Aerogel far infrared vacuum fiber and preparation method thereof

Abstract

The invention relates to an aerogel far-infrared vacuum fiber and a preparation method thereof, and relates to the technical field of fiber material preparation, the aerogel far-infrared vacuum fiber comprises the following components by mass: 20-30 parts of aerogel, 10-15 parts of tourmaline, 4-8 parts of an anti-radiation agent, 40-60 parts of polyvinyl alcohol, 3-5 parts of a dispersant, and 1-3 parts of a cross-linking agent. The aerogel is prepared from the following raw materials: ethyl orthosilicate and cellulose nanowhiskers; the anti-radiation agent comprises a carbon nano tube. The preparation method comprises the following steps: S1, mixing a dispersing agent into a solvent, sequentially adding aerogel, tourmaline, an anti-radiation agent, polyvinyl alcohol and a cross-linking agent, and stirring for reaction to obtain a spinning solution; s2, carrying out wet spinning on the spinning solution, solidifying in a coagulating bath, winding, and drying to obtain preliminarily solidified fibers; and carrying out vacuum treatment on the preliminarily cured fiber to obtain the aerogel far-infrared vacuum fiber. The fiber has the effect of improving the comprehensive performance of the fiber, and the fiber has good heat insulation performance, far infrared performance and radiation resistance.

Description

Technical Field

[0001] The present application relates to the technical field of fiber material preparation, and in particular to an aerogel far-infrared vacuum fiber and a preparation method thereof. Background Art

[0002] With the continuous advancement of science and technology and the significant improvement in people's living standards, functional fiber materials are playing an increasingly important role in modern society. With the widespread use of electronic devices, various types of radiation are prevalent in people's living environment, and their potential impact on human health has attracted widespread attention. Fiber materials with radiation resistance have shown great application potential in many fields such as clothing and protective equipment, becoming a hot topic for research and development. At the same time, people's functional demands for fiber materials are becoming increasingly diverse. They are no longer satisfied with a single function, but expect fiber materials to integrate multiple beneficial functions to better adapt to different usage scenarios and meet higher quality of life requirements. This has driven the entire functional fiber materials industry towards a more diversified and high-performance direction.

[0003] In the past, the traditional approach to imparting radiation resistance to fibers was to add metals or metal oxides. This approach exploits the properties of metals or metal oxides, which can block radiation to a certain extent, thereby achieving radiation resistance. However, the addition of metals or metal oxides to traditional radiation-resistant fibers makes them stiff, significantly reducing wearing comfort. Furthermore, some existing functional fibers only have a single function, failing to meet the demand for multifunctional fiber materials, and thus require improvement. Summary of the Invention

[0004] In order to improve the functionality and comfort of fibers, the present application provides an aerogel far-infrared vacuum fiber and a preparation method thereof.

[0005] The present application provides an aerogel far-infrared vacuum fiber and a preparation method thereof using the following technical solutions: In the first aspect, the present application provides an aerogel far-infrared vacuum fiber and a preparation method thereof, which adopts the following technical solution: an aerogel far-infrared vacuum fiber, the preparation raw materials of which include the following components in parts by weight: 20-30 parts of aerogel 10-15 parts tourmaline 4-8 parts of anti-radiation agent 40-60 parts of polyvinyl alcohol 3-5 parts dispersant 1-3 parts crosslinking agent The raw materials for preparing the aerogel include tetraethyl orthosilicate and cellulose nano whiskers; The anti-radiation agent includes carbon nanotubes.

[0006] Aerogel is made of tetraethyl orthosilicate and cellulose nanowhiskers. Its unique nanoporous structure and lightweight properties give the fiber excellent thermal insulation properties; tourmaline, as a far-infrared powder, can efficiently radiate far-infrared rays, which can promote human blood circulation and improve metabolism; carbon nanotubes, as anti-radiation agents, can effectively absorb and scatter radiation with their high specific surface area, good conductivity and special electronic structure, thereby enhancing the fiber's radiation resistance; polyvinyl alcohol, as a polymer matrix, provides good film-forming properties and mechanical strength, ensuring the flexibility and durability of the fiber; dispersants can evenly disperse the components to avoid agglomeration and ensure uniform and stable fiber performance; cross-linking agents enhance the degree of cross-linking between polymer molecules through chemical bonds, further improving the mechanical strength, dimensional stability and chemical stability of the fiber; multiple components cooperate and work synergistically with each other to improve the comprehensive performance of aerogel far-infrared vacuum fiber, and enhance its thermal insulation properties, far-infrared health effects and anti-radiation protection functions.

