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CN-119411252-B - Polyether-ether-ketone aerogel fiber and preparation method thereof

CN119411252BCN 119411252 BCN119411252 BCN 119411252BCN-119411252-B

Abstract

The invention relates to a polyether-ether-ketone aerogel fiber and a preparation method thereof, belonging to the technical field of aerogel fibers. The preparation method of the polyether-ether-ketone aerogel fiber comprises the steps of firstly preparing soluble polyether-ether-ketone-1, 3-dithiolane from crystalline polyether-ether-ketone materials, then dissolving the soluble polyether-ether-ketone-1, 3-dithiolane and polyvinylpyrrolidone in a polar solvent, stirring to obtain a spinning solution, removing bubbles from the spinning solution in vacuum, extruding the spinning solution into a coagulating bath, finally replacing the spinning solution with the solvent, and performing vacuum freeze drying to obtain the polyether-ether-ketone aerogel fiber. The preparation method is simple in process, continuous in subsequent flow, and expected to realize large-scale production, and the prepared aerogel fiber has a typical three-dimensional network structure, low linear density, high strength and good toughness, and good spinnability, and the porous structure provides possibility for subsequent filling or adsorbing of phase change materials and further application in the heat preservation fields of textiles, special clothing and the like.

Inventors

  • LUAN JIASHUANG
  • Ju meng
  • WANG GUIBIN
  • WANG YU
  • YANG YANCHAO

Assignees

  • 吉林大学

Dates

Publication Date
20260512
Application Date
20241129

Claims (10)

  1. 1. The preparation method of the polyether-ether-ketone aerogel fiber is characterized by comprising the following steps of: (1) Dissolving soluble polyether-ether-ketone-1, 3-dithiolane and polyvinylpyrrolidone in a polar solvent, and uniformly dispersing to obtain spinning solution; Under the protection of inert atmosphere, dissolving crystalline polyether-ether-ketone in a solvent added with an auxiliary agent, adding boron trifluoride diethyl ether and 1, 2-ethanedithiol, reacting for 24-48 hours at room temperature, discharging a product into absolute ethyl alcohol or absolute methyl alcohol, and crushing, washing and drying to obtain the soluble polyether-ether-ketone-1, 3-dithiolane; The structural formula of the crystalline polyether-ether-ketone is as follows: wherein n is a positive integer, n is more than or equal to 10 and less than or equal to 200; the concentration of the crystalline polyether-ether-ketone in a solvent added with an auxiliary agent is 0.05g/ml to 0.5g/ml, the molar ratio of the carbonyl content of the crystalline polyether-ether-ketone to the 1, 2-ethanedithiol is 1:2 to 1:5, and the molar ratio of the boron trifluoride diethyl ether to the 1, 2-ethanedithiol is 1:3 to 1:1; the auxiliary agent is trifluoroacetic acid or trifluoro benzoic acid, the solvent is dichloromethane or trichloromethane, and the volume ratio of the auxiliary agent to the solvent is 1:10-1:5; (2) After the spinning solution is defoamed, extruding and spinning into a coagulating bath, and collecting through winding to obtain polyether-ether-ketone-1, 3-dithiolane wet gel fiber; (3) Placing the polyether-ether-ketone-1, 3-dithiolane wet gel fiber in a displacement bath for solvent displacement for a plurality of times, and obtaining the polyether-ether-ketone-1, 3-dithiolane fiber after freezing treatment; (4) And drying the polyether-ether-ketone-1, 3-dithiolane fiber to obtain the polyether-ether-ketone aerogel fiber.
  2. 2. The method for preparing polyether-ether-ketone aerogel fibers according to claim 1, wherein in the step (1), the inert atmosphere is nitrogen.
  3. 3. The method for preparing polyether-ether-ketone aerogel fibers according to claim 1, wherein in the step (1), The polar solvent comprises one or more of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide, dimethylacetamide and tetrahydrofuran which are mixed according to any proportion; In the spinning solution, the mass fraction of the soluble polyether-ether-ketone-1, 3-dithiolane is 5-30%, and the mass fraction of the polyvinylpyrrolidone is 3-5%; the stirring and dispersing are uniform, the stirring time is 6 hours, and the stirring speed is 500-1000rpm.
  4. 4. The method for preparing polyether-ether-ketone aerogel fibers according to claim 1, wherein in the step (2), The extrusion spinning method is wet spinning; The coagulating bath is a mixture of one or more of polar solvent, absolute ethyl alcohol, water, acetone and methanol in any proportion in the step (1); the defoaming is vacuum defoaming.
  5. 5. The preparation method of the polyether-ether-ketone aerogel fiber, according to claim 4, is characterized in that the spinning solution after vacuum defoamation is injected into a coagulating bath through an injector by an injection pump to obtain the polyether-ether-ketone-1, 3-dithiolane wet gel fiber, wherein the injection speed is 4-10ml/h, and the diameter of the needle head of the injector is 0.41-0.84 mm; The coagulating bath is an ethanol water solution with the volume fraction of 10-50%.
  6. 6. The method for preparing polyether-ether-ketone aerogel fibers according to claim 1, wherein in the step (3), The replacement bath is a mixture of one or more of water, absolute ethyl alcohol and methanol according to any proportion; The solvent replacement time is 24-72h, and the replacement bath is replaced every 3-6 h; the freezing treatment is to treat the materials in a low-temperature refrigerator at-25 ℃ to-40 ℃ for 6-8 hours or liquid nitrogen at-196 ℃ for 1-3 hours.
  7. 7. The method of claim 6, wherein the displacement bath is an aqueous ethanol solution with a volume fraction of 10% -50%.
  8. 8. The method for preparing a polyether-ether-ketone aerogel fiber according to claim 1, wherein in the step (4), the drying is vacuum freeze drying, supercritical drying or normal pressure drying.
  9. 9. The method for preparing the polyether-ether-ketone aerogel fiber according to claim 8, wherein the drying is vacuum freeze drying, the vacuum degree is 0Pa, the freeze drying temperature is-50 ℃ to-70 ℃, and the drying time is 24-72h.
  10. 10. The polyetheretherketone aerogel fiber prepared by the method for preparing a polyetheretherketone aerogel fiber according to any one of claims 1 to 9.

