Preparation process and application of a zirconium-silicon-aluminum multinuclear complex anti-cracking and anti-dispersing agent

Abstract

This invention relates to the field of concrete materials technology, specifically disclosing a preparation process and application of a zirconium-silicon-aluminum multinuclear complex anti-cracking and anti-dispersing agent, comprising the following steps: (1) adding silicate solution dropwise to aluminum sulfate solution and shearing and stirring during the process to obtain reaction solution a. (2) adding concentrated sulfuric acid dropwise to reaction solution a under stirring conditions, and heating the reaction after completion to obtain reaction solution b. (3) adding a modification solution formed by zirconium sulfate and zirconium oxychloride dropwise to reaction solution b under stirring conditions to obtain reaction solution c. (4) adding ATMP, liquid polyethylene glycol, and tartaric acid sequentially to reaction solution c and reacting under heating and stirring conditions. Then adjusting the pH of the reaction system to obtain the composite anti-cracking agent. The anti-cracking agent prepared by this invention can simultaneously achieve anti-dispersibility, anti-cracking, and durability improvement, solving the problem that it is difficult to balance the anti-dispersibility and anti-cracking performance of underwater non-dispersible concrete.

Description

Technical Field

[0001] This invention relates to the field of concrete materials technology, specifically to a preparation process and application of a zirconium-silicon-aluminum multinuclear complex anti-cracking and anti-dispersing agent. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Underwater non-dispersible concrete (NDC) is a key material in marine engineering, hydraulic structure repair, and bridge pier foundations. It relies on anti-dispersants (such as cellulose ethers) to ensure resistance to water erosion during pouring. However, it still faces a serious problem of early cracking during the hardening process: high cementitious material content leads to concentrated release of hydration heat, causing temperature stress; chemical shrinkage and drying shrinkage generate tensile stress under external constraints, exceeding the early tensile strength of the concrete and forming cracks. These cracks not only weaken the integrity of the concrete structure but also become channels for harmful media such as chloride ions and sulfates to penetrate, threatening service safety.

[0004] Traditional anti-dispersants (such as cellulose ethers and polyacrylamides) can only guarantee performance during the pouring stage (including anti-segregation, self-leveling, and pumpability), but cannot prevent cracking after hardening. Although adding expansive agents can reduce cracking, their effectiveness depends on ideal curing conditions and is inconsistent in underwater environments. While fibrous materials also help inhibit crack propagation, they can impair the fluidity and self-compacting properties of concrete, conflicting with the requirements of underwater vibration-free construction. Furthermore, the addition of these admixtures not only easily leads to compatibility issues but also increases the cost of concrete materials and complicates control. Summary of the Invention

[0005] This invention provides a preparation process and application of a zirconium-silicon-aluminum multinuclear complex anti-cracking and anti-dispersing agent. This anti-cracking agent can simultaneously achieve anti-dispersibility, anti-cracking, and durability improvement, solving the problem of the difficulty in achieving both anti-dispersibility and anti-cracking performance in underwater non-dispersible concrete. Specifically, the technical method of this invention is as follows.

[0006] In a first aspect of the present invention, a preparation process for a zirconium-silicon-aluminum multinuclear complex anti-cracking and anti-dispersing agent is provided, comprising the following steps: (1) The silicate solution is added dropwise to the aluminum sulfate solution and sheared and stirred during the process to allow the silicate ions and aluminum ions to undergo preliminary copolymerization by forming Al-O-Si bonds. After completion, reaction solution a is obtained.

[0007] (2) Concentrated sulfuric acid is added dropwise to the reaction solution a under stirring conditions. After the reaction is completed, the reaction is heated to further polymerize the Al-O-Si bonds to form a network structure, thus obtaining the reaction solution b.

[0008] (3) Under stirring conditions, the modified solution formed by zirconium sulfate and zirconium oxychloride is added dropwise to the reaction solution b to carry out the reaction, and the reaction system is kept under heating and heat preservation during the process, so that Zr 4+ The ligands in the network structure undergo ligand exchange to form a “Zr-O-Al-O-Si” polynuclear complex structure, resulting in reaction solution c.