[0007] Preferably, the tourmaline is modified and prepared by the following steps: S1, grinding and sieving the tourmaline, and drying it to obtain pretreated tourmaline; S2. The pretreated tourmaline is mixed with a dopamine hydrochloride buffer solution, and the pH is adjusted to alkaline. After the reaction, the mixture is filtered, washed, and dried to obtain the modified tourmaline.

[0008] Dopamine hydrochloride can undergo self-polymerization reaction to form an amino-rich polydopamine film on the tourmaline surface. The amino group not only enhances the interfacial bonding strength between tourmaline and polyvinyl alcohol, but can also further combine with other components; the polydopamine film has far-infrared emission properties, and synergizes with tourmaline to broaden the far-infrared emission band, enhance the far-infrared emission efficiency, and can better resonate with human cells to promote blood circulation; at the same time, the surface activity of tourmaline is improved after modification, and its own negative ion release ability is enhanced. Negative ions can improve human microcirculation, activate cells, and further enhance the effect of stimulating blood circulation; the formation of the polydopamine film also provides a good attachment basis for the anti-radiation agent, enabling it to be combined with the tourmaline surface, thereby improving the overall anti-radiation performance of the fiber, and achieving a synergistic improvement in multiple functions such as anti-radiation performance, far-infrared emission warmth, and promotion of blood circulation.

[0009] Preferably, the raw materials for preparing the modified tourmaline further include zirconium hydroxide, and are prepared by the following steps: S1, grinding and sieving the tourmaline, and drying it to obtain pretreated tourmaline; S2. Add citric acid to the zirconium hydroxide solution and stir to obtain a zirconium oxide precursor solution; add the pretreated tourmaline to the zirconium oxide precursor solution, adjust the pH to alkaline after ultrasonication, heat and stir to react, centrifuge, wash, dry, calcine, cool and grind to obtain a composite powder; S3. Add the composite powder to dopamine hydrochloride buffer, adjust the pH to alkaline, and after the reaction, filter, wash, and dry to obtain modified tourmaline.

[0010] Zirconium oxide generated by the reaction of zirconium hydroxide has excellent infrared emission properties, and produces a synergistic effect with tourmaline, effectively broadening the far-infrared emission band, enhancing thermal radiation efficiency, and being able to resonate with human cells more efficiently to promote blood circulation; the composite structure formed by zirconium oxide on the surface of tourmaline improves the stability and mechanical properties of the powder, making the fiber more durable during processing and use; the polydopamine film formed by the self-polymerization of dopamine hydrochloride strengthens the interfacial bonding between the powder and polyvinyl alcohol through rich amino groups, ensuring the stability of the overall structure of the fiber, and its own far-infrared emission characteristics cooperate with tourmaline and zirconium oxide to further enhance the far-infrared emission performance; in addition, the polydopamine film can also serve as a functional carrier, providing a good attachment basis for anti-radiation agents, thereby better enhancing the fiber's radiation resistance and achieving a synergistic improvement in properties such as radiation resistance, far-infrared emission, blood circulation promotion, and structural enhancement.

[0011] Preferably, the mass ratio of the pretreated tourmaline, zirconium hydroxide and dopamine hydrochloride is 1:(0.14-0.29):0.1.

[0012] The modified tourmaline prepared according to the above mass ratio has good dispersibility and compatibility, and can effectively improve the material's far-infrared emission and warmth retention properties and promote blood circulation.

[0013] Preferably, the anti-radiation agent further comprises fullerene.

[0014] Fullerene has excellent radiation resistance. Its highly symmetrical cage structure can effectively capture and disperse radiation particles. By absorbing radiation energy and converting it into vibration and rotational energy within the molecules, it reduces radiation damage to the fiber. Fullerene and carbon nanotubes work synergistically to build multiple radiation protection networks inside the fiber. The former absorbs high-energy radiation particles, while the latter enhances electromagnetic response by changing the electronic structure. The combination of the two greatly improves the fiber's absorption and scattering ability for high-frequency radiation. In addition, fullerene can also interact with components such as aerogel and tourmaline to optimize the internal microstructure of the fiber, further enhance the far-infrared emission performance and negative ion release capacity, and improve the radiation resistance and far-infrared health care effects of aerogel far-infrared vacuum fibers.

