Isobutenyl triethoxy silane impregnant and preparation method thereof

Abstract

The invention discloses an isobutenyl triethoxy silane impregnant and a preparation method thereof, and relates to the technical field of building materials, the impregnant comprises the following components: isobutenyl triethoxy silane, a metal organic framework material, a halogenated hydrocarbon compound and modified metal nanoparticles; the invention relates to a metal organic framework material, which is prepared from the following components in parts by mass: 100 parts of isobutenyl triethoxy silane, 5 to 15 parts of metal organic framework material, 10 to 30 parts of halogenated hydrocarbon compound and 0.4 to 1.6 parts of modified metal nanoparticles. The isobutylene triethoxy silane forms an organic silicon network protection layer as basic protection, the halogenated hydrocarbon compound further enhances hydrophobicity, the modified nano-silver particles provide an antibacterial function, and the metal organic framework material plays a role in loading and slowly releasing the modified nano-silver particles and the isobutylene triethoxy silane; meanwhile, the structural stability of the protective layer is enhanced. The components are matched with one another, so that the impregnant has excellent waterproofness, antibacterial property and durability.

Description

Technical Field

[0001] The invention belongs to the technical field of building materials, and in particular relates to an isobutylene triethoxysilane impregnating agent and a preparation method thereof. Background Art

[0002] As a widely used building material, concrete is indispensable in the construction of buildings and infrastructure. Since the advent of concrete materials, people have been committed to developing higher-strength materials. However, during its service, concrete is easily affected by the physical and chemical and biological factors of the surrounding environment. In particular, the porous characteristics of concrete provide channels for the invasion of harmful ions such as chloride ions and carbonates, causing serious corrosion and damage, thereby weakening the structural strength of concrete. In severe cases, it may even cause structural collapse, posing a serious threat to people's production and life.

[0003] Coating the concrete surface can effectively solve the corrosion problem and has a high cost-effectiveness. Silane impregnating agent is a commonly used coating protection material. Among them, the research and development of isobutylene triethoxysilane impregnating agent began in the 1970s and was first used in Europe, America, Australia and other regions. It can penetrate into the interior of the concrete, react chemically with the air and water molecules in the substrate exposed to acidic or alkaline environments, and form a hydrophobic treatment layer, thereby inhibiting the entry of moisture into the substrate. The product has been widely used worldwide. For example, the Chinese patent application with publication number CN104529528A discloses a silane impregnation solution, whose main components are silane emulsions such as isobutylene triethoxysilane, siloxane emulsions, dispersants and preservatives, which have beneficial effects such as anti-corrosion, breathability, and stain resistance, but the effective content is low and the waterproof performance needs to be strengthened. The ideal isobutylene triethoxysilane impregnating agent needs to have excellent permeability, good durability, waterproofness, corrosion resistance, and antibacterial properties, while ensuring performance and still having a high cost-effectiveness. However, the currently disclosed formula technology cannot fully meet the above requirements. Summary of the invention

[0004] The present invention aims at the deficiencies of the prior art in the background technology and provides an isobutylene triethoxysilane impregnating agent and a preparation method thereof, so as to solve the problem that the waterproofness and durability of the impregnating agent need to be enhanced in the above-mentioned technical problem.

[0005] To achieve the above object, the present invention provides the following technical solutions: An isobutylene triethoxysilane impregnating agent, whose components include isobutylene triethoxysilane, metal organic framework materials, halogenated hydrocarbon compounds, and modified metal nanoparticles; in parts by mass, the components include 100 parts of isobutylene triethoxysilane, 5 to 15 parts of metal organic framework materials, 10 to 30 parts of halogenated hydrocarbon compounds, and 0.4 to 1.6 parts of modified metal nanoparticles.

[0006] Isobutylene triethoxysilane is the main component of the impregnating agent. It is an important organosilicon compound with a small molecular structure, which can smoothly penetrate into the voids and capillaries existing in the concrete during the pouring and hardening process. When isobutylene triethoxysilane enters the voids, the ethoxy group (-OC2H5) in its molecule will undergo a hydrolysis reaction with the water molecules in the environment. The specific reaction equation is: C4H9-Si(OC2H5)3+ 3H2O→ Si(OH)4 + 3C2H5OH+ C4H9OH. The silanol generated by the hydrolysis reaction will further undergo a condensation reaction with the hydroxyl groups in the concrete to form -Si-O-Si- chemical bonds, forming a waterproof membrane with a mesh structure, which can effectively prevent the entry of water molecules and harmful substances such as chloride ions and sulfates, thereby playing a role in waterproofing and anti-corrosion.