[0009] (4) In the reaction solution c, aminotrimethylene phosphonic acid (ATMP), liquid polyethylene glycol, and tartaric acid are added sequentially and reacted under heating and stirring conditions, thereby utilizing the phosphonic acid group of ATMP and the Zr in the polynuclear complex structure. 4+ Al 3+ A stable chelate ring is formed. Then, the pH of the reaction system is adjusted to obtain the composite crack-resistant agent.

[0010] Further, in step (1), the ratio of silicate to aluminum sulfate is 8-15 parts by weight: 18-32 parts by weight.

[0011] Further, in step (1), the silicate includes at least one of sodium silicate, potassium silicate, etc.

[0012] Further, in step (1), the dropping acceleration rate is 1~2 mL / min. Optionally, the shear stirring rate is 1500~2000 r / min, and the time is 30~45 min.

[0013] Further, in step (2), the concentrated sulfuric acid is added to adjust the pH of the system to 3.5~4.5.

[0014] Furthermore, in step (2), the heating temperature is 35~45℃ and the reaction time is 2~3 hours.

[0015] Further, in step (3), the modification solution is formed by zirconium sulfate, zirconium oxychloride, and water in a ratio of 2.5-4 parts by weight: 0.8-1.2 parts by weight: 5-10 parts by weight. This invention utilizes zirconium oxychloride to provide highly active, easily hydrolyzable zirconium cations and chloride ions, ensuring the system possesses high charge density and good solubility stability, thus achieving rapid charge neutralization and adsorption of cement particles. The strong coordination bridging effect of the divalent sulfate ions provided by zirconium sulfate promotes the crosslinking of linear molecules into a three-dimensional network structure, significantly increasing the molecular weight and density of the polymer; facilitating the formation of the structurally stable, highly adsorbent bridging polynuclear complex structure.

[0016] Further, in step (3), the ratio of reaction solution b to modification solution is 28~46 parts by weight: 4.1~7.6 parts by weight.

[0017] Further, in step (3), the heating and heat preservation temperature is 35~45℃, and the reaction time is 1~1.5 hours. Optionally, the dropping rate of the modification solution is 0.5~0.8 mL / min. The stirring rate is 800~1000 r / min.

[0018] Further, in step (4), the ratio of the reaction solution c, aminotrimethylenephosphonic acid, liquid polyethylene glycol, and tartaric acid is 32~54 parts by weight: 0.5~1.0 parts by weight: 0.5~2 parts by weight: 1~3 parts by weight.

[0019] Further, in step (4), the heating temperature is 35~45℃, and the reaction time is 1~1.5 hours. Optionally, the stirring rate is 600~800 r / min.

[0020] Further, in step (4), the pH of the reaction system is adjusted to 5-6. Optionally, at least one of sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, etc., is used to adjust the pH.

[0021] In a second aspect of the invention, the zirconium-silicon-aluminum polynuclear complex anti-cracking and anti-dispersing agent is provided for use in underwater non-dispersible concrete. Optionally, the dosage of the anti-cracking agent is 1.5 to 3% of the mass of the cement component in the concrete.