[0015] Preferably, the mass ratio of carbon nanotubes to fullerenes in the anti-radiation agent is (1.5-2.5):1.

[0016] The anti-radiation agent compounded according to the above mass ratio can effectively improve the anti-radiation performance and far-infrared health care effect of the aerogel far-infrared vacuum fiber.

[0017] Preferably, the carbon nanotubes are modified and prepared by the following steps: S1, purifying the carbon nanotubes to obtain purified carbon nanotubes; S2. Mix ferric nitrate and cerium nitrate in a solvent to obtain a metal salt solution; add purified carbon nanotubes to the metal salt solution, ultrasonically stir, adjust the pH to alkaline, stir for reaction, centrifuge, wash, calcine and then grind to obtain modified carbon nanotubes.

[0018] By purifying carbon nanotubes, impurities on their surface can be effectively removed and their intrinsic performance can be improved; iron nitrate and cerium nitrate introduce iron ions and cerium ions, which can change the electronic structure and energy band structure of carbon nanotubes, enhance their electromagnetic response characteristics, and significantly improve the carbon nanotubes' absorption and scattering capabilities of high-frequency radiation, thereby improving the electromagnetic shielding effectiveness and neutron shielding capabilities of the fiber; the metal ions on the surface of carbon nanotubes can transfer charge with fullerenes, forming electron traps at the interface, extending the dissipation path of radiation energy, and improving the shielding efficiency against high-energy radiation; modified carbon nanotubes and fullerenes can also promote electron transitions on the tourmaline surface through a synergistic catalytic effect, converting more energy into far-infrared radiation, improving the far-infrared emissivity of the fiber, and combining the infrared absorption characteristics of fullerenes themselves to further enhance the fiber's thermal insulation performance.

[0019] Preferably, the aerogel is prepared by the following steps: The method comprises mixing tetraethyl orthosilicate and cellulose nanowhiskers into an ethanol aqueous solution and stirring to obtain a mixed solution; adjusting the pH of the mixed solution to acidic, stirring, pouring the mixed solution into a mold, heating to perform a gelation reaction, and performing an aging treatment after gelation is completed. The mixed solution is dried and then ball-milled to obtain an aerogel.

[0020] Preferably, the mass ratio of the tetraethyl orthosilicate to the cellulose nanowhiskers is 1:0.2.

[0021] TEOS is hydrolyzed and polycondensed to form a silicon-oxygen bond network, and cellulose nanowhiskers are interwoven with the silicon-oxygen bond network to enhance the overall structure; heating is used to undergo a gelation reaction to form an aerogel with a porous structure, and aging treatment further strengthens the network structure, thereby enhancing the stability and mechanical properties of the aerogel; drying treatment can completely retain the unique pore structure of the aerogel, giving it excellent thermal insulation properties, while providing a good dispersion and loading environment for components such as tourmaline and anti-radiation agents, and synergizing with other raw materials to improve the thermal insulation properties, far-infrared emission properties and anti-radiation properties of the aerogel far-infrared vacuum fiber.

[0022] Preferably, the gelation reaction conditions are: reacting at 40-50° C. for 1-2 hours, and heating to 60-70° C. for 3-4 hours.

[0023] Controlling the temperature in stages for the gelation reaction can form a gradient pore structure; first, the gelation reaction is carried out at low temperature, so that the reaction system is in a mild reaction environment, so that the outer layer of the aerogel slowly forms a gel structure first, thereby generating an outer layer with small pore size and dense structure. This outer layer can effectively block the invasion of external heat and provide a stable framework for internal gelation; after the temperature is raised, the reaction is continued. The increased reaction temperature accelerates the internal hydrolysis and condensation reaction process, prompting the molecular chains to quickly cross-link and aggregate, forming a core layer structure with a large pore size inside the aerogel. This large pore structure gives the aerogel a lower density and better thermal insulation performance; the gradient pore structure enables the aerogel to have both the barrier properties of the outer layer and the thermal insulation properties of the core layer, effectively reducing the overall thermal conductivity and enhancing the thermal insulation effect; at the same time, the reasonable pore size distribution provides sufficient and stable dispersion space for other components such as tourmaline and anti-radiation agent, which helps each component to fully exert its performance and synergistically improve the comprehensive performance of aerogel far-infrared vacuum fiber in terms of thermal insulation, far-infrared emission, and anti-radiation.

