Visible light self-cleaning nylon fiber and its preparation method and application

Abstract

The present invention discloses a method for preparing a visible light self-cleaning nylon fiber. Specifically, the method comprises: soaking a nylon fiber in an acetic acid solution and then stirring at high temperature to obtain a modified nylon fiber; dissolving 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) in a sodium carbonate solution and stirring to ionize the TCPP; adding the obtained nylon fiber to the mixed solution and heating the solution; adding the acetic acid solution to the obtained nylon fiber, stirring, washing, and drying to obtain the visible light self-cleaning nylon fiber. The visible light self-cleaning nylon fiber of the present invention can be used in the photocatalytic degradation of pollutants. The method of the present invention, by supporting TCPP on the nylon fiber, is simple and easy to process, has the potential for large-scale production, and exhibits excellent pollutant degradation and self-cleaning properties under visible light conditions.

Description

Technical Field

[0001] The present invention belongs to the technical field of fiber composite material preparation, and in particular relates to a preparation method of visible light self-cleaning nylon fiber, and also relates to the visible light self-cleaning nylon fiber and application thereof. Background Art

[0002] With the rapid development of society and the improvement of living standards, clothing has become more than just a tool for protecting the body; it has also gradually become an embodiment of personal style and fashion. However, the cleaning and maintenance of clothing has become a major concern. Traditional washing methods not only consume large amounts of water resources and can pollute the environment, but also easily damage the material of clothing during the washing process, shortening its lifespan. Therefore, the development of self-cleaning clothing technologies has become a research hotspot.

[0003] Photocatalytic technology, which uses light energy to excite catalysts to generate electron-hole pairs, triggering a series of chemical reactions, is considered an effective strategy for achieving self-cleaning clothing. Photocatalytic materials applied to clothing fabrics can automatically remove or lighten stains under light. Reported self-cleaning photocatalytic materials include nano-TiO2, ZnO, SnO2, Ag, and their hybrids. Among these photocatalytic materials, titanium dioxide has attracted significant research attention due to its chemical stability, low cost, and excellent photocatalytic performance. However, TiO2 exhibits high catalytic activity only under ultraviolet light, limiting its application. While some modified TiO2 materials exhibit some activity under visible light, their efficiency is generally lower than that of TiO2 under UV light. Furthermore, due to the weak bonding between inorganic materials and organic fabrics, the adhesion of photocatalytic materials to textiles is a key issue. After repeated washing, the photocatalyst may fall off or lose activity, resulting in a decrease in self-cleaning performance. Summary of the Invention

[0004] The present invention aims to provide a method for preparing visible light self-cleaning nylon fiber, which exhibits excellent pollutant degradation and self-cleaning properties under visible light conditions.

[0005] Another object of the present invention is to provide visible light self-cleaning nylon fibers.

[0006] A third object of the present invention is to provide the use of visible light self-cleaning nylon fibers in photocatalytic degradation of pollutants.

[0007] The technical solution adopted by the present invention is a method for preparing visible light self-cleaning nylon fiber, which is specifically implemented according to the following steps:

[0008] Step 1: soaking nylon fiber in an acetic acid solution and then stirring at high temperature to obtain modified nylon fiber;

[0009] Step 2: dissolving 5, 10, 15, 20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) in a sodium carbonate solution and stirring to ionize TCPP;

[0010] Step 3, adding the nylon fiber obtained in step 1 to the mixed solution of step 2, and heating the mixture in an oil bath for reaction;

[0011] Step 4, adding acetic acid solution to the nylon fiber obtained in step 3 and stirring to acidify it thoroughly;

[0012] Step 5, washing the nylon fiber obtained in step 4 with deionized water until the pH of the washing solution is 7;

[0013] Step 6: drying the nylon fiber obtained in step 5 to obtain visible light self-cleaning nylon fiber.