[0022] Compared with the prior art, the technical solution of the present invention has at least the following beneficial effects: (1) The composite crack-resistant agent of the present invention utilizes multiple high-valence metal ions (zirconium, aluminum) as positively charged core nodes, interconnected through ligands such as hydroxyl, oxygen, and sulfate ions as chemical bridges, and introduces polysilicic acid chains as a reinforcing skeleton. At the microscopic level, it cross-links and polymerizes to form a zirconium-silicon-aluminum multinuclear complex structure with high charge density and a large molecular weight, resembling a microscopic "powerful fishing net." This endows the composite crack-resistant agent of the present invention with extremely strong adsorption bridging and trapping capabilities, enabling it to tightly aggregate cement particles to resist water flow dispersion. When this crack-resistant and anti-dispersing agent of the present invention is added to concrete materials, on the one hand, the positively charged Al-OH in its multinuclear complex structure... + Zr-OH +The functional groups can be rapidly adsorbed onto the surface of cement particles in concrete materials, thereby neutralizing the surface charge of the particles, reducing interparticle repulsion, and decreasing the dispersibility of the concrete paste, thus helping to reduce the loss rate during underwater pouring. On the other hand, the long-chain structure of "Zr-O-Al-O-Si" in the multinuclear complex structure interacts with the Ca atoms on the surface of cement particles through its hydroxyl groups. 2+ SiO3 2- This combination forms a three-dimensional bridging network that runs through the entire slurry, tightly connecting cement particles and aggregates and preventing particle separation and slurry loss during underwater pouring. Furthermore, the uncomplexed Zr(OH)4 colloidal particles in the crack-resistant agent are uniformly dispersed in the gaps between cement particles, which helps enhance the slurry's cohesiveness while reducing the damage of moisture to the slurry structure, effectively improving the concrete's resistance to dispersal and reducing its loss rate during underwater pouring.

[0023] (2) The zirconium-silicon-aluminum multinuclear complex anti-cracking and anti-dispersing agent of the present invention can inhibit the cracking of concrete materials from the root cause, because: on the one hand, the Si(OH)4 therein reacts with the Ca released by the dissolution of cement. 2+ The rapid reaction generates early CSH gel, which encapsulates cement particles to form a "complexed gel-cement" composite micelle, constructing a temporary framework and reducing early microcracks caused by plastic shrinkage. On the other hand, the Zr in the multinucleated complex structure... 4+ As a catalytic center, it can induce calcium aluminate hydrate (CAH) in concrete materials. 10 The process transforms the ZrO2 nanoparticles into a more stable CASH gel. Simultaneously, during the formation of the multinuclear complex structure, the ZrO2 nanoparticles formed by the microcrystalline nuclei of the Zr-O-Zr inorganic framework in the system act as nuclei, promoting the directional growth of the CSH gel and thus forming a "CSH-ZrO2-CASH" interwoven structure. This significantly reduces the porosity of hydration products and enhances the crack resistance of the concrete matrix. Furthermore, the multinuclear complex structure utilizes its ATMP to undergo a condensation reaction with the hydroxyl groups on the surface of the hydration products CSH and CASH gel, thereby forming an "integrated" structure through chemical bonding to avoid interfacial delamination. At the same time, the elastic deformation capacity of the multinuclear structure can absorb hydration thermal stress and volumetric deformation stress, effectively reducing cracking of the concrete material.

[0024] (3) The anti-cracking and anti-dispersing agent of the present invention can also repel Cl by utilizing the negative charge layer formed on the surface of its multinucleated complex structure. - SO4 2- Corrosive ions prevent them from reacting with cement hydration products to form expansive substances (such as ettringite and chlorides), while Zr... 4+It can also inhibit excessive Ca(OH)2 precipitation, reduce the risk of alkali-aggregate reaction, and improve long-term durability. In addition, the high bond energy of the "Zr-O-Al-O-Si" long-chain structure in the multinuclear complex structure, combined with the stabilizing effect of the ATMP chelate ring, enables the anti-cracking and anti-dispersing agent of the present invention to maintain structural stability in the low temperature and high pressure environment underwater, which helps to prevent failure and improves the freeze-thaw cycle resistance of underwater non-dispersible concrete. Attached Figure Description

[0025] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0026] Figure 1 The image shows a sample of the anti-cracking and anti-dispersing agent prepared in Example 1 below.

[0027] Figure 2 The image shows a sample of the anti-cracking and anti-dispersing agent prepared in Example 2 below.

[0028] Figure 3 The image shows a sample of the anti-cracking and anti-dispersing agent prepared in Example 3 below.