[0024] In a second aspect, the present application provides a method for preparing an aerogel far-infrared vacuum fiber, which adopts the following technical solution: A method for preparing an aerogel far-infrared vacuum fiber, comprising the following steps: S1. Mix the dispersant into the solvent, add the aerogel after stirring, add tourmaline and anti-radiation agent after ultrasonication, add polyvinyl alcohol after stirring and ultrasonication, add the cross-linking agent after stirring, and stir to obtain a spinning solution after reaction; S2. Wet-spinning the spinning solution, coagulating it in a coagulation bath, winding it up, and drying it to obtain a preliminarily solidified fiber; vacuum-treating the preliminarily solidified fiber to obtain an aerogel far-infrared vacuum fiber.

[0025] The dispersant first forms a stable dispersion environment in the solvent, and ultrasonic treatment makes the aerogel evenly dispersed and forms a nano-scale dispersed phase. The tourmaline and anti-radiation agent added subsequently form a three-dimensional network structure with the aerogel under the action of ultrasound. Polyvinyl alcohol further enhances the binding force between the components through hydrogen bonds and physical entanglement. The cross-linking agent enables the system to form a chemical cross-linked network to improve structural stability. During the wet spinning process, the diffusion-induced phase separation of the solvent and the non-solvent is used to induce phase separation, so that the porous skeleton of the aerogel and the fiber cortex are synchronously formed, and through-holes are formed inside. The subsequent vacuum treatment extracts the residual solvent and gas in the pores through a negative pressure environment, causing the aerogel pores to collapse and reconstruct to form a stable vacuum cavity. At the same time, the anti-radiation agent is spontaneously oriented and arranged under the action of vacuum contraction force, ultimately making the fiber have the characteristics of lightweight, good radiation resistance and far-infrared emission warmth retention effect, which can promote blood circulation and has good functionality and comfort.

[0026] In summary, this application includes at least one of the following beneficial technical effects: 1. Aerogel is made of tetraethyl orthosilicate and cellulose nanowhiskers. Its unique nanoporous structure and lightweight properties give the fiber excellent thermal insulation properties; tourmaline, as a far-infrared powder, can efficiently radiate far-infrared rays, which can promote blood circulation and improve metabolism in the human body; carbon nanotubes, as anti-radiation agents, can effectively absorb and scatter radiation with their high specific surface area, good conductivity and special electronic structure, enhancing the fiber's radiation resistance; polyvinyl alcohol, as a polymer matrix, provides good film-forming properties and mechanical strength, ensuring the flexibility and durability of the fiber; dispersants can evenly disperse the components to avoid agglomeration and ensure uniform and stable fiber performance; cross-linking agents enhance the degree of cross-linking between polymer molecules through chemical bonding, further improving the mechanical strength, dimensional stability and chemical stability of the fiber; multiple components cooperate and work synergistically with each other to improve the comprehensive performance of aerogel far-infrared vacuum fiber, enhancing its thermal insulation properties, far-infrared health effects and anti-radiation protection functions.

[0027] 2. Zirconium oxide generated by the reaction of zirconium hydroxide has excellent infrared emission properties, and produces a synergistic effect with tourmaline, effectively broadening the far-infrared emission band, enhancing thermal radiation efficiency, and being able to resonate with human cells more efficiently, thereby promoting blood circulation; the composite structure formed by zirconium oxide on the surface of tourmaline improves the stability and mechanical properties of the powder, making the fiber more durable during processing and use; the polydopamine film formed by the self-polymerization of dopamine hydrochloride strengthens the interfacial bonding between the powder and polyvinyl alcohol through rich amino groups, ensuring the stability of the overall fiber structure, and its own far-infrared emission characteristics cooperate with tourmaline and zirconium oxide to further enhance the far-infrared emission performance; in addition, the polydopamine film can also serve as a functional carrier, providing a good attachment basis for anti-radiation agents, thereby better enhancing the fiber's radiation resistance and achieving a synergistic improvement in properties such as radiation resistance, far-infrared emission, blood circulation promotion, and structural enhancement.

