CN-121976418-A - Low-temperature energy-saving zirconium potassium carbonate water repellent agent and preparation method thereof

CN121976418ACN 121976418 ACN121976418 ACN 121976418ACN-121976418-A

Abstract

The invention discloses a low-temperature energy-saving zirconium potassium carbonate water-repellent agent and a preparation method thereof, belonging to the technical field of inorganic water-repellent agents, the water-repellent agent is a water-based composite solution, the active ingredients of the catalyst are prepared by reacting zirconium compounds, organic hydroxy carboxylic acid modifier, alkali metal hydroxide, carbonate donor, nano zirconia sol and low-temperature reaction accelerator. The preparation method mainly comprises the steps of preparation of an organic zirconium complex precursor solution, alkalization and carbonation reaction, nano-composite and synergy and curing post-treatment. The water repellent agent obviously reduces the reaction activation energy through an organic-inorganic composite modification technology, so that the water repellent agent can realize excellent water repellent effect at a lower temperature, and simultaneously keeps good storage stability and application adaptability.

Inventors

Luo Dezhen
FANG CHANGJIN
GUO MENGYAO

Assignees

山东根源精细化工股份有限公司

Dates

Publication Date: 20260505
Application Date: 20260204

Claims (8)

1. The low-temperature energy-saving zirconium potassium carbonate water repellent is characterized by being a water-based composite solution containing an organic ligand modified zirconium complex, nano zirconia sol and a low-temperature reaction promoter, wherein the active ingredients of the water-based composite solution are prepared by reacting the following raw materials in percentage by mass: 8% -15% of zirconium compound in terms of ZrO 2 ; 3% -10% of organic hydroxy carboxylic acid modifier calculated by citric acid; 12% -20% of alkali metal hydroxide in terms of KOH; 5% -10% of carbonate donor in terms of CO 3 2 ; 0.5% -3% of nano zirconia sol calculated by ZrO 2 ; 0.1% -2% of low-temperature reaction accelerator; The balance of deionized water.
2. The low-temperature energy-saving zirconium potassium carbonate water repellent agent according to claim 1, wherein the zirconium compound is zirconium oxychloride or zirconyl nitrate.
3. The low-temperature energy-saving zirconium potassium carbonate water repellent agent according to claim 1, wherein the organic hydroxycarboxylic acid modifier is one or more selected from the group consisting of citric acid, tartaric acid and glycolic acid.
4. The low-temperature energy-saving zirconium potassium carbonate water repellent agent according to claim 1, wherein the alkali metal hydroxide is potassium hydroxide.
5. The low-temperature energy-saving zirconium potassium carbonate water repellent agent according to claim 1, wherein the carbonate donor is potassium carbonate or introduced carbon dioxide gas.
6. The low-temperature energy-saving zirconium potassium carbonate water repellent agent according to claim 1, wherein the average particle size of the nano zirconia sol is 5-50 nm.
7. The low-temperature energy-saving zirconium potassium carbonate water repellent agent according to claim 1, wherein the low-temperature reaction promoter is one or more selected from choline chloride, tetramethyl ammonium chloride and triethanolamine.
8. A method for preparing the low-temperature energy-saving zirconium potassium carbonate water repellent agent according to any one of claims 1 to 7, comprising the following steps: firstly, preparing an organic precursor solution, namely adding metered deionized water and an organic hydroxy carboxylic acid modifier into a reaction kettle, stirring and dissolving, slowly adding a zirconium compound solution at 40-60 ℃, and reacting for 1-2 hours under the condition of heat preservation and stirring to form a clear organic zirconium complex precursor solution. Step two, alkalizing and carbonating, namely cooling the reaction system to below 30 ℃, slowly adding a metered potassium hydroxide solution under strong stirring, controlling the adding speed to ensure that the system temperature is not more than 40 ℃, continuously stirring for 0.5 hour at 30-40 ℃ after adding, slowly adding potassium carbonate solid or introducing carbon dioxide gas to carry out carbonating reaction, and finally controlling the pH value to be stable between 10.5 and 12.0 to obtain the basic zirconium potassium carbonate modified liquid. Step three, nano-compounding and synergy, namely slowly adding metered nano zirconia sol into the base solution obtained in the step two under stirring, continuously stirring for 1 hour after adding, uniformly mixing, adding metered low-temperature reaction promoter, and uniformly stirring. Curing and post-treatment, namely curing the mixed solution obtained in the step three at a constant temperature of 50-60 ℃ for 4-8 hours; And after curing, cooling to room temperature, and filtering to remove a small amount of insoluble substances possibly existing, thus obtaining the low-temperature solidified zirconium potassium carbonate water repellent agent finished product.

