thereby effectively preventing structural damage and electrical failures, and ensuring the long-term stability of the water-stopping effect. In terms of acid and alkali resistance, the nanomaterials for water-stopping the cavity of the wall cable trench of Examples 1-3 are stable in acidic and alkaline environments, without powdering or cracking, while the materials of Comparative Examples 1-3 have these changes. This shows that the introduction of modifying agents can enhance the environmental stability of the material and extend its service life. In terms of combustion performance, the materials of Examples 1-3 have reached Class A1, which can effectively prevent the spread of fire in a fire. In contrast, the materials of Comparative Examples 1-3 have poor combustion performance, which increases the risk of fire. Therefore, the nanomaterials adjusted by adjusting the ratio of each raw material and introducing a modifying agent also perform better in terms of safety.

[0042] Although the embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present application, and that the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A nanomaterial for waterproofing a wall cable trench cavity, characterized in that: The invention comprises the following raw materials in parts by weight: 5-10 parts of sebacic acid, 50-70 parts of acrylic acid, 10-20 parts of olivine powder, 10-20 parts of magnesium aluminum silicate, 20-30 parts of calcium acrylate, 1-2 parts of aluminate coupling agent, 1-2 parts of curing agent, 1-2 parts of accelerator, 1-2 parts of water reducing agent, 1-2 parts of modification auxiliary agent, 30-40 parts of deionized water, and 0.5-1 parts of ammonium persulfate. The preparation method of the modification auxiliary agent is as follows: Step S1, adding 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine to anhydrous ethanol at 80-90° C. with stirring, reacting for 2-3 hours, cooling to room temperature, and purifying to obtain intermediate 1; Step S2, adding intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid to toluene at 100-110° C. with stirring, reacting for 5.5-6.5 hours, cooling to room temperature, and purifying to obtain intermediate 2; Step S3, at 50-60° C. and acidic conditions, add intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid to N,N-dimethylformamide, stir and react for 6-7 hours, cool to room temperature, purify, and obtain a modified auxiliary agent.

2. The nano material for waterproofing a wall cable trench cavity according to claim 1, characterized in that: The molar ratio of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid, 5,6-epoxyhexyltriethoxysilane and triphenylphosphine in step S1 is 1:0.9-1.1:0.01-0.02, and the amount of 2-(diethoxyphosphoryl)-2,2-difluoroacetic acid added to anhydrous ethanol is 0.06-0.08 g / mL.

3. The nano material for waterproofing a wall cable trench cavity according to claim 1, characterized in that: In step S2, the molar ratio of the intermediate 1, 2-aminododecanoic acid and p-toluenesulfonic acid is 1:0.9-1:0.01-0.02, and the amount of 2-aminododecanoic acid added to toluene is 0.04-0.05 g / mL.

4. The nano material for waterproofing a wall cable trench cavity according to claim 1, characterized in that: In step S3, the molar ratio of the intermediate 2, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and citric acid is 3:0.85-1:6-6.5, and the amount of citric acid added to N,N-dimethylformamide is 0.05-0.06 g / mL.

5. The nano material for waterproofing a wall cable trench cavity according to claim 1, characterized in that: The curing agent is selected from one or more of 2-methyl ethyl peroxide, m-phenylenediamine, and 4,4'-diaminodiphenyl sulfone.

6. The nano material for waterproofing a wall cable trench cavity according to claim 1, characterized in that: The coagulant is water glass or aluminum sulfate.

7. The nano material for waterproofing a wall cable trench cavity according to claim 1, characterized in that: The water reducer is a polycarboxylate water reducer.

8. The nano material for waterproofing a wall cable trench cavity according to claim 1, characterized in that: The aluminate coupling agent is isopropyl distearoyloxy aluminate.

9. The method for preparing the nano material for water-stopping in the cavity of a wall cable trench according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) grinding olivine powder, magnesium aluminum silicate and calcium acrylate by ball milling, adding part of deionized water and mixing evenly to obtain a mixture; (2) Adding sebacic acid, acrylic acid, aluminate coupling agent, curing agent, accelerator, water reducing agent, modification aid, ammonium persulfate and remaining deionized water to the mixture obtained in step (1) and reacting for 2-3 hours to obtain a nanomaterial for water-stopping the cavity of a wall cable trench.

Images