Aminated polyacrylonitrile fiber as well as preparation method and application thereof

Abstract

The invention is applicable to the technical field of materials, and provides an aminated polyacrylonitrile fiber as well as a preparation method and application thereof, and the preparation method comprises the following steps: heating 1.00 g of polyacrylonitrile fiber, 50.0 mL of N-methyl-1, 3-propane diamine and 25.0 mL of distilled water until boiling, continuing for 2.5 hours, filtering, washing and drying to obtain the aminated polyacrylonitrile fiber. When the obtained aminated polyacrylonitrile fiber is immersed in a p-benzoquinone solution, the aminated polyacrylonitrile fiber can be rapidly converted from light yellow to dark brown within 30 seconds, and the detection sensitivity is as low as 500 ppb. Even in a low-temperature environment of 0 DEG C, the material provided by the invention can still maintain the detection sensitivity and shows stable color change. In addition, the material provided by the invention is applicable in a wide range of pH values of 3-10. The adsorption capacity is extremely high, the maximum adsorption capacity can reach 312.8 mg g <-1 >, and synchronous removal of p-benzoquinone is effectively achieved.

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 acceleration of the pace of industrialization, the monitoring and control of environmental pollutants have become the focus of global attention. 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 process of industrial chemicals such as polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and alkylphenols. However, given its irritation and toxicity, p-benzoquinone in industrial wastewater not only poses a potential threat to the environment, but may also be absorbed by the human body through the respiratory tract and skin, posing serious risks to human health. In addition, p-benzoquinone vapor has an irritating effect on the cornea and mucous membranes of the eyes, and long-term exposure to high concentrations of p-benzoquinone vapor may cause eye damage. Therefore, it is particularly important to detect and effectively remove p-benzoquinone from industrial wastewater.

[0003] At present, many researchers have developed a variety of chromatographic techniques for detecting 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 lack 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 sewage due to their low cost, high efficiency, and ability to significantly reduce pollutant concentrations, and the adsorbent can be reused many times. Many polymer materials are used as carriers for the adsorption of p-benzoquinone, including activated carbon, 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 fiber, 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, and inability to simultaneously remove pollutants.

[0006] The embodiment of the present application is implemented as follows: a method for preparing 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, wherein the aminated polyacrylonitrile fiber is prepared by the above-mentioned method for preparing the aminated polyacrylonitrile fiber.

[0009] The embodiment of the present application also provides an application 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. By using cheap organic amines and accurately controlling the preparation time of amino-functionalized polyacrylonitrile fiber under relatively simple experimental conditions, amino-functionalized polyacrylonitrile fiber can be prepared. 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 at a low temperature 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 simultaneous 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 is the 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 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 solution and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0015] The present application embodiment provides a method for preparing 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] Optionally, 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 obtained fiber is washed with 60-70° C. water 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. The fiber contains more than 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 to accurately control the preparation time of amino-functionalized polyacrylonitrile fibers. 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 fibers, thereby damaging their structural integrity.

[0020] The embodiment of the present application further provides an aminated polyacrylonitrile fiber, wherein the aminated polyacrylonitrile fiber is prepared by the above-mentioned method for preparing 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 is immersed in a solution containing p-benzoquinone, and the color change of the aminated polyacrylonitrile fiber is 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 the maximum absorption wavelength by 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.

[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 is a detailed description of the aminated polyacrylonitrile fiber and its application in the recognition and adsorption of p-benzoquinone by specific examples, as shown below. The experimental methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents, etc. used are all commercially available unless otherwise specified.

[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. Subsequently, the mixture was heated to boiling for 2.5 hours. 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 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. Subsequently, the mixture was heated to boiling for 45 min. 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 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. Subsequently, the mixture was heated to boiling for 45 min. 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 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 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 50 min. 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. 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 for identification of 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, respectively). The color changes of the fibers were 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 ), stirred and adsorbed for a certain period of time (1 to 960 minutes) at room temperature, and the absorbance of each pollutant was measured at the maximum absorption wavelength using an ultraviolet spectrophotometer, and the corresponding concentration was calculated according to the corresponding standard curve. The adsorption performance of amino-functionalized polyacrylonitrile fiber on p-benzoquinone was calculated by the reduction in the concentration of the substance before and after adsorption. The adsorption amount calculation formula is 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 time 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), stirred at room temperature for 600 minutes, and the absorbance of each pollutant was measured at the maximum absorption wavelength by an ultraviolet spectrophotometer, and the corresponding concentration was calculated according to the corresponding standard curve. The adsorption performance of amino-functionalized polyacrylonitrile fiber on p-benzoquinone was calculated by the reduction in the concentration of the substance 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 ), stirred and adsorbed for 600 min at room temperature, and the absorbance of each pollutant was measured at the maximum absorption wavelength by an ultraviolet spectrophotometer, and the corresponding concentration was calculated according to the corresponding standard curve. The adsorption performance of amino-functionalized polyacrylonitrile fiber to p-benzoquinone was calculated by the reduction in the concentration of the substance 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 embodiments of the present application NP F, can simultaneously identify and adsorb and remove benzoquinone. When the material is immersed in a 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 simultaneous 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 result is 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 ), stirred at room temperature for 600 min, and the absorbance of each pollutant was measured at the 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 on p-benzoquinone was calculated based on the reduction in substance concentration before and after adsorption. The results are shown in 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-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the present application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the attached 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 substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope 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, filtered, washed and dried to obtain aminated polyacrylonitrile fiber.

2. The method for preparing aminated polyacrylonitrile fiber according to claim 1, 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. After drying at 60-70° C., aminated polyacrylonitrile fiber was obtained.

3. 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 or 2.

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

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

6. The use of the aminated polyacrylonitrile fiber in identifying and adsorbing p-benzoquinone according to claim 5, characterized in that: 10 mg of the aminated polyacrylonitrile fiber according to claim 3 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.

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

8. The use of the aminated polyacrylonitrile fiber in identifying and adsorbing p-benzoquinone according to claim 7, 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.

9. The use of the aminated polyacrylonitrile fiber in identifying and adsorbing p-benzoquinone according to claim 7, characterized in that: The adsorption time is 420-600min.

10. Use of the aminated polyacrylonitrile fiber according to any one of claims 5 to 9 in identifying and adsorbing p-benzoquinone, characterized in that: The pH of the solution containing p-benzoquinone is 4-10.

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