Functionalized modified glass fiber and modification method thereof

Abstract

The invention provides a functional modified glass fiber and a modification method thereof, and the modification method comprises the following steps: (1) immersing magnetic nanoparticles into a carbon source solution, and reacting to obtain magnetic nanoparticles deposited with a carbon source; (2) immersing glass fibers into the modifier aqueous solution for reaction to obtain modified glass fibers; and (3) adding the modified glass fiber and the magnetic nanoparticles deposited with the carbon source into water, uniformly stirring and mixing, and reacting in an inert atmosphere to obtain the functional modified glass fiber. According to the invention, the functionalized modified glass fiber with stable, uniform and firm surface loaded with the carbon-coated magnetic nanoparticles can be obtained; the loading capacity of the carbon-coated magnetic nanoparticles on the glass fiber exceeds 8%, and the saturation magnetization of the glass fiber after functional modification is improved to about 70 emu / g.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber modification, and in particular to a functionalized modified glass fiber and a modification method thereof. Background Art

[0002] Functionalized fibers are ordinary fibers that have been given special functions through physical or chemical methods. The main preparation methods include surface coating, graft copolymerization, and blending modification. Surface coating involves applying a substance with specific functions to the fiber surface, such as applying an antimicrobial agent to produce antimicrobial fibers. Graft copolymerization involves grafting monomers with functional groups onto the fiber macromolecular chain, thereby imparting new functions to the fiber. Blending modification involves the spinning of functional additives into the fiber matrix, such as adding nanoparticles to improve the mechanical properties and functionality of the fiber. To achieve functional design of glass fibers, they are magnetized and modified to produce functional materials. However, glass fibers tend to agglomerate during processing, requiring inorganic acid-assisted dispersion. However, acidic environments corrode the fibers and magnetic components, resulting in a decrease in the chemical stability of the fiber material. Furthermore, existing magnetization methods, while achieving a stable, uniform, and robust bond between magnetic nanoparticles and glass fibers, result in a weakening of the fiber material's magnetic function and insufficient structural reliability, making them incapable of meeting the application requirements of functional materials.

[0003] Based on this, there is an urgent need to provide a functional modified glass fiber and a modification method thereof. Summary of the Invention

[0004] The embodiments of the present invention provide a functional modified glass fiber and a modification method thereof, which can solve the problem that traditional magnetization methods are difficult to achieve stable, uniform and firm bonding of magnetic nanoparticles and glass fibers.

[0005] In a first aspect, the present invention provides a method for modifying a functionalized modified glass fiber, the method comprising the following steps: (1) Immersing magnetic nanoparticles in a carbon source solution to obtain magnetic nanoparticles deposited with carbon source after reaction; (2) Immersing the glass fiber in a modifier aqueous solution to react and obtain modified glass fiber; (3) Adding the modified glass fiber and the magnetic nanoparticles of the deposited carbon source into water, stirring and mixing, and reacting under an inert atmosphere to obtain the functionalized modified glass fiber.

[0006] Preferably, in step (1), the magnetic nanoparticles are Fe3O4 magnetic nanoparticles, Fe2O3 magnetic nanoparticles, CoFe2O4 magnetic nanoparticles or MnZnFe2O4 magnetic nanoparticles.

[0007] More preferably, the magnetic nanoparticles are Fe3O4 magnetic nanoparticles.

[0008] Preferably, the Fe3O4 magnetic nanoparticles are prepared by adding a pH regulator to a metal ion aqueous solution under an inert atmosphere to react, so as to obtain the Fe3O4 magnetic nanoparticles.

[0009] More preferably, the solute of the metal ion aqueous solution is obtained by mixing ferric chloride and ferrous chloride; wherein the molar ratio of the ferric chloride to the ferrous chloride is (1-3):1.

[0010] More preferably, the pH regulator is ammonia water, and the pH value of the ferric ion aqueous solution is adjusted to 10-11 to react.

[0011] Preferably, in step (1), the temperature of the reaction is 80-90℃, and the time is 1-2h.

[0012] Preferably, in step (1), the carbon source solution is a tannic acid aqueous solution; preferably, the concentration of the tannic acid aqueous solution is 5-10g / L, and the soaking time is 30-60min.

[0013] More preferably, in step (2), the solute of the modifier aqueous solution is one of polyethyleneimine, chitosan or casein.

[0014] Preferably, the mass concentration of the modifier aqueous solution is 0.5-1.5%, and the soaking time is 60-80min.

