Low-temperature energy-saving potassium zirconium carbonate water repellent agent and preparation method thereof

Abstract

The invention discloses a low-temperature energy-saving type potassium zirconium carbonate water repellent agent and a preparation method thereof, and belongs to the technical field of inorganic water repellent agents. Effective components of the zirconium-based composite material are prepared from a zirconium compound, an organic hydroxy carboxylic acid modifier, alkali metal hydroxide, a carbonate donor, nano zirconium oxide sol and a low-temperature reaction accelerant through reaction. The preparation method mainly comprises the steps of preparation of an organic zirconium complex precursor solution, alkalization and carbonation reaction, nano compounding and synergism, and curing post-treatment. According to the water-resistant agent, through an organic-inorganic composite modification technology, reaction activation energy is remarkably reduced, so that the water-resistant agent can achieve an excellent water-resistant effect at a lower temperature, and meanwhile, good storage stability and application adaptability are kept.

Description

Technical Field

[0001] This invention relates to the field of inorganic water-resistant agent processing, specifically to a low-temperature energy-saving potassium zirconium carbonate water-resistant agent and its preparation method. Background Technology

[0002] Potassium zirconium carbonate, as a highly efficient formaldehyde-free water-repellent agent, is widely used in water-repellent finishing of cellulose materials such as chemical textiles. Its mechanism of action is that active zirconium species undergo a cross-linking reaction with the hydroxyl groups on the material surface to form a hydrophobic network.

[0003] However, traditional potassium zirconium carbonate water-resistant agents have the following drawbacks: Most potassium zirconium carbonate water-resistant agents require high curing temperatures (usually ≥120℃) to achieve a complete and rapid cross-linking reaction, which can easily lead to increased energy consumption, higher production costs, and increased carbon emissions during the production process.

[0004] High-temperature environments limit its application on heat-sensitive substrates (such as certain specialty papers and fabrics containing synthetic fibers). In addition, its water-resistant performance cannot be fully utilized on some production lines with limited drying capacity.

[0005] To solve the above problems, common methods include adding conventional catalysts or simply compounding with other additives. However, these methods often have problems such as insignificant effects, affecting product storage stability, or poor water resistance and durability.

[0006] Therefore, developing a potassium zirconium carbonate water-resistant agent that can be efficiently cured at medium and low temperatures, has stable performance, and is easy to produce has important industrial value and environmental significance. Summary of the Invention

[0007] The present invention aims to overcome the shortcomings of the prior art and provide a low-temperature energy-saving potassium zirconium carbonate water-resistant agent and its preparation method. This water-resistant agent significantly reduces the reaction activation energy through organic-inorganic composite modification technology, so that it can achieve excellent water-resistant effect at a lower temperature, while maintaining good storage stability and application adaptability.

[0008] The technical solution of this invention is as follows: This invention proposes a low-temperature energy-saving potassium zirconium carbonate water-resistant agent, comprising an organic ligand-modified zirconium complex, nano-zirconia sol, and a water-based composite solution of a catalytic component; its effective components are prepared by reacting the following raw materials in the following mass percentages: Zirconium compounds (based on ZrO2): 8%~15%; Organic hydroxycarboxylic acid modifier (based on citric acid): 3%~10%; Alkali metal hydroxides (calculated as KOH): 12%~20%; carbonate donor (in the form of CO3) 2 (Calculated): 5%~10%; Nano-zirconia sol (based on ZrO2): 0.5%~3%; Low-temperature reaction accelerator: 0.1%~2%; The remainder is deionized water.

[0009] Preferably, the zirconium compound is zirconium oxychloride or zirconium oxynitrate.

[0010] Preferably, the organic hydroxycarboxylic acid modifier is selected from one or more of citric acid, tartaric acid, and glycolic acid, with citric acid being the most preferred.

[0011] Preferably, the alkali metal hydroxide is potassium hydroxide.

[0012] Preferably, the carbonate donor is potassium carbonate or carbon dioxide gas.

[0013] Preferably, the average particle size of the nano-zirconia sol is 5-50 nm.

[0014] Preferably, the low-temperature reaction promoter is one or more selected from choline chloride, tetramethylammonium chloride, and triethanolamine.

[0015] The present invention also provides a method for preparing the aforementioned low-temperature energy-saving potassium zirconium carbonate water-resistant agent, comprising the following steps: Step 1: Preparation of the organic precursor solution: Add measured amounts of deionized water and organic hydroxycarboxylic acid modifier to the reaction vessel and stir to dissolve; At 40-60℃, a zirconium compound solution is slowly added, and the mixture is kept warm and stirred for 1-2 hours to form a clear organozirconium complex precursor solution.

[0016] Step 2, Alkalization and Carbonation: Cool the reaction system to below 30°C, and slowly add a measured amount of potassium hydroxide solution under strong stirring, controlling the addition rate to keep the system temperature below 40°C. After adding the ingredients, continue stirring at 30-40℃ for 0.5 hours. Slowly add solid potassium carbonate or introduce carbon dioxide gas to carry out the carbonation reaction, and control the pH value to eventually stabilize between 10.5 and 12.0 to obtain the basic potassium zirconium carbonate modified solution.

