Aminated polyacrylonitrile fiber and its preparation method and application

Abstract

The present application is applicable to the field of material technology, and provides an aminated polyacrylonitrile fiber and its preparation method and application, including: heating 1.00g of polyacrylonitrile fiber, 50.0mL of N-methyl-1,3-propylenediamine and 25.0mL of distilled water to boiling for 2.5 hours, filtering, washing and drying to obtain the aminated polyacrylonitrile fiber. When the aminated polyacrylonitrile fiber obtained in the present application is immersed in a benzoquinone solution, it can quickly change from light yellow to dark brown within 30 seconds, and the detection sensitivity is as low as 500ppb. Even in a low temperature environment of 0°C, the material of the present application can still maintain its detection sensitivity and show a stable color change. In addition, the material of the present application is applicable in a wide range of pH values from 3 to 10. It has a very strong adsorption capacity, and the maximum adsorption capacity can reach 312.8mg g ‑1 , effectively achieving the synchronous removal of benzoquinone.

Description

Technical Field

[0001] The present application belongs to the field of material technology, and in particular relates to an aminated polyacrylonitrile fiber and a preparation method and application thereof. Background Art

[0002] With the accelerating pace of industrialization, the monitoring and control of environmental pollutants have become a global focus. p-Benzoquinone, also known as benzoquinone or 1,4-benzoquinone, is a key non-aromatic organic compound that is widely present in the oxidative degradation of industrial chemicals such as polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and alkylphenols. However, due to its irritation and toxicity, p-Benzoquinone in industrial wastewater not only poses a potential threat to the environment but can also be absorbed through the respiratory tract and skin, posing a serious risk to human health. Furthermore, p-Benzoquinone vapor is irritating to the cornea and mucous membranes of the eye, and long-term exposure to high concentrations of p-Benzoquinone vapor may cause eye damage. Therefore, the detection and effective removal of p-Benzoquinone from industrial wastewater is particularly important.

[0003] At present, many researchers have developed a variety of chromatographic techniques for the detection of p-benzoquinone, including spectrophotometry, gas chromatography and high-performance liquid chromatography. These chromatography-based methods usually require the operator to have skilled techniques, use expensive equipment, and the operation process is time-consuming, so they are not suitable for large-scale real-time monitoring of p-benzoquinone. In contrast, colorimetry has significantly expanded the range of analyzable substances due to its simple operation, low cost and the absence of complex spectroscopic instruments, and is widely used in the detection of various ions and compounds. At the same time, adsorption methods are widely used in the efficient removal of pollutants in wastewater due to their low cost, high efficiency, ability to significantly reduce pollutant concentrations, and the fact that adsorbents can be reused many times. Many polymer materials are used as carriers for the adsorption of p-benzoquinone, including activated carbon, sugarcane bagasse and various biochar materials.

[0004] In summary, current methods for identifying and removing p-benzoquinone from water have many limitations, including the need for expensive equipment, the operator must have skilled techniques, the operation process is cumbersome and time-consuming, and the chromatography method cannot achieve the simultaneous removal of pollutants. Summary of the Invention

[0005] The purpose of the embodiments of the present application is to provide a method for preparing aminated polyacrylonitrile fibers, aiming to provide a new multifunctional material that can quickly and easily detect the presence of p-benzoquinone in water and effectively adsorb it, thereby solving the problems of existing methods for identifying and removing p-benzoquinone in water, such as high cost, cumbersome and time-consuming operation procedures, and inability to simultaneously remove pollutants.

[0006] The embodiment of the present application is achieved by a method for preparing an aminated polyacrylonitrile fiber, comprising:

[0007] 1.00 g of polyacrylonitrile fiber, 50.0 mL of N-methyl-1,3-propylenediamine and 25.0 mL of distilled water were heated to boiling for 2.5 hours, filtered, washed and dried to obtain aminated polyacrylonitrile fiber.

[0008] The embodiment of the present application further provides an aminated polyacrylonitrile fiber, which is prepared by the above-mentioned preparation method of the aminated polyacrylonitrile fiber.