[0014] The present invention is also characterized in that:

[0015] In step 1, the acetic acid solution is prepared by mixing acetic acid and water in a volume ratio of 1:15; during soaking, the acetic acid solution is heated in a water bath to 40-50 o C, soaking time is 30~40min; while stirring, heat the acetic acid solution in an oil bath to 100~110 o C, stirring time is 60~80min.

[0016] In step 2, the concentration of the sodium carbonate solution is 0.1 mol / L; and the stirring time is 30-40 min.

[0017] In step 3, the reaction temperature is 100~110 o C, reaction time is 120~130min.

[0018] In step 4, the acetic acid solution is prepared by mixing acetic acid and water in a volume ratio of 20:20; the stirring time is 30-40 minutes.

[0019] In step 6, the drying temperature is 100~120 o C, drying time is 90~120min.

[0020] Another technical solution adopted by the present invention is the nylon fiber prepared by the method for preparing visible light self-cleaning nylon fiber.

[0021] The third technical solution adopted by the present invention is the application of visible light self-cleaning nylon fibers in the photocatalytic degradation of pollutants.

[0022] The beneficial effects of the present invention are:

[0023] (1) The method of the present invention, which supports TCPP on nylon fibers, is simple and easy to implement, has the potential for large-scale production, and exhibits excellent pollutant degradation and self-cleaning properties under visible light conditions;

[0024] (2) In the method of the present invention, the porphyrin molecules and the nylon fibers are bound by ionic bonds, which has a strong interaction force and effectively improves the stability of the loaded photocatalyst. In addition, the nylon fibers significantly reduce the amount of photocatalyst used and are easy to recycle, thereby reducing the overall cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a protonation roadmap for the nylon fiber surface in the method of the present invention;

[0026] Figure 2 is the TCPP ionization roadmap in the method of the present invention;

[0027] Figure 3 The figure is a roadmap for the nylon fiber-supported TCPP ion in the method of the present invention;

[0028] Figure 4 The figure is a roadmap for the hydrolysis of nylon fiber-supported TCPP ions in the method of the present invention;

[0029] Figure 5 The color of the nylon fiber before TCPP is supported in the method of the present invention;

[0030] Figure 6 The color of the nylon fiber after supporting TCPP in the method of the present invention;

[0031] Figure 7 The infrared spectra of the nylon fiber prepared by the method of the present invention before and after TCPP support;

[0032] Figure 8 The UV-visible absorption spectra of the nylon fiber prepared by the method of the present invention before and after TCPP support;

[0033] Figure 9 This is a scanning electron microscope image of the nylon fiber before TCPP is supported in the method of the present invention;

[0034] Figure 10 This is a scanning electron microscope image of the nylon fiber supported on TCPP in the method of the present invention;

[0035] Figure 11 This is a contact angle test diagram before the nylon fiber supports TCPP in the method of the present invention;

[0036] Figure 12 This is a contact angle test diagram of nylon fiber supported TCPP in the method of the present invention;

[0037] Figure 13The self-cleaning performance of coffee after the nylon fiber supported TCPP in the method of the present invention;

[0038] Figure 14 The self-cleaning performance of nylon fiber supported TCPP on dragon fruit juice in the method of the present invention. DETAILED DESCRIPTION

[0039] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0040] The method for preparing visible light self-cleaning nylon fiber of the present invention is specifically implemented according to the following steps:

[0041] Step 1: soaking nylon fiber in an acetic acid solution, and then stirring at high temperature to completely protonate the nitrogen of the amide bond on the nylon fiber to obtain modified nylon fiber;

[0042] The acetic acid solution is a mixture of acetic acid and water in a volume ratio of 1:15;

[0043] When soaking, heat the acetic acid solution in a water bath to 40~50 o C, the soaking time is 30~40min, so that the nylon fiber is fully wetted, which is conducive to the subsequent protonation reaction;

[0044] While stirring, heat the acetic acid solution in an oil bath to 100-110 o C, stirring time is 60~80min, so that it can fully react with acetic acid and complete the protonation of N in the amide bond, such as Figure 1 As shown in Figure 3, after protonation, the nitrogen on the amide bond carries a positive charge and becomes a reactive site on the nylon fiber, thereby modifying the nylon surface.

