Nanometer / micrometer particle polymer composite fiber and preparation method thereof

Abstract

The invention provides a nano / micron particle polymer composite fiber and a preparation method thereof, a mixed solution of nano / micron particles and a polymer is extruded by wet spinning to form a liquid fiber, and a coaxial shell layer water flow is applied to the periphery of the liquid fiber while the liquid fiber is extruded, so that the nano / micron particle polymer composite fiber is obtained. The flow velocity of the coaxial shell layer water flow is greater than that of the liquid fiber, and the liquid fiber is stretched and cured under the action of the coaxial shell layer water flow to form the nano / micron particle polymer composite fiber. According to the preparation method of the nano / micron particle polymer composite fiber, the micron fiber can be directly prepared, the method has the advantages that the method is simple, the diameter of the fiber is easy to adjust, and the universality is good, and the problems that only millimeter fiber can be prepared and micron fiber is difficult to prepare in the current wet spinning method are solved.

Description

Technical Field

[0001] The invention relates to the technical field of nano composite materials, in particular to a nano / micron particle polymer composite fiber and a preparation method thereof. Background Art

[0002] Nanomaterials are a large class of functional materials that are currently widely studied and applied. Due to their special molecular structure, good dispersibility, and large specific surface area, nanomaterials are widely used in energy, optoelectronics, environment, coatings, chemistry, biology, daily necessities, and other fields. However, nanomaterials have small particle sizes and are difficult to disperse, which makes them difficult to collect and reuse. In order to promote the recycling of nanomaterials, it is necessary to develop a highly dispersed, micron-fiberized, porous, large-surface, and easy-to-use nanocomposite material.

[0003] At present, the methods for preparing nano / micron particle polymer composite fibers are: electrospinning, melt spinning, and wet spinning. Electrospinning is to use a high voltage electric field to pull a nano / micron particle polymer mixed solution into nanofilaments. Since the electric polarization characteristics of nano / micron particles are different from those of polymers, the nano / micron particles in the nano / micron particle polymer composite fibers prepared by electrospinning are easily separated from the nanofibers, and the composite fibers generally made by electrospinning are non-porous solid fibers. Melt spinning generally heats and melts the polymer, mixes the nano / micron particles, and then extrudes it into fibers through high pressure. Generally, solid fibers are also prepared. The purpose is to improve the physical properties of polymer fibers by doping with nano / micron particles. Wet spinning is to use high pressure to extrude the polymer-nano / micron particle mixed solution directly into an aqueous solution, but due to the blocking effect of nano / micron particles and the high viscosity of the polymer, wet spinning can generally only prepare millimeter fibers, and it is difficult to prepare micron fibers; sometimes in order to reduce the fiber diameter, mechanical pulling of the fiber ends is also used, but due to the limited stretching ratio of the fiber, direct mechanical stretching is easy to break the fiber. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a nano / micron particle polymer composite fiber and a preparation method thereof. The preparation method of the nano / micron particle polymer composite fiber provided by the present invention can directly prepare micron fibers, and also has the advantages of simple method, easy adjustment of fiber diameter and good versatility.

[0005] The present invention provides a method for preparing nano / micron particle polymer composite fibers, comprising the following steps: A mixed solution of nano / micro particles and polymers is extruded by wet spinning to form liquid fibers. While the liquid fibers are being extruded, a coaxial shell water flow is applied to the periphery of the liquid fibers. The flow rate of the coaxial shell water flow is greater than the flow rate of the liquid fibers. Under the action of the coaxial shell water flow, the liquid fibers are stretched and solidified to form nano / micro particle polymer composite fibers.