[0015] Preferably, in step (3), the temperature of the reaction is 450-550℃, and the time is 1.5-2.5h.

[0016] Preferably, in step (3), the mass concentration of the mixed solution is 0.2-0.5wt%, and the addition amount of the magnetic nanoparticles deposited with the carbon source is 2.5-10wt% of the addition amount of the modified glass fiber.

[0017] In the second aspect, the application provides a functionalized modified glass fiber prepared by the above-mentioned modified method of any one of the first aspect.

[0018] Compared with the prior art, the application has at least the following beneficial effects: In the present invention, magnetic nanoparticles are first immersed in a carbon source solution to deposit a carbon source on the surface of the magnetic nanoparticles. Then, a modifier aqueous solution is used to modify glass fibers, thereby introducing new active functional groups on the surface of the glass fibers. Finally, the modified glass fibers are mixed with the carbon source-deposited magnetic nanoparticles. The carbon source-deposited magnetic nanoparticles are evenly distributed on the surface of the glass fibers under the action of chemical bonds and physical adsorption. After heating reaction, a functionalized modified glass fiber with a stable, uniform and firmly loaded carbon-coated magnetic nanoparticle surface is obtained. The loading amount of the carbon-coated magnetic nanoparticles on the glass fibers exceeds 8%, and the saturation magnetization of the functionalized modified glass fibers is increased to about 70 emu / g. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0020] Figure 1 is a SEM image of a functionalized modified glass fiber provided in Example 9 of the present invention; Figure 2 is a SEM image of a functionalized modified glass fiber provided in Example 4 of the present invention; Figure 3 This is an SEM image of a functionalized modified glass fiber provided in Comparative Example 3 of the present invention; Figure 4 It is a SEM image of the glass fiber provided by the present invention. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0022] An embodiment of the present invention provides a method for modifying functionalized modified glass fiber, the method comprising the following steps: (1) Immersing magnetic nanoparticles in a carbon source solution to obtain magnetic nanoparticles deposited with carbon source after reaction; (2) Immersing the glass fiber in a modifier aqueous solution to react and obtain modified glass fiber; (3) Adding the modified glass fiber and the magnetic nanoparticles of the deposited carbon source into water, stirring and mixing, and reacting under an inert atmosphere to obtain the functionalized modified glass fiber.

[0023] In an embodiment of the present invention, magnetic nanoparticles are first immersed in a carbon source solution to deposit a carbon source on the surface of the magnetic nanoparticles. Then, a modifier aqueous solution is used to modify the glass fiber, thereby introducing new functional groups on the surface of the glass fiber. Finally, the modified glass fiber is mixed with the magnetic nanoparticles on which the carbon source is deposited. The magnetic nanoparticles on which the carbon source is deposited are evenly distributed on the surface of the glass fiber under the action of chemical bonds and physical adsorption. After a heating reaction, a functionalized modified glass fiber having a stable, uniform, and firmly loaded carbon-coated magnetic nanoparticle surface is obtained. The loading amount of the carbon-coated magnetic nanoparticles on the glass fiber exceeds 8%, and the saturation magnetization intensity of the functionalized modified glass fiber is increased to about 70 emu / g.

[0024] According to some preferred embodiments, in step (1), the magnetic nanoparticles are Fe3O4 magnetic nanoparticles, Fe2O3 magnetic nanoparticles, CoFe2O4 magnetic nanoparticles or MnZnFe2O4 magnetic nanoparticles.

[0025] In an embodiment of the present invention, the aforementioned types of magnetic nanoparticles are immersed in a carbon source solution, so that the carbon source is deposited on the surface of the magnetic nanoparticles. After sintering, carbon-coated magnetic nanoparticles are formed. The carbon-coated magnetic nanoparticles not only improve the stability of the magnetic nanoparticle loading on the surface of the glass fiber, but also impart a certain electrical conductivity to the glass fiber, thereby ensuring the antistatic properties of the material after subsequent papermaking. Furthermore, experiments conducted by the present invention have confirmed that, under the same loading conditions, when Fe3O4 magnetic nanoparticles are used, the stable and firm bonding of the magnetic nanoparticles to the glass fiber is maximized, thereby ensuring the high magnetic strength of the functionalized glass fiber.

[0026] According to some preferred embodiments, the magnetic nanoparticles are Fe3O4 magnetic nanoparticles.