[0028] 3. By purifying carbon nanotubes, impurities on their surface can be effectively removed and their intrinsic performance can be improved; iron nitrate and cerium nitrate introduce iron ions and cerium ions, which can change the electronic structure and energy band structure of carbon nanotubes, enhance their electromagnetic response characteristics, and significantly improve the absorption and scattering ability of carbon nanotubes to high-frequency radiation, thereby improving the electromagnetic shielding effectiveness and neutron shielding capability of the fiber; the metal ions on the surface of carbon nanotubes can transfer charge with fullerenes, forming electron traps at the interface, extending the dissipation path of radiation energy, and improving the shielding efficiency against high-energy radiation; modified carbon nanotubes and fullerenes can also promote electron transitions on the tourmaline surface through a synergistic catalytic effect, converting more energy into far-infrared radiation, improving the far-infrared emissivity of the fiber, and combining the infrared absorption characteristics of fullerene itself to further enhance the thermal insulation performance of the fiber. DETAILED DESCRIPTION

[0029] The present application discloses an aerogel far-infrared vacuum fiber and a preparation method thereof. Unless otherwise specified, the raw materials used in the present application can be obtained from commercially available raw materials. The present application is further described in detail below in conjunction with the examples: Description of raw materials: tetraethyl orthosilicate (CAS No.: 78-10-4), cellulose nanowhiskers of brand ZC-19, purchased from Guilin Qihong Technology Co., Ltd., tourmaline purchased from Lingshou County Zhongshi Hengda Mineral Products Processing Plant, particle size is 50 nm, carbon nanotubes numbered XFM13, purchased from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd., polyvinyl alcohol specification is 100-27, purchased from Shanghai Shenmu New Materials Co., Ltd., polyethylene glycol-4000 purchased from Nantong Renda Chemical Co., Ltd., glutaraldehyde (CAS No.: 111-30-8), dopamine hydrochloride (CAS No.: 62-31-7), fullerene (CAS No.: 131159-39-2).

[0030] Example 1 Preparation of aerogel 25 g of tetraethyl orthosilicate and 5 g of cellulose nanowhiskers were mixed and dispersed in 80 mL of ethanol-water solution (the volume ratio of ethanol to water was 1:1), and stirred at 300 rpm for 30 min to obtain a mixed solution; the pH of the mixed solution was adjusted to 3 with 0.1 mol / L hydrochloric acid, and after stirring at 200 rpm for 20 min, the mixture was poured into a mold for gelation reaction, and the reaction was carried out at 40°C for 2 h and at 60°C for 4 h. After the gelation reaction was completed, it was aged at 25°C for 24 h, vacuum dried at 60°C, and ball milled at 500 rpm for 2 h to obtain aerogel.

[0031] Preparation of aerogel far-infrared vacuum fibers Weigh 20 g of aerogel, 10 g of tourmaline, 4 g of an anti-radiation agent, 40 g of polyvinyl alcohol, 3 g of a dispersant, 1 g of a cross-linking agent, and 80 mL of a solvent consisting of water, dimethyl sulfoxide, and ethanol in a volume ratio of 6:3:1. The anti-radiation agent is carbon nanotubes, the dispersant is polyethylene glycol-4000, and the cross-linking agent is glutaraldehyde.

[0032] S1. Mix the dispersant into the solvent, stir at 400 rpm for 20 min, add the aerogel, ultrasonicate for 30 min, add the tourmaline and the anti-radiation agent, stir at 500 rpm for 40 min, ultrasonicate for 20 min, add polyvinyl alcohol, stir at 300 rpm for 1 h, add the cross-linking agent, stir at 200 rpm for 40 min, and obtain the spinning solution; S2. The spinning solution was wet-spun at a spinneret extrusion speed of 10 m / min, coagulated in a coagulation bath (25% sodium sulfate by mass + 5% boric acid aqueous solution by mass), wound at a speed of 15 m / min, and dried at 60°C for 8 h to obtain a preliminarily solidified fiber; the preliminarily solidified fiber was vacuum-treated and dried at a vacuum degree of 10 -4 The aerogel far-infrared vacuum fiber was obtained by treating it at 100°C for 4 hours.