[0006] The present invention provides a method for preparing a nano / micron particle polymer composite fiber. By applying a high-speed coaxial shell water flow around the liquid fiber while the liquid fiber is being extruded, on the one hand, the liquid fiber formed by extruding a mixed solution of nano / micron particles and a polymer can achieve a rapid phase transition from liquid phase to solid phase and quickly solidify, thereby locking the nano / micron particles on the surface and inside of the composite fiber; on the other hand, since the flow rate of the coaxial shell water flow is greater than the flow rate of the liquid fiber, the coaxial shell water flow stretches the thicker millimeter-level fiber into a thinner micron fiber. Compared with the existing method for preparing micron fibers by mechanical stretching, the method provided by the present invention The preparation method of nano / micron particle polymer composite fiber does not need to be divided into multiple wet areas and dry areas, and does not need to be equipped with multi-stage mechanical rollers, which is simpler; the diameter of the nano / micron particle polymer composite fiber can be adjusted only by adjusting the extrusion speed of the mixed solution of nano / micron particles and polymer and the flow rate of the coaxial shell water flow, and the diameter of the composite fiber is easier to adjust; because the micron fiber is stretched in liquid state instead of being stretched after solidification, the problem of fiber being torn is not easy to occur in the preparation process; and it is suitable for polymer mixed solutions with nano / micron particles dispersed in different types and concentrations, and has good versatility.

[0007] In one possible implementation, the volume flow rate of the mixed solution of nano / micro particles and polymer is 0.01 mL / min-50 mL / min, preferably 0.1 mL / min-1 mL / min. Controlling the flow rate of the mixed solution of nano / micro particles and polymer within the above range is conducive to forming uniform and continuous fibers.

[0008] In a possible implementation, the volume flow rate of the coaxial shell water flow is 1 mL / min-2000 mL / min, preferably 2 mL / min-200 mL / min. Controlling the volume flow rate of the coaxial shell water flow within the above range is more conducive to obtaining stable micron fibers.

[0009] In a possible embodiment, the ratio of the volume flow rate of the mixed solution of the nano / micro particles and the polymer to the volume flow rate of the coaxial shell water flow is 1:(1.5-40), preferably 1:(2-10). By adjusting the relative flow rates of the mixed solution and the coaxial shell water flow, composite fibers of different diameters can be obtained.

[0010] In a possible implementation, the nano / micron particles are one or more of nano / micron particles of inorganic oxides, nano / micron particles of carbon materials, nano / micron particles of metals, nano / micron particles of inorganic salts, and nano / micron particles of framework compounds. Nano / micron particles of inorganic oxides, carbon materials, metals, inorganic salts, and framework compounds as raw materials are all suitable for the above-mentioned method for preparing nano / micron particle polymer composite fibers, and micron-level fibers can be prepared.

[0011] In a possible implementation, the inorganic oxide is one or more of silicon oxide, titanium oxide, zinc oxide and magnesium oxide. Inorganic oxides such as silicon oxide, titanium oxide, zinc oxide and magnesium oxide have good photoelectric properties, and are compounded with polymers to form composite fibers, which is beneficial to improving the photoelectric properties of the composite fibers, making the nano / micron particle polymer composite fibers more suitable for application in the field of optoelectronics.

[0012] In a possible embodiment, the carbon material is one or more of graphene, carbon nanotubes, mesoporous carbon, carbon molecular sieves and activated carbon. Carbon materials such as graphene, carbon nanotubes, mesoporous carbon, carbon molecular sieves and activated carbon have a large specific surface area, and are compounded with polymers to form composite fibers, which is beneficial to increase the specific surface area of ​​the composite fibers, making the nano / micron particle polymer composite fibers more suitable for application in the field of catalysis.

[0013] In a possible implementation, the metal is one or more of gold, silver, copper, iron and zinc. Metal materials such as gold, silver, copper, iron and zinc have good electrical conductivity, and when combined with polymers to form composite fibers, it is beneficial to improve the conductivity of the fibers.

[0014] In a possible embodiment, the inorganic salt is one or more of calcium carbonate, barium sulfate and silver chloride. Calcium carbonate, barium sulfate and silver chloride have good affinity with polymers, and compounding with polymers to make fibers can effectively increase or adjust the rigidity, toughness and bending strength of fiber materials.

[0015] In a possible embodiment, the framework compound is one or more of an inorganic molecular sieve, a metal organic framework compound, and a covalent organic framework compound. The pore size and specific surface area of ​​inorganic molecular sieves, metal organic framework compounds, and covalent organic framework compounds are more convenient to adjust. When they are compounded with polymers to form fibers, the pore size and specific surface area can be adjusted and controlled according to the needs of the actual application scenarios of nano / micron particle polymer composite fibers.

[0016] In a possible implementation, the particle size of the nano / micro particles is 1 nm-5 μm, preferably 10 nm-1 μm. When the particle size of the nano / micro particles is within the above range, they can be better combined with the polymer to form composite fibers.