[0017] Step 3: Nanocompositing and Enhancement Add the measured amount of nano-zirconia sol slowly to the base solution obtained in step two while stirring. After the addition is complete, continue stirring for 1 hour to ensure that the mixture is homogeneous. Add the measured amount of low-temperature reaction accelerator and stir until homogeneous.

[0018] Step 4: Aging and Post-processing: The mixture obtained in step 3 is aged at a constant temperature of 50-60℃ for 4-8 hours; After the curing process is completed, the mixture is cooled to room temperature and filtered to remove any possible small amounts of insoluble matter, thus obtaining the finished low-temperature energy-saving potassium zirconium carbonate water-resistant agent.

[0019] The beneficial effects achieved by the present invention using the above technical solution are as follows: The product of this invention significantly reduces the energy required for cross-linking reactions through the modification of zirconium active centers by organic ligands, the synergistic effect of nano-zirconia sol, and the catalysis of a special promoter. The organic-inorganic composite system constructs a denser and more uniform hydrophobic cross-linked network on and inside the fiber surface. Its water resistance (measured by Cobb value) can reach or exceed the level of traditional products after high-temperature treatment under low-temperature curing conditions, and its hot water washing resistance is better. The product can be stored stably at room temperature without stratification or precipitation. Its application process is similar to that of ordinary potassium zirconium carbonate, making it highly versatile and suitable for temperature-sensitive substrates. The production process emits no toxic or harmful substances, and the product itself does not contain formaldehyde, APEO, or other restricted substances, resulting in significant overall energy-saving and consumption-reducing effects. Attached Figure Description

[0020] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings: Figure 1 This is a schematic diagram of the preparation method of the present invention; Figure 2 This is a schematic diagram showing the percentage composition of the raw materials in this invention; Figure 3 This is a schematic diagram of the process steps and parameters of the present invention. Detailed Implementation

[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0022] It should be noted that the terms “front,” “back,” “left,” “right,” “up,” and “down” used in the following description refer to the directions shown in the attached diagram, while the terms “inside” and “outside” refer to the directions toward or away from the geometric center of a specific component, respectively.

[0023] like Figure 1 — Figure 3As shown, the present invention proposes a low-temperature energy-saving potassium zirconium carbonate water-resistant agent, comprising an organic ligand-modified zirconium complex, nano-zirconia sol, and a water-based composite solution of a catalytic component; its active ingredient is prepared by reacting the following raw materials in the following mass percentages: Zirconium compounds (based on ZrO2): 8%~15%; Organic hydroxycarboxylic acid modifiers (based on citric acid): 3%~10%; Alkali metal hydroxides (as KOH): 12%~20%; carbonate donors (as CO3) 2 5%~10% (calculated as ZrO2); 0.5%~3% (calculated as ZrO2); 0.1%~2% (low-temperature reaction promoter); balance: deionized water.

[0024] Example 1 1. Preparation of organic precursor solutions In a 500 mL four-necked flask equipped with a stirrer, thermometer and condenser, add 200 g of deionized water and 20 g of citric acid, stir to dissolve, and heat to 50 °C. A solution prepared by dissolving 100 g of zirconium oxychloride octahydrate (ZrOCl2·8H2O, with a content of approximately 35% based on ZrO2) in 50 g of deionized water was slowly added dropwise over a period of approximately 1 hour. After the addition was complete, the mixture was kept at 50°C and stirred for 1.5 hours to obtain a clear organic zirconium complex precursor solution.

[0025] 2. Alkalization and Carbonation Cool solution A to below 30°C, and while stirring, slowly add a solution prepared by dissolving 56 g of potassium hydroxide in 50 g of deionized water, controlling the system temperature to not exceed 35°C; After the addition is complete, continue stirring at 35°C for 0.5 hours; Add 28 g of anhydrous potassium carbonate solid in batches, controlling the addition rate to mitigate gas release; After the addition is complete, continue stirring until the pH of the system stabilizes at approximately 11.5, thus obtaining the basic potassium zirconium carbonate modified solution.

[0026] 3. Nanocomposites and Enhancement Add 5 g of nano-zirconia sol with an average particle size of about 20 nm (solid content of 20%, equivalent to 1 g of ZrO2) to the above base solution and stir for 1 hour to disperse it evenly. Then add 2 g of choline chloride and stir to mix evenly.

[0027] 4. Aging and Post-processing Transfer the mixture to a constant temperature oven and mature at 55°C for 6 hours; After maturation, the product was cooled to room temperature and filtered through a 300-mesh filter cloth to obtain a pale yellow transparent liquid product. The product's solid content was measured to be approximately 25%, and its pH value was 11.3.

[0028] Example 2 The preparation steps in this embodiment are basically the same as those in Example 1, with the only difference being: The organic hydroxycarboxylic acid modifier was replaced with an equimolar amount of tartaric acid; The amount of nano-zirconia sol added was adjusted to 2.5 g (solid content 20%, equivalent to 0.5 g of ZrO2); The low-temperature reaction promoter was changed to 1 g of tetramethylammonium chloride.