[0027] According to some preferred embodiments, the Fe3O4 magnetic nanoparticles are prepared by the following method: under an inert atmosphere, a pH regulator is added to a metal ion aqueous solution for reaction to obtain Fe3O4 magnetic nanoparticles; the solute of the metal ion aqueous solution is obtained by mixing ferric chloride and ferrous chloride; wherein the molar ratio of ferric chloride to ferrous chloride is 2:1; the pH regulator is ammonia water, and the pH value of the iron ion aqueous solution is adjusted to 10-11 for reaction.

[0028] According to some preferred embodiments, in step (1), the reaction temperature is 80-90°C (for example, 80°C, 85°C or 90°C), and the reaction time is 1-2h (for example, 1h, 1.5h or 2h).

[0029] In the embodiment of the present invention, under an inert atmosphere and heating conditions (such as nitrogen protection), ammonia water is added dropwise to the aqueous solution formed by ferric chloride and ferrous chloride to adjust the pH value to a strong alkaline state, and the molar ratio of ferric chloride and ferrous chloride in the solution is controlled so that Fe 2+ and Fe 3+ The ions / Fe(OH)2 and Fe(OH)3 fully react to produce black Fe3O4 magnetic nanoparticles with less impurities.

[0030] It should be noted that, in the embodiment of the present invention, after the reaction is completed, the reaction product is centrifuged to collect the Fe3O4 magnetic nanoparticle solid product, and the Fe3O4 magnetic nanoparticle solid product is washed 3-5 times with ethanol and distilled water respectively to obtain Fe3O4 magnetic nanoparticles.

[0031] According to some preferred embodiments, in step (1), the carbon source solution is a tannic acid aqueous solution; preferably, the concentration of the tannic acid aqueous solution is 5-10 g / L (for example, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 9 g / L or 10 g / L), and the soaking time is 30-60 min (for example, 30 min, 40 min, 50 min or 60 min).

[0032] In the embodiment of the present invention, considering that tannic acid contains a large amount of catechol and pyrogallol groups and can be carbonized after heat treatment, by immersing the prepared magnetic nanoparticles in a tannic acid solution of a certain concentration, the groups can undergo a strong coordination effect with the trivalent iron ions on the surface of the Fe3O4 magnetic nanoparticles, thereby stably depositing on the surface of the magnetic nanoparticles, and after subsequent heat treatment, stable carbon-encapsulated Fe3O4 magnetic nanoparticles can be formed; the experiments of the present invention have confirmed that if the concentration of the tannic acid solution is too low, the carbon source deposited on the surface of the magnetic nanoparticles will be less, which is not conducive to ensuring the stable binding of the magnetic nanoparticles on the surface of the glass fiber; and if the concentration of the tannic acid solution is too high, the magnetic nanoparticles will easily agglomerate, which is not conducive to the subsequent uniform distribution of the magnetic nanoparticles on the surface of the glass fiber.

[0033] According to some preferred embodiments, in step (2), the solute of the modifier aqueous solution is one of polyethyleneimine, chitosan or casein; the mass concentration of the modifier aqueous solution is 0.5-1.5% (for example, it can be 0.5%, 1% or 1.5%), and the soaking time is 60-80 min (for example, it can be 60 min, 65 min, 70 min, 75 min or 80 min).

[0034] In the embodiment of the present invention, by immersing the glass fiber in a certain concentration of a modifier aqueous solution for a period of time, a large number of active functional groups can be introduced on the surface of the glass fiber. The presence of the active functional groups can provide the glass fiber with abundant reaction sites and interaction sites. When the glass fiber is mixed with a magnetic hybrid nanoparticle solution, the glass fiber can form stronger chemical bonds, hydrogen bonds or stronger physical adsorption with the corresponding groups in the tannic acid deposited on the surface of the magnetic nanoparticles through the reaction sites on its surface, thereby significantly enhancing the interfacial bonding strength between the magnetic nanoparticles and the glass fiber. At the same time, it was found in the embodiment of the present invention that if the concentration of the modifier aqueous solution is too low, the binding sites of the magnetic nanoparticles and the glass fiber will be insufficient, and the interfacial bonding effect will decrease; if the concentration of the modifier aqueous solution is too high, the modifier concentration on the surface of the glass fiber will be too high, thereby causing the magnetic nanoparticles to agglomerate, affecting the dispersibility of the magnetic nanoparticles.

