Preparation method of fiber material, fiber material and application

Abstract

The invention discloses a preparation method of a fiber material, the fiber material and application, and belongs to the technical field of uranium extraction materials.The preparation method comprises the steps that firstly, polyguanidine is grafted to acrylic fibers through a hydrothermal method, then zwitterionic monomers with double bonds are functionalized to the surfaces of the acrylic fibers through a tert-butyl hydroperoxide surface grafting polymerization method, and the fiber material is obtained. And finally, carrying out amidoximation in a weakly alkaline hydroxylamine solution, washing and drying to obtain the double-effect anti-pollution high-efficiency uranium extraction fiber material. The fiber material is prepared by the preparation method. The fiber material is used for extracting uranium from a water body. The fiber material prepared by the invention has active and passive double-effect anti-fouling performance (namely antibacterial and anti-adhesion), and is high in adsorption rate and adsorption capacity, meanwhile, the preparation method is simple, convenient and efficient, large-scale production is easy, and the fiber material has a good market prospect in the field of extraction of uranium from seawater as a novel and efficient uranyl ion adsorption material.

Description

Technical Field

[0001] The present application belongs to the technical field of uranium extraction materials, and in particular relates to a preparation method of a fiber material, the fiber material and its use. Background Art

[0002] Uranium extraction from water refers to the extraction of uranium from water, which is crucial for ensuring a sufficient supply of uranium resources in my country. Various water resources can be used, such as seawater, brine, and uranium-containing wastewater. Taking seawater uranium extraction as an example, marine biofouling severely impacts the adsorption properties of seawater uranium extraction materials. Therefore, developing seawater uranium extraction materials with improved antifouling properties and higher uranium extraction efficiency is crucial. Fiber-based adsorbents are currently recognized as the most viable materials for seawater uranium extraction. However, reported seawater uranium extraction fiber materials exhibit only one of the following antifouling functions: active antifouling (killing bacteria or microorganisms) or passive antifouling (preventing bacteria or microorganisms from attaching), resulting in insufficient antifouling performance. Furthermore, existing materials suffer from poor mass transfer performance and low adsorption rates. These issues contribute to the low adsorption efficiency of existing fiber-based seawater uranium extraction materials, limiting their practical applications. Therefore, developing new seawater uranium extraction fiber materials with improved antifouling properties, adsorption rates, and adsorption capacity is crucial. Summary of the Invention

[0003] The present application aims to at least to some extent solve the current technical problem that it is impossible to prepare an adsorbent fiber material that has both active and passive anti-fouling capabilities. To this end, the present application provides a method for preparing a fiber material, a fiber material and its use, which can prepare a fiber material that is both actively and passively anti-fouling, significantly improve the anti-fouling performance of the material, and also improve the adsorption efficiency of the fiber material.

[0004] In a first aspect, an embodiment of the present application provides a method for preparing a fiber material, comprising:

[0005] Add acrylic fiber, polyguanidine and ultrapure water into a reaction vessel, and adjust the pH of the reaction system to between 12.0 and 13.0 with sodium hydroxide;

[0006] The reaction system is heated to 120-150° C. and maintained for 18-36 hours to perform a hydrothermal reaction, and the product of the hydrothermal reaction is washed several times with ultrapure water and dried to obtain polyguanidine-modified acrylic fiber;

[0007] Adding polyguanidine-modified acrylic fiber, a zwitterionic monomer with a double bond, tert-butyl hydroperoxide solution, and ultrapure water into a reaction vessel, heating to 70-100° C. and maintaining for 8-24 hours to graft the amino groups of the guanidine on the surface of the polyguanidine-modified acrylic fiber, and then washing the surface-grafted product several times with ultrapure water and drying to obtain a zwitterionic and polyguanidine dual-functionalized acrylic fiber;

[0008] The bifunctional acrylic fiber is placed in a hydroxylamine hydrochloride solution with a pH of 7.2 to 9.0 for 6 to 12 hours to oxime the remaining cyanamide in the bifunctional acrylic fiber; the oxime product is then washed several times with ultrapure water and dried to obtain a fiber material.

[0009] In some embodiments, the weight percentage of the raw materials added during the entire process is as follows:

[0010] acrylic fiber, 6.15% to 7.27%;

[0011] Polyguanidine, 1.54% to 1.82%;

[0012] zwitterionic monomers with double bonds, 54.55% to 61.54%;

[0013] Hydroxylamine hydrochloride, 30.77%~36.36%.

[0014] In some embodiments, when polyguanidine-modified acrylic fiber, zwitterionic monomer with double bonds, tert-butyl hydroperoxide solution, and ultrapure water are added to a reaction container, the mass percentage of the tert-butyl hydroperoxide solution is 0.067-0.069%.

[0015] In some embodiments, the grafting rate of the polyguanidine-modified acrylic fiber is 10-20%.

[0016] In some embodiments, the grafting rate of the bifunctionalized acrylic fiber is 18-50%.