[0017] In a possible implementation, the content of the nano / micro particles in the mixed solution of the nano / micro particles and the polymer is ≤20wt.%, preferably 0.1wt.%-5wt.%. When the content of the nano / micro particles is within the above range, a composite fiber with a more uniform distribution of nano / micro particles can be obtained.

[0018] In a possible implementation, the content of the polymer in the mixed solution of the nano / micro particles and the polymer is 0.05wt.%-20wt.%, preferably 1wt.%-5wt.%. When the content of the polymer is within the above range, it is more conducive to obtaining composite fibers with a porous structure.

[0019] In a possible implementation, the polymer is one or more of polyacrylonitrile, polymethyl methacrylate, polycarbonate, polybenzimidazole and polyimide. The composite fiber prepared by using the above polymers has better mechanical properties.

[0020] In a possible implementation, the solvent of the mixed solution of the nano / micro particles and the polymer is one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methyl carbonate, ethyl carbonate and N-methylpyrrolidone. The use of the above solvents can make the nanoparticles dispersed better in the mixed solution.

[0021] In a possible implementation, the diameter of the nano / micro particle polymer composite fiber is 10 μm-1000 μm, preferably 25 μm-100 μm.

[0022] In a possible embodiment, the preparation method of the nano / micron particle polymer composite fiber also includes a post-treatment step: drying the nano / micron particle polymer composite fiber to remove moisture and solvent inside the nano / micron particle polymer composite fiber to obtain the nano / micron particle polymer composite porous fiber.

[0023] The invention also provides nanometer / micron particle polymer composite fiber prepared by the method.

[0024] Based on the common knowledge in this field, the above-mentioned implementation modes can be combined arbitrarily.

[0025] The reagents and raw materials used in the present invention are commercially available.

[0026] The positive and progressive effects of the present invention are: The preparation method of the nano / micron particle polymer composite fiber provided by the present invention utilizes a coaxial shell water flow to directly stretch the millimeter-level liquid fiber into a micron fiber during the solidification process. Only a single water flow driving device is required to load a high-speed water flow, and spinning and stretching are completed in the same zone. There are no multiple dry and wet partitions, and no multi-stage mechanical rollers are required, which is simpler. The diameter of the nano / micron particle polymer composite fiber can be adjusted by only adjusting the extrusion speed of the nano / micron particle polymer solution and the flow rate of the coaxial shell water flow, and the operation is easy. The method is applicable to a variety of nano / micron particle polymer mixed systems and has good versatility. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a scanning electron microscope image of the carbon nanotube-polyacrylonitrile composite porous fiber prepared in Example 1; Figure 2 is a scanning electron microscope image of the carbon powder particle-polyacrylonitrile composite porous fiber prepared in Example 2; Figure 3 This is a scanning electron microscope image of the nano copper-polyacrylonitrile composite porous fiber prepared in Example 3; Figure 4 is a scanning electron microscope image of the mesoporous silica-polyacrylonitrile composite porous fiber prepared in Example 4; Figure 5 is a scanning electron microscope image of the ZIF-8-polyacrylonitrile composite porous fiber prepared in Example 5; Figure 6 This is a scanning electron microscope image of the zinc oxide-polyacrylonitrile composite porous fiber prepared in Example 6. DETAILED DESCRIPTION

[0028] In order to make the above-mentioned purposes, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation method and typical parameters of the present invention, and are not used to limit the parameter range described in the present invention. Reasonable changes derived therefrom are still within the scope of protection of the claims of the present invention.

[0029] It should be noted that the endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this article.

[0030] Unless otherwise defined, all terms, symbols and other scientific terms used herein are intended to have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. In some cases, terms with conventionally understood meanings are defined herein for the purpose of clarification or ease of reference, and such definitions herein should not be construed as indicating significant differences from conventional understandings in the art. The technical methods described or cited herein are generally well understood by those skilled in the art and are adopted by conventional methods. Unless otherwise stated, the use of commercially available kits, reagents and instruments is carried out in accordance with the protocols and parameters given by the manufacturer.

[0031] In the present invention, the nano / micro particle polymer solution refers to a mixed solution formed by uniformly dispersing nano / micro particles in a polymer solution.

