An oleophilic hydrophobic modified fabric material and its preparation method and application

Abstract

The application provides an oleophilic and hydrophobic modified fabric material and a preparation method and application thereof, and the preparation method comprises the following steps: (1) mixing; (2) standing; and (3) drying. The method comprises the following steps: a mixed solution is prepared by using a solution containing ferrous ions and a lauryl gallate solution, then a fabric is immersed into the mixed solution of the two to be treated, and the fabric is dried at a constant temperature to obtain an oleophilic and hydrophobic modified fabric material capable of separating oil and water. The hydrophobic performance of the oleophilic and hydrophobic modified fabric material prepared by using the method is significantly improved, the self-cleaning performance is realized, the fabric material can be used for oil-water separation, the added value of the fabric is improved, the fabric material can maintain good stability in an extreme environment, has good practical performance, and provides technical support for simply and greenly preparing a fabric with oil-water separation performance.

Description

Technical Field

[0001] This invention relates to the field of hydrophobic modification of fabrics, specifically to an oleophilic-hydrophobic modified fabric material, its preparation method, and its application. Background Technology

[0002] Fabrics are composed of hydrophilic fibers, making them highly susceptible to adhering to and absorbing various pollutants and liquids. With the diversification of functional products, fabrics are increasingly being developed into functional products, such as flame-retardant, hydrophobic, and flexible conductive fabrics. Among these, hydrophobic textiles have wide applications in medical protective equipment, oil-water separation, and outdoor clothing, and have become a research hotspot in functional textiles in recent years.

[0003] However, the preparation of hydrophobic fabrics is currently limited to the laboratory, and many practical problems still need to be solved before they can be truly applied and widely used. Low surface energy materials are essential raw materials for preparing hydrophobic surfaces, but the currently used fluorinated compounds or organosilanes are expensive and pose serious environmental problems, becoming a major factor hindering the development of functionalized fabrics. Durable hydrophobic textiles have not yet been realized, which also limits the application of superhydrophobic textiles in many situations.

[0004] In recent years, the modification of phenolic compounds with metal ions has been found to be an effective and green approach for preparing hydrophobic modified fabrics. This method can develop hydrophobic modified fabrics with ideal oil-water separation properties, and the preparation process is simple, stable, and exhibits good self-cleaning properties and oil-water separation effects. However, the structures of phenolic compounds vary greatly; differences in molecular weight, functional group content, and type directly affect their chelation effect with metal ions, thus influencing the construction and formation of the rough surface structure of the modified fabric. Current research mainly focuses on the chelation of catechol-containing phenolic acid compounds with ferrous ions, which still requires the use of laccase for self-polymerization or self-polymerization in an alkaline system with the addition of alkylamines. Inventing a superhydrophobic system that enriches the chelation of phenolic compounds with metal ions without the need for other substances is of great significance to the field of hydrophobic modification of fabrics. Summary of the Invention

[0005] To address the aforementioned shortcomings of existing technologies, this invention provides an oleophilic-hydrophobic modified fabric material, its preparation method, and its application. The process of this invention is simple, the parameters are easy to control, and it does not require the use of other substances for self-polymerization. The oleophilic-hydrophobic fabric prepared has excellent oil-water separation function and can maintain good stability under extreme environments.

[0006] This invention is achieved through the following technical solution:

[0007] A method for preparing an oleophilic and hydrophobic modified fabric material includes the following steps:

[0008] (1) Mixing: Mix gallic acid lauryl ester solution with solution containing ferrous ions to obtain co-solution system;

[0009] (2) Let stand: Place the fabric in the co-solution system obtained in step (1) and let it stand;

[0010] (3) Drying: The fabric treated in step (2) is dried at a constant temperature to obtain oleophilic and hydrophobic modified fabric material.

[0011] The beneficial effects of adopting the above technical solution are as follows:

[0012] The phenolic hydroxyl groups in gallic acid lauryl ester chelate with ferrous ions, which can increase the roughness of the fabric surface and thus increase its hydrophobic properties.