[0017] In some embodiments, the polyguanidine is polyhexamethyleneguanidine hydrochloride, polyhexamethylenebiguanidine hydrochloride, polyaminopropylbiguanidine, polyetherguanidine, polyacrylamideguanidine, or polycarboxyguanidine.

[0018] In some embodiments, the zwitterionic monomer having a double bond is 2-methacryloyloxyethyl sulfobetaine, 2-methacryloyloxyethyl phosphorylcholine, 2-methacrylamidoethyl sulfobetaine, or 2-methacryloyloxyethyl carboxybetaine.

[0019] In a second aspect, an embodiment of the present application provides a fiber material, which is prepared using the above-mentioned preparation method.

[0020] In some embodiments, the fiber material is a polymer formed by grafting formula (1), formula (2) and formula (3) on the surface of acrylic fiber:

[0021]

[0022]

[0023] In a third aspect, an embodiment of the present application provides a use of a fiber material, which uses the fiber material as described above to extract uranium from water.

[0024] It can be seen from the above technical solution that the beneficial effects of this application are:

[0025] 1. The preparation method of the present application is to place acrylic fiber, polyguanidine and ultrapure water in an alkaline environment with a pH of 12 to 13 and a temperature of 120 to 150°C to perform a hydrothermal reaction, so that the polyguanidine is stably bound to the surface of the acrylic fiber, and the polyguanidine can be electrostatically adsorbed with the cell membrane of the microorganism, thereby destroying the membrane structure and achieving a sterilization effect; the acrylic fiber modified with polyguanidine is reacted with a zwitterionic monomer with a double bond, a tert-butyl hydroperoxide solution and ultrapure water at a temperature of 70 to 100°C to graft part of the cyanide group in the acrylic fiber on the surface, so that the zwitterionic monomer with a double bond can bring a super hydrophilic surface to the acrylic fiber, which can It can utilize ion solvation to adsorb a large amount of water molecules, thereby repelling and blocking microorganisms, particulate pollutants and oily stains, etc.; by placing bifunctional acrylic fiber in hydroxylamine hydrochloride at pH7.2-9.0, an amine oxime acrylic fiber is formed. The amine oxime group has a strong affinity with uranyl, which can effectively improve the adsorption performance of the material and also give the material a certain active anti-fouling performance; polyguanidine and amine oxime group (active sterilization) and zwitterion (passive anti-fouling) can form a double protection, and polyguanidine can form a synergistic effect with zwitterion monomers and amine oxime groups, weakening microbial adhesion and inhibiting microbial growth, while utilizing zwitterion to improve the mass transfer performance of the material. In this way, the preparation method of the present application is simple and easy to implement, has high applicability, can prepare a fiber material with dual-effect anti-fouling properties of active anti-fouling and passive anti-fouling, significantly improves the anti-fouling performance of the fiber material, and can also improve the adsorption efficiency of the fiber material.

[0026] 2. The fiber material of the present application, due to the grafted polymerization of guanidine groups, can electrostatically adsorb with the microbial cell membrane, thereby destroying the membrane structure and achieving a sterilization effect; due to the polymerization of zwitterionic groups, a super-hydrophilic surface is created, which can utilize ion solvation to adsorb a large amount of water molecules, thereby repelling and blocking microorganisms, particulate pollutants, and oily stains; due to the strong affinity between the amidoxime group and uranyl, the polymerization of the amidoxime group can effectively improve the adsorption performance of the material, further improving the uranium extraction performance and active anti-fouling performance of the material. The above three groups can also produce a synergistic effect, and utilize zwitterions to improve the mass transfer performance of the material, enhance the transfer efficiency of substances (such as gas, liquid or ions) within the material or between interfaces, and thus significantly improve the anti-fouling performance of the fiber, ultimately achieving dual-effect anti-fouling capabilities of active and passive anti-fouling, with a sterilization rate exceeding 99% (active anti-fouling) and an anti-bacterial attachment rate exceeding 90% (passive anti-fouling).

[0027] 3. The purpose of the present application is to use the above-mentioned fiber material for uranium extraction in water bodies. The synergistic effect of the above-mentioned multiple groups can significantly enhance the active and passive anti-fouling capabilities of the fiber material for uranium extraction. Due to the introduction of zwitterionic groups, the fiber material has a strong hydrophilicity, which can greatly improve the uranium extraction efficiency of the fiber material and increase the adsorption capacity, effectively solving the problems of insufficient anti-fouling performance and low adsorption efficiency of existing fiber materials in the use of uranium extraction from seawater. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments one by one. Obviously, the drawings described below are some embodiments of the present application. For those of ordinary skill in the art, other embodiments and drawings can be obtained based on these drawings without inventive work. Various schematic diagrams according to the embodiments of the present application are shown in the drawings. These drawings are not necessarily drawn to scale. For the purpose of clarity, some details are magnified and some details may be omitted.