[0029] Figure 4 The image shows a sample of the anti-cracking and anti-dispersing agent prepared in Example 4 below.

[0030] Figure 5 The image shows a sample of the anti-cracking and anti-dispersing agent prepared in Example 5 below.

[0031] Figure 6 The image shows a sample of the anti-cracking and anti-dispersing agent prepared in Example 6 below.

[0032] Figure 7 The image shows a sample of the anti-cracking and anti-dispersing agent prepared in Example 7 below. Detailed Implementation

[0033] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer.

[0034] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as those skilled in the art. All reagents and raw materials used in this invention are readily available through conventional means, and unless otherwise specified, they shall be used in accordance with conventional methods in the art or as per the product instructions.

[0035] Furthermore, any methods and materials similar to or equivalent to those described herein can be applied to the method of this invention. The technical solution of this invention will now be further described in conjunction with the accompanying drawings and specific embodiments.

[0036] Example 1: A preparation process for a zirconium-silicon-aluminum polynuclear complex anti-cracking and anti-dispersing agent includes the following steps: (1) According to the ratio of sodium silicate to aluminum sulfate = 12 parts by weight: 25 parts by weight, 45 wt.% sodium silicate solution was added dropwise to 45 wt.% aluminum sulfate solution at a rate of 1.5 mL / min, while simultaneously shearing and stirring at a high speed of 1800 r / min for 40 min. During the dropwise addition, the system temperature was controlled not to exceed 30℃. After completion, reaction solution a was obtained.

[0037] (2) Concentrated sulfuric acid was added dropwise to the reaction solution a at a stirring rate of 500 r / min to adjust the pH of the system to 4. After completion, the mixture was heated to 40°C and kept at that temperature for 2.5 hours to obtain reaction solution b.

[0038] (3) Add 3 parts by weight of zirconium sulfate and 1 part by weight of zirconium oxychloride to 7.5 parts by weight of water, mix, and sonicate for 10 min to obtain a modified solution. Then, according to the ratio of reaction solution b to modified solution = 35 parts by weight: 6 parts by weight, add the modified solution dropwise to reaction solution b at a rate of 0.5 mL / min while stirring at 800 r / min, and continue stirring for 1 hour, while maintaining the temperature of the reaction system at 40 °C during the process. After completion, reaction solution c is obtained.

[0039] (4) In the reaction solution c, aminotrimethylenephosphonic acid (ATMP), liquid polyethylene glycol (PEG400), and tartaric acid were added sequentially in a ratio of 45 parts by weight: 0.8 parts by weight: 1.5 parts by weight: 2 parts by weight. The system was then kept at 40°C and stirred for 1 hour (stirring rate 600 r / min). After completion, the pH of the system was adjusted to 6 with a 5 wt.% sodium hydroxide solution, stirred for 15 minutes, and then cooled to room temperature. Finally, the reaction solution was filtered through a 5 μm filter membrane to remove solid impurities, thus obtaining the anti-cracking and anti-dispersing agent, such as... Figure 1 As shown.

[0040] Performance Testing: The crack-resistant and anti-dispersing agent prepared in this embodiment was added to underwater non-dispersible concrete material (composed of the following raw materials in the following proportions: 370 parts by weight of ordinary Portland cement, 45 parts by weight of fly ash, 630 parts by weight of river sand with a fineness modulus of 2.6, 900 parts by weight of 7-18mm continuously graded crushed stone, 15 parts by weight of nano-silica powder, and 22 parts by weight of early-strength agent), with an addition amount of 1.5% of the mass of the ordinary Portland cement. The various performance indicators of the resulting concrete material were then tested, and the results are shown in Table 1 below.