[0013] Further, in step (1), the solution containing ferrous ions is a ferrous sulfate solution, and the concentration of lauryl gallate in the co-solution system is 0.1-4 g / L, the concentration of ferrous ions is 0.1-12 g / L, preferably the concentration of lauryl gallate is 2 g / L, and the concentration of ferrous ions is 3 g / L.

[0014] The beneficial effects of adopting the above-mentioned further technical solutions are as follows:

[0015] By configuring a co-solution system with the optimal concentration, the phenolic hydroxyl groups in gallic acid lauryl ester can be chelated with ferrous ions as much as possible, thereby maximizing the oleophilic and hydrophobic properties of the fabric.

[0016] Furthermore, in step (2), the settling temperature is 35-42°C, preferably 40°C, and the settling time is 22-26 hours, preferably 24 hours.

[0017] Furthermore, in step (2), the fabric is turned over every 3.5 to 4.5 hours, preferably 4 hours.

[0018] The beneficial effects of adopting the above-mentioned further technical solutions are as follows:

[0019] The fabric is placed in a co-solution system at a certain temperature and turned over during the process to ensure thorough and uniform deposition, so that the fabric surface can uniformly acquire oleophilic and hydrophobic properties.

[0020] Furthermore, in step (3), the drying temperature is 38-45°C, preferably 45°C, and the drying time is 4-7 hours, preferably 6 hours.

[0021] The oleophilic and hydrophobic modified fabric material was prepared using the above method.

[0022] The above-mentioned oleophilic and hydrophobic modified fabric materials are used in the preparation of medical or outdoor clothing.

[0023] The above-mentioned oleophilic and hydrophobic modified fabric materials are used in oil-water separation.

[0024] In summary, the beneficial effects of adopting the technical solution of this invention are as follows:

[0025] In this invention, the phenolic hydroxyl groups in lauryl gallate chelate chelate with ferrous ions, increasing the surface roughness of the fabric. Furthermore, lauryl gallate contains a long 12-carbon chain, a hydrophobic structure. In addition to increasing surface roughness, the introduction of long-chain hydrophobic groups reduces the surface energy of the fabric. The pretreated fabric is immersed in a co-solution system obtained by mixing a lauryl gallate solution with a solution containing ferrous ions, allowing for thorough and uniform deposition to prepare an oleophilic-hydrophobic modified fabric material. The hydrophobic properties of the fabric are significantly improved, achieving self-cleaning and oil-water separation capabilities. Moreover, the prepared oleophilic-hydrophobic cotton fabric material maintains strong stability even in extreme environments. The preparation process is simple, requiring no laccase or alkylamines and avoiding the use of fluorine-containing and environmentally polluting substances, making it highly practical. The final drying process, using constant temperature drying, reduces operating costs compared to vacuum drying. This invention can be applied to various fields, and the lauryl gallate used is a phenolic compound without a carboxyl group, broadening the application range and fields of phenolic compounds. Attached Figure Description

[0026] Figure 1 This is a diagram of an oil-water separation operating device.

[0027] Figure 2 The figure shows the effect of the number of separations on the separation efficiency of the oleophilic and hydrophobic modified fabric material.

[0028] Figure 3 The diagram shows the self-cleaning properties of (a) oleophilic and hydrophobic modified fabric materials and (b) the original fabric treated with Congo red aqueous solution.

[0029] Figure 4 The diagram shows the self-cleaning properties of (a) oleophilic and hydrophobic modified fabric materials and (b) original fabrics treated with Congo red powder.

[0030] Figure 5 The image shows the hydrophobic effect of oleophilic and hydrophobic modified fabric materials on water, milk, coffee, and vinegar. Detailed Implementation

[0031] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0032] Example 1

[0033] (1) Washing: Wash the round polyester fibers with a diameter of 7cm in sequence with deionized water, anhydrous ethanol, acetone and deionized water for 5 minutes, take them out and dry them at 45℃ for later use.