[0033] Example 2 Preparation of aerogel 25 g of tetraethyl orthosilicate and 5 g of cellulose nanowhiskers were mixed and dispersed in 80 mL of ethanol-water solution (the volume ratio of ethanol to water was 1:1), and stirred at 300 rpm for 30 min to obtain a mixed solution; the pH of the mixed solution was adjusted to 3 with 0.1 mol / L hydrochloric acid, and after stirring at 200 rpm for 20 min, the mixture was poured into a mold for gelation reaction, reacted at 50°C for 1 h and at 70°C for 3 h. After the gelation reaction was completed, it was aged at 25°C for 24 h, vacuum dried at 60°C, and ball milled at 500 rpm for 2 h to obtain aerogel.

[0034] Preparation of aerogel far-infrared vacuum fibers Weigh 30 g of aerogel, 15 g of tourmaline, 8 g of an anti-radiation agent, 60 g of polyvinyl alcohol, 5 g of a dispersant, 3 g of a cross-linking agent, and 100 mL of a solvent, where the solvent consists of water, dimethyl sulfoxide, and ethanol in a volume ratio of 6:3:1. The anti-radiation agent is carbon nanotubes, the dispersant is polyethylene glycol-4000, and the cross-linking agent is glutaraldehyde.

[0035] S1. Mix the dispersant into the solvent, stir at 400 rpm for 20 min, add the aerogel, ultrasonicate for 30 min, add the tourmaline and the anti-radiation agent, stir at 500 rpm for 40 min, ultrasonicate for 20 min, add polyvinyl alcohol, stir at 300 rpm for 1 h, add the cross-linking agent, stir at 200 rpm for 40 min, and obtain the spinning solution; S2. The spinning solution is wet-spun with a spinneret extrusion speed of 10 m / min, coagulated in a coagulation bath (25% sodium sulfate by mass + 5% boric acid aqueous solution by mass), wound at a speed of 15 m / min, and dried at 60°C for 8 h to obtain a preliminarily solidified fiber; the preliminarily solidified fiber is vacuum-treated at a vacuum degree of 10-4 Pa and 100°C for 4 h to obtain an aerogel far-infrared vacuum fiber.

[0036] Example 3 Preparation of aerogel 25 g of tetraethyl orthosilicate and 5 g of cellulose nanowhiskers were mixed and dispersed in 80 mL of ethanol-water solution (the volume ratio of ethanol to water was 1:1), and stirred at 300 rpm for 30 min to obtain a mixed solution; the pH of the mixed solution was adjusted to 3 with 0.1 mol / L hydrochloric acid, and after stirring at 200 rpm for 20 min, the mixture was poured into a mold for gelation reaction, and the reaction was carried out at 45 ° C for 1.5 h and at 65 ° C for 3.5 h. After the gelation reaction was completed, it was aged at 25 ° C for 24 h, vacuum dried at 60 ° C, and ball milled at 500 rpm for 2 h to obtain aerogel.

[0037] Preparation of aerogel far-infrared vacuum fibers Weigh 25 g of aerogel, 12.5 g of tourmaline, 6 g of an anti-radiation agent, 50 g of polyvinyl alcohol, 4 g of a dispersant, 2 g of a cross-linking agent, and 90 mL of a solvent consisting of water, dimethyl sulfoxide, and ethanol in a volume ratio of 6:3:1. The anti-radiation agent is carbon nanotubes, the dispersant is polyethylene glycol-4000, and the cross-linking agent is glutaraldehyde.

[0038] S1. Mix the dispersant into the solvent, stir at 400 rpm for 20 min, add the aerogel, ultrasonicate for 30 min, add the tourmaline and the anti-radiation agent, stir at 500 rpm for 40 min, ultrasonicate for 20 min, add polyvinyl alcohol, stir at 300 rpm for 1 h, add the cross-linking agent, stir at 200 rpm for 40 min, and obtain the spinning solution; S2. The spinning solution was wet-spun at a spinneret extrusion speed of 10 m / min, coagulated in a coagulation bath (25% sodium sulfate by mass + 5% boric acid aqueous solution by mass), wound at a speed of 15 m / min, and dried at 60°C for 8 h to obtain a preliminarily solidified fiber; the preliminarily solidified fiber was vacuum-treated and dried at a vacuum degree of 10 -4 The aerogel far-infrared vacuum fiber was obtained by treating it at 100°C for 4 hours.