[0041] Table 1 result 3.5% 460mm 86.4% 32.7% 450με 78.1% Example 2: A preparation process for a zirconium-silicon-aluminum polynuclear complex anti-cracking and anti-dispersing agent includes the following steps: (1) According to the ratio of sodium silicate to aluminum sulfate = 8 parts by weight: 18 parts by weight, 45 wt.% sodium silicate solution was added dropwise to 45 wt.% aluminum sulfate solution at a rate of 1 mL / min, while the mixture was sheared and stirred at a high speed of 1500 r / min for 30 min. During the dropwise addition, the system temperature was controlled not to exceed 30℃. After the addition was completed, reaction solution a was obtained.

[0042] (2) Concentrated sulfuric acid was added dropwise to the reaction solution a at a stirring rate of 500 r / min to adjust the pH of the system to 4.5. After completion, the mixture was heated to 35°C and kept at that temperature for 3 hours to obtain reaction solution b.

[0043] (3) A modified solution was obtained by mixing 2.5 parts by weight of zirconium sulfate and 0.8 parts by weight of zirconium oxychloride with 5 parts by weight of water and then sonicating for 10 min. Then, the modified solution was added dropwise to the reaction solution b at a rate of 0.8 mL / min at a stirring rate of 1000 r / min, according to the ratio of reaction solution b to modified solution = 46 parts by weight: 7.6 parts by weight. The reaction was continued to be stirred for 1.5 hours, and the temperature of the reaction system was maintained at 35°C during the process. After completion, reaction solution c was obtained.

[0044] (4) Add aminotrimethylenephosphonic acid (ATMP), liquid polyethylene glycol (PEG400), and tartaric acid sequentially to the reaction solution c in a ratio of 32 parts by weight: 0.5 parts by weight: 0.5 parts by weight: 1 part by weight. Then maintain the system temperature at 35°C and stir for 1.5 hours (stirring rate at 800 r / min). After completion, adjust the pH of the system to 6 with 5 wt.% sodium hydroxide solution, stir for 15 minutes, cool to room temperature, and finally filter through a 5 μm filter membrane to remove solid impurities in the reaction solution, thus obtaining the anti-cracking and anti-dispersing agent, such as... Figure 2 As shown.

[0045] Performance testing: The crack-resistant and anti-dispersing agent prepared in this embodiment was added to the concrete material (the same as in Example 1 above), at a dosage of 2% of the cement mass. Then, the various performance indicators of the concrete material obtained in this embodiment were tested using the same method as in Example 1 above, and the results are shown in Table 2 below.

[0046] Table 2 result 1.5% 490mm 96.2% 25.4% 310με 91.5% Example 3:A preparation process for a zirconium-silicon-aluminum polynuclear complex anti-cracking and anti-dispersing agent includes the following steps: (1) According to the ratio of sodium silicate to aluminum sulfate = 15 parts by weight: 32 parts by weight, 45 wt.% sodium silicate solution was added dropwise to 45 wt.% aluminum sulfate solution at a rate of 2 mL / min, while the mixture was sheared and stirred at a high speed of 2000 r / min for 45 min. During the dropwise addition, the system temperature was controlled not to exceed 30℃. After the addition was completed, reaction solution a was obtained.

[0047] (2) Concentrated sulfuric acid was added dropwise to the reaction solution a at a stirring rate of 500 r / min to adjust the pH of the system to 3.5. After completion, the mixture was heated to 45°C and kept at that temperature for 2 hours to obtain reaction solution b.

[0048] (3) Mix 4 parts by weight of zirconium sulfate and 1.2 parts by weight of zirconium oxychloride with 10 parts by weight of water, and sonicate for 15 min to obtain a modified solution. Then, according to the ratio of reaction solution b to modified solution = 28 parts by weight: 4.1 parts by weight, add the modified solution dropwise to reaction solution b at a rate of 0.5 mL / min while stirring at 800 r / min. Continue stirring for 1 hour, and maintain the temperature of the reaction system at 45 °C during the process. After completion, reaction solution c is obtained.