[0032] Example 1

[0033] This embodiment provides a method for preparing a carbon nanotube-polyacrylonitrile composite porous fiber, comprising the following steps: S1. Ultrasonic dispersion of carbon nanotubes in dimethylformamide solution, the concentration of carbon nanotubes is 4wt.%, and then polyacrylonitrile powder is added to the solution, shaken and dispersed, the concentration of polyacrylonitrile is 5wt.%; and then stirred at room temperature for 24h to form a uniform carbon nanotube-polyacrylonitrile solution; S2, adding the carbon nanotube-polyacrylonitrile solution into a high-pressure wet spinning device, extruding the carbon nanotube-polyacrylonitrile solution from the nozzle of the high-pressure wet spinning device to form a thicker liquid fiber, and setting a coaxial shell water flow on the periphery of the liquid fiber, setting the flow rate of the carbon nanotube-polyacrylonitrile mixed solution to 25 mL / min, setting the flow rate of the coaxial shell water flow to 100 mL / min, and the flow rate of the shell water flow to 4 times the flow rate of the mixed solution. Since the water flow rate is higher than the flow rate of the mixed solution, the water flow stretches the thicker fiber into a thinner fiber, and obtains a carbon nanotube-polyacrylonitrile composite micron fiber with an average diameter of about 25 μm; S3. Collect the carbon nanotube-polyacrylonitrile composite micron fibers, and place them in a vacuum oven for drying to obtain carbon nanotube-polyacrylonitrile composite porous fibers.

[0034] The morphology of the carbon nanotube-polyacrylonitrile composite porous fiber prepared in this example is as follows: Figure 1 As shown in the figure, it can be seen that the surface of the carbon nanotube-polyacrylonitrile composite porous fiber prepared in this embodiment is smooth and flat, and the average diameter of the fiber is about 25 μm. It can be seen from the broken part of the fiber that there are a large number of micropores inside the fiber.

[0035] Example 2

[0036] This embodiment provides a method for preparing a carbon powder particle-polyacrylonitrile composite porous fiber, comprising the following steps: S1. Ultrasonic dispersion of carbon powder with a diameter of 1 μm into a dimethylformamide solution, the concentration of the carbon powder being 1 wt.%, and then adding polyacrylonitrile powder into the solution, shaking and dispersing, the concentration of the polyacrylonitrile being 5 wt.%; and then stirring at room temperature for 24 hours to form a uniform carbon powder particle-polyacrylonitrile solution; S2, adding the carbon powder particle-polyacrylonitrile solution to a high-pressure wet spinning device, extruding the carbon powder particle-polyacrylonitrile solution from the nozzle of the high-pressure wet spinning device to form a relatively thick liquid fiber, and setting a coaxial shell water flow on the periphery of the liquid fiber, setting the flow rate of the carbon powder particle-polyacrylonitrile mixed solution to 25 mL / min, setting the flow rate of the coaxial shell water flow to 50 mL / min, and the flow rate of the shell water flow to 2 times the flow rate of the mixed solution. Since the water flow rate is higher than the flow rate of the mixed solution, the water flow stretches the relatively thick fiber into a relatively thin fiber, and obtains a carbon powder particle-polyacrylonitrile composite micron fiber with an average diameter of about 50 μm; S3. Collect the carbon powder particle-polyacrylonitrile composite micron fiber, and place it in a vacuum oven for drying to obtain the carbon powder particle-polyacrylonitrile composite porous fiber.

[0037] The morphology of the carbon powder particle-polyacrylonitrile composite porous fiber prepared in this embodiment is as follows: Figure 2 As shown in the figure, it can be seen that the surface of the carbon powder particle-polyacrylonitrile composite porous fiber prepared in this embodiment is smooth and flat, the average diameter of the fiber is about 50 μm, and there are a large number of micropores inside the fiber.