Description

Polyether-ether-ketone aerogel fiber and preparation method thereof Technical Field The invention belongs to the technical field of aerogel fibers, and particularly relates to a polyether-ether-ketone aerogel fiber and a preparation method thereof. Background Aerogel is a nano-scale porous solid material formed by adopting a certain drying mode to replace liquid phase in gel with gas through a sol-gel method, has the advantages of low density, high porosity, large specific surface area and the like, and has wide application in the aspects of heat insulation, catalytic loading, adsorption filtration and the like. The aerogel fiber has the flexibility and good mechanical property of the fiber on the basis of having the excellent performance of the aerogel. Most of the existing aerogel fibers are aramid aerogel fibers, polyimide aerogel fibers, cellulose aerogel fibers and various inorganic aerogel fibers, but the mechanical properties of the aerogel fibers are still in a weaker level, the mechanical properties of the aerogel fibers are improved by subsequent processing and modification, and the complicated preparation process also makes the production of the aerogel fibers face a great challenge. For example, patent CN116905120A discloses a preparation method of polyimide composite aerogel fiber, which comprises the steps of adding silica aerogel precursor hydrolysate into polyamic acid salt solution to prepare composite spinning solution, carrying out wet spinning, and then sequentially carrying out solvent replacement and freeze drying to obtain the polyimide aerogel fiber. In the patent, the chemical imidization of the polyamic acid is directly performed in a coagulating bath, so that the reaction condition is mild, the reaction process is controllable, and the method is suitable for mass production. Patent CN115073803B discloses a preparation method of high-toughness aramid aerogel fiber, in the method, the aerogel fiber is not processed by traditional freeze drying or supercritical drying, but is dried under normal pressure to prepare the aerogel fiber with high porosity, nanoscale pore diameter and extremely high fracture toughness, thereby not only improving the production efficiency, but also reducing the production cost. Patent CN117127281a discloses a preparation method of bacterial cellulose/polyurethane composite aerogel fiber, in the preparation method, the introduction of thermoplastic polyurethane protects the aerogel skeleton to a certain extent, effectively enhances the mechanical strength of the aerogel fiber, and the three-dimensional network skeleton and the porous structure of the composite aerogel fiber enable the aerogel fiber to have excellent mechanical property and good heat preservation and insulation properties. Polyaryletherketone materials are widely applied to various fields due to excellent mechanical properties, temperature resistance, acid and alkali resistance and the like, but solvent resistance and higher processing temperature of the polyaryletherketone materials bring a plurality of difficulties to the preparation and production of the polyaryletherketone aerogel fibers. Disclosure of Invention In view of the above, the invention aims to provide a polyether-ether-ketone aerogel fiber and a preparation method thereof, wherein the polyether-ether-ketone aerogel fiber not only has the advantages of low density, high porosity and the like of the aerogel, but also has the flexibility and the braiding property of the fiber. The technical scheme adopted by the invention for achieving the purpose is as follows. In a first aspect, the invention provides a method for preparing polyether-ether-ketone aerogel fibers, comprising the following steps: (1) Dissolving soluble polyether-ether-ketone-1, 3-dithiolane and polyvinylpyrrolidone in a polar solvent, and uniformly dispersing to obtain spinning solution; (2) After the spinning solution is defoamed, extruding and spinning into a coagulating bath, and collecting through winding to obtain polyether-ether-ketone-1, 3-dithiolane wet gel fiber; (3) Placing the polyether-ether-ketone-1, 3-dithiolane wet gel fiber in a displacement bath for solvent displacement for a plurality of times, and obtaining the polyether-ether-ketone-1, 3-dithiolane fiber after freezing treatment; (4) And drying the polyether-ether-ketone-1, 3-dithiolane fiber to obtain the polyether-ether-ketone aerogel fiber. Preferably, in the step (1), the preparation method of the soluble polyether-ether-ketone-1, 3-dithiolane comprises the steps of dissolving crystalline polyether-ether-ketone in a solvent added with an auxiliary agent under the protection of inert atmosphere, adding boron trifluoride diethyl etherate and 1, 2-dithiol, reacting for 24-48 hours at room temperature, discharging a product into absolute ethyl alcohol or absolute methyl alcohol, and crushing, washing and drying to obtain the soluble polyether-ether-ketone-1, 3-dithiolane; more preferably, the i