[0049] (4) In the reaction solution c, aminotrimethylenephosphonic acid (ATMP), liquid polyethylene glycol (PEG200), and tartaric acid were added sequentially in a ratio of 54 parts by weight: 1 part by weight: 2 parts by weight: 3 parts by weight. The system was then kept at 45°C and stirred for 1 hour (stirring rate 600 r / min). After completion, the pH of the system was adjusted to 5 with a 5 wt.% potassium hydroxide solution, stirred for 15 min, and then cooled to room temperature. Finally, the reaction solution was filtered through a 5 μm filter membrane to remove solid impurities, thus obtaining the anti-cracking and anti-dispersing agent, such as... Figure 3 As shown.

[0050] Performance testing: The crack-resistant and anti-dispersing agent prepared in this embodiment was added to the concrete material (the same as in Example 1 above), at a dosage of 3% of the cement mass. Then, the various performance indicators of the concrete material obtained in this embodiment were tested using the same method as in Example 1 above, and the results are shown in Table 3 below.

[0051] Table 3 result 1.8% 535mm 95.4% 33.1% 327με 89.2% Example 4: A preparation process for a zirconium-silicon-aluminum polynuclear complex anti-cracking and anti-dispersing agent includes the following steps: (1) According to the ratio of sodium silicate to aluminum sulfate = 12 parts by weight: 25 parts by weight, 45 wt.% sodium silicate solution was added dropwise to 45 wt.% aluminum sulfate solution at a rate of 1.5 mL / min, while simultaneously shearing and stirring at a high speed of 1800 r / min for 40 min. During the dropwise addition, the system temperature was controlled not to exceed 30℃. After completion, reaction solution a was obtained.

[0052] (2) Concentrated sulfuric acid was added dropwise to the reaction solution a at a stirring rate of 500 r / min to adjust the pH of the system to 4. After completion, the mixture was heated to 40°C and kept at that temperature for 2.5 hours to obtain reaction solution b.

[0053] (3) Add 3 parts by weight of zirconium sulfate and 1 part by weight of zirconium oxychloride to 7.5 parts by weight of water, mix, and sonicate for 10 min to obtain a modified solution. Then, according to the ratio of reaction solution b to modified solution = 35 parts by weight: 6 parts by weight, add the modified solution dropwise to reaction solution b at a rate of 0.5 mL / min while stirring at 800 r / min, and continue stirring for 1 hour, while maintaining the temperature of the reaction system at 40 °C during the process. After completion, reaction solution c is obtained.

[0054] (4) Liquid polyethylene glycol (PEG400) and tartaric acid were added sequentially to the reaction solution c in a ratio of 45 parts by weight: 1.5 parts by weight: 2 parts by weight. The system was then kept at 40°C and stirred for 1 hour (stirring rate 600 r / min). After completion, the pH of the system was adjusted to 6 with 5 wt.% sodium hydroxide solution, stirred for 15 min, and then cooled to room temperature. Finally, the reaction solution was filtered through a 5 μm filter membrane to remove solid impurities, thus obtaining the anti-cracking and anti-dispersing agent. Figure 4 As shown.

[0055] Performance testing: The crack-resistant and anti-dispersing agent prepared in this embodiment was added to the concrete material (the same as in Example 1 above), at a dosage of 1.5% of the cement mass. Then, the various performance indicators of the concrete material obtained in this embodiment were tested using the same method as in Example 1 above, and the results are shown in Table 4 below.

[0056] Table 4 result 6.8% 410mm 78.8% 45.3% 620με 62.6% Example 5: A process for preparing a silicon-aluminum anti-cracking and anti-dispersion agent includes the following steps: (1) According to the ratio of sodium silicate to aluminum sulfate = 15 parts by weight: 32 parts by weight, 45 wt.% sodium silicate solution was added dropwise to 45 wt.% aluminum sulfate solution at a rate of 2 mL / min, while the mixture was sheared and stirred at a high speed of 2000 r / min for 45 min. During the dropwise addition, the system temperature was controlled not to exceed 30℃. After the addition was completed, reaction solution a was obtained.