[0007] Metal-Organic Frameworks (MOFs) are a type of open crystalline skeleton material with permanent pores that is self-assembled by metal ions or clusters and organic ligands through coordination. It has the advantages of high porosity, large specific surface area, and good controllability. It can increase the adsorption capacity of the impregnant on the concrete surface, allowing the impregnant to better penetrate into the concrete and improve the protective effect. MOFs materials can well adsorb isobutylene triethoxysilane molecules through physical adsorption mechanisms and mechanisms of interaction with organic ligands, making their distribution on the concrete surface more uniform and enhancing waterproof and anti-corrosion properties. MOFs materials also have good chemical stability and thermal stability, which can improve the durability of the impregnant and ensure that the protective effect of the impregnant is more lasting.

[0008] Halogenated hydrocarbon compounds contain long-chain alkyl groups. Under appropriate reaction conditions, the halogen atoms in them act as electrophilic reagents and undergo nucleophilic substitution reactions with the nucleophilic groups in isobutylene triethoxysilane. During this reaction, the halogen atoms are replaced and the long-chain alkyl groups are introduced into the isobutylene triethoxysilane molecules, thereby changing the surface properties of the silane molecules and making them more hydrophobic. The addition of halogenated hydrocarbon compounds can reduce the surface tension of the impregnant, making it easier to spread on the concrete surface and penetrate into the interior, improving the wettability of the impregnant to the concrete and forming a more effective protective layer.

[0009] The addition of metal nanoparticles makes the impregnating agent have antibacterial effect. They can destroy the cell membrane structure of bacteria, interfere with the metabolic process of bacteria, and cause bacterial death. Metal nanoparticles can be loaded in the gaps by MOFs materials, and form a network structure with isobutylene triethoxysilane and halogenated hydrocarbon compounds, and the higher hardness of metal nanoparticles makes the impregnating agent more wear-resistant. However, metal nanoparticles have the problems of large specific surface area and high surface energy, and are prone to agglomeration. Generally, a dispersant needs to be added to improve it. However, in this application, the metal nanoparticles are modified by a surface coating method to prevent the agglomeration of the metal nanoparticles, so that they are evenly dispersed in the impregnating agent, and the modified metal nanoparticles have better antibacterial properties.

[0010] Preferably, the metal organic framework (MOFs) material is a chromium-based metal organic framework material (MIL-101); the chemical formula of the halogenated hydrocarbon compound is , wherein X represents a halogen atom, n is a positive integer, n≤20; the modified metal nanoparticles are modified nanosilver particles. MIL-101 has a large specific surface area and a rich pore structure, and can adsorb a large number of isobutylene triethoxysilane molecules. This enables more impregnants to be effectively delivered to the surface of the target material or structure in practical applications, thereby improving the utilization efficiency and protective effect of the impregnant. The isobutylene triethoxysilane impregnant itself can form a hydrophobic organic silicon network protective layer on the surface of the material to prevent the invasion of external moisture and harmful substances. The addition of modified nanosilver particles can further enhance this protective effect, because the antibacterial effect of nanosilver can reduce the damage of microorganisms to the organic silicon protective layer, thereby extending the service life of the material.

[0011] Preferably, the halogen atom X is any one of a bromine atom, a chloride ion, and an iodide ion; n can be 12, 14, 16, 18 or 20; more preferably, the halogenated hydrocarbon compound is hexadecane bromide (C 16 H 33 Br) or iodotetradecane (C 14 H 29 I). The silicon atom in isobutylene triethoxysilane carries a partial positive charge and can act as a nucleophile to attack the carbon atom in the halogenated hydrocarbon compound. The halogen ion in the halogenated hydrocarbon compound ( or ) are good leaving groups and when they are removed from the carbon atom, a new carbon-silicon bond is formed.

[0012] As a general technical concept, the present invention also provides a method for preparing an isobutylene triethoxysilane impregnating agent, comprising the following steps: Step (1), weighing the corresponding isobutylene triethoxysilane, metal organic framework (MOFs) material, halogenated hydrocarbon compound and modified nano silver particles according to the proportions. Adding the MOFs material into a solvent containing isobutylene triethoxysilane, stirring to allow the isobutylene triethoxysilane to react fully, so that the isobutylene triethoxysilane is fully adsorbed onto the surface and pores of the MOFs material; Step (2), dispersing the prepared modified nano-silver particles into the solution containing the MOFs material and isobutylene triethoxysilane in step (1), and continuing to stir to allow the solution to react fully, so that the modified nano-silver particles can be loaded onto the MOFs material; Step (3), adding a halogenated hydrocarbon compound to step (2), reacting, adding a catalyst, allowing the halogenated hydrocarbon compound to react with the isobutylene triethoxysilane on the MOFs material, and stirring thoroughly to finally obtain an isobutylene triethoxysilane impregnating agent.

[0013] Preferably, in step (1), the solvent is toluene; the reaction temperature is 30-70° C., and the stirring time is 2-6 hours.

