A self-healing superhydrophilic-superoleophobic fabric with a low fluorine content and its preparation method

Abstract

The present invention discloses a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content, which is characterized by including the following steps: (1) Using ethanol as a solvent, preparing a propoxy polyglycidyl ether solution; (2) Using ethanol as a solvent, preparing a mixture solution of 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine; (3) Mixing the solution prepared in step (1) and the solution prepared in step (2) in different proportions, and then heating and stirring; (4) Immersing different types of fabrics into the solution prepared in step (3), and then heating and drying to obtain a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content. The present invention also discloses a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content prepared by using the preparation method. Compared with the prior art, the preparation method of the superhydrophilic-superoleophobic fabric of the present invention has the characteristics of a low fluorine content and self-healing without external stimulation.

Description

Technical Field

[0001] The present invention relates to the technical field of fabric surface functional finishing, and specifically refers to a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content and a preparation method thereof. Background Art

[0002] In recent years, surface materials with special wettability have developed rapidly, such as superhydrophilicity, superhydrophobicity, superoleophilicity, and superoleophobicity, which usually exhibit anti-fouling, anti-corrosion, self-cleaning, anti-icing, and anti-fogging capabilities. In recent years, there have also been some reports on the hydrophilic-oleophobic wettability, which is considered "abnormal" by the classical surface free energy theory. Due to its special wettability, the hydrophilic-oleophobic surface has broad application prospects in the fields of self-cleaning, anti-fogging, oil-water separation, and controllable oil droplet transportation.

[0003] Although more and more researchers are involved in the preparation and application research of hydrophilic-oleophobic surfaces, there are still problems to be solved: the oleophobic components in hydrophilic-oleophobic coatings usually use long-chain perfluoroalkyl compounds, which pose potential hazards to the environment and human health. As is well known, fluorinated chemicals have excellent oleophobic effects due to their extremely low surface free energy, and researchers often use long-chain perfluoroalkyl compounds in the process of preparing hydrophilic-oleophobic compounds. In recent years, studies have shown that long-chain perfluoroalkyl compounds, especially fluorinated chemicals with a perfluoroalkyl chain length exceeding 8 carbons, are difficult to degrade during use, have a long half-life in organisms, are bioaccumulative, will accumulate in the human body and pose potential hazards, and will also pollute the environment. Many countries have already stipulated the prohibition of using such compounds. Therefore, it is urgent to develop a new type of hydrophilic-oleophobic compound with a low fluorine content.

[0004] In addition, there is a problem with the poor firmness of superhydrophilic-superoleophobic coatings in this field. The current solution is to introduce self-healing functions, but the reported self-healing methods currently require external condition stimuli, such as heating.

[0005] The present invention uses short-chain perfluoroalkyl compounds and long-chain non-perfluoroalkyl compounds together as the oleophobic components in hydrophilic-oleophobic compounds, thereby improving the safety of fluorine-containing compounds to the environment and human health by reducing the usage content of fluorine elements. At the same time, through the supramolecular interaction between short-chain perfluoroalkyl compounds and long-chain non-perfluoroalkyl compounds, after the coating is damaged by the outside world and its performance decreases, it can achieve self-healing and restore superhydrophilic-superoleophobic properties without external stimulation. Summary of the Invention

[0006] The first technical problem to be solved by the present invention is to provide a preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content in view of the current situation of the prior art.

[0007] The second technical problem to be solved by the present invention is to provide a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content prepared by the above preparation method.

[0008] The technical solution adopted by the present invention to solve the above first technical problem is: a preparation method of a superhydrophilic-superoleophobic fabric with a low fluorine content, comprising the following steps:

[0009] ((1) Select an organic solvent and prepare a propoxytriglycidyl ether solution;

[0010] (2) Select an organic solvent and prepare a 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine solution;

[0011] (3) Mix the solution prepared in step (1) and the solution prepared in step (2) in different proportions, and then heat and stir;

[0012] (4) Immerse different types of fabrics in the solution prepared in step (3), and then heat and dry to obtain a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content.

[0013] Preferably, the concentration of the propoxytriglycidyl ether solution is 1-5 wt%.

[0014] Preferably, in step (2), the concentration of the 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine solution is 1-3 wt%, wherein 1H,1H-perfluorohexylamine:oxafluoroalkylamidopropyl betaine = 1:1.

[0015] Preferably, the organic solvent is one of toluene, ethanol, acetone, tetrahydrofuran or N,N-dimethylformamide.

[0016] Preferably, in step (3), the volume ratio of the solution prepared in step (1) to the solution prepared in step (2) is 1:1-1:3.

[0017] Preferably, in step (3), the heating temperature is 40°C-80°C.

[0018] Preferably, in step (4), after the fabric is soaked in the solution for 1-5 minutes, the heating and drying temperature is 100°C-130°C.

[0019] Preferably, in step (4), the fabric is at least one of cotton cloth, polyester cloth and wool cloth.