[0035] According to some preferred embodiments, in step (3), the mass concentration of the mixed solution is 0.2-0.5 wt% (for example, it can be 0.2 wt%, 0.3 wt%, 0.4 wt% or 0.5 wt%), and the added amount of magnetic nanoparticles of the deposited carbon source is 2.5-10 wt% (for example, it can be 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%).

[0036] In an embodiment of the present invention, magnetic nanoparticles of a deposited carbon source and modified glass fibers are dispersed in water in proportion and stirred to form a mixed solution of a certain concentration. Tannic acid deposited on the surface of the magnetic nanoparticles can promote the binding of the magnetic nanoparticles to the glass fibers through chemical bonding with active groups on the surface of the modified glass fibers, thereby stably, uniformly, and firmly loading the magnetic nanoparticles onto the glass fiber surface. At the same time, the magnetization effect of different addition amounts of magnetic nanoparticles is studied in an embodiment of the present invention. The addition amount of magnetic nanoparticles of a deposited carbon source is 10.0 wt%, which is close to the peak value. Further addition will only slightly improve the magnetization effect of the glass fibers and increase the manufacturing cost.

[0037] According to some preferred embodiments, in step (3), the temperature of the reaction is 450-550℃ (for example, it can be 450℃, 500℃ or 550℃), and the time is 1.5-2.5h (for example, it can be 1.5h, 2h or 2.5h).

[0038] In the embodiments of the present application, the modified glass fibers after the mixing reaction and the magnetic nanoparticles with the deposited carbon source are reacted under an inert atmosphere and heated to a certain temperature. During the reaction process, the magnetic nanoparticles Fe3O4 can act as catalytic sites to reduce the activation energy of tannic acid carbonization and promote the uniform coating of the carbon layer on the Fe3O4 magnetic nanoparticles, thereby forming core-shell magnetic nanoparticles with carbon-coated Fe3O4 magnetic nanoparticles on the surface of the glass fibers. The presence of the carbon-coated layer not only imparts good electrical conductivity to the glass fibers, but also inhibits the agglomeration of the magnetic nanoparticles and enhances the stability of the magnetic nanoparticles on the surface of the glass fibers.

[0039] Further, by precisely controlling the temperature during the heating reaction, a uniform carbon layer can be coated on the surface of the magnetic nanoparticles without damaging the magnetic properties of the magnetic nanoparticles. If the reaction temperature is too low, the tannic acid carbonization will not be complete and organic groups will be left over. If the reaction temperature is too high, the magnetic particles will be reduced to FeO or metallic iron, which is not conducive to maintaining the magnetic strength of the glass fibers, and the glass fibers may be damaged.

[0040] The present application also provides a functionalized modified glass fiber prepared by any of the above modification methods.

[0041] Further, the embodiments of the present application also provide a preparation method of a functionalized filter material using the functionalized modified glass fiber described above, which comprises the following steps: S1, modifying the first glass fiber with magnetic nanoparticles and a modified water solution to obtain a functionalized modified glass fiber; (using the modification method of the functionalized modified fiber described above) S2, respectively beating the second glass fiber and the functionalized glass fiber to obtain glass fiber pulp and functionalized modified glass fiber pulp; wherein the second glass fiber is unmodified glass fiber; S3, mixing and conveying the glass fiber pulp and the functionalized modified glass fiber pulp to the net part for molding, and applying a magnetic field to control the settlement of the functionalized glass fiber during the molding process, and obtaining the functionalized filter material after drying.

[0042] In an embodiment of the present invention, the glass fiber is first modified using an aqueous solution of magnetic nanoparticles and a modifier. The magnetic nanoparticles and the modifier can be stably, uniformly and firmly loaded on the surface of the glass fiber under the synergistic action of chemical bonds and physical adsorption, thereby obtaining a functionalized modified glass fiber coated with carbon-coated magnetic nanoparticles. Subsequently, the functionalized modified glass fiber and the unmodified glass fiber are pulped and mixed separately, and the mixed fiber pulp is further transported to a mesh for molding. At the same time, an external magnetic field is used to induce graded sedimentation of the glass fiber, thereby forming a functionalized filter material with a gradient structure. The presence of the magnetic nanoparticles increases the specific surface area of ​​the fiber, improves the filtration efficiency of the filter material, and increases its dust holding capacity by 130%. In addition, the magnetic nanoparticles make the filter material have a certain conductivity, and the electrostatic voltage half-life of the filter material is shortened by 6.5s.