[0057] (2) Concentrated sulfuric acid was added dropwise to the reaction solution a at a stirring rate of 500 r / min to adjust the pH of the system to 3.5. After completion, the mixture was heated to 45°C and kept at that temperature for 2 hours to obtain reaction solution b.

[0058] (3) In the reaction solution b, aminotrimethylenephosphonic acid (ATMP), liquid polyethylene glycol (PEG200), and tartaric acid were added sequentially in a ratio of 54 parts by weight: 1 part by weight: 2 parts by weight: 3 parts by weight. The system was then kept at 45°C and stirred for 1 hour (stirring rate 600 r / min). After completion, the pH of the system was adjusted to 5 with a 5 wt.% potassium hydroxide solution, stirred for 15 min, and then cooled to room temperature. Finally, the reaction solution was filtered through a 5 μm filter membrane to remove solid impurities, thus obtaining the anti-cracking and anti-dispersing agent, such as... Figure 5 As shown.

[0059] Performance testing: The crack-resistant and anti-dispersing agent prepared in this embodiment was added to the concrete material (the same as in Example 1 above), at a dosage of 3% of the cement mass. Then, the various performance indicators of the concrete material obtained in this embodiment were tested using the same method as in Example 1 above, and the results are shown in Table 5 below.

[0060] Table 5 result 6.2% 360mm 72.2% 46.9% 880με 52.8% Example 6: A process for preparing a silicon-aluminum anti-cracking and anti-dispersion agent includes the following steps: (1) According to the ratio of sodium silicate to aluminum sulfate = 12 parts by weight: 25 parts by weight, 45 wt.% sodium silicate solution was added dropwise to 45 wt.% aluminum sulfate solution at a rate of 1.5 mL / min, while simultaneously shearing and stirring at a high speed of 1800 r / min for 40 min. During the dropwise addition, the system temperature was controlled not to exceed 30℃. After completion, reaction solution a was obtained.

[0061] (2) Concentrated sulfuric acid was added dropwise to the reaction solution a at a stirring rate of 500 r / min to adjust the pH of the system to 4. After completion, the mixture was heated to 40°C and kept at that temperature for 2.5 hours to obtain reaction solution b, which was used as an anti-cracking and anti-dispersing agent. Figure 6 As shown.

[0062] Performance testing: The crack-resistant and anti-dispersing agent prepared in this embodiment was added to the concrete material (the same as in Example 1 above), at a dosage of 1.5% of the cement mass. Then, the various performance indicators of the concrete material obtained in this embodiment were tested using the same method as in Example 1 above, and the results are shown in Table 6 below.

[0063] Table 6 result 4.8% 410mm 81.3% 52.9% 650με 68.6% Example 7: A process for preparing a silicon-aluminum anti-cracking and anti-dispersing agent includes the following steps: A 45 wt.% sodium silicate solution is added dropwise to a 45 wt.% aluminum sulfate solution at a rate of 1 mL / min, according to a sodium silicate to aluminum sulfate ratio of 8 parts by weight: 18 parts by weight. Simultaneously, the mixture is high-speed sheared and stirred at a rate of 1500 r / min for 30 min. During the dropwise addition, the system temperature is controlled to not exceed 30°C. After completion, reaction solution a is obtained, which is used as the anti-cracking and anti-dispersing agent. Figure 7 As shown.

[0064] Performance testing: The crack-resistant and anti-dispersing agent prepared in this embodiment was added to the concrete material (the same as in Example 1 above), at a dosage of 2% of the cement mass. Then, the various performance indicators of the concrete material obtained in this embodiment were tested using the same method as in Example 1 above, and the results are shown in Table 7 below.