[0038] Example 3

[0039] This embodiment provides a method for preparing nano copper-polyacrylonitrile composite porous fibers, comprising the following steps: S1. Ultrasonic dispersion of nano-copper particles with a diameter of 100 nm into a dimethylformamide solution, the concentration of nano-copper is 4 wt.%, and then polyacrylonitrile powder is added to the solution, shaken and dispersed, the concentration of polyacrylonitrile is 5 wt.%; and then stirred at room temperature for 24 h to form a uniform nano-copper-polyacrylonitrile solution; S2, adding the nano copper-polyacrylonitrile solution to a high-pressure wet spinning device, extruding the nano copper-polyacrylonitrile solution from the nozzle of the high-pressure wet spinning device to form a thicker liquid fiber, and setting a coaxial shell water flow on the periphery of the liquid fiber, setting the flow rate of the nano copper-polyacrylonitrile mixed solution to 25 mL / min, setting the flow rate of the coaxial shell water flow to 100 mL / min, and the flow rate of the shell water flow is 4 times the flow rate of the mixed solution. Since the water flow rate is higher than the flow rate of the mixed solution, the water flow stretches the thicker fiber into a thinner fiber, and obtains a nano copper-polyacrylonitrile composite micron fiber with an average diameter of about 50 μm; S3. Collect the nano copper-polyacrylonitrile composite micron fibers and place them in a vacuum oven for drying to obtain carbon powder particles-polyacrylonitrile composite porous fibers.

[0040] The morphology of the nano copper-polyacrylonitrile composite porous fiber prepared in this embodiment is as follows: Figure 3 As shown in the figure, it can be seen that the surface of the nano copper-polyacrylonitrile composite porous fiber prepared in this embodiment is smooth and flat, the average diameter of the fiber is about 50 μm, and there are a large number of micropores inside the fiber.

[0041] Example 4

[0042] This embodiment provides a method for preparing a mesoporous silica-polyacrylonitrile composite porous fiber, comprising the following steps: S1. Ultrasonic dispersion of mesoporous silica SBA-5 with a diameter of 1 μm into dimethylformamide solution, the concentration of mesoporous silica SBA-5 is 1 wt.%, and then polyacrylonitrile powder is added to the solution, shaken and dispersed, the concentration of polyacrylonitrile is 5 wt.%; and then stirred at room temperature for 24 hours to form a uniform mesoporous silica-polyacrylonitrile solution; S2, adding the mesoporous silica-polyacrylonitrile solution into a high-pressure wet spinning device, extruding the mesoporous silica-polyacrylonitrile solution from the nozzle of the high-pressure wet spinning device to form a thicker liquid fiber, and setting a coaxial shell water flow on the periphery of the liquid fiber, setting the flow rate of the mesoporous silica-polyacrylonitrile mixed solution to 25 mL / min, setting the flow rate of the coaxial shell water flow to 100 mL / min, and the flow rate of the shell water flow to 4 times the flow rate of the mixed solution. Since the water flow rate is higher than the flow rate of the mixed solution, the water flow stretches the thicker fiber into a thinner fiber, and obtains a mesoporous silica-polyacrylonitrile composite micron fiber with an average diameter of about 50 μm; S3. Collect the mesoporous silica-polyacrylonitrile composite micron fibers and place them in a vacuum oven for drying to obtain mesoporous silica-polyacrylonitrile composite porous fibers.

[0043] The morphology of the mesoporous silica-polyacrylonitrile composite porous fiber prepared in this example is as follows: Figure 4 As shown in the figure, it can be seen that the surface of the mesoporous silica-polyacrylonitrile composite porous fiber prepared in this embodiment is smooth and flat, the average diameter of the fiber is 50 μm, and there are a large number of micropores inside the fiber.

[0044] Example 5

[0045] This embodiment provides a method for preparing a ZIF-8-polyacrylonitrile composite porous fiber, comprising the following steps: S1. Ultrasonic dispersion of metal organic framework material (MOFs) ZIF-8 nano / micro particles into dimethylformamide solution, the concentration of ZIF-8 is 1wt.%, and then polyacrylonitrile powder is added to the solution, shaken and dispersed, the concentration of polyacrylonitrile is 5wt.%; and then stirred at room temperature for 24h to form a uniform ZIF-8-polyacrylonitrile solution; S2, adding the ZIF-8-polyacrylonitrile solution to a high-pressure wet spinning device, extruding the ZIF-8-polyacrylonitrile solution from the nozzle of the high-pressure wet spinning device to form a thicker liquid fiber, and setting a coaxial shell water flow on the periphery of the liquid fiber, setting the flow rate of the ZIF-8-polyacrylonitrile mixed solution to 50 mL / min, since the water flow rate is higher than the flow rate of the mixed solution, the water flow stretches the thicker fiber into a thinner fiber, setting the flow rate of the coaxial shell water flow to 100 mL / min, and the flow rate of the shell water flow is twice the flow rate of the mixed solution, to obtain a ZIF-8-polyacrylonitrile composite micron fiber with an average diameter of about 50 μm; S3. Collect the ZIF-8-polyacrylonitrile composite micron fibers, and place them in a vacuum oven for drying to obtain ZIF-8-polyacrylonitrile composite porous fibers.