[0014] Preferably, in step (2), the reaction temperature is 30-70° C., and the stirring time is 4-8 hours.

[0015] Preferably, in step (3), the reaction temperature is between 60 and 100° C., the reaction time is 6 to 12 hours, the catalyst is triethylamine, and the mass ratio of triethylamine to halogenated hydrocarbon compound is 1:2 to 5.

[0016] Preferably, the preparation method of isobutylene triethoxysilane comprises the following steps: Active metal, 2-halopropane, iodine and solvent are added to a reactor equipped with a reflux device, a stirring device and filled with nitrogen to fully react; the obtained product is filtered, and the filtrate is added to chloromethyltriethoxysilane for reaction to obtain a crude isobutylenyltriethoxysilane product; the crude product is distilled under reduced pressure, and the fraction at a temperature of 65-68° C. is collected to obtain high-purity isobutylenyltriethoxysilane.

[0017] Preferably, the active metal is magnesium, the 2-halopropane is 2-bromopropane, the solvent is diethyl ether, and the reduced pressure distillation condition is to perform reduced pressure distillation at 2 kPa; the molar ratio of the active metal magnesium to 2-bromopropane is 1:2; the amount of iodine is 0.01% of the active metal magnesium; the molar ratio of chloromethyltriethoxysilane to 2-bromopropane is 1:1; the molar ratio of diethyl ether to 2-bromopropane is 1:1.

[0018] Preferably, the preparation method of the modified nanosilver particles comprises the following steps: using acrylic acid (AA) as a monomer and ammonium persulfate (APS) as an initiator, in-situ polymerization of acrylic acid on the surface of nanosilver particles. The temperature is controlled between 60 and 80°C, and the reaction is carried out for 8 to 25 hours to obtain coated nanosilver particles, which are washed with deionized water and then vacuum dried to obtain modified nanosilver particles, wherein the mass ratio of the nanosilver particles to acrylic acid is 1:5 to 20, and the mass ratio of the nanosilver particles to ammonium persulfate is 1:0.01 to 0.5.

[0019] Compared with the prior art, the present invention has the following beneficial effects: (1) Isobutylene triethoxysilane itself has good permeability and can easily penetrate into the interior of concrete. Its active ingredients react chemically with moisture in the air and the moisture in the substrate to generate hydroxyl groups. The reaction equation involved is: C4H9-Si(OC2H5)3+ 3H2O→ Si(OH)4 + 3C2H5OH + C4H9OH. These hydroxyl groups will cross-link and accumulate with each other to form a strong hydrophobic silicone network protective layer on the inner wall of the material's pores. This protective layer can effectively prevent the invasion of external moisture and harmful substances, such as preventing material corrosion and freeze-thaw damage caused by moisture infiltration, while allowing internal water vapor and harmful gases to escape, thereby improving the durability and service life of the material.

[0020] (2) MIL-101, which has high porosity and large specific surface area, can not only physically adsorb isobutylene triethoxysilane molecules close to the surface of MIL-101 through the van der Waals force between molecules, but also react with the ethoxy group (-OC2H5) in isobutylene triethoxysilane through its own organic ligands (carboxyl, hydroxyl). The ethoxy group can undergo esterification reaction with the carboxyl group or hydrogen bond with the hydroxyl group. These interactions make the isobutylene triethoxysilane molecules more firmly bonded to MIL-101. As the environment around the concrete changes, it is gradually released, which makes the service life of isobutylene triethoxysilane longer.

[0021] (3) The reaction of hexadecane bromide or tetradecane iodide with isobutylene triethoxysilane is a nucleophilic substitution reaction. The halogen atoms in hexadecane bromide or tetradecane iodide act as electrophilic reagents and undergo nucleophilic substitution reactions with the nucleophilic groups in butenyl triethoxysilane. During this reaction, the halogen atoms are replaced and long-chain alkyl groups are introduced into the isobutylene triethoxysilane molecules, thereby changing the surface properties of the silane molecules and making them more hydrophobic. The specific reaction equation is: C 16 H 33 Br+C4H9-Si(OC2H5)3→C 16 H 33-C4H9-Si(OC2H5)3+HBr or C 14 H 29 I+C4H9-Si(OC2H5)3→C 14 H 29 -C4H9-Si(OC2H5)3+HI.

[0022] (4) The modified nanosilver particles have strong antibacterial properties and can inhibit and kill a variety of bacteria, fungi, molds and other microorganisms. They can be evenly dispersed in the pores of MIL-101 to achieve a sustained release effect, allowing them to continue to exert their antibacterial and antiseptic effects for a long time. Nanosilver particles may have certain catalytic activity, which can promote the chemical reaction between isobutylene triethoxysilane and the surface of the material, accelerate the formation of the protective layer, and improve the use efficiency of the impregnant.