[0029] Figure 1 A schematic diagram showing the principle of an embodiment of a method for preparing a fiber material of the present invention is shown. DETAILED DESCRIPTION

[0030] The following will be combined with the accompanying drawings corresponding to the specific embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. The following detailed description of the embodiments of the present application provided in the accompanying drawings is not intended to limit the scope of the present application for protection. The described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, various different configurations can be arranged and designed. All other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0031] The present application is described below with reference to specific embodiments and with reference to the accompanying drawings:

[0032] Reference Figure 1 In a first embodiment of the present application, a method for preparing a fiber material is provided, which comprises:

[0033] S1. Add acrylic fiber, polyguanidine and ultrapure water to a reaction vessel, and adjust the pH of the reaction system to between 12.0 and 13.0 with sodium hydroxide. Acrylic fiber, polyguanidine and ultrapure water are added in a certain proportion. Regardless of the proportion of acrylic fiber and polyguanidine, both can react in the next step. The reaction vessel is a reactor. Acrylic fiber, also known as polyacrylonitrile fiber, has the chemical formula It is an important synthetic fiber; polyguanidine is a kind of High molecular compounds such as polyhexamethylene guanidine, and other polyguanidines can also be used; ultrapure water, also known as UP water, refers to water with a resistivity of 18MΩ*cm (25℃). In addition to water molecules, this water contains almost no impurities, let alone organic matter such as bacteria and viruses. In other words, it is water from which almost all atoms except oxygen and hydrogen have been removed.

[0034] S2. Heat the reaction system to 120-150°C and maintain for 18-36 hours to carry out a hydrothermal reaction. Then, wash the product of the hydrothermal reaction several times with ultrapure water and dry it to obtain polyguanidine-modified acrylic fiber. In the process of preparing polyguanidine-modified acrylic fiber, the hydrothermal reaction is the core step. Using a constant temperature heating device or oil bath heating method, heat the above-mentioned reactor to 120-150°C and maintain this temperature range for the above-mentioned time. The acrylic fiber and polyguanidine undergo a hydrothermal reaction. After the reaction is completed, wash it several times with ultrapure water, and it can be washed 3-5 times with the assistance of ultrasound. After cleaning, place it in a vacuum drying oven or other drying device for drying.

[0035] S3. Add polyguanidine-modified acrylic fiber, zwitterionic monomer with double bonds, tert-butyl hydrogen peroxide solution, and ultrapure water into a reaction vessel, heat to 70-100°C and maintain the temperature for 8-24 hours to graft the amino groups in the guanidine on the surface of the polyguanidine-modified acrylic fiber. Then wash the surface-grafted product with ultrapure water several times and dry it to obtain zwitterionic and polyguanidine dual-functionalized acrylic fiber. The optimal ratio of polyguanidine-modified acrylic fiber, zwitterionic monomer with double bonds, and tert-butyl hydrogen peroxide solution can be determined according to needs, and the reaction can be carried out in any ratio. Polyguanidine modification refers to the combination of polyguanidine groups with other polymer matrices, here referring to acrylic fibers grafted with polyguanidine groups through hydrothermal reaction; zwitterionic monomer with double bonds is a type of functional molecule with both zwitterionic groups and polymerizable double bonds, such as 2-methacryloyloxyethylcarboxybetaine; tert-butyl hydrogen peroxide, also known as tert-butyl hydroperoxide, is an organic compound with the chemical formula C4H 10 O2 is a colorless, transparent liquid. The above raw materials are added to a reaction vessel. The reaction vessel here generally refers to a clean container used for the reaction. The reaction vessel can be the same as the reaction vessel used in the previous step, but it must be cleaned and then heated in a water bath or other constant temperature device. Finally, the reaction vessel is cleaned and dried in a manner similar to that in step S2.

[0036] S4, placing the bifunctionalized acrylic fiber in a hydroxylamine hydrochloride solution with a pH of 7.2 to 9.0 for 6 to 12 hours to oxime the remaining cyano groups in the bifunctionalized acrylic fiber; then washing the oxime-treated product with ultrapure water several times and drying it to obtain a fiber material. After completing the bifunctionalization of the zwitterion and polyguanidine, the remaining cyano groups (-CN) in the acrylic fiber need to be further oxime-modified to introduce oxime groups (-C(NH2)=N-OH), thereby improving the performance of the fiber material; similarly, this step can be performed using a reaction container, first pouring the hydroxylamine hydrochloride solution with a pH of 7.2 to 9.0 into the container, then placing the bifunctionalized acrylic fiber therein, and after the reaction is completed, washing and drying it with ultrapure water in a similar manner to the above step S2.

[0037] The fiber material preparation method of the existing technology only has one of the anti-fouling functions of "active anti-fouling" (killing bacteria or microorganisms) or "passive anti-fouling" (preventing bacteria or microorganisms from attaching). The experimental results show that there is only weak active anti-fouling performance and no passive anti-fouling performance. It is impossible to prepare an adsorption fiber material with both anti-fouling capabilities. Although it has good anti-fouling performance, in the current situation of increasing water pollution, the anti-fouling ability needs to be improved.