[0020] The technical solution adopted by the present invention to solve the above second technical problem is: a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content prepared by the above preparation method.

[0021] Compared with the prior art, the advantages of the present invention are as follows:

[0022] The present invention provides a surface treatment method for a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content. After preparing the solution, a one-step dipping and coating process is adopted, and the method is simple and easy to operate. Compared with the conventional preparation method that uses fluorinated chemicals with a perfluoroalkyl chain length of 8 carbons, the inventor uses a mixture of fluorinated chemicals with a perfluoroalkyl chain length of 6 carbons and non-perfluoro long-chain alkyl compounds, reducing the usage amount of fluorine elements. At the same time, after the superhydrophilic-superoleophobic properties of the fabric are damaged, no external stimulation is required, and the performance can be self-healed only by being placed at room temperature for several hours, greatly improving the service life of the fabric and having good application prospects; Description of the Drawings

[0023] Figure 1 The water and oil contact angles of the fabric treated in Example 1 of the present invention;

[0024] Figure 2 The photos of water droplets and oil droplets on the fabric treated in Example 1 of the present invention. Detailed Embodiments

[0025] The present invention will be further described below with reference to the drawings and specific embodiments.

[0026] Example 1:

[0027] The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content involved in this example includes the following steps:

[0028] (1) Using toluene as a solvent, prepare a 3 wt% propoxytriglycidyl ether solution;

[0029] (2) Using toluene as a solvent, prepare a 2 wt% 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine solution, where 1H,1H-perfluorohexylamine:oxafluoroalkylamidopropyl betaine = 1:1 (mass ratio);

[0030] (3) Mix the solution prepared in step (1) and the solution prepared in step (2) according to a volume ratio of 1:2, and then seal and heat and stir at 60 °C for 2 minutes;

[0031] (4) Immerse the cotton cloth in the solution prepared in step (3) for 5 minutes, then take out the cloth and place it in an oven to dry at 120 °C, and the self-healing superhydrophilic-superoleophobic fabric with a low fluorine content is obtained.

[0032] Example 2:

[0033] The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content involved in this example includes the following steps:

[0034] (1) Using ethanol as a solvent, prepare a 1 wt% propoxytriglycidyl ether solution;

[0035] (2) Using ethanol as a solvent, prepare a 1 wt% 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine solution, where 1H,1H-perfluorohexylamine:oxafluoroalkylamidopropyl betaine = 1:1;

[0036] (3) Mix the solution prepared in step (1) and the solution prepared in step (2) in a volume ratio of 1:1, and then stir with heating in a sealed manner at 40 °C for 5 minutes;

[0037] (4) Immerse the cotton cloth in the solution prepared in step (3) for 2 minutes, then take out the cloth and place it in an oven to dry by heating at 100 °C, thus obtaining a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content.

[0038] Example 3:

[0039] A method for preparing a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content involved in this example includes the following steps:

[0040] (1) Using acetone as a solvent, prepare a 5 wt% propoxytriglycidyl ether solution;

[0041] (2) Using acetone as a solvent, prepare a 3 wt% 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine solution, where 1H,1H-perfluorohexylamine:oxafluoroalkylamidopropyl betaine = 1:1;

[0042] (3) Mix the solution prepared in step (1) and the solution prepared in step (2) in a volume ratio of 1:3, and then stir with heating in a sealed manner at 80 °C for 1 minute;

[0043] (4) Immerse the cotton cloth in the solution prepared in step (3) for 3 minutes, then take out the cloth and place it in an oven to dry by heating at 130 °C, thus obtaining a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content.

[0044] Example 4:

[0045] A method for preparing a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content involved in this example includes the following steps:

[0046] (1) Using tetrahydrofuran as a solvent, prepare a 3 wt% propoxytriglycidyl ether solution;

[0047] (2) Using tetrahydrofuran as a solvent, prepare a 2 wt% 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine solution, where 1H,1H-perfluorohexylamine:oxafluoroalkylamidopropyl betaine = 1:1;

[0048] (3) Mix the solution prepared in step (1) and the solution prepared in step (2) according to a volume ratio of 1:2, and then heat and stir at 60 °C for 2 minutes with sealing.

[0049] (4) Immerse the polyester fabric in the solution prepared in step (3) for 5 minutes, then take out the fabric and place it in an oven to heat and dry at 120 °C, thus obtaining a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content.

[0050] Example 5:

[0051] A preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content involved in this example includes the following steps:

[0052] (1) Use N,N-dimethylformamide as a solvent to prepare a 3 wt% propoxytriglycidyl ether solution.

[0053] (2) Use N,N-dimethylformamide as a solvent to prepare a 2 wt% solution of 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine, where 1H,1H-perfluorohexylamine:oxafluoroalkylamidopropyl betaine = 1:1.

[0054] (3) Mix the solution prepared in step (1) and the solution prepared in step (2) according to a volume ratio of 1:2, and then heat and stir at 40 °C for 5 minutes with sealing.