[0023] (5) The hydrophobic organosilicon network protective layer formed by isobutylene triethoxysilane is the basic protection, hexadecane bromide or tetradecane iodide further enhances the hydrophobicity, the modified nanosilver particles provide antibacterial and anticorrosive functions, and the MOFs material plays the role of loading and slowly releasing the modified nanosilver particles and isobutylene triethoxysilane, while enhancing the structural stability of the protective layer. These components cooperate with each other, so that the protective performance of the impregnant on the material is significantly enhanced, and it can better resist the erosion of moisture, harmful substances and microorganisms. The preparation method of an isobutylene triethoxysilane impregnant provided by the present invention can achieve a better balance in terms of waterproof performance, antibacterial performance, durability, etc. through the synergy of various components, so that the impregnant can be applied to a variety of different materials and usage environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The present invention is a flow chart of the preparation method of isobutylene triethoxysilane impregnating agent. DETAILED DESCRIPTION

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the technical solutions in the embodiments of the present invention or the prior art are described in detail below, and the described embodiments are only some embodiments of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention. The present invention is further described below in conjunction with specific embodiments.

[0026] In the present application, the isobutylene triethoxysilane, metal organic framework (MOFs) material, halogenated hydrocarbon compound, metal nanoparticles and the components and solvents required for their preparation are all existing products.

[0027] Nonionic surfactants were purchased from Merck, Darmstadt, Germany.

[0028] 2-Bromopropane and chloromethyltriethoxysilane were purchased from Shandong Delan Chemical Co., Ltd.

[0029] Metal organic frameworks (MOFs) materials were purchased from Guangdong Carbon Language New Materials Co., Ltd.

[0030] Hexadecane bromide or tetradecane iodide was purchased from Shanghai MacLean Biotechnology Co., Ltd.

[0031] Silver nanoparticles were purchased from Nanjing Donna Biotechnology Co., Ltd.

[0032] Toluene and ether were purchased from Sinopharm Group.

[0033] Example 1 A method for preparing an isobutylene triethoxysilane impregnating agent, the specific steps of which are as follows: (1) Add 0.1 mol of magnesium chips, 0.2 mol of 2-chloropropane, 0.2 mol of ether and iodine to a three-necked flask, the amount of iodine being 0.01% of the magnesium chips. Place the flask in a water bath at 20°C under the protection of nitrogen and stir for 3.5 h. Filter the obtained product, add the filtrate dropwise to 0.2 mol of chloromethyltriethoxysilane, stir for 1.5 h at 30°C to obtain a crude isobutyltriethoxysilane product. Perform vacuum distillation under a negative pressure of 2 kPa, collect the distillation fraction at 66°C to obtain a high-purity isobutyltriethoxysilane product.

[0034] (2) Add 0.1 g of nanosilver particles, 0.5 g of acrylic acid, and 0.05 g of ammonium persulfate into a conical flask, and react at 70° C. for 15 hours to obtain coated nanosilver particles, which are then washed with deionized water and then vacuum dried to obtain modified nanosilver particles.

[0035] (3) Prepare, by mass, 100 parts of isobutylene triethoxysilane, 5 parts of MIL-101 material, 10 parts of hexadecane bromide, and 0.4 parts of modified nanosilver particles.

[0036] (4) Add 5 parts of MIL-101 material into a reactor containing 100 parts of isobutylene triethoxysilane and toluene solvent, control the reaction temperature to 50°C, and stir thoroughly for 4 hours.

[0037] (5) Disperse 0.4 parts of the prepared modified nanosilver particles into the above solution containing MIL-101 material and isobutylene triethoxysilane, continue stirring for 6 hours, and maintain the temperature at 50°C.

[0038] (6) Slowly add 10 parts of hexadecane bromide to the above reaction system, react at 80°C for 8 hours, add 2 parts of catalyst triethylamine to react hexadecane bromide with isobutylene triethoxysilane on the MIL-101 material. Stir thoroughly to obtain the isobutylene triethoxysilane impregnating agent.

[0039] Example 2 A method for preparing an isobutylene triethoxysilane impregnating agent, the specific steps of which are as follows: (1) Add 0.1 mol of magnesium chips, 0.2 mol of 2-chloropropane, 0.2 mol of ether and iodine to a three-necked flask, the amount of iodine being 0.01% of the magnesium chips. Place the flask in a water bath at 20°C under the protection of nitrogen and stir for 3.5 h. Filter the obtained product, add the filtrate dropwise to 0.2 mol of chloromethyltriethoxysilane, stir for 1.5 h at 30°C to obtain a crude isobutyltriethoxysilane product. Perform vacuum distillation under a negative pressure of 2 kPa, collect the distillation fraction at 65°C to obtain a high-purity isobutyltriethoxysilane product.