[0038] The present invention can carry out a hydrothermal reaction by placing acrylic fiber, polyguanidine and ultrapure water in an alkaline environment of pH 12 to 13 and a temperature environment of 120-150°C, so that the polyguanidine is stably bound to the surface of the acrylic fiber, and the polyguanidine can be electrostatically adsorbed with the cell membrane of the microorganism, thereby destroying the membrane structure and achieving a sterilization effect; the acrylic fiber modified with polyguanidine is reacted with a zwitterionic monomer with a double bond, a tert-butyl hydrogen peroxide solution and ultrapure water at a temperature environment of 70-100°C, so that some cyano groups in the acrylic fiber are surface grafted, so that the zwitterionic monomer with a double bond can bring a super hydrophilic surface to the acrylic fiber, which can utilize the ion The subsolvation effect adsorbs a large amount of water molecules, thereby repelling and blocking microorganisms, particulate pollutants and oily stains, etc.; by placing the bifunctionalized acrylic fiber in hydroxylamine hydrochloride at pH 7.2 to 9.0, an amine oxime-modified acrylic fiber is formed. The amine oxime group has a strong affinity with uranyl, which can effectively improve the adsorption performance of the material and also give the material a certain active anti-fouling performance; polyguanidine and amine oxime groups (active sterilization) and zwitterions (passive anti-fouling) can form a double protection, and polyguanidine can form a synergistic effect with zwitterion monomers and amine oxime groups, weakening microbial adhesion and inhibiting microbial growth, while using zwitterions to improve the mass transfer performance of the material. In this way, the present application can prepare a fiber material with dual-effect anti-fouling properties of active anti-fouling and passive anti-fouling, significantly improving the anti-fouling performance of the material, and also improving the adsorption efficiency of the fiber material.

[0039] In some embodiments, the weight percentage of the raw materials added during the entire process is as follows:

[0040] Acrylic fiber, 6.15% to 7.27%; such as 6.15%, 7% or 7.27%;

[0041] Polyguanidine, 1.54% to 1.82%; such as 1.54%, 1.65%, or 1.82%

[0042] Zwitterionic monomers with double bonds, 54.55% to 61.54%; such as 54.55%, 58% or 61.54%;

[0043] Hydroxylamine hydrochloride, 30.77% to 36.36%; such as 30.77%, 33.5% or 36.36%.

[0044] The above ratio of the reaction raw materials is a preferred ratio of raw materials for preparing fiber materials. Under this ratio, each raw material can fully participate in the reaction.

[0045] In some embodiments, in the above step S1, when acrylic fiber, polyguanidine and ultrapure water are added to the reaction container, the mass percentage of ultrapure water in the total amount in the reaction container in this step is at least 95%; in the above step S3, the mass percentage of ultrapure water in the total amount in the reaction container in this step is 92.0~89.9%.

[0046] In some embodiments, in step S3, when the polyguanidine-modified acrylic fiber, the zwitterionic monomer with double bonds, the tert-butyl hydroperoxide solution, and ultrapure water are added to the reaction container, the mass percentage of the tert-butyl hydroperoxide solution is 0.067-0.069%.

[0047] In some embodiments, after step S2, the grafting rate of the polyguanidine-modified acrylic fiber is 10-20%, such as 10, 15, or 20%. Grafting rate = (product weight / raw material weight - 1) * 100%. The grafting rate can be measured by infrared spectroscopy or electronic weighing instrument.

[0048] In the above step S2, the polyguanidine used is polyhexamethyleneguanidine, including polyhexamethyleneguanidine hydrochloride and polyhexamethyleneguanidine phosphate, and the reaction formula is as follows:

[0049]

[0050] In some embodiments, after step S3, the grafting rate of the bifunctionalized acrylic fiber is 18 to 50%, such as 18, 26, 30, 38, 42, or 50%. The zwitterion used in step S3 is 2-methacryloyloxyethyl sulfobetaine, and the reaction formula is as follows:

[0051]

[0052] In some embodiments, the reaction formula of step S4 is as follows:

[0053]

[0054] In some embodiments, the polyguanidine is polyhexamethyleneguanidine, polyhexamethylenebiguanidine, polyaminopropylbiguanidine, polyetherguanidine, polyacrylamideguanidine, or polycarboxyguanidine; and the zwitterionic monomer with a double bond is 2-methacryloyloxyethylsulfobetaine, 2-methacryloyloxyethylphosphocholine, 2-methacrylamidoethylsulfobetaine, or 2-methacryloyloxyethylcarboxybetaine. Various zwitterionic monomers are available, and CAS numbers 3637-26-1, 67881-98-5, 5205-95-8, and 24249-95-4 may be used in this application.

[0055] The following experiment was carried out according to the preparation method of this application:

[0056] Experiment 1

[0057] 1. Add 2g acrylic fiber, 0.5g polyhexamethylene guanidine and ultrapure water to a reactor and adjust the pH of the reaction system to between 12.0 and 13.0 with sodium hydroxide;

[0058] 2. After a hydrothermal reaction at 130°C for 24 hours, the fibers were washed several times with ultrapure water and dried to obtain polyguanidine-modified acrylic fibers with a grafting efficiency of 15.6%.