[0034] (2) Mixing: Weigh 0.1g of lauryl gallate and dissolve it in 20mL of anhydrous ethanol to prepare lauryl gallate ethanol solution; weigh 0g, 0.15g, 0.30g, 0.45g and 0.60g of ferrous sulfate heptahydrate and dissolve them in 10mL of deionized water to prepare ferrous sulfate aqueous solution; mix the five groups of lauryl gallate ethanol solutions of the same concentration with the ferrous sulfate aqueous solution of different concentrations thoroughly, and then make up to 50mL with deionized water to obtain five co-solution systems with lauryl gallate concentration of 2g / L and ferrous ion concentrations of 0 / L, 3g / L, 6g / L, 9g / L and 12g / L respectively;

[0035] (3) Standing: Place the polyester treated in step (1) into a petri dish, pour in the co-solution system prepared in step (2), place it on a magnetic stirrer and stand at 40°C for 24 hours, and turn the fabric over every 4 hours.

[0036] (4) Drying: Place the fabric treated in step (3) in a 45°C oven and dry for 6 hours;

[0037] (5) The water contact angle of the oleophilic and hydrophobic modified fabric material was tested using an optical contact angle meter. 5 μL of water was dropped onto the test sample surface using a syringe. The contact angle was measured at 0 s, 10 min, 20 min and 30 min after the drop was added. The average value of the three tests was taken as the test result. The results are shown in Table 1.

[0038] Table 1 Fe 2+ Effect of concentration on the water contact angle CA (°) of oleophilic-hydrophobic modified fabric materials

[0039]

[0040] Note: The original fabric contact angle was 71.6°, and the water droplet residence time on the fabric was less than 2 seconds. The lauryl gallate concentration was 2 g / L. The "\" indicates that the contact angle value was too small to be measured.

[0041] Table 1 shows that, with a fixed concentration of 2 g / L, the original fabric exhibited good hydrophobicity after modification, with a maximum contact angle of 150.4°, and the droplets could remain stationary for a certain period, resulting in a significant increase in the dynamic contact angle. When Fe... 2+ The modified fabric exhibits the best hydrophobic effect at a concentration of 3 g / L.

[0042] Example 2

[0043] (1) Washing: Wash the round polyester fibers with a diameter of 7cm in sequence with deionized water, anhydrous ethanol, acetone and deionized water for 5 minutes, take them out and dry them at 45℃ for later use.

[0044] (2) Mixing: Weigh 0.15g of ferrous sulfate heptahydrate and dissolve it in 10mL of deionized water to prepare a ferrous sulfate aqueous solution; weigh 0, 0.05g, 0.10g, 0.15g and 0.20g of lauryl gallate and dissolve them in 20mL of anhydrous ethanol to prepare lauryl gallate ethanol solutions. Mix the lauryl gallate ethanol solutions of different concentrations with the five groups of ferrous sulfate aqueous solutions of the same concentration, and then make up to 50mL with deionized water to obtain five co-solution systems with lauryl gallate concentrations of 0g / L, 1g / L, 2g / L, 3g / L and 4g / L, and ferrous ion concentration of 3g / L for each system.

[0045] (3) Standing: Place the polyester treated in step (1) into a petri dish, pour in the co-solution system prepared in step (2), place it on a magnetic stirrer and stand at 40°C for 24 hours, and turn the fabric over every 4 hours.

[0046] (4) Drying: Place the fabric treated with water in step (3) in a 45℃ oven and dry for 6 hours;

[0047] (5) The water contact angle of the modified fabric surface was tested using an optical contact angle meter. 5 μL of water was dropped onto the test sample surface using a syringe. The contact angle was measured at 0 s, 10 min, 20 min and 30 min after the drop was added. The average value of the three tests was taken as the test result. The results are shown in Table 2.

[0048] Table 2. Effect of gallic acid lauryl ester concentration on water contact angle (CA) (°) of oleophilic-hydrophobic modified fabric materials.

[0049]

[0050] Note: The original fabric contact angle was 71.6°, and the water droplet remained on the fabric for less than 2 seconds. Fe 2+ The concentration is 3 g / L. The "\" indicates that the contact angle value is too small to be measured.