[0040] (2) Add 0.2 g of nanosilver particles, 2 g of acrylic acid, and 0.03 g of ammonium persulfate into a conical flask, and react at 60° C. for 12 hours to obtain coated nanosilver particles, which are then washed with deionized water and then vacuum dried to obtain modified nanosilver particles.

[0041] (3) Prepare, by mass, 100 parts of isobutylene triethoxysilane, 10 parts of MIL-101 material, 20 parts of hexadecane bromide, and 1 part of modified nanosilver particles.

[0042] (4) Add 10 parts of MIL-101 material into a reactor containing 100 parts of isobutylene triethoxysilane and toluene solvent, control the reaction temperature to 40°C, and stir thoroughly for 6 hours.

[0043] (5) Disperse the prepared modified nanosilver particles into the solution containing the MIL-101 material and isobutylene triethoxysilane, continue stirring for 6 hours, and maintain the temperature at 40°C.

[0044] (6) Slowly add 20 parts of hexadecane bromide to the above reaction system, react at 90°C for 10 hours, add 5 parts of catalyst triethylamine to react hexadecane bromide with isobutylene triethoxysilane on the MIL-101 material. Stir thoroughly to obtain the isobutylene triethoxysilane impregnating agent.

[0045] Example 3 A method for preparing an isobutylene triethoxysilane impregnating agent, the specific steps of which are as follows: (1) Add 0.1 mol of magnesium chips, 0.2 mol of 2-chloropropane, 0.2 mol of ether and iodine to a three-necked flask, the amount of iodine being 0.01% of the magnesium chips. Place the flask in a water bath at 20°C under the protection of nitrogen and stir for 3.5 h. Filter the obtained product, add the filtrate dropwise to 0.2 mol of chloromethyltriethoxysilane, stir for 1.5 h at 30°C to obtain a crude isobutyltriethoxysilane product. Perform vacuum distillation under a negative pressure of 2 kPa, collect the distillation fraction at 68°C to obtain a high-purity isobutyltriethoxysilane product.

[0046] (2) Add 0.5 g of nanosilver particles, 7.5 g of acrylic acid, and 0.04 g of ammonium persulfate into a conical flask, and react at 65° C. for 10 hours to obtain coated nanosilver particles, which are then washed with deionized water and then vacuum dried to obtain modified nanosilver particles.

[0047] (3) Prepare, by mass, 100 parts of isobutylene triethoxysilane, 15 parts of MIL-101 material, 30 parts of hexadecane bromide, and 1.6 parts of modified nanosilver particles.

[0048] (4) Add 15 parts of MIL-101 material into a reactor containing 100 parts of isobutylene triethoxysilane and toluene solvent, control the reaction temperature to 70°C, and stir thoroughly for 3 hours.

[0049] (5) Disperse 1.6 parts of the prepared modified nanosilver particles into the above solution containing MIL-101 material and isobutylene triethoxysilane, continue stirring for 4 hours, and maintain the temperature at 70°C.

[0050] (6) Slowly add 30 parts of hexadecane bromide to the above reaction system, react at 100°C for 6 hours, add 10 parts of catalyst triethylamine to react hexadecane bromide with isobutylene triethoxysilane on the MIL-101 material. Stir thoroughly to obtain the isobutylene triethoxysilane impregnating agent.

[0051] Example 4 A method for preparing an isobutylene triethoxysilane impregnating agent, the specific steps of which are as follows: (1) Add 0.1 mol of magnesium chips, 0.2 mol of 2-chloropropane, 0.2 mol of ether and iodine to a three-necked flask, the amount of iodine being 0.01% of the magnesium chips. Place the flask in a water bath at 20°C under the protection of nitrogen and stir for 3.5 h. Filter the obtained product, add the filtrate dropwise to 0.2 mol of chloromethyltriethoxysilane, stir for 1.5 h at 30°C to obtain a crude isobutyltriethoxysilane product. Perform vacuum distillation under a negative pressure of 2 kPa, collect the distillation fraction at 68°C to obtain a high-purity isobutyltriethoxysilane product.

[0052] (2) Add 0.3 g of nanosilver particles, 6 g of acrylic acid, and 0.012 g of ammonium persulfate into a conical flask, and react at 80° C. for 20 hours to obtain coated nanosilver particles, which are then washed with deionized water and then vacuum dried to obtain modified nanosilver particles.

[0053] (3) Prepare, by mass, 100 parts of isobutylene triethoxysilane, 5 parts of MIL-101 material, 10 parts of iodotetradecane, and 0.4 parts of modified nanosilver particles.