[0043] According to some preferred embodiments, the first glass fiber and the second glass fiber have different diameters.

[0044] In an embodiment of the present invention, a first glass fiber is first modified using magnetic nanoparticles and a modifier aqueous solution so that a certain amount of magnetic nanoparticles is loaded on the surface of the first glass fiber to impart magnetization strength. An unmodified second glass fiber is then mixed with the modified second fiber slurry and transported to a mesh section for forming. During the forming process, the sedimentation rate of the modified glass fiber is controlled by a magnetic field, thereby achieving graded sedimentation of the modified glass fiber and the unmodified glass fiber, thereby obtaining a functionalized filter material with a gradient structure.

[0045] In an embodiment of the present invention, to obtain a functionalized filter material with a gradient structure, the first and second glass fibers have different diameters. For example, when the first glass fiber is a coarse glass fiber, the second glass fiber is a fine glass fiber; and when the first glass fiber is a fine glass fiber, the second glass fiber is a coarse glass fiber. The coarse glass fiber has a diameter of 4-6 μm, and the fine glass fiber has a diameter of 0.5-1 μm. The first glass fiber is preferably a fine glass fiber, and the second glass fiber is preferably a coarse glass fiber. By adjusting the ratio of the two fiber diameters, a functionalized filter material with excellent filtration efficiency and dust holding capacity can be prepared.

[0046] In some specific embodiments, the functionalized modified glass fiber and the second glass fiber (unmodified glass fiber) are mixed with water and beaten according to a certain beating degree. During the beating process, the beating degree of the glass fiber with a larger diameter (coarse glass fiber) is controlled to be 10-30°SR, and the beating degree of the glass fiber with a smaller diameter (fine glass fiber) is controlled to be 30-60°SR, which is conducive to obtaining glass fiber slurry and functionalized modified glass fiber slurry with good water filterability and web uniformity.

[0047] According to some preferred embodiments, in step (3), the mass ratio of the glass fiber slurry to the functionalized modified glass fiber slurry is 1:(0.5-2) (for example, it can be 1:0.5, 1:1, 1:1.5 or 1:2), and the slurry speed of the mixed fiber slurry is 40-60 m / min.

[0048] In an embodiment of the present invention, glass fibers and functionalized modified glass fiber slurry are mixed in a certain proportion to form a mixed fiber slurry. This slurry is then fed to a mesh for shaping. By controlling the slurry velocity and applying a certain magnetic field to the functionalized modified glass fibers, the magnetic fiber units in the slurry are oriented along the magnetic field, thereby forming a filter material with good mechanical strength, dust holding capacity, and a gradient structure. A too fast slurry velocity results in a too short residence time of the fibers in the magnetic field, resulting in poor graded sedimentation, while a too slow slurry velocity results in low production efficiency.

[0049] According to some preferred embodiments, in step S3 , the intensity of the applied magnetic field is 0.4-0.6 T (for example, 0.4 T, 0.5 T, or 0.6 T).

[0050] According to some preferred embodiments, in step S3, the intensity of the applied magnetic field is distributed in three sections; wherein the three sections distribution includes a decreasing distribution or a uniform distribution.

[0051] In an embodiment of the present invention, after the mixed fiber slurry is transported to the mesh portion, an external magnetic field of a certain strength (such as an electromagnetic generator) is set above the mesh portion, and the setting position and strength of the external magnetic field are controlled to utilize the external magnetic field force to break the disordered state of the internal structure of the slurry, thereby prompting the fiber units to move or arrange in a directional manner along the direction of force application. The glass fibers are modified using magnetic nanoparticles so that the modified fibers can slowly settle under the action of the magnetic field, while the unmodified glass fibers settle by gravity, thereby achieving graded sedimentation of the modified glass fibers and the unmodified glass fibers, and thus preparing a functional filter material with a gradient structure.

[0052] Furthermore, in an embodiment of the present invention, the decreasing distribution is specifically that starting from the slurry feeding, the magnetic field decreases with an intensity of 0.6, 0.4, and 0.2T; the uniform distribution is specifically that the three sections of magnetic field are all 0.6T or the three sections of magnetic field are all 0.4T; by adjusting the distribution form, distribution range, intensity and content of magnetic nanofibers of the magnetic field, the graded sedimentation of glass fibers can be achieved, thereby being able to prepare a functional filter material with a gradient structure, high dust holding capacity, high filtration efficiency and good mechanical strength; and this method has the advantages of simple operation, strong controllability and wide range of application.