Description

Low-temperature energy-saving zirconium potassium carbonate water repellent agent and preparation method thereof Technical Field The invention relates to the field of inorganic water-repellent agent processing, in particular to a low-temperature energy-saving zirconium potassium carbonate water-repellent agent and a preparation method thereof. Background The zirconium potassium carbonate is used as a high-efficiency formaldehyde-free water repellent agent and is widely applied to water-resistant finishing of cellulose materials such as chemical textile processing, and the action mechanism is that active zirconium species and hydroxyl on the surface of the material undergo a crosslinking reaction to form a hydrophobic network. However, conventional potassium zirconium carbonate water-repellent agents suffer from the following disadvantages: Most potassium zirconium carbonate water-repellent agents require higher curing temperatures (typically ≡120 ℃) to achieve complete, rapid crosslinking reactions, which can easily lead to increased energy consumption, increased production costs and increased carbon emissions in the production process. The high temperature environment limits its application to heat sensitive substrates such as certain specialty papers, chemical fiber containing fabrics. In addition, for a production line with limited partial drying capacity, the water-resistant performance of the production line cannot be fully exerted. In order to solve the problems, the conventional catalyst is usually added or simply compounded with other auxiliary agents, but the problems of insignificant effect, influence on the storage stability of the product, poor water resistance and durability and the like are often caused. Therefore, the zirconium potassium carbonate water repellent agent which can be efficiently solidified at medium and low temperature, has stable performance and is easy to produce is developed, and has important industrial value and environmental protection significance. Disclosure of Invention The invention aims to overcome the defects of the prior art, and provides a low-temperature energy-saving zirconium potassium carbonate water-repellent agent and a preparation method thereof, wherein the water-repellent agent adopts an organic-inorganic composite modification technology, the reaction activation energy is obviously reduced, so that the water-resistant effect can be realized at a lower temperature, and meanwhile, the good storage stability and application adaptability are maintained. The low-temperature energy-saving zirconium potassium carbonate water repellent agent provided by the invention comprises an organic ligand modified zirconium complex, nano zirconia sol and a water-based composite solution of catalytic components, wherein the active ingredients of the water-based composite solution are prepared by reacting the following raw materials in percentage by mass: Zirconium compound (calculated by ZrO 2) 8-15%; 3% -10% of organic hydroxy carboxylic acid modifier (calculated by citric acid); 12% -20% of alkali metal hydroxide (calculated by KOH); 5% -10% of carbonate radical donor (calculated by CO 32); 0.5% -3% of nano zirconia sol (calculated by ZrO 2); 0.1% -2% of low-temperature reaction accelerator; The balance of deionized water. Preferably, the zirconium compound is zirconium oxychloride or zirconyl nitrate. Preferably, the organic hydroxycarboxylic acid modifier is selected from one or more of citric acid, tartaric acid, glycolic acid, preferably citric acid. Preferably, the alkali metal hydroxide is potassium hydroxide. Preferably, the carbonate donor is potassium carbonate or carbon dioxide gas introduced. Preferably, the average particle size of the nano zirconia sol is 5-50 nm. Preferably, the low-temperature reaction promoter is one or more selected from choline chloride, tetramethyl ammonium chloride and triethanolamine. The invention also provides a preparation method of the low-temperature energy-saving zirconium potassium carbonate water repellent agent, which comprises the following steps: Step one, preparing an organic precursor solution: adding metered deionized water and an organic hydroxy carboxylic acid modifier into a reaction kettle, stirring and dissolving; slowly adding the zirconium compound solution at 40-60 ℃, and reacting for 1-2 hours under heat preservation and stirring to form a clear organic zirconium complex precursor solution. Step two, alkalization and carbonation: cooling the reaction system to below 30 ℃, slowly adding a metered potassium hydroxide solution under strong stirring, and controlling the adding speed to ensure that the temperature of the system is not more than 40 ℃; after the addition is finished, stirring is continued for 0.5 hour at the temperature of 30-40 ℃; Slowly adding potassium carbonate solid or introducing carbon dioxide gas to carry out carbonation reaction, and controlling the pH value to be finally stabilized between 10