[0046] The morphology of the ZIF-8-polyacrylonitrile composite porous fiber prepared in this example is as follows Figure 5 As shown in the figure, it can be seen that the surface of the ZIF-8-polyacrylonitrile composite porous fiber prepared in this embodiment is smooth and flat, the average diameter of the fiber is 50 μm, and there are a large number of micropores inside the fiber.

[0047] Example 6

[0048] This embodiment provides a method for preparing zinc oxide nano-polyacrylonitrile composite porous fibers, comprising the following steps: S1. Ultrasonic dispersion of zinc oxide nanoparticles with a diameter of about 200 nm into a dimethylformamide solution, the concentration of zinc oxide is 3 wt.%, and then polyacrylonitrile powder is added to the solution, and the dispersion is shaken to obtain a concentration of 5 wt.% of polyacrylonitrile; and then stirred at room temperature for 24 h to form a uniform zinc oxide-polyacrylonitrile solution; S2, adding zinc oxide-polyacrylonitrile solution to a high-pressure wet spinning device, extruding the zinc oxide-polyacrylonitrile solution from the nozzle of the high-pressure wet spinning device to form a thicker liquid fiber, and setting a coaxial shell water flow on the periphery of the liquid fiber, setting the flow rate of the zinc oxide-polyacrylonitrile mixed solution to 50 mL / min, setting the flow rate of the coaxial shell water flow to 100 mL / min, and the flow rate of the shell water flow is twice the flow rate of the mixed solution. Since the water flow rate is higher than the flow rate of the mixed solution, the water flow stretches the thicker fiber into a thinner fiber, and obtains a zinc oxide-polyacrylonitrile composite micron fiber with an average diameter of about 50 μm; S3. Collect the zinc oxide-polyacrylonitrile composite micron fibers, and place them in a vacuum oven for drying to obtain zinc oxide-polyacrylonitrile composite porous fibers.

[0049] The morphology of the zinc oxide-polyacrylonitrile composite porous fiber prepared in this example is as follows: Figure 6 As shown in the figure, it can be seen that the surface of the zinc oxide-polyacrylonitrile composite porous fiber prepared in this embodiment is smooth and flat, the average diameter of the fiber is about 50 μm, and there are a large number of micropores inside the fiber.

[0050] The above-mentioned embodiment provided by the present invention can be prepared by constructing a high-pressure wet method nozzle coupling coaxial shell flow device, which uses a constant-current high-pressure plunger pump or a pneumatic high-pressure pump as a high-pressure source to drive a nano / micron particle polymer solution to flow out from a quartz capillary connected to the outlet of the constant-current high-pressure plunger pump or the pneumatic high-pressure pump, wherein the outer diameter of the quartz capillary is 365 μm and the inner diameter is 100 μm; the quartz capillary passes through the straight-through inner cavity of the T-type tee, enters from the first straight-through port of the T-type tee and exits from the second straight-through port of the T-type tee, and the quartz capillary is connected to the first straight-through port of the T-type tee. The intersection of a straight port is tightly sealed; a section of PEEK plastic tube with an inner diameter greater than 500 μm is used to tightly seal the second straight port of the T-type tee, and the quartz capillary is completely contained in the PEEK plastic tube, and the quartz capillary does not leak out of the port of the PEEK plastic tube; a water pipe is connected to the third vertical port of the T-type tee, and a peristaltic pump or other pump is used to drive the water flow in the water pipe to enter the inner cavity of the T-type tee, and flow through the interlayer of the PEEK tube-quartz capillary, so that the nano / micron particle polymer solution is quickly phase-converted to lock the nano / micron particles and stretch them into micron fibers.

[0051] The above-mentioned embodiments further prove that the preparation method of the polymer-nano / micron particle composite porous fiber provided by the present invention has the advantages of simple method, wide adaptability, adjustable fiber diameter, etc., and realizes the stable dispersion, easy recovery and reusability of functional nanomaterials.