[0059] 3. The polyguanidine-modified acrylic fiber product from the previous step, 15 g of 2-methacryloyloxyethyl sulfobetaine (54.55% by mass), 150 μL of tert-butyl hydroperoxide solution, and 200 ml of ultrapure water were added to a reaction vessel and surface grafted at 85°C for 8 h. The fiber was then rinsed several times with ultrapure water and dried to obtain a zwitterionic 2-methacryloyloxyethyl sulfobetaine and polyguanidine-bifunctionalized acrylic fiber with a grafting efficiency of 23.1%.

[0060] 4. The bifunctionalized acrylic fiber product from the previous step was placed in 200 ml of a weakly alkaline 5% hydroxylamine solution to oximize the remaining cyanamide in the acrylic fiber. Infrared spectroscopy revealed that all cyanide peaks disappeared, indicating that all cyanide groups in the acrylic fiber were involved. After washing several times with ultrapure water and drying, the dual-effect, anti-fouling, and high-efficiency seawater uranium extraction fiber material was finally obtained.

[0061] After testing, the above material was found to have an adsorption capacity of 169.29 mg / g after 3 days of adsorption in uranium-added seawater with a pH of 8.0 and containing 10 ppm uranium (the uranium-added seawater with 10 ppm uranium is closer to the real seawater system, and is different from the existing technology that uses a 20 ppm pure uranium solution. The uranium-added seawater experiment has a stronger reference value). The adsorption capacity after 3 days of adsorption was 169.29 mg / g, the adsorption capacity after 5 days of adsorption was 184.10 mg / g, and the adsorption capacity after 7 days of adsorption was 192.37 mg / g. The adsorption percentage after 3 days was 88.0%, and the adsorption percentage after 5 days was 95.7%. 6 The antibacterial rate of marine bacteria in the CFU / ml bacterial solution was 99.5% (the experimental sample count was 2, and the blank control sample count was 423), and the anti-attachment rate was 90.2% (the experimental sample count was 20, and the blank control sample count was 204).

[0062] Experiment 2

[0063] 1. 2g of acrylic fiber, 0.5g of polyhexamethylene guanidine, and ultrapure water were added to a reactor. The pH of the reaction system was adjusted to between 12.0 and 13.0 with sodium hydroxide. After a hydrothermal reaction at 130°C for 24 hours, the reaction mixture was washed several times with ultrapure water and dried to obtain polyguanidine-modified acrylic fiber with a grafting efficiency of 15.6%.

[0064] 2. The polyguanidine-modified acrylic fiber product from the previous step, 17.5 g of 2-methacryloyloxyethyl sulfobetaine (58.33% by mass), 150 μL of tert-butyl hydroperoxide solution, and 200 ml of ultrapure water were added to a reaction vessel and surface grafted at 85°C for 8 h. The fiber was then rinsed several times with ultrapure water and dried to obtain a zwitterionic 2-methacryloyloxyethyl sulfobetaine and polyguanidine-bifunctionalized acrylic fiber with a grafting efficiency of 35.8%.

[0065] 3. The bifunctionalized acrylic fiber product of the previous step is placed in 200 ml of weakly alkaline 5% hydroxylamine solution to oximize the remaining cyanamide in the acrylic fiber. The fiber is then washed several times with ultrapure water and dried to finally obtain the dual-effect anti-fouling and high-efficiency seawater uranium extraction fiber material.

[0066] After testing, the above material has an adsorption capacity of 165.04 mg / g after 3 days of adsorption in uranium-added seawater with a pH of 8.0 and containing 10 ppm uranium, 172.99 mg / g after 5 days of adsorption, and 178.52 mg / g after 7 days of adsorption; the adsorption percentage is 92.4% after 3 days and 96.9% after 5 days. 6 The antibacterial rate of marine bacteria in the CFU / ml bacterial solution was 99.3% (the experimental sample count was 3, and the blank control sample count was 423), and the anti-attachment rate was 94.1% (the experimental sample count was 12, and the blank control sample count was 204).

[0067] Experiment 3

[0068] 1. 2g of acrylic fiber, 0.5g of polyhexamethylene guanidine, and ultrapure water were added to a reactor. The pH of the reaction system was adjusted to between 12.0 and 13.0 with sodium hydroxide. After a hydrothermal reaction at 130°C for 24 hours, the reaction mixture was washed several times with ultrapure water and dried to obtain polyguanidine-modified acrylic fiber with a grafting efficiency of 15.6%.

[0069] 2. The polyguanidine-modified acrylic fiber product from the previous step, 20 g of 2-methacryloyloxyethyl sulfobetaine (61.54% by mass), 150 μL of tert-butyl hydroperoxide solution, and 200 ml of ultrapure water were added to a reaction vessel and surface grafted at 85°C for 8 h. The fiber was then rinsed several times with ultrapure water and dried to obtain a zwitterionic 2-methacryloyloxyethyl sulfobetaine and polyguanidine-bifunctionalized acrylic fiber with a grafting efficiency of 47.7%.