[0053] The present invention also compared the effects of magnetic field distribution on the performance of functionalized filter materials. If a uniformly distributed magnetic field is used, when the magnetic field intensity is too high, the fibers tend to adhere to the equipment, preventing smooth paper production. If the magnetic field is too low, turbulence near the slurry inlet can affect the fiber suspension. Therefore, the present invention preferably uses a three-stage decreasing magnetic field, which ensures effective fiber suspension in the slurry while allowing subsequent fibers to settle.

[0054] In order to more clearly illustrate the technical solutions and advantages of the present invention, a functionalized modified glass fiber and a modification method thereof are described in detail through the following examples.

[0055] Example 1: (1) Ferric chloride and ferrous chloride were added to water in proportion to prepare a metal ion aqueous solution (wherein the molar ratio of ferric chloride to ferrous chloride was 2:1). Under a nitrogen atmosphere, the temperature of the reaction solution was raised to 85°C and stirred at a speed of 900 r / min. A pH regulator (ammonia water) was added to the metal ion aqueous solution to adjust the pH value to 11 and then reacted for 1 hour. After centrifugation, the solution was washed four times with ethanol and distilled water in sequence to obtain Fe3O4 magnetic nanoparticles. (2) Fe3O4 magnetic nanoparticles were immersed in a carbon source solution (tannic acid aqueous solution with a concentration of 8 g / L) and immersed in the solution for 30 min to obtain Fe3O4 magnetic nanoparticles with deposited carbon source; (3) Immersing the glass fiber in a modifier aqueous solution (chitosan aqueous solution with a mass concentration of 1%) for reaction for 60 minutes to obtain a modified glass fiber; (4) The modified glass fiber and Fe3O4 magnetic nanoparticles as a deposited carbon source were added to water and stirred for 3 h to form a mixed solution with a mass concentration of 0.5 wt%, and then heated to 500 °C under a nitrogen atmosphere for 2 h to obtain functionalized modified glass fiber; wherein the amount of Fe3O4 magnetic nanoparticles as a deposited carbon source added was 5 wt% of the amount of modified glass fiber added.

[0056] Example 2: Example 2 is basically the same as Example 1, except that in step (3), the modifier aqueous solution is a polyethyleneimine aqueous solution with a mass concentration of 1%.

[0057] Example 3: Example 3 is basically the same as Example 1, except that in step (3), the modifier aqueous solution is a casein aqueous solution with a mass concentration of 1%.

[0058] Example 4: Example 4 is basically the same as Example 1, except that in step (3), the modifier aqueous solution is a polyethyleneimine aqueous solution with a mass concentration of 0.5%.

[0059] Example 5: Example 5 is basically the same as Example 1, except that in step (3), the modifier aqueous solution is a polyethyleneimine aqueous solution with a mass concentration of 1.5%.

[0060] Example 6 Example 6 is basically the same as Example 1, except that: in step (4), the modified glass fiber and Fe3O4 magnetic nanoparticles as a deposited carbon source are added to water and stirred for 3 hours to form a mixed solution with a mass concentration of 0.5wt%, and then heated to 500°C under a nitrogen atmosphere for reaction for 2 hours to obtain functionalized modified glass fiber; wherein the amount of Fe3O4 magnetic nanoparticles as a deposited carbon source added is 10wt% of the amount of modified glass fiber added.

[0061] Example 7 Example 7 is basically the same as Example 1, except that: the modified glass fiber and Fe3O4 magnetic nanoparticles as a deposited carbon source are added to water and stirred for 3 hours to form a mixed solution with a mass concentration of 0.5wt%, and then heated to 500°C under a nitrogen atmosphere for 2 hours to obtain functionalized modified glass fiber; wherein the amount of Fe3O4 magnetic nanoparticles as a deposited carbon source added is 15wt% of the amount of modified glass fiber added.

[0062] Example 8 Example 8 is basically the same as Example 1, except that: the modified glass fiber and Fe3O4 magnetic nanoparticles as a deposited carbon source are added to water and stirred for 3 hours to form a mixed solution with a mass concentration of 0.5wt%, and then heated to 500°C under a nitrogen atmosphere for 2 hours to obtain functionalized modified glass fiber; wherein the amount of Fe3O4 magnetic nanoparticles as a deposited carbon source added is 20wt% of the amount of modified glass fiber added.