[0045] Step 2: Dissolve 5, 10, 15, 20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) in sodium carbonate solution and stir at room temperature for 30-40 minutes to ensure that TCPP is completely dissolved and ionized.

[0046] The concentration of sodium carbonate solution is 0.1 mol / L;

[0047] like Figure 2 As shown in the figure, the dissolution process of TCPP is the ionization process of TCPP. After ionization, all the original carboxyl groups (-COOH) in TCPP will become carboxylate ions (-COO-), which are negatively charged and become reactive sites on the TCPP molecule, which can be used to modify the surface of nylon.

[0048] Step 3: Add the nylon fiber obtained in step 1 to the mixed solution of step 2, and heat the mixture in an oil bath to react so that TCPP is loaded on the nylon fabric.

[0049] The reaction temperature is 100~110 o C, reaction time is 120~130min;

[0050] like Figure 3 As shown, due to the electrostatic interaction between the quaternized N on the nylon fiber and the carboxylate ions on TCPP, TCPP will spontaneously graft onto the nylon fiber, thereby improving the adhesion of the supported photocatalyst;

[0051] Step 4, adding acetic acid solution to the nylon fiber obtained in step 3, stirring at a constant temperature to completely acidify it;

[0052] The acetic acid solution was prepared by mixing acetic acid and water in a volume ratio of 20:20; stirred at room temperature for 30-40 minutes;

[0053] like Figure 4 As shown in the figure, the TCPP ions supported on the nylon fiber will be transformed from highly reactive carboxylate ions (-COO-) into carboxylic acid groups (-COOH) under the action of acetic acid solution, which reduces the reactivity of the nylon fiber and improves the hydrophilicity of nylon. Moreover, since TCPP becomes neutral in this process, there is no repulsive force between molecules. Due to the π-π interaction between TCPP molecules, they will spontaneously self-assemble into TCPP molecular membranes.

[0054] Step 5, washing the nylon fiber obtained in step 4 with deionized water 4 to 6 times until the pH of the washing solution is 7;

[0055] Step 6, drying the nylon fiber obtained in step 5 to obtain visible light self-cleaning nylon fiber;

[0056] The drying temperature is 100~120 o C, drying time is 90~120 min;

[0057] Example 1

[0058] The method for preparing visible light self-cleaning nylon fiber of the present invention comprises the following steps:

[0059] Step 1: Heat the nylon fiber in a water bath to 40 o C acetic acid solution for 30 min; then heat the nylon fiber in an oil bath to 100 o C in acetic acid solution and stir for 60 min;

[0060] Step 2: dissolving 5, 10, 15, 20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) in sodium carbonate solution and stirring at room temperature for 30 min;

[0061] Step 3: Add the nylon fiber treated in step 1 to the mixed solution in step 2, and heat at a constant temperature to load TCPP on the nylon fiber.

[0062] The reaction system was heated in an oil bath and the temperature was maintained at 100 o C, reaction time is 120 min;

[0063] Step 4: adding the nylon fiber treated in step 3 to an acetic acid solution and soaking and stirring at room temperature for 30 minutes; the acetic acid solution is a mixture of acetic acid and water in a volume ratio of 20:20;

[0064] Step 5: Take out the nylon fiber treated in step 4 and wash it with deionized water for 4 times until the washing liquid becomes neutral.

[0065] Step 6: Dry the nylon fiber at a temperature of 100 o C, the drying time is 90 min, and visible light self-cleaning nylon fiber is obtained.

[0066] Example 2

[0067] The method for preparing visible light self-cleaning nylon fiber of the present invention comprises the following steps:

[0068] Step 1: Heat the nylon fiber in a water bath to 45 o C acetic acid solution for 35 min; then heat the nylon fiber in an oil bath to 105 o C in acetic acid solution and stir for 70 min;

[0069] The acetic acid solution is a mixture of acetic acid and water in a volume ratio of 1:15;

[0070] Step 2: Dissolve 5, 10, 15, 20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) in sodium carbonate solution and stir at room temperature for 35 min; the concentration of sodium carbonate solution is 0.1 mol / L.