[0070] 3. The bifunctionalized acrylic fiber product of the previous step is placed in 200 ml of weakly alkaline 5% hydroxylamine solution to oximize the remaining cyanamide in the acrylic fiber. The fiber is then washed several times with ultrapure water and dried to finally obtain the dual-effect anti-fouling and high-efficiency seawater uranium extraction fiber material.

[0071] After testing, the above material has an adsorption capacity of 159.59 mg / g after 3 days of adsorption in uranium-added seawater with a pH of 8.0 and containing 10 ppm uranium, 162.56 mg / g after 5 days of adsorption, and 165.04 mg / g after 7 days of adsorption; the adsorption percentage is 96.7% after 3 days and 98.5% after 5 days. 6 The antibacterial rate of marine bacteria in the CFU / ml bacterial solution was 99.1% (the experimental sample count was 4, and the blank control sample count was 423), and the anti-attachment rate was 96.6% (the experimental sample count was 7, and the blank control sample count was 204).

[0072] Experiment 4

[0073] 1. 2g of acrylic fiber, 0.5g of polyhexamethylene biguanide, and ultrapure water were added to a reactor. The pH of the reaction system was adjusted to between 12.0 and 13.0 with sodium hydroxide. After a hydrothermal reaction at 130°C for 24 hours, the reaction mixture was washed several times with ultrapure water and dried to obtain polybiguanide-modified acrylic fiber with a grafting efficiency of 16.0%.

[0074] 2. The polybiguanidine-modified acrylic fiber product from the previous step, 20 g of 2-methacryloyloxyethyl sulfobetaine (61.54% by mass), 150 μL of tert-butyl hydroperoxide solution, and 200 ml of ultrapure water were added to a reaction vessel and surface grafted at 85°C for 8 h. The fiber was then rinsed several times with ultrapure water and dried to obtain a zwitterionic 2-methacryloyloxyethyl sulfobetaine and polyguanidine-functionalized acrylic fiber with a grafting efficiency of 43.2%.

[0075] 3. The bifunctionalized acrylic fiber product of the previous step is placed in 200 ml of weakly alkaline 5% hydroxylamine solution to oximize the remaining cyanamide in the acrylic fiber. The fiber is then washed several times with ultrapure water and dried to finally obtain the dual-effect anti-fouling and high-efficiency seawater uranium extraction fiber material.

[0076] After testing, the above material has an adsorption capacity of 163.50 mg / g after 3 days of adsorption in uranium-added seawater with a pH of 8.0 and containing 10 ppm uranium. The adsorption capacity after 5 days of adsorption is 168.11 mg / g, and the adsorption capacity after 7 days of adsorption is 170.32 mg / g. The adsorption percentage after 3 days is 96.0%, and the adsorption percentage after 5 days is 98.7%. 6 The antibacterial rate of marine bacteria in the CFU / ml bacterial solution was 99.5% (the experimental sample count was 2, and the blank control sample count was 423), and the anti-attachment rate was 97.1% (the experimental sample count was 6, and the blank control sample count was 204).

[0077] Experiment 5

[0078] 1. 2g of acrylic fiber, 0.5g of polyhexamethylene guanidine, and ultrapure water were added to a reactor. The pH of the reaction system was adjusted to between 12.0 and 13.0 with sodium hydroxide. After a hydrothermal reaction at 130°C for 24 hours, the reaction mixture was washed several times with ultrapure water and dried to obtain polyguanidine-modified acrylic fiber with a grafting efficiency of 15.6%.

[0079] 2. The polyguanidine-modified acrylic fiber product from the previous step, 20 g of 2-methacryloyloxyethyl phosphorylcholine (61.54% by mass), 150 μL of tert-butyl hydroperoxide solution, and 200 ml of ultrapure water were added to a reaction vessel and surface grafted at 85°C for 8 hours. The fiber was then rinsed several times with ultrapure water and dried to obtain a zwitterionic 2-methacryloyloxyethyl phosphorylcholine and polyguanidine-functionalized acrylic fiber with a grafting efficiency of 36.3%.

[0080] 3. The bifunctionalized acrylic fiber product of the previous step is placed in 200 ml of weakly alkaline 5% hydroxylamine solution to oximize the remaining cyanamide in the acrylic fiber. The fiber is then washed several times with ultrapure water and dried to finally obtain the dual-effect anti-fouling and high-efficiency seawater uranium extraction fiber material.

[0081] After testing, the above material has an adsorption capacity of 154.95 mg / g after 3 days of adsorption in uranium-added seawater with a pH of 8.0 and containing 10 ppm uranium. The adsorption capacity after 5 days of adsorption is 156.90 mg / g, and the adsorption capacity after 7 days of adsorption is 161.28 mg / g. The adsorption percentage after 3 days is 96.1%, and the adsorption percentage after 5 days is 97.3%. 6 The antibacterial rate of marine bacteria in the CFU / ml bacterial solution was 99.1% (the experimental sample count was 4, and the blank control sample count was 423), and the anti-adhesion rate was 95.1% (the experimental sample count was 10, and the blank control sample count was 204).