[0039] Example 4 Example 4 is based on Example 3. The only difference between Example 4 and Example 3 is that in Example 4, the gelation reaction is not carried out by staged temperature control.

[0040] Preparation of aerogel 25 g of tetraethyl orthosilicate and 5 g of cellulose nanowhiskers were mixed and dispersed in 80 mL of ethanol-water solution (the volume ratio of ethanol to water was 1:1), and stirred at 300 rpm for 30 min to obtain a mixed solution; the pH of the mixed solution was adjusted to 3 with 0.1 mol / L hydrochloric acid, and after stirring at 200 rpm for 20 min, the mixture was poured into a mold for gelation reaction, and the reaction was carried out at 55°C for 5 h. After the gelation reaction was completed, it was aged at 25°C for 24 h, vacuum dried at 60°C, and ball milled at 500 rpm for 2 h to obtain aerogel.

[0041] Example 5 Example 5 is based on Example 3. The only difference between Example 5 and Example 3 is that the tourmaline in Example 5 is modified and prepared by the following steps: The mass ratio of pretreated tourmaline to dopamine hydrochloride is 1:0.1.

[0042] S1, grinding the tourmaline through a 200-mesh sieve and drying at 80° C. for 4 h to obtain pretreated tourmaline; S2. The pretreated tourmaline was mixed with 3 mg / mL dopamine hydrochloride buffer, the pH was adjusted to 9 with 0.1 mol / L sodium hydroxide solution, the mixture was reacted at 20° C. for 12 h, filtered, washed with deionized water, and vacuum dried at 60° C. to obtain modified tourmaline.

[0043] Example 6 Example 6 is based on Example 3. The only difference between Example 6 and Example 3 is that the raw material for preparing the modified tourmaline in Example 6 also includes zirconium hydroxide, and the preparation is carried out using the following steps: The mass ratio of pretreated tourmaline, zirconium hydroxide and dopamine hydrochloride is 1:0.14:0.1.

[0044] S1, grinding the tourmaline through a 200-mesh sieve and drying at 80° C. for 4 h to obtain pretreated tourmaline; S2. Add citric acid (the molar ratio of citric acid to zirconium ion is 2:1) to a 0.2 mol / L zirconium hydroxide solution, and stir at 300 rpm for 40 min to obtain a zirconium oxide precursor solution; add the pretreated tourmaline to the zirconium oxide precursor solution, adjust the pH to 10 after ultrasonic treatment for 15 min, heat to 80°C, stir at 500 rpm for 2 h, centrifuge, wash alternately with deionized water and anhydrous ethanol until neutral, vacuum dry at 80°C, heat to 500°C at a heating rate of 10°C / min, calcine for 4 h, cool to below 30°C, and grind to obtain a composite powder; S3. The pretreated tourmaline was mixed with 3 mg / mL dopamine hydrochloride buffer, the pH was adjusted to 9 with 0.1 mol / L sodium hydroxide solution, the mixture was reacted at 20° C. for 12 h, filtered, washed with deionized water, and vacuum dried at 60° C. to obtain modified tourmaline.

[0045] Example 7 Example 7 is based on Example 3. The only difference between Example 7 and Example 3 is that the raw material for preparing the modified tourmaline in Example 7 also includes zirconium hydroxide, and the preparation is carried out using the following steps: The mass ratio of pretreated tourmaline, zirconium hydroxide and dopamine hydrochloride is 1:0.29:0.1.

[0046] S1, grinding the tourmaline through a 200-mesh sieve and drying at 80° C. for 4 h to obtain pretreated tourmaline; S2. Add citric acid (the molar ratio of citric acid to zirconium ion is 2:1) to a 0.2 mol / L zirconium hydroxide solution, and stir at 300 rpm for 40 min to obtain a zirconium oxide precursor solution; add the pretreated tourmaline to the zirconium oxide precursor solution, adjust the pH to 10 after ultrasonic treatment for 15 min, heat to 80°C, stir at 500 rpm for 2 h, centrifuge, wash alternately with deionized water and anhydrous ethanol until neutral, vacuum dry at 80°C, heat to 500°C at a heating rate of 10°C / min, calcine for 4 h, cool to below 30°C, and grind to obtain a composite powder; S3. The pretreated tourmaline was mixed with 3 mg / mL dopamine hydrochloride buffer, the pH was adjusted to 9 with 0.1 mol / L sodium hydroxide solution, the mixture was reacted at 20° C. for 12 h, filtered, washed with deionized water, and vacuum dried at 60° C. to obtain modified tourmaline.