[0071] Step 3, adding the nylon fiber treated in step 1 to the mixed solution in step 2 and heating at a constant temperature;

[0072] The reaction system was heated in an oil bath and the temperature was maintained at 105 o C, reaction time 125 min.

[0073] Step 4: Take out the nylon fiber treated in step 3, add acetic acid solution, and stir at room temperature for 35 minutes; the acetic acid solution is a mixture of acetic acid and water in a volume ratio of 20:20;

[0074] Step 5: Take out the nylon fiber treated in step 4 and wash it with deionized water for 5 times until the washing liquid becomes neutral.

[0075] Step 6: Dry the nylon fiber at a temperature of 110 o C, the drying time is 105 min, and visible light self-cleaning nylon fiber is obtained.

[0076] Example 3

[0077] The method for preparing visible light self-cleaning nylon fiber of the present invention comprises the following steps:

[0078] Step 1: Heat the nylon fiber in a water bath to 50 o C acetic acid solution for 40 min; then heat the nylon fiber in an oil bath to 110 o C in acetic acid solution and stir for 80 min;

[0079] Step 2: dissolving 5, 10, 15, 20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) in sodium carbonate solution and stirring at room temperature for 40 min;

[0080] Step 3, adding the nylon fiber treated in step 1 to the mixed solution in step 2 and heating at a constant temperature;

[0081] The reaction system was heated in an oil bath and the temperature was maintained at 110 o C, reaction time 130 min.

[0082] Step 4: Take out the nylon fiber treated in step 3, add acetic acid solution, and stir at room temperature for 40 minutes; the acetic acid solution is a mixture of acetic acid and water in a volume ratio of 20:20;

[0083] Step 5: Take out the nylon fiber treated in step 4 and wash it with deionized water for 6 times until the washing liquid becomes neutral.

[0084] Step 6: Dry the nylon fiber at a temperature of 120 o C, the drying time is 120 min, and visible light self-cleaning nylon fiber is obtained.

[0085] Example 4

[0086] The photocatalytic pollutant degradation performance results of the visible light self-cleaning nylon fibers of Examples 1-3 of the present invention are shown in Table 1;

[0087] Table 1 Photocatalytic pollutant degradation performance of the self-cleaning nylon fibers of Examples 1-3

[0088]

[0089] Note: All experiments were carried out at room temperature of 20°C, pH value of 7, and xenon lamp power of 500W.

[0090] The above tests were conducted in accordance with the national standard for photocatalysis, GB / T 23762-2009 (Test Method for Purification of Aqueous Solutions of Photocatalytic Materials). Table 1 shows that the degradation efficiency of TCPP-supported nylon fibers after 60 minutes exceeded 80% for both methylene blue and methyl orange, with the exception of rhodamine, which was slightly lower. Furthermore, the degradation efficiency of TCPP-supported nylon fibers decreased minimally after five cycles, indicating their high stability.

[0091] Example 5

[0092] The nylon fiber prepared by the method of the present invention is characterized as follows:

[0093] (1) The color of nylon fiber supported TCPP is off-white. Figure 5 As shown, it turns dark purple after loading, as shown Figure 6 As shown in the figure, since the color of pure TCPP is dark purple, it can be inferred that TCPP is loaded on the surface of nylon fibers.

[0094] (2) Nicolet 5700 Fourier transform infrared spectrometer was used to measure the structure of nylon fiber before and after TCPP was supported, such as Figure 7 As shown, after loading, the infrared spectrum shows a distinct peak at 3500 nm. This is because the primary absorption band of the NH bond within the TCPP molecule is between 3000 and 3500 nm. Peaks also appear at 1000, 1500, and 1750 nm, corresponding to the absorption bands of the C=O double bond within the TCPP molecule. Furthermore, the absorption band of the carboxyl group within the TCPP molecule is primarily at 650 nm. In summary, TCPP has been successfully loaded onto nylon fibers.