[0029] The final product is similar in appearance and properties.

[0030] Ordinary potassium zirconium carbonate water-resistant agent was prepared using a conventional method: zirconium oxychloride solution was reacted with potassium hydroxide solution, followed by direct carbon dioxide gas introduction for carbonation until the pH reached approximately 11. After aging, the product was obtained. This product does not contain organic hydroxycarboxylic acid modifiers, nano-zirconia sol, or low-temperature reaction accelerators.

[0031] Application effect test The products obtained in Examples 1 and 2, as well as the comparative product, were added to the pulp at an oven-dry addition rate of 1.0% (calculated as ZrO2), with a papermaking basis of 80 g / m³. 2 The paper sheets were placed in ovens at 105℃, 120℃, and 135℃ respectively to simulate drying for 1 minute, and their surface Cobb value (60 s, water) was tested. The results are shown in the table below:

[0032] Test Result Analysis: As shown in the table above, under low-temperature treatment at 105℃, the Cobb value of the products of this invention (Examples 1 and 2) has decreased to 20 g / m³. 2 The following demonstrates excellent immediate water resistance, while the Cobb value of the conventional comparative product is as high as 45.6 g / m³. 2 The water resistance was poor. The comparative product required treatment at 135℃ to achieve a water resistance level close to that of the product of this invention at 105℃ (19.0 vs 18.5). This fully demonstrates that this invention, through formulation and process modification, achieves a significant reduction in the curing temperature of the water-resistant agent, resulting in significant energy-saving advantages.

[0033] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, material, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, material, or apparatus.

[0034] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A low-temperature energy-saving potassium zirconium carbonate water-resistant agent, characterized in that, It is an aqueous composite solution containing organic ligand-modified zirconium complex, nano-zirconia sol, and a low-temperature reaction promoter; its active ingredients are prepared by reacting the following raw materials in the following mass percentages: Zirconium compounds, calculated as ZrO2: 8%~15%; Organic hydroxycarboxylic acid modifier, calculated as citric acid: 3%~10%; Alkali metal hydroxides, calculated as KOH: 12%~20%; carbonate donor, with CO3 2 Total: 5%~10%; Nano-zirconia sol, calculated as ZrO2: 0.5%~3%; Low-temperature reaction accelerator: 0.1%~2%; The remainder is deionized water.

2. The low-temperature energy-saving potassium zirconium carbonate water-resistant agent according to claim 1, characterized in that: The zirconium compound is zirconium oxychloride or zirconium oxynitrate.

3. The low-temperature energy-saving potassium zirconium carbonate water-resistant agent according to claim 1, characterized in that: The organic hydroxycarboxylic acid modifier is selected from one or more of citric acid, tartaric acid, and glycolic acid.

4. The low-temperature energy-saving potassium zirconium carbonate water-resistant agent according to claim 1, characterized in that: The alkali metal hydroxide is potassium hydroxide.

5. The low-temperature energy-saving potassium zirconium carbonate water-resistant agent according to claim 1, characterized in that: The carbonate donor is potassium carbonate or carbon dioxide gas.

6. The low-temperature energy-saving potassium zirconium carbonate water-resistant agent according to claim 1, characterized in that: The average particle size of the nano-zirconia sol is 5-50 nm.

7. The low-temperature energy-saving potassium zirconium carbonate water-resistant agent according to claim 1, characterized in that: The low-temperature reaction promoter is selected from one or more of choline chloride, tetramethylammonium chloride, and triethanolamine.

8. A method for preparing a low-temperature energy-saving potassium zirconium carbonate water-resistant agent according to any one of claims 1-7, characterized in that, Includes the following steps: Step 1: Preparation of organic precursor solution: Add measured amounts of deionized water and organic hydroxycarboxylic acid modifier to the reaction vessel and stir to dissolve; At 40-60℃, a zirconium compound solution is slowly added, and the mixture is kept warm and stirred for 1-2 hours to form a clear organozirconium complex precursor solution. Step 2, Alkalization and Carbonation: Cool the reaction system to below 30°C, and slowly add a measured amount of potassium hydroxide solution under vigorous stirring, controlling the addition rate so that the system temperature does not exceed 40°C; after the addition is complete, continue stirring at 30-40°C for 0.5 hours; slowly add solid potassium carbonate or introduce carbon dioxide gas to carry out the carbonation reaction, controlling the pH value to eventually stabilize between 10.5-12.0, to obtain the basic potassium zirconium carbonate modified solution. Step 3, Nanocomposite and Enhancement: Slowly add the measured amount of nano-zirconia sol to the base solution obtained in Step 2 while stirring. After the addition is complete, continue stirring for 1 hour to ensure uniform mixing. Add the measured amount of low-temperature reaction promoter and stir until uniform. Step 4, Aging and Post-treatment: Aging the mixture obtained in Step 3 at a constant temperature of 50-60℃ for 4-8 hours; After curing, the mixture is cooled to room temperature and filtered to remove any possible small amount of insoluble matter, thus obtaining the low-temperature curing potassium zirconium carbonate water-resistant agent product.

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