[0009] The embodiments of the present application also provide a use of the above-mentioned aminated polyacrylonitrile fiber in identifying and adsorbing p-benzoquinone.

[0010] The embodiment of the present application provides a method for preparing aminated polyacrylonitrile fiber, which utilizes cheap organic amines and accurately controls the preparation time of amino-functionalized polyacrylonitrile fiber under relatively simple experimental conditions to prepare amino-functionalized polyacrylonitrile fiber. This aminated polyacrylonitrile fiber material can simultaneously identify and adsorb and remove p-benzoquinone. When the material is immersed in a p-benzoquinone solution, it can quickly change from light yellow to dark brown within 30 seconds, and the detection sensitivity is as low as 500ppb. Even in a low temperature environment of 0°C, the material can still maintain its detection sensitivity and show stable color changes. In addition, the material is applicable to a wide range of pH values from 3 to 10. Its adsorption capacity is extremely strong, and the maximum adsorption capacity can reach 312.8mg g -1 , effectively achieving the synchronous removal of benzoquinone. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 The aminated polyacrylonitrile fiber PAN provided in Example 1 of the present application NP F. Response time and detection limit of p-benzoquinone;

[0012] Figure 2 The aminated polyacrylonitrile fiber PAN provided in Example 1 of the present application NP Color change diagram of F at different (a) pH and (b) temperature of p-benzoquinone solution;

[0013] Figure 3 This is a comparison chart of the recognition and adsorption of p-benzoquinone by different types of aminated polyacrylonitrile fibers provided in Application Example 3 of this application. DETAILED DESCRIPTION

[0014] In order to make the purpose, technical solutions and advantages of this application more clearly understood, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0015] The present invention provides a method for preparing an aminated polyacrylonitrile fiber, comprising:

[0016] 1.00 g of polyacrylonitrile fiber, 50.0 mL of N-methyl-1,3-propylenediamine and 25.0 mL of distilled water were heated to boiling for 2.5 hours, filtered, washed and dried to obtain aminated polyacrylonitrile fiber.

[0017] Alternatively, 1.00 g of polyacrylonitrile fiber, 50.0 mL of N-methyl-1,3-propylenediamine, and 25.0 mL of distilled water are heated to boiling for 2.5 hours, filtered, and the resulting fiber is washed with water at 60-70° C. until the washing water reaches neutrality, and dried at 60-70° C. to obtain aminated polyacrylonitrile fiber.

[0018] Among them, polyacrylonitrile fiber (PANF) is known for its excellent chemical stability and affordable price. This fiber contains over 85% acrylonitrile. The surface of polyacrylonitrile fiber has cyano and ester functional groups, which can be converted into other functional groups such as amide and carboxylic acid through chemical reactions. It is precisely because of this chemical activity that PANF can achieve deep and high-density surface modification, thereby promoting the construction of a specific microenvironment composed of small molecules and polymer chains on the fiber surface. In addition, compared with powdered materials, it is easy to recycle and can be directly extracted with tweezers after the reaction is completed.

[0019] It is worth noting that one of the key technical points of this application is the precise control of the preparation time of the amino-functionalized polyacrylonitrile fiber. If the preparation time is too short, the sensitivity of the recognition process will be insufficient; conversely, if the preparation time is too long, it may cause excessive cross-linking of the functionalized fiber, thereby compromising its structural integrity.

[0020] The embodiment of the present application further provides an aminated polyacrylonitrile fiber, which is prepared by the above-mentioned preparation method of the aminated polyacrylonitrile fiber.

[0021] Furthermore, the embodiments of the present application also provide the use of the above-mentioned aminated polyacrylonitrile fiber in the recognition and adsorption of p-benzoquinone.

[0022] In the examples of the present application, the above-mentioned aminated polyacrylonitrile fiber was immersed in a solution containing p-benzoquinone, and the color change of the aminated polyacrylonitrile fiber was observed.

[0023] Optionally, 10 mg of the above-mentioned aminated polyacrylonitrile fiber is immersed in 20 mL of a solution containing p-benzoquinone; the concentration of the solution containing p-benzoquinone is preferably not less than 0.5 ppm.