[0082] Experiment 6

[0083] 1. 2g of acrylic fiber, 0.5g of polyhexamethylene guanidine, and ultrapure water were added to a reactor. The pH of the reaction system was adjusted to between 12.0 and 13.0 with sodium hydroxide. After a hydrothermal reaction at 130°C for 24 hours, the reaction mixture was washed several times with ultrapure water and dried to obtain polyguanidine-modified acrylic fiber with a grafting efficiency of 15.6%.

[0084] 2. The polyguanidine-modified acrylic fiber product from the previous step was directly placed in 200 ml of a weakly alkaline 5% hydroxylamine solution to oxime the remaining cyanamide in the acrylic fiber. The fiber was then washed several times with ultrapure water and dried to obtain a polyguanidine-functionalized amidoxime seawater uranium extraction fiber material without the introduction of zwitterions.

[0085] After testing, the above material has an adsorption capacity of 101.08 mg / g after 3 days of adsorption in uranium-added seawater with a pH of 8.0 and containing 10 ppm uranium, 128.05 mg / g after 5 days of adsorption, and 148.21 mg / g after 7 days of adsorption; the adsorption percentage is 68.2% after 3 days and 86.4% after 5 days. 6 The antibacterial rate of marine bacteria in the CFU / ml bacterial solution was 99.9% (the experimental sample count was 0, and the blank control sample count was 423), and the anti-attachment rate was 18.6% (the experimental sample count was 166, and the blank control sample count was 204).

[0086] Through the above experimental comparison, it can be seen that: different fiber materials were adsorbed in real seawater with added uranium for 3 days and 7 days. By comparing the adsorption percentage of different materials within 3 days, the adsorption percentage within 5 days and the saturated adsorption capacity after 7 days, it was found that the polyguanidine functionalized fiber material without the introduction of zwitterions (Experiment 6) had an adsorption percentage of uranium less than 70% within 3 days, an adsorption percentage less than 90% within 5 days, and a saturated adsorption capacity less than 150 mg / g; while the bifunctionalized fiber materials with the introduction of double-bonded zwitterionic monomers and polyguanidine (Experiments 1-5) had an adsorption percentage of uranium exceeding 88% within 3 days, an adsorption percentage exceeding 95% within 5 days, and a saturated adsorption capacity of up to 190 mg / g. On the other hand, the fiber material of the present application has active anti-fouling ability (antibacterial rate data in Experiments 1-5) and passive anti-fouling ability (anti-attachment rate data in Experiments 1-5). At the same time, the fiber material of the present application greatly improves the uranium extraction rate. Through the percentage of uranium adsorption on days 3 and 5 (comparison of Experiments 1 to 5 with Experiment 6), it can be seen that after the introduction of zwitterionic monomers with double bonds, the adsorption rate of the fiber material is significantly improved, and the rate of uranium adsorption on days 3 is increased by at least 29%.

[0087] The second embodiment of the present application provides a fiber material prepared by the above-mentioned preparation method. For example, the fiber material is prepared by the above-mentioned experiments 1 to 5, and its performance is also as described in the corresponding effects in the above-mentioned experiments 1 to 5.

[0088] The fiber material of the present application, due to the grafted polymerization of guanidine groups, can electrostatically adsorb with the cell membrane of microorganisms, thereby destroying the membrane structure and achieving a sterilization effect; due to the polymerization of zwitterionic groups, a super-hydrophilic surface is brought, which can utilize ion solvation to adsorb a large amount of water molecules, thereby repelling and blocking particulate pollutants and oily stains; due to the strong affinity between the amidoxime group and uranyl, the polymerization of the amidoxime group can effectively improve the adsorption performance of the material, further improving the uranium extraction performance and active anti-fouling performance of the material. The above three groups can produce a synergistic effect, and utilize zwitterions to improve the mass transfer performance of the material, enhance the transfer efficiency of substances (such as gas, liquid or ions) within the material or between interfaces, and thus significantly improve the anti-fouling performance of the fiber, ultimately achieving active and passive anti-fouling dual-effect anti-fouling capabilities, with a sterilization rate of more than 99% (active anti-fouling) and an anti-bacterial attachment rate of more than 90% (passive anti-fouling).

[0089] In some embodiments, the fiber material is a polymer formed by grafting formula (1), formula (2) and formula (3) on the surface of acrylic fiber:

[0090]

[0091] Wherein, n is the degree of polymerization, which has no specific value, formula (1) is guanidine group, which is obtained by graft polymerization in the above step S4, formula (2) is, which is obtained by graft polymerization in the above step S2, and formula (3) is, which is obtained by graft polymerization in the above step S3.

[0092] In some embodiments, the fiber material of the present application is prepared using steps S1-S4 above, wherein the polyguanidine is polyhexamethyleneguanidine hydrochloride, and the zwitterionic monomer with a double bond is 2-methacryloyloxyethyl sulfobetaine. The molecular formula of the finally obtained fiber material is as follows:

[0093]

[0094] In a third aspect, an embodiment of the present application provides a use of a fiber material, which utilizes the fiber material described above and can be manufactured using the fiber material preparation method described above. The fiber material of the present application is used to extract uranium from water, which can be seawater, salt water, uranium-containing wastewater, etc. The fiber material can be used for large-scale production of uranium extraction from seawater. Experimental descriptions of uranium extraction from seawater are as described in Experiments 1-5 above.