[0065] Table 7 result 5.9% 420mm 76.4% 65.6% 780με 61.7% The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A preparation process for a zirconium-silicon-aluminum polynuclear complex anti-cracking and anti-dispersing agent, characterized in that, Includes the following steps: (1) The silicate solution is added dropwise to the aluminum sulfate solution while shearing and stirring in the process, so that the silicate ions and aluminum ions undergo preliminary copolymerization by forming Al-O-Si bonds. After completion, reaction solution a is obtained. (2) Concentrated sulfuric acid was added dropwise to the reaction solution a under stirring conditions. After the reaction was completed, the reaction was heated to further polymerize the Al-O-Si bonds to form a network structure, thus obtaining reaction solution b. (3) Under stirring conditions, the modified solution formed by zirconium sulfate and zirconium oxychloride is added dropwise to the reaction solution b to carry out the reaction, and the reaction system is kept under heating and heat preservation during the process, so that Zr 4+ The ligands in the hydroxyl groups of the network structure undergo ligand exchange to form a "Zr-O-Al-O-Si" polynuclear complex structure, yielding reaction solution c; (4) In the reaction solution c, aminotrimethylene phosphonic acid, liquid polyethylene glycol, and tartaric acid are added sequentially and reacted under heating and stirring conditions, thereby utilizing the phosphonic acid group of the ATMP and the Zr in the polynuclear complex structure. 4+ Al 3+ A stable chelate ring is formed; then the pH of the reaction system is adjusted to obtain the composite crack-resistant agent.

2. The preparation process of the composite crack-resistant agent according to claim 1, characterized in that, In step (1), the ratio of silicate to aluminum sulfate is 8-15 parts by weight: 18-32 parts by weight.

3. The preparation process of the composite crack-resistant agent according to claim 1, characterized in that, In step (1), the silicate includes at least one of sodium silicate and potassium silicate; Optionally, in step (1), the dropping rate is 1~2 mL / min; Optionally, in step (1), the shearing and stirring rate is 1500~2000 r / min and the time is 30~45 min.

4. The preparation process of the composite crack-resistant agent according to claim 1, characterized in that, In step (2), concentrated sulfuric acid is added to adjust the pH of the system to 3.5-4.5; optionally, in step (2), the heating temperature is 35-45°C and the reaction time is 2-3 hours.

5. The preparation process of the composite crack-resistant agent according to claim 1, characterized in that, In step (3), the modification solution is formed by zirconium sulfate, zirconium oxychloride and water in a ratio of 2.5-4 parts by weight: 0.8-1.2 parts by weight: 5-10 parts by weight.

6. The preparation process of the composite crack-resistant agent according to claim 1, characterized in that, In step (3), the ratio of reaction solution b to modification solution is 28~46 parts by weight: 4.1~7.6 parts by weight.

7. The preparation process of the composite crack-resistant agent according to claim 1, characterized in that, In step (3), the heating and heat preservation temperature is 35~45℃, and the reaction time is 1~1.5 hours; optionally, the dropping rate of the modification solution is 0.5~0.8mL / min; and the stirring rate is 800~1000r / min.

8. The preparation process of the composite crack-resistant agent according to claim 1, characterized in that, In step (4), the ratio of reaction solution c, aminotrimethylenephosphonic acid, liquid polyethylene glycol, and tartaric acid is 32~54 parts by weight: 0.5~1.0 parts by weight: 0.5~2 parts by weight: 1~3 parts by weight; Optionally, in step (4), the heating temperature is 35~45℃ and the reaction time is 1~1.5 hours; Optionally, in step (4), the stirring rate is 600~800 r / min.

9. The preparation process of the composite crack-resistant agent according to any one of claims 1-8, characterized in that, In step (4), the pH of the reaction system is adjusted to 5-6; optionally, at least one of sodium hydroxide, potassium hydroxide, ammonia, and sodium carbonate is used to adjust the pH.

10. The zirconium-silicon-aluminum polynuclear complex anti-cracking and anti-dispersing agent obtained by the preparation process according to any one of claims 1-9 is used in underwater non-dispersible concrete; optionally, the dosage of the anti-cracking agent is 1.5 to 3% of the mass of cement component in the concrete.

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