[0054] (4) Add 5 parts of MIL-101 material into a reactor containing 100 parts of isobutylene triethoxysilane and toluene solvent, control the reaction temperature to 50°C, and stir thoroughly for 4 hours.

[0055] (5) Disperse 0.4 parts of the prepared modified nanosilver particles into the above solution containing MIL-101 material and isobutylene triethoxysilane, continue stirring for 6 hours, and maintain the temperature at 50°C.

[0056] (6) Slowly add 10 parts of iodidetradecane to the above reaction system, react at 80°C for 8 hours, add 2 parts of catalyst triethylamine to react iodidetradecane with isobutylene triethoxysilane on the MIL-101 material. Stir thoroughly to obtain the isobutylene triethoxysilane impregnating agent.

[0057] Example 5 A method for preparing an isobutylene triethoxysilane impregnating agent, the specific steps of which are as follows: (1) Add 0.1 mol of magnesium chips, 0.2 mol of 2-chloropropane, 0.2 mol of ether and iodine to a three-necked flask, the amount of iodine being 0.01% of the magnesium chips. Place the flask in a water bath at 20°C under the protection of nitrogen and stir for 3.5 h. Filter the obtained product, add the filtrate dropwise to 0.2 mol of chloromethyltriethoxysilane, stir for 1.5 h at 30°C to obtain a crude isobutyltriethoxysilane product. Perform vacuum distillation under a negative pressure of 2 kPa, collect the distillation fraction at 66°C to obtain a high-purity isobutyltriethoxysilane product.

[0058] (2) Add 0.6 g of nanosilver particles, 7.8 g of acrylic acid, and 0.18 g of ammonium persulfate into a conical flask, and react at 75° C. for 16 hours to obtain coated nanosilver particles, which are then washed with deionized water and then vacuum dried to obtain modified nanosilver particles.

[0059] (3) Prepare, by mass, 100 parts of isobutylene triethoxysilane, 10 parts of MIL-101 material, 20 parts of iodotetradecane, and 1 part of modified nanosilver particles.

[0060] (4) Add 10 parts of MIL-101 material into a reactor containing 100 parts of isobutylene triethoxysilane and toluene solvent, control the reaction temperature to 40°C, and stir thoroughly for 6 hours.

[0061] (5) Disperse 1 portion of the prepared modified nanosilver particles into the above solution containing the MIL-101 material and isobutylene triethoxysilane, continue stirring for 6 hours, and maintain the temperature at 40°C.

[0062] (6) Slowly add 20 parts of iodidetradecane to the above reaction system, react at 90°C for 10 hours, add 4 parts of catalyst triethylamine to react iodidetradecane with isobutylene triethoxysilane on the MIL-101 material. Stir thoroughly to obtain the isobutylene triethoxysilane impregnating agent.

[0063] Example 6 A method for preparing an isobutylene triethoxysilane impregnating agent, the specific steps of which are as follows: (1) Add 0.1 mol of magnesium chips, 0.2 mol of 2-chloropropane, 0.2 mol of ether and iodine to a three-necked flask, the amount of iodine being 0.01% of the magnesium chips. Place the flask in a water bath at 20°C under the protection of nitrogen and stir for 3.5 h. Filter the obtained product, add the filtrate dropwise to 0.2 mol of chloromethyltriethoxysilane, stir for 1.5 h at 30°C to obtain a crude isobutyltriethoxysilane product. Perform vacuum distillation under a negative pressure of 2 kPa, collect the distillation fraction at 67°C, and obtain a high-purity isobutyltriethoxysilane product.

[0064] (2) Add 0.8 g of nanosilver particles, 14.4 g of acrylic acid, and 0.072 g of ammonium persulfate into a conical flask, and react at 72° C. for 13 hours to obtain coated nanosilver particles, which are then washed with deionized water and then vacuum dried to obtain modified nanosilver particles.

[0065] (3) Prepare, by mass, 100 parts of isobutylene triethoxysilane, 15 parts of MIL-101 material, 30 parts of iodotetradecane, and 1.6 parts of modified nanosilver particles.

[0066] (4) Add 15 parts of MIL-101 material into a reactor containing 100 parts of isobutylene triethoxysilane and toluene solvent, control the reaction temperature to 70°C, and stir thoroughly for 3 hours.

[0067] (5) Disperse 1.6 parts of the prepared modified nanosilver particles into the above solution containing MOFs material and isobutylene triethoxysilane, continue stirring for 4 hours, and maintain the temperature at 70°C.

[0068] (6) Slowly add 30 parts of iodidetradecane to the above reaction system, react at 100°C for 6 hours, add 15 parts of catalyst triethylamine to react iodidetradecane with isobutylene triethoxysilane on the MIL-101 material. Stir thoroughly to obtain the isobutylene triethoxysilane impregnating agent.