[0095] (3) The light response ability of nylon fiber before and after TCPP loading was measured using UV-2450 UV-visible photometer. Figure 8 As shown in the figure, it can be seen that the response of nylon fiber in the visible light region is significantly enhanced after TCPP loading, indicating that the loading and self-assembly of TCPP greatly improve the response of nylon fiber in the visible light region, which is beneficial to improving the visible light photocatalytic performance of nylon fiber.

[0096] (4) Figure 9 and Figure 10 The scanning electron microscope images of nylon fiber before and after TCPP loading are shown. As can be seen from the figure, the surface of the nylon fiber changes from smooth to very rough, further demonstrating the successful loading of TCPP.

[0097] (5) The contact angle of nylon fiber before and after TCPP support was measured using contact angle meter DSA100E, as shown in the following figure: Figure 11 、 Figure 12As shown in Figure 3, the contact angle of the nylon fiber supported by TCPP increases due to the hydrophilicity of the TCPP carboxyl group.

[0098] Example 6

[0099] 0.5 mL of coffee and dragon fruit juice (50 mg / L) were dripped onto the surface of nylon fabric with a size of 5 cm × 5 cm using a dropper. The self-cleaning performance of nylon fiber supported by TCPP was compared with that of unmodified nylon fiber as a control. The contaminated fabric was irradiated under a 500 W xenon lamp with the fabric 20 cm away from the light source for 60 minutes. Figure 13 and Figure 14 It can be seen that the degradation effect of nylon fiber-supported TCPP on coffee and dragon fruit juice is significant, and the effect decreases slightly after 5 cycles, indicating its high stability.

Claims

1. A method for preparing visible light self-cleaning nylon fiber, characterized in that: Please follow the steps below to implement: Step 1: Soak the nylon fiber in acetic acid solution, then o C and stirred to obtain modified nylon fiber; Step 2: dissolving 5, 10, 15, 20-tetrakis(4-carboxyphenyl)porphyrin in a sodium carbonate solution and stirring to ionize TCPP; Step 3, adding the nylon fiber obtained in step 1 to the mixed solution of step 2, and heating the mixture in an oil bath for reaction; Step 4, adding acetic acid solution to the nylon fiber obtained in step 3 and stirring to acidify it thoroughly; Step 5, washing the nylon fiber obtained in step 4 with deionized water until the pH of the washing solution is 7; Step 6: drying the nylon fiber obtained in step 5 to obtain visible light self-cleaning nylon fiber.

2. The method for preparing visible light self-cleaning nylon fiber according to claim 1, wherein: In step 1, the acetic acid solution is prepared by mixing acetic acid and water in a volume ratio of 1:15; during soaking, the acetic acid solution is heated in a water bath to 40-50 o C, soaking time is 30~40min; stirring time is 60~80min.

3. The method for preparing visible light self-cleaning nylon fiber according to claim 1, wherein: In step 2, the concentration of the sodium carbonate solution is 0.1 mol / L; and the stirring time is 30-40 min.

4. The method for preparing visible light self-cleaning nylon fiber according to claim 1, wherein: In step 3, the reaction temperature is 100-110 o C, reaction time is 120~130min.

5. The method for preparing visible light self-cleaning nylon fiber according to claim 1, wherein: In step 4, the acetic acid solution is prepared by mixing acetic acid and water in a volume ratio of 20:20; and the stirring time is 30 to 40 minutes.

6. The method for preparing visible light self-cleaning nylon fiber according to claim 1, wherein: In step 6, the drying temperature is 100~120 o C, drying time is 90~120min.

7. Nylon fiber prepared by the method for preparing visible light self-cleaning nylon fiber according to any one of claims 1 to 6.

8. Use of the visible light self-cleaning nylon fiber according to any one of claims 1 to 6 in photocatalytic degradation of pollutants.

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