[0024] In an embodiment of the present application, the above-mentioned aminated polyacrylonitrile fiber is immersed in a solution containing p-benzoquinone and stirred until adsorption equilibrium is reached. The absorbance of various pollutants is measured at their maximum absorption wavelengths using an ultraviolet spectrophotometer, and the corresponding concentrations are calculated based on the corresponding standard curves. The adsorption performance of the aminated polyacrylonitrile fiber for p-benzoquinone is calculated based on the reduction in the concentration of the substance before and after adsorption.

[0025] Optionally, 10 mg of the above-mentioned aminated polyacrylonitrile fiber is immersed in 40 mL of a solution containing p-benzoquinone; the concentration of the solution containing p-benzoquinone is preferably 100-300 ppm.

[0026] Optionally, the adsorption time is preferably 420-600 min.

[0027] Preferably, the pH of the solution containing p-benzoquinone is preferably 4-10.

[0028] The following examples describe in detail the aminated polyacrylonitrile fiber and its application in the recognition and adsorption of p-benzoquinone. The experimental methods used in the following examples are conventional methods unless otherwise noted. Materials and reagents used are commercially available unless otherwise noted.

[0029] Example 1: Amination of polyacrylonitrile fiber PAN NP Preparation of F

[0030] 1.00 g of dried PANF, 50.0 mL of N-methyl-1,3-propylenediamine, and 25.0 mL of distilled water were added to a 100.0 mL round-bottom flask equipped with a condenser. The mixture was then heated to boiling for 2.5 hours. The fiber was then filtered and washed with water at 60-70°C until the washing water reached neutrality. Finally, the fiber was dried at 60°C overnight to obtain aminated polyacrylonitrile fiber PAN. NP F.

[0031]

[0032] Comparative Example 1: Amination of polyacrylonitrile fiber PAN E Preparation of F

[0033] 1.00 g of dried PANF, 50.0 mL of ethylenediamine, and 25.0 mL of distilled water were added to a 100.0 mL round-bottom flask equipped with a condenser. The mixture was then heated to boiling for 45 minutes. The fibers were then filtered and washed with water at 60-70°C until the wash water reached neutrality. Finally, the fibers were dried at 60°C overnight to obtain aminated polyacrylonitrile fibers (PAN). E F.

[0034] Comparative Example 2: Amination of polyacrylonitrile fiber PAN P Preparation of F

[0035] 1.00 g of dried PANF, 50.0 mL of propylene diamine, and 25.0 mL of distilled water were added to a 100.0 mL round-bottom flask equipped with a condenser. The mixture was then heated to boiling for 45 minutes. The fibers were then filtered and washed with water at 60-70°C until the wash water reached neutrality. Finally, the fibers were dried at 60°C overnight to obtain aminated polyacrylonitrile fibers (PAN). P F.

[0036] Comparative Example 3: Amination of polyacrylonitrile fiber PAN B Preparation of F

[0037] 1.00 g of dried PANF, 50.0 mL of butanediamine, and 25.0 mL of distilled water were added to a 100.0 mL round-bottom flask equipped with a condenser. The mixture was then heated to boiling for 50 minutes. The fibers were then filtered and washed with water at 60-70°C until the water reached neutrality. Finally, the fibers were dried at 60°C overnight to obtain aminated polyacrylonitrile fibers (PAN). B F.

[0038] Comparative Example 4: Amination of polyacrylonitrile fiber PAN DNP Preparation of F

[0039] 1.00 g of dried PANF, 50.0 mL of N,N-dimethyl-1,3-propylenediamine, and 25.0 mL of distilled water were added to a 100.0 mL round-bottom flask equipped with a condenser. Subsequently, the mixture was heated to boiling for 3 hours and 15 minutes. Afterwards, the fiber was filtered out and washed with 60-70 ° C water until the washing water reached neutrality. Finally, the fiber was dried at 60 ° C overnight to obtain aminated polyacrylonitrile fiber PAN DNP F.