[0095] The purpose of the present application is to use the above-mentioned fiber material for uranium extraction in water bodies. The synergistic effect of the above-mentioned multiple groups can significantly improve the active and passive anti-fouling capabilities of the fiber material for uranium extraction. Due to the introduction of zwitterionic groups, the fiber material has strong hydrophilicity, which can greatly improve the uranium extraction efficiency of the fiber material and increase the adsorption capacity, effectively solving the problems of insufficient anti-fouling performance and low adsorption efficiency of existing fiber materials in the use of uranium extraction from seawater.

[0096] Regarding the specific implementation of this application, it should be noted that:

[0097] In the description of this application, reference to the terms "some embodiments", "optional embodiments", "examples", "specific examples", "optional examples" or "optional embodiments" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of this application, but does not mean that these embodiments illustrate and describe all possible forms of the invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification.

[0098] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. The above description is illustrative, not exhaustive, and is not limited to the disclosed embodiments; the above description cannot be understood as a limitation of the present invention. The technical solutions between the various embodiments can be combined with each other, but must be based on the ability of ordinary technicians in this field to implement. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection required by this application. Although the embodiments of the present application have been shown and described, these embodiments can be subjected to various changes, modifications, substitutions and variations without departing from the principles and purpose of the present application. Ordinary technicians in this field can understand that various other specific changes and combinations of embodiments that do not depart from the essence of the present application are made according to the technical inspirations disclosed in this application, and are still within the scope of protection defined by the claims of the present invention and its equivalent technical solutions.

Claims

1. A method for preparing a fiber material, characterized in that: include: Add acrylic fiber, polyguanidine and ultrapure water into a reaction vessel, and adjust the pH of the reaction system to between 12.0 and 13.0 with sodium hydroxide; The reaction system is heated to 120-150° C. and maintained for 18-36 hours to perform a hydrothermal reaction, and the product of the hydrothermal reaction is washed several times with ultrapure water and dried to obtain polyguanidine-modified acrylic fiber; Adding polyguanidine-modified acrylic fiber, a zwitterionic monomer with a double bond, tert-butyl hydroperoxide solution, and ultrapure water into a reaction vessel, heating to 70-100° C. and maintaining for 8-24 hours to graft the amino groups of the guanidine on the surface of the polyguanidine-modified acrylic fiber, and then washing the surface-grafted product several times with ultrapure water and drying to obtain a zwitterionic and polyguanidine dual-functionalized acrylic fiber; The bifunctionalized acrylic fiber is placed in a hydroxylamine hydrochloride solution with a pH of 7.2 to 9.0 for 6 to 12 hours to oximize the remaining cyanamide in the bifunctionalized acrylic fiber; the oximated product is then washed several times with ultrapure water and dried to obtain a fiber material.

2. The method for preparing the fiber material according to claim 1, characterized in that: During the whole process, the mass percentage components of the raw materials added are as follows: The acrylic fiber, 6.15% to 7.27%; The polyguanidine, 1.54% to 1.82%; The zwitterionic monomer with a double bond, 54.55% to 61.54%; The hydroxylamine hydrochloride is 30.77% to 36.36%.

3. The method for preparing the fiber material according to claim 2, characterized in that: When the polyguanidine-modified acrylic fiber, the zwitterionic monomer with double bonds, the tert-butyl hydroperoxide solution and ultrapure water are added into a reaction container, the mass percentage of the tert-butyl hydroperoxide solution is 0.067-0.069%.

4. The method for preparing the fiber material according to claim 2, characterized in that: The grafting rate of the polyguanidine-modified acrylic fiber is 10-20%.

5. The method for preparing the fiber material according to claim 4, characterized in that: The grafting rate of the bifunctional acrylic fiber is 18 to 50%.

6. The method for preparing the fiber material according to claim 1, characterized in that: The polyguanidine is polyhexamethyleneguanidine, polyhexamethylenebiguanidine, polyaminopropylbiguanidine, polyetherguanidine, polyacrylamideguanidine or polycarboxylguanidine.

7. The method for preparing the fiber material according to claim 1, characterized in that: The zwitterionic monomer with a double bond is 2-methacryloyloxyethyl sulfobetaine, 2-methacryloyloxyethyl phosphorylcholine, 2-methacrylamidoethyl sulfobetaine or 2-methacryloyloxyethyl carboxybetaine.

8. A fiber material, characterized in that The product is prepared by the preparation method according to any one of claims 1 to 7.

9. The fiber material according to claim 8, characterized in that The fiber material is a polymer formed by grafting formula (1), formula (2) and formula (3) on the surface of acrylic fiber:

10. A use of a fiber material, characterized in that: The fiber material as claimed in claim 8 or 9 is used for extracting uranium from water.

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