[0052] 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 replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing nano / micron particle polymer composite fibers, characterized in that: The following steps are involved: A mixed solution of nano / micro particles and polymers is extruded by wet spinning to form liquid fibers. While the liquid fibers are being extruded, a coaxial shell water flow is applied to the periphery of the liquid fibers. The flow rate of the coaxial shell water flow is greater than the flow rate of the liquid fibers. Under the action of the coaxial shell water flow, the liquid fibers are stretched and solidified to form nano / micro particle polymer composite fibers.

2. The method for preparing nano / micron particle polymer composite fibers according to claim 1, characterized in that: The volume flow rate of the mixed solution of the nano / micro particles and the polymer is 0.01 mL / min-50 mL / min; And / or, the volume flow rate of the coaxial shell water flow is 1 mL / min-2000 mL / min; And / or, the ratio of the volume flow rate of the mixed solution of the nano / micro particles and the polymer to the volume flow rate of the coaxial shell water flow is 1:(1.5-40).

3. The method for preparing nano / micron particle polymer composite fibers according to claim 2, characterized in that: The volume flow rate of the mixed solution of nano / micro particles and polymer is 0.1 mL / min-1 mL / min; and / or the volume flow rate of the coaxial shell water flow is 2 mL / min-200 mL / min; and / or, the ratio of the volume flow rate of the mixed solution of the nano / micro particles and the polymer to the volume flow rate of the coaxial shell water flow is 1:(2-10); And / or, the nano / micro particles are one or more of nano / micro particles of inorganic oxides, nano / micro particles of carbon materials, nano / micro particles of metals, nano / micro particles of inorganic salts and nano / micro particles of framework compounds.

4. The method for preparing nano / micron particle polymer composite fibers according to claim 3, characterized in that: The inorganic oxide is one or more of silicon oxide, titanium oxide, zinc oxide and magnesium oxide; And / or, the carbon material is one or more of graphene, carbon nanotubes, mesoporous carbon, carbon molecular sieve and activated carbon; and / or, the metal is one or more of gold, silver, copper, iron and zinc; And / or, the inorganic salt is one or more of calcium carbonate, barium sulfate and silver chloride; And / or, the framework compound is one or more of an inorganic molecular sieve, a metal organic framework compound and a covalent organic framework compound.

5. The method for preparing nano / micron particle polymer composite fibers according to claim 1, characterized in that: The particle size of the nano / micro particles is 1nm-5μm; and / or, the content of the nano / micro particles in the mixed solution of the nano / micro particles and the polymer is ≤20wt.%; And / or, the content of the polymer in the mixed solution of the nano / micro particles and the polymer is 0.05 wt.%-20 wt.%.

6. The method for preparing nano / micron particle polymer composite fibers according to claim 5, characterized in that: The particle size of the nano / micro particles is 10nm-1μm; and / or, the content of the nano / micro particles in the mixed solution of the nano / micro particles and the polymer is 0.1wt.%-5wt.%; And / or, the content of the polymer in the mixed solution of the nano / micro particles and the polymer is 1 wt.%-5 wt.%.

7. The method for preparing nano / micron particle polymer composite fibers according to claim 1, characterized in that: The polymer is one or more of polyacrylonitrile, polymethyl methacrylate, polycarbonate, polybenzimidazole and polyimide; and / or, the solvent of the mixed solution of the nano / micro particles and the polymer is one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methyl carbonate, ethyl carbonate and N-methylpyrrolidone; And / or, the diameter of the nano / micro particle polymer composite fiber is 10 μm-1000 μm.

8. The method for preparing nano / micron particle polymer composite fibers according to claim 7, characterized in that: The diameter of the nano / micro particle polymer composite fiber is 25 μm-100 μm.

9. The method for preparing nano / micron particle polymer composite fibers according to claim 1, characterized in that: The preparation method of the nano / micro particle polymer composite fiber also includes a post-processing step: drying the nano / micro particle polymer composite fiber to remove moisture and solvent inside the nano / micro particle polymer composite fiber to obtain the nano / micro particle polymer composite porous fiber.

10. A nano / micron particle polymer composite fiber, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.

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