[0040] Application example 1: Amination of polyacrylonitrile fiber PAN NP F is used to identify p-benzoquinone

[0041] (1) 10 mg of dry PAN NP F was immersed in a solution containing p-benzoquinone (volume 20 mL, pH 5, temperature 25 ° C, initial concentrations of 0.5 ppm, 1 ppm, 10 ppm, 20 ppm, 50 ppm, 100 ppm), and the color change of the fiber was observed at 0 s, 30 s, 1 min, 10 min, 30 min, and 12 h, respectively. The results are as follows: Figure 1 shown.

[0042] (2) 10 mg of dry PAN NP F was immersed in a solution containing p-benzoquinone (volume 20 mL, temperature 25 ° C, initial concentration 100 ppm, pH 3-11), and the color change of the fiber was observed. The results are as follows Figure 2 shown.

[0043] (3) 10 mg of dry PAN NP F was immersed in a solution containing p-benzoquinone (volume 20 mL, pH 5, initial concentration 100 ppm, temperature 0°C, 5°C, 10°C, 15°C, 20°C, 25°C), and the color change of the fiber was observed. The results are as follows: Figure 2 shown.

[0044] Application example 2: Amination of polyacrylonitrile fiber PAN NP F is used to adsorb p-benzoquinone

[0045] (1) 10 mg of dry PAN NP F was immersed in 40 mL of a solution containing p-benzoquinone (pH 5, initial concentration 100 mg L -1 ) were stirred and adsorbed at room temperature for a specific period of time (1 to 960 minutes). The absorbance of each pollutant at its maximum absorption wavelength was measured using a UV spectrophotometer, and the corresponding concentration was calculated using the corresponding standard curve. The adsorption performance of amino-functionalized polyacrylonitrile fiber for p-benzoquinone was calculated based on the decrease in substance concentration before and after adsorption. The adsorption capacity was calculated as follows:

[0046]

[0047] q e is the equilibrium adsorption capacity of p-benzoquinone by fiber (mg g -1 ), C0 and C e Corresponding to the initial and final concentrations of adsorption (mg L -1 ), V is the volume of the pollutant (L), and m is the mass of the functionalized fiber (g).

[0048] Effect of different adsorption times on PAN NP The results of the effect of F adsorption on benzoquinone are shown in Table 1 below.

[0049] Table 1

[0050]

[0051] (2) 10 mg of dry PAN NP F was immersed in 40 mL of a solution containing p-benzoquinone (pH 5, initial concentration 100-600 mg L -1) were stirred and adsorbed at room temperature for 600 minutes. The absorbance of each pollutant at its maximum absorption wavelength was measured using a UV spectrophotometer, and the corresponding concentration was calculated using the corresponding standard curve. The adsorption performance of amino-functionalized polyacrylonitrile fiber for p-benzoquinone was calculated based on the decrease in concentration before and after adsorption. The test results are shown in Table 2 below.

[0052] Table 2

[0053]

[0054] (3) 10 mg of dry PAN NP F was immersed in 40 mL of a solution containing p-benzoquinone (pH 3-11, initial concentration 100 mg / L -1 ) were stirred and adsorbed at room temperature for 600 minutes. The absorbance of each pollutant at its maximum absorption wavelength was measured using a UV spectrophotometer, and the corresponding concentration was calculated using the corresponding standard curve. The adsorption performance of amino-functionalized polyacrylonitrile fiber for p-benzoquinone was calculated based on the decrease in concentration before and after adsorption. The test results are shown in Table 3 below.

[0055] Table 3

[0056]

[0057]

[0058] In summary, the aminated polyacrylonitrile fiber PAN provided in the embodiment of the present application NP F, can simultaneously identify and adsorb and remove p-benzoquinone. When the material is immersed in a p-benzoquinone solution, it can quickly change from light yellow to dark brown within 30 seconds, with a detection sensitivity as low as 500ppb. Even at a low temperature of 0°C, the material can still maintain its detection sensitivity and show a stable color change. In addition, the material is applicable to a wide range of pH values from 3 to 10. It has a very strong adsorption capacity, with a maximum adsorption capacity of 312.8mg g -1 , effectively achieving the synchronous removal of benzoquinone.