[0063] Example 9 Example 9 is basically the same as Example 6, except that step (1) is removed. In step (2), Fe2O3 magnetic nanoparticles are immersed in a carbon source solution (an aqueous solution of tannic acid with a concentration of 8 g / L), and the Fe2O3 magnetic nanoparticles with deposited carbon source are obtained after immersion reaction for 30 minutes.

[0064] Example 10 Example 10 is substantially the same as Example 6, except that step (1) is omitted. In step (2), Fe2O3 magnetic nanoparticles are immersed in a carbon source solution (an aqueous solution of tannic acid having a concentration of 8 g / L), and the Fe2O3 magnetic nanoparticles with deposited carbon source are obtained after immersion reaction for 30 minutes.

[0065] Example 11 Example 11 is basically the same as Example 6, except that step (1) is removed. In step (2), the CoFe2O4 magnetic nanoparticles are immersed in a carbon source solution (an aqueous solution of tannic acid with a concentration of 8 g / L), and the CoFe2O4 magnetic nanoparticles with deposited carbon source are obtained after immersion reaction for 30 minutes.

[0066] Example 12 Example 12 is basically the same as Example 1, except that in step (2), the concentration of the tannic acid aqueous solution is 15 g / L.

[0067] Example 13 Example 13 is basically the same as Example 1, except that in step (3), the mass concentration of the modifier aqueous solution is 2%.

[0068] Comparative Example 1 The glass fiber was immersed in a modifier aqueous solution (chitosan aqueous solution with a mass concentration of 1%) and reacted for 60 minutes to obtain a functionalized modified glass fiber.

[0069] Comparative Example 2 Glass fibers and Fe2O3 magnetic nanoparticles were added to water and stirred for 3 hours to form a mixed solution with a mass concentration of 0.5 wt% to obtain functionalized modified glass fibers; wherein the amount of Fe2O3 magnetic nanoparticles added was 5 wt% of the amount of glass fibers added.

[0070] Comparative Example 3 (1) Immersing the glass fiber in a modifier aqueous solution (a polyethyleneimine aqueous solution with a mass concentration of 1%) for reaction for 60 minutes to obtain a modified glass fiber; (2) The modified glass fiber and Fe3O4 magnetic nanoparticles were added into water and stirred for 3 h to form a mixed solution with a mass concentration of 0.5 wt% to obtain functionalized modified glass fiber; wherein the amount of Fe3O4 magnetic nanoparticles added was 5 wt% of the amount of modified glass fiber added.

[0071] Comparative Example 4 (1) Immersing the glass fiber in a modifier aqueous solution (chitosan aqueous solution with a mass concentration of 1%) for reaction for 60 minutes to obtain a modified glass fiber; (2) The modified glass fiber and CoFe2O4 magnetic nanoparticles (5 wt%) were added to water and stirred for 3 h to form a mixed solution with a mass concentration of 0.5 wt% to obtain functionalized modified glass fiber; wherein the amount of CoFe2O4 magnetic nanoparticles added was 5 wt% of the amount of modified glass fiber added.

[0072] Comparative Example 5 (1) Immersing the glass fiber in a modifier aqueous solution (chitosan aqueous solution with a mass concentration of 1%) for reaction for 60 minutes to obtain a modified glass fiber; (2) The modified glass fiber and MnZnFe2O4 magnetic nanoparticles were added into water and stirred for 3 h to form a mixed solution with a mass concentration of 0.5 wt% to obtain functionalized modified glass fiber; wherein the amount of MnZnFe2O4 magnetic nanoparticles added was 5 wt% of the amount of modified glass fiber added.

[0073] Comparative Example 6 Comparative Example 6 is basically the same as Example 1, except that step (3) is removed, that is, the glass fiber is not modified using the modifier aqueous solution.

[0074] Comparative Example 7 (1) Immersing the glass fiber in a modifier aqueous solution (chitosan aqueous solution with a mass concentration of 1%) for reaction for 60 minutes to obtain a modified glass fiber; (2) The modified glass fiber and silica-coated Fe3O4 magnetic nanoparticles were added to water and stirred for 3 h to form a mixed solution with a mass concentration of 0.5 wt% to obtain functionalized modified glass fiber; wherein the amount of silica-coated Fe3O4 magnetic nanoparticles added was 5 wt% of the amount of modified glass fiber added.

[0075] The functionalized modified glass fibers in Examples 1 to 13 and Comparative Examples 1 to 7 were subjected to performance tests. The test results are shown in Table 1.