[0055] (4) Immerse the wool fabric in the solution prepared in step (3) for 2 minutes, then take out the fabric and place it in an oven to heat and dry at 120 °C, thus obtaining a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content.

[0056] The contact angles of the fabrics prepared in all examples and the contact angles after firmness testing are shown in Table 1 below.

[0057] Table 1:

[0058] Water contact angle Oil contact angle Example 1 0° 155° Example 2 0° 152° Example 3 0° 153° Example 4 0° 156° Example 5 0° 154°

[0059] The water and oil contact angles of the fabric after treatment in Example 1 are as Figure 1 shown.

[0060] The photos of water droplets and oil droplets on the fabric after treatment in Example 1 are as Figure 2 shown.

[0061] Table 2:

[0062]

[0063] Note:

[0064] (1) Abrasion resistance test: Tested according to ASTM D4966 standard;

[0065] (2) Self-healing process: After every 1000 abrasion cycles, let the fabric stand still at room temperature for 3 hours.

[0066] From Table 1 and Figures 1-2 it can be seen that:

[0067] (1) It can be seen from Table 1 that the fabrics prepared in Examples 1 to 5 have superhydrophilic-superoleophobic properties. From Figures 1-2 it can be seen that the fabric prepared in Example 1 has excellent hydrophilic and oleophobic characteristics; it can be seen from Table 2 that after abrasion treatment, its contact angle only decreases significantly, but only by letting the fabric stand still at room temperature for three hours can the superhydrophilic-superoleophobic properties be restored. Moreover, this self-healing process can be carried out multiple times. After we tested the self-healing property ten times, the fabric still maintained the superhydrophilic-superoleophobic properties, which can prove that this method greatly improves the service life of the fabric.

[0068] The working principle of the embodiments of this application is as follows: First, propoxy polyglycidyl ether is used as the hydrophilic component in the functional coating formulation, and 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine are used as the oleophobic formulation in the functional coating. The inventor prepared a superhydrophilic-superoleophobic coating by changing the ratio of the hydrophilic and oleophobic components. The prepared coating was modified on the fabric surface to obtain the superhydrophilic-superoleophobic surface. The inventor used fluorinated chemicals with a perfluoroalkyl chain length of 6 carbons and non-perfluorinated long-chain alkyl compounds, reducing the usage amount of fluorine elements. In addition, 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine can form a supramolecular structure through non-covalent bonds, and this structure has a self-healing function. When the coating is damaged by external mechanical force, only by standing still at room temperature for a period of time, the damaged coating can be repaired through the non-covalent bond interaction between molecules, and the original superhydrophilic-superoleophobic properties can be restored. It should be noted that this self-healing does not require external stimulation, such as heating.

[0069] The above has described in detail the preferred specific embodiments of the present invention. It should be understood that those of ordinary skill in the art can make many modifications and variations based on the concept of the present invention without creative labor. Therefore, all technical solutions that can be obtained by those skilled in the art in the technical field of this application based on the concept of the present invention through logical analysis, reasoning, or limited experiments on the basis of the prior art should be within the protection scope determined by the claims.

Claims

1. A preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content, characterized in that, It includes the following steps: (1) Select an organic solvent and prepare a propoxytriglycidyl ether solution; (2) Select an organic solvent and prepare a 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine solution; (3) Mix the solution prepared in step (1) and the solution prepared in step (2) in different proportions, and then heat and stir; (4) Immerse different types of fabrics into the solution prepared in step (3), and then heat and dry them to obtain a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content.

2. The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content according to claim 1, characterized in that, The concentration of the propoxytriglycidyl ether solution is 1-5 wt%.

3. The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content according to claim 1, characterized in that, In step (2), the concentration of the 1H,1H-perfluorohexylamine and oxafluoroalkylamidopropyl betaine solution is 1-3 wt%, and 1H,1H-perfluorohexylamine:oxafluoroalkylamidopropyl betaine = 1:

1.

4. The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content according to claim 1, characterized in that, The organic solvent is one of toluene, ethanol, acetone, tetrahydrofuran or N,N-dimethylformamide.

5. The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content according to claim 1, characterized in that, In step (3), the volume ratio of the solution prepared in step (1) to the solution prepared in step (2) is 1:1-1:

3.

6. The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content according to claim 1, characterized in that, In step (3), the heating temperature is 40°C-80°C.

7. The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content according to claim 1, characterized in that, In step (4), after the fabric is immersed in the solution for 1-5 minutes, the heating and drying temperature is 100°C-130°C.

8. The preparation method of a self-healing superhydrophilic-superoleophobic fabric with a low fluorine content according to claim 1, characterized in that, In step (4), the fabric is at least one of cotton cloth, polyester cloth, and wool cloth.

9. A self-healing superhydrophilic-superoleophobic fabric with a low fluorine content prepared by the preparation method described in claim 1.

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