[0051] As shown in Table 2, the fixed Fe 2+ At a concentration of 3 g / L, the modified fabric exhibited good hydrophobicity, with a maximum contact angle of 149.6°, and the droplets could remain stationary for a certain period, resulting in a significant increase in the dynamic contact angle. The modified fabric showed the best hydrophobic effect when the lauryl gallate concentration was 2 g / L.

[0052] Experimental Example 1

[0053] In Example 1, an oil-water separation experiment was conducted on an oleophilic and hydrophobic modified fabric material prepared with a gallic acid lauryl ester concentration of 2 g / L and a ferrous ion concentration of 3 g / L.

[0054] (1) Prepare an oil-water mixture using 20 mL of oil and 20 mL of water for Congo red staining, as follows: Figure 1 As shown, a continuous rapid separation method was used to conduct oil-water separation experiments using chloroform, dichloromethane, and carbon tetrachloride as heavy oil.

[0055] (2) In order to remove toluene, n-hexane and petroleum ether, which are less dense than water, a vacuum pump is used as the driving force.

[0056] (3) Calculate the oil-water separation efficiency η. The calculation formula is as follows:

[0057]

[0058] In the formula, M0: mass of water before separation; M1: mass of water after separation.

[0059] Repeat the above operation four times to test the repeatability of the obtained modified fabric. The results are as follows: Figure 2 As shown, Trichloromethane, Dichloromethane, Tetrachloromethane, Hexane, Methylbenzene, and Petroleum ether represent the 1st, 2nd, 3rd, and 4th separations, respectively, from left to right.

[0060] like Figure 2 As shown, oil is rapidly separated under gravity, while water is trapped on the fabric surface, with separation efficiencies of 99.3%, 96.7%, and 98.9%, respectively. The separation efficiencies for light oils such as hexane, toluene, and petroleum ether are 99.1%, 96.9%, and 95.9%, respectively. Even after four repeated oil-water separation cycles, the oil-water separation efficiency of the fabric remains above 95%. These results demonstrate that the oleophilic-hydrophobic modified fabric material obtained in this invention possesses excellent oil-water separation capabilities.

[0061] Experiment Example 2

[0062] The self-cleaning properties of oleophilic and hydrophobic modified fabric materials were observed using two methods.

[0063] (1) The oleophilic-hydrophobic modified fabric material prepared in Example 1 with a gallic acid lauryl ester concentration of 2 g / L and a ferrous ion concentration of 3 g / L was fixed on an inclined glass slide along with the untreated original fabric. The slide was then tilted and immersed in a Congo red aqueous solution. After removal, the surface of the modified fabric was observed. The results are as follows: Figure 3 As shown.

[0064] Depend on Figure 3It can be seen that when the oleophilic and hydrophobic modified fabric material is placed in Congo red liquid and then taken out, the surface of the oleophilic and hydrophobic modified fabric material (a) does not change and remains clean and tidy, without being contaminated by the dye; while the surface of the untreated original fabric (b) is clearly stained with red Congo red marks, which indicates that the modified fabric has good self-cleaning properties.

[0065] (2) The oleophilic and hydrophobic modified fabric material prepared in Example 1 with a gallic acid lauryl ester concentration of 2 g / L and a ferrous ion concentration of 3 g / L, and the untreated original fabric were fixed separately on tilted glass slides and placed together in a large petri dish, keeping the surface flat. Congo red was used to simulate dirt and impurities and sprinkled on the fabric surface. Water droplets were added through the fabric surface using a dropper, and it was observed whether the impurities on the fabric surface would be carried away by the water droplets. The results are as follows: Figure 4 As shown.

[0066] Depend on Figure 4 It can be seen that when Congo red powder is sprinkled on the surface of the fabric and a few drops of water are dripped through a dropper, the powder on the oleophilic and hydrophobic modified fabric material (Figure a) can be seen sliding off with the water droplets, while the original fabric (Figure b) has more powder left and is stained; the Congo red powder did not leave any dust on the oleophilic and hydrophobic modified fabric material, and the fabric surface was as clean as before, indicating that the oleophilic and hydrophobic modified fabric material has good self-cleaning properties.