[0069] Comparative Example 1 A method for preparing an isobutylene triethoxysilane impregnating agent, except that the metal organic framework material MIL-101 component is not included, the remaining steps are the same as those of Example 1.

[0070] Comparative Example 2 A method for preparing an isobutylene triethoxysilane impregnating agent, except that the component halogenated hydrocarbon compound is not included, the remaining steps are the same as those of Example 1.

[0071] Comparative Example 3 A method for preparing a self-crosslinking alkyl impregnating agent free of isobutylene triethoxysilane, the specific steps of which are as follows: (1) Methyltriethoxysilane, deionized water and ethanol were added into a reactor in a molar ratio of 1:3:1, stirred at room temperature for 5 min, and 0.01 mol / L HCl solution was added to adjust the pH value of the system to 4. The temperature was raised to 40°C and stirring was continued to hydrolyze methyltriethoxysilane for 5 h. After the reaction, 0.01 mol / L NaOH solution was added to adjust the pH value of the system to 6-8. The ethanol was removed by stirring at a pressure of 0.005 MPa and a temperature of 40°C for 120 min to obtain methylsilanol.

[0072] (2) The methylsilanol prepared in step (1) and methyltriethoxysilane are uniformly mixed in a mass ratio of 5:95 to obtain a silane impregnating agent containing 5% methylsilanol.

[0073] Performance parameter detection: Referring to JTJ 275-2000 "Technical Specification for Anticorrosion of Concrete Structures in Seaport Engineering", the performance indicators such as the immersion depth, water absorption rate, chloride ion absorption reduction rate and air permeability ratio of the silane impregnation solutions prepared in the above Examples 1 to 6 and Comparative Examples 1 to 3 were measured, and the measurement results are shown in Table 1.

[0074] Table 1 Performance test results of isobutylene triethoxysilane impregnating agents prepared in different embodiments and comparative examples

[0075] The penetration depth, water absorption rate and the reduction rate of chloride ion absorption are the main evaluation criteria for evaluating the protective effect of silane impregnants on concrete. Water absorption rate is the most important criterion, which directly determines the use effect of the impregnant. The waterproof effect is inversely proportional to the water absorption rate. The lower the water absorption rate, the better the waterproof effect. The embodiments provided by the present invention all have extremely low water absorption rates; the penetration depth represents the durability of the impregnant, and the reduction rate of chloride ion absorption is a significant feature of silane impregnants. Referring to Table 1, it can be clearly found that after using the impregnant prepared by the present invention, the highest water absorption rate of the concrete is only 0.00316mm / min. 1 / 2； The minimum penetration depth can reach 6.16 mm, and the maximum penetration depth can reach 7.25 mm, showing excellent waterproofness and durability. Among them, the isobutylene triethoxysilane impregnating agent prepared in Example 1 has the best comprehensive effect.

[0076] Compared with Example 1, the impregnating agent component in Comparative Example 1 does not contain metal organic framework materials, so the penetration depth of the silane impregnating agent prepared in Comparative Example 1 is only 4.75 mm, which is not only lower than Example 1, but also has the smallest penetration depth in all test experiments. The larger the penetration depth value, the longer the service life of the impregnating agent. The presence of the metal organic framework material combines isobutylene triethoxysilane through physical adsorption and pairing of organic groups. As the environment around the concrete changes, isobutylene triethoxysilane is gradually released, extending the service life of the silane impregnating agent. The addition of metal organic framework materials to the formula provided in the present application can significantly increase the penetration depth, making the impregnating agent more durable.

[0077] Compared with Example 1, Comparative Example 2 does not contain halogenated hydrocarbon compounds, so in Comparative Example 2, the water absorption rate is 0.00359, which is higher than Example 1 and also higher than Examples 2 to 6. The higher the water absorption rate, the worse the waterproof effect. The addition of halogenated hydrocarbon compounds can react with isobutylene triethoxysilane to undergo nucleophilic substitution reaction, and long-chain alkyl groups are introduced into isobutylene triethoxysilane molecules, thereby changing the surface properties of the silane molecules and making them more hydrophobic. Therefore, the formula provided by the present invention contains halogenated compounds, which can enhance the hydrophobicity of the silane impregnating agent and show better waterproof effect.

[0078] Compared with Example 1, Comparative Example 3 is a method for preparing a self-crosslinking alkyl impregnating agent, wherein methylsilanol is prepared from methyltriethoxysilane, deionized water and ethanol, and then methylsilanol is mixed with methyltriethoxysilane to obtain a silane impregnating agent of methylsilanol. However, as shown in Table 1, its penetration depth is 6.17 mm, which is lower than 7.25 mm in Example 1, and its water absorption rate is 0.00386 mm / min. 1 / 2 Higher than 0.00225 mm / min of Example 1 1 / 2 The reduction rate of chloride ion absorption is 92.8%, which is also lower than 96.3% in Example 1, and is not as good as the effect of Example 1. Therefore, the silane impregnating agent provided in the present application has a better effect.