[0047] Example 8 Example 8 is based on Example 3. The only difference between Example 8 and Example 3 is that the raw material for preparing the modified tourmaline in Example 8 also includes zirconium hydroxide, and the preparation is carried out using the following steps: The mass ratio of pretreated tourmaline, zirconium hydroxide and dopamine hydrochloride is 1:0.215:0.1.

[0048] S1, grinding the tourmaline through a 200-mesh sieve and drying at 80° C. for 4 h to obtain pretreated tourmaline; S2. Add citric acid (the molar ratio of citric acid to zirconium ion is 2:1) to a 0.2 mol / L zirconium hydroxide solution, and stir at 300 rpm for 40 min to obtain a zirconium oxide precursor solution; add the pretreated tourmaline to the zirconium oxide precursor solution, adjust the pH to 10 after ultrasonic treatment for 15 min, heat to 80°C, stir at 500 rpm for 2 h, centrifuge, wash alternately with deionized water and anhydrous ethanol until neutral, vacuum dry at 80°C, heat to 500°C at a heating rate of 10°C / min, calcine for 4 h, cool to below 30°C, and grind to obtain a composite powder; S3. The pretreated tourmaline was mixed with 3 mg / mL dopamine hydrochloride buffer, the pH was adjusted to 9 with 0.1 mol / L sodium hydroxide solution, the mixture was reacted at 20° C. for 12 h, filtered, washed with deionized water, and vacuum dried at 60° C. to obtain modified tourmaline.

[0049] Example 9 Example 9 is based on Example 8. The only difference between Example 9 and Example 8 is that in Example 9, the mass ratio of pretreated tourmaline, zirconium hydroxide and dopamine hydrochloride is 1:0.35:0.1.

[0050] Example 10 Example 10 is based on Example 8. The only difference between Example 10 and Example 8 is that the anti-radiation agent in Example 10 further includes fullerene.

[0051] Preparation of aerogel far-infrared vacuum fibers Weigh 25 g aerogel, 12.5 g tourmaline, 6 g anti-radiation agent, 50 g polyvinyl alcohol, 4 g dispersant, 2 g cross-linking agent, and 90 mL solvent, where the solvent consists of water, dimethyl sulfoxide, and ethanol in a volume ratio of 6:3:1, the anti-radiation agent consists of a mixture of carbon nanotubes and fullerenes in a mass ratio of 1.5:1, the dispersant is polyethylene glycol-4000, and the cross-linking agent is glutaraldehyde.

[0052] S1. Mix the dispersant into the solvent, stir at 400 rpm for 20 min, add the aerogel, ultrasonicate for 30 min, add the tourmaline and the anti-radiation agent, stir at 500 rpm for 40 min, ultrasonicate for 20 min, add polyvinyl alcohol, stir at 300 rpm for 1 h, add the cross-linking agent, stir at 200 rpm for 40 min, and obtain the spinning solution; S2. The spinning solution is wet-spun with a spinneret extrusion speed of 10 m / min, coagulated in a coagulation bath (25% sodium sulfate by mass + 5% boric acid aqueous solution by mass), wound at a speed of 15 m / min, and dried at 60°C for 8 h to obtain a preliminarily solidified fiber; the preliminarily solidified fiber is vacuum-treated at a vacuum degree of 10-4 Pa and 100°C for 4 h to obtain an aerogel far-infrared vacuum fiber.

[0053] Example 11 Example 11 is based on Example 3. The only difference between Example 11 and Example 3 is that the anti-radiation agent in Example 11 further includes fullerene.

[0054] Preparation of aerogel far-infrared vacuum fibers Weigh 25 g aerogel, 12.5 g tourmaline, 6 g anti-radiation agent, 50 g polyvinyl alcohol, 4 g dispersant, 2 g cross-linking agent, and 90 mL solvent, where the solvent consists of water, dimethyl sulfoxide, and ethanol in a volume ratio of 6:3:1, the anti-radiation agent consists of a mixture of carbon nanotubes and fullerenes in a mass ratio of