[0059] Application Example 3: Different types of aminated polyacrylonitrile fibers (PAN NP F. PAN E F. PAN P F. PAN B F. PAN DNP F) for the recognition and adsorption of benzoquinone

[0060] (1) 10 mg of the dried aminated polyacrylonitrile fibers prepared in Example 1 and Comparative Examples 1-4 were immersed in a solution containing p-benzoquinone (volume: 20 mL, pH: 5, temperature: 25° C., initial concentration: 100 mg L-1 ), observe the color change of the fiber, the results are as follows Figure 3 shown.

[0061] (2) 10 mg of dry PAN NP F was immersed in 40 mL of a solution containing p-benzoquinone (pH 5, initial concentration 100 mg L -1 ) was stirred and adsorbed at room temperature for 600 minutes. The absorbance of each pollutant was measured at its maximum absorption wavelength using an ultraviolet spectrophotometer, and the corresponding concentration was calculated based on the corresponding standard curve. The adsorption performance of amino-functionalized polyacrylonitrile fiber for p-benzoquinone was calculated based on the decrease in substance concentration before and after adsorption. The results are shown in Figure 2. Figure 3 As shown, Figure 3 The amine compounds in (a) are ethylenediamine, propylenediamine, butylenediamine, N-methyl-1,3-propylenediamine, and N,N-dimethyl-1,3-propylenediamine from left to right.

[0062] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person of ordinary skill in the art may make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

[0063] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing aminated polyacrylonitrile fiber, characterized in that: include: 1.00 g of polyacrylonitrile fiber, 50.0 mL of N-methyl-1,3-propylenediamine, and 25.0 mL of distilled water were heated to boiling for 2.5 hours. After filtering, the obtained fiber was washed with water at 60-70° C. until the washing water reached neutrality. The fiber was dried at 60-70° C. to obtain aminated polyacrylonitrile fiber.

2. An aminated polyacrylonitrile fiber, characterized in that: The aminated polyacrylonitrile fiber is prepared by the preparation method of the aminated polyacrylonitrile fiber according to claim 1.

3. Use of the aminated polyacrylonitrile fiber according to claim 2 in identifying and adsorbing p-benzoquinone.

4. The use of the aminated polyacrylonitrile fiber according to claim 3 in identifying and adsorbing p-benzoquinone, characterized in that: The aminated polyacrylonitrile fiber according to claim 2 is immersed in a solution containing p-benzoquinone, and the color change of the aminated polyacrylonitrile fiber is observed.

5. The use of the aminated polyacrylonitrile fiber according to claim 4 in identifying and adsorbing p-benzoquinone, characterized in that: 10 mg of the aminated polyacrylonitrile fiber according to claim 2 is immersed in 20 mL of a solution containing p-benzoquinone; the concentration of the solution containing p-benzoquinone is not less than 0.5 ppm.

6. Use of the aminated polyacrylonitrile fiber according to claim 3 in identifying and adsorbing p-benzoquinone, characterized in that: The aminated polyacrylonitrile fiber according to claim 2 is immersed in a solution containing p-benzoquinone and stirred until adsorption equilibrium is reached. The absorbance of each pollutant is measured at its maximum absorption wavelength using an ultraviolet spectrophotometer, and the corresponding concentration is calculated according to the corresponding standard curve. The adsorption performance of the aminated polyacrylonitrile fiber for p-benzoquinone is calculated based on the reduction in the concentration of the substance before and after adsorption.

7. Use of the aminated polyacrylonitrile fiber according to claim 6 in identifying and adsorbing p-benzoquinone, characterized in that: 10 mg of the aminated polyacrylonitrile fiber according to claim 3 is immersed in 40 mL of a solution containing p-benzoquinone; the concentration of the solution containing p-benzoquinone is 100-300 ppm.

8. The use of the aminated polyacrylonitrile fiber according to claim 6 in identifying and adsorbing p-benzoquinone, characterized in that: The adsorption time is 420-600min.

9. Use of the aminated polyacrylonitrile fiber according to any one of claims 4 to 8 in identifying and adsorbing p-benzoquinone, characterized in that: The pH of the solution containing p-benzoquinone is 4-10.

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