[0076] Magnetic nanoparticle loading test: After modification, wash and dry, and calculate the ratio of the mass difference before and after modification to the original fiber Saturation magnetization test: The vibrating sample magnetometer (VSM) is used for testing. The sample is placed in a uniform magnetic field. When the sample is magnetized, it vibrates under an external alternating magnetic field or mechanical vibration, thereby generating an induced electromotive force. The magnetization intensity can be calculated by measuring the electromotive force. Remanence test: Similar to the saturation magnetization test, the remanence magnetization is directly read when the magnetic field is zero by measuring the vibration-induced electromotive force of the sample in the magnetic field and drawing a hysteresis loop.

[0077] Table 1 The saturation magnetization reflects the maximum degree of arrangement of the magnetic moments in the material. Generally speaking, the higher the saturation magnetization, the greater the maximum magnetic strength that the material can achieve, that is, the stronger the magnetism of the material as a whole. The magnitude of the remanent magnetism directly reflects the residual magnetic strength of the material in the absence of an external magnetic field. As can be seen from Table 1, neither the glass fiber itself nor the modifier has magnetism, and the saturation magnetization mainly comes from the magnetic nanoparticles; Comparative Examples 2-5 use unwrapped magnetic nanoparticles, which have poor stability under acidic conditions and low retention on the glass fiber after the reaction. Further, combined with Figures 1 to 4 It can be seen that the method in the embodiment of the present invention can uniformly and stably fix the magnetic nanoparticles on the surface of the glass fiber, and as the loading amount of the magnetic nanoparticles increases, the saturation magnetization intensity of the functionalized modified glass fiber is enhanced, wherein the addition amount of 10.0% is close to the peak value, and further addition will have little improvement in the magnetization effect and will increase the manufacturing cost.

[0078] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for modifying functionalized modified glass fiber, characterized in that: The modification method comprises the following steps: (1) immersing magnetic nanoparticles in a carbon source solution to obtain magnetic nanoparticles depositing carbon source after reaction; (2) immersing the glass fiber in a modifier aqueous solution to react and obtain a modified glass fiber; (3) adding the modified glass fiber and the magnetic nanoparticles of the deposited carbon source into water, stirring and mixing, and reacting under an inert atmosphere to obtain the functionalized modified glass fiber.

2. The modification method according to claim 1, characterized in that In step (1), the magnetic nanoparticles are Fe3O4 magnetic nanoparticles, Fe2O3 magnetic nanoparticles, CoFe2O4 magnetic nanoparticles or MnZnFe2O4 magnetic nanoparticles.

3. The modification method according to claim 2, characterized in that The magnetic nanoparticles are Fe3O4 magnetic nanoparticles.

4. The modification method according to claim 3, characterized in that The Fe3O4 magnetic nanoparticles are prepared by the following method: adding a pH regulator to a metal ion aqueous solution under an inert atmosphere to react to obtain Fe3O4 magnetic nanoparticles; Preferably, the solute of the metal ion aqueous solution is obtained by mixing ferric chloride and ferrous chloride; wherein the molar ratio of ferric chloride to ferrous chloride is 2:1; More preferably, the pH adjuster is ammonia water, and the pH value of the iron ion aqueous solution is adjusted to 10-11 for reaction.

5. The modification method according to claim 1, characterized in that In step (1), the reaction temperature is 80-90° C. and the reaction time is 1-2 h.

6. The modification method according to claim 1, characterized in that In step (1), the carbon source solution is a tannic acid aqueous solution; preferably, the concentration of the tannic acid aqueous solution is 5-10 g / L, and the soaking time is 30-60 min.

7. The modification method according to claim 1, characterized in that In step (2), the solute of the modifier aqueous solution is one of polyethyleneimine, chitosan or casein; and / or The mass concentration of the modifier aqueous solution is 0.5-1.5%, and the soaking time is 60-80 minutes.

8. The modification method according to claim 1, characterized in that In step (3), the mass concentration of the mixed solution is 0.2-0.5 wt %, and the amount of magnetic nanoparticles added as the deposited carbon source is 2.5-10 wt % of the amount of modified glass fiber added.

9. The modification method according to claim 1, characterized in that In step (3), the reaction temperature is 450-550° C. and the reaction time is 1.5-2.5 h.

10. A functionalized modified glass fiber, characterized in that: The invention is prepared by the modification method according to any one of claims 1 to 9.

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