[0079] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An isobutylene triethoxysilane impregnating agent, characterized in that The invention comprises isobutylene triethoxysilane, metal organic framework material, halogenated hydrocarbon compound and modified metal nanoparticles; in parts by mass, the isobutylene triethoxysilane is 100 parts, the metal organic framework material is 5 to 15 parts, the halogenated hydrocarbon compound is 10 to 30 parts and the modified metal nanoparticles are 0.4 to 1.6 parts.

2. An isobutylene triethoxysilane impregnating agent according to claim 1, characterized in that: The metal organic framework material is a chromium-based metal organic framework material; the chemical formula of the halogenated hydrocarbon compound is , wherein X represents a halogen atom, n is a positive integer, and n≤20; the modified metal nanoparticles are modified nanosilver particles.

3. An isobutylene triethoxysilane impregnating agent according to claim 2, characterized in that: The halogen atom X is any one of a bromine atom, a chloride ion, and an iodine ion; and n is 12, 14, 16, 18 or 20.

4. The method for preparing an isobutylene triethoxysilane impregnating agent according to claim 3, characterized in that: The steps include: Step (1), weighing isobutylene triethoxysilane, metal organic framework material, halogenated hydrocarbon compound and modified nano silver particles according to the proportions, adding the metal organic framework material into a solvent containing isobutylene triethoxysilane, stirring to allow the mixture to react fully, and allowing the isobutylene triethoxysilane to be fully adsorbed onto the surface and pores of the metal organic framework material; Step (2), dispersing the modified nano silver particles into the solution containing the metal organic framework material and isobutylene triethoxysilane in step (1), and continuing to stir to allow the solution to react fully, so that the modified nano silver particles can be loaded onto the metal organic framework material; Step (3), adding a halogenated hydrocarbon compound to step (2), reacting, adding a catalyst to react the halogenated hydrocarbon compound with the isobutylene triethoxysilane on the metal organic framework material, stirring thoroughly to finally obtain the isobutylene triethoxysilane impregnating agent.

5. The method for preparing an isobutylene triethoxysilane impregnating agent according to claim 4, characterized in that: In step (1), the solvent is toluene; the reaction temperature is 30-70° C., and the stirring time is 2-6 hours.

6. The method for preparing an isobutylene triethoxysilane impregnating agent according to claim 4, characterized in that: In step (2), the reaction temperature is 30-70° C., and the stirring time is 4-8 hours.

7. The method for preparing an isobutylene triethoxysilane impregnating agent according to claim 4, characterized in that: In step (3), the reaction temperature is 60-100° C., the reaction time is 6-12 hours, the catalyst is triethylamine, and the mass ratio of triethylamine to halogenated hydrocarbon compound is 1:2-5.

8. The method for preparing an isobutylene triethoxysilane impregnating agent according to claim 4, characterized in that: The preparation method of the isobutylene triethoxysilane comprises the following steps: Add active metal, 2-halopropane, iodine and solvent to a reactor equipped with a reflux device, a stirring device and filled with nitrogen to fully react; filter the obtained product, take the filtrate and add chloromethyltriethoxysilane to react to obtain a crude product of isobutylenyltriethoxysilane; distill the crude product under reduced pressure, collect the fraction at a temperature of 65-68°C, and obtain isobutylenyltriethoxysilane.

9. The method for preparing an isobutylene triethoxysilane impregnating agent according to claim 8, characterized in that: The active metal is magnesium, the 2-halopropane is 2-bromopropane, the solvent is ether, and the reduced pressure distillation condition is to carry out reduced pressure distillation at 2kPa; the molar ratio of the active metal magnesium to 2-bromopropane is 1:2; the amount of iodine is 0.01% of the active metal magnesium; the molar ratio of chloromethyltriethoxysilane to 2-bromopropane is 1:1; the molar ratio of ether to 2-bromopropane is 1:

1.

10. The method for preparing an isobutylene triethoxysilane impregnating agent according to claim 4, characterized in that: The preparation method of the modified nano silver particles comprises the following steps: Acrylic acid is used as a monomer and ammonium persulfate is used as an initiator to perform in-situ polymerization of acrylic acid on the surface of nanosilver particles; the temperature is controlled between 60 and 80° C., the reaction is performed for 8 to 25 hours to obtain coated nanosilver particles, which are washed with deionized water and then vacuum dried to obtain modified nanosilver particles; the mass ratio of the nanosilver particles to acrylic acid is 1:5 to 20, and the mass ratio of the nanosilver particles to ammonium persulfate is 1:0.01 to 0.5.

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