[0067] Experimental Example 3

[0068] Observe the hydrophobic properties of oleophilic and hydrophobic modified fabric materials.

[0069] The oleophilic-hydrophobic modified fabric material prepared in Example 1 with a gallic acid lauryl ester concentration of 2 g / L and a ferrous ion concentration of 3 g / L was fixed and adhered to a glass slide. 30 μL of water, milk, coffee, and vinegar were respectively dropped onto the surface of the hydrophobic fabric, and the surface of the oleophilic-hydrophobic modified fabric material was observed. The results are as follows: Figure 5 As shown.

[0070] Depend on Figure 5 It can be seen that when water, milk, coffee and vinegar are dropped onto the surface of the oleophilic and hydrophobic modified fabric material in sequence, the droplets remain stable on the fiber surface and maintain an intact spherical shape, and the fabric is not wetted. This indicates that the oleophilic and hydrophobic modified fabric material has good hydrophobic properties, and the droplets remain on the fabric surface and maintain their shape well.

[0071] Experiment Example 4

[0072] The stability of oleophilic and hydrophobic modified fabric materials was tested under extreme conditions.

[0073] The oleophilic and hydrophobic modified fabric material prepared in Example 1 with a gallic acid lauryl ester concentration of 2 g / L and a ferrous ion concentration of 3 g / L was placed under several different corrosive liquids, organic solvents, sodium chloride salt solutions and extreme temperature conditions for 6 h. After treatment, the water contact angle of the oleophilic and hydrophobic modified fabric material was measured, and the results are shown in Table 3.

[0074] Table 3. Water contact angles of oleophilic and hydrophobic modified fabric materials after treatment under different conditions.

[0075]

[0076] As shown in Table 3, when the obtained oleophilic and hydrophobic modified fabric materials were placed under different conditions for 6 hours, the contact angle of the oleophilic and hydrophobic modified fabric materials decreased, but the contact angle was still above 135°, indicating that the oleophilic and hydrophobic modified fabric materials prepared by the present invention can still maintain good stability under extreme environments.

Claims

1. A method for preparing an oleophilic and hydrophobic modified fabric material, characterized in that, Includes the following steps: (1) Mixing: Mix gallic acid lauryl ester solution with solution containing ferrous ions to obtain co-solution system; (2) Settling: Place the fabric in the co-solution system obtained in step (1) and let it stand; (3) Drying: The fabric treated in step (2) is dried at a constant temperature to obtain an oleophilic and hydrophobic modified fabric material; In step (1), the solution containing ferrous ions is a ferrous sulfate solution, and the concentration of lauryl gallate in the co-solution system is 0.1~4 g / L, and the concentration of ferrous ions is 0.1~12 g / L; In step (2), the settling temperature is 35~42℃ and the time is 22~26h; In step (2), the fabric is turned over every 3.5 to 4.5 hours of resting.

2. The method for preparing the oleophilic-hydrophobic modified fabric material according to claim 1, characterized in that, In step (1), the concentration of gallic acid lauryl ester in the co-solution system is 2 g / L, and the concentration of ferrous ions is 3 g / L.

3. The method for preparing the oleophilic-hydrophobic modified fabric material according to claim 1, characterized in that, In step (3), the drying temperature is 38~45℃ and the time is 4~7h.

4. The method for preparing the oleophilic-hydrophobic modified fabric material according to claim 1 or 3, characterized in that, In step (3), the drying temperature is 45°C and the time is 6 hours.

5. The oleophilic and hydrophobic modified fabric material prepared by the method of any one of claims 1 to 4.

6. The application of the oleophilic and hydrophobic modified fabric material according to claim 5 in the preparation of medical or outdoor clothing.

7. The application of the oleophilic and hydrophobic modified fabric material according to claim 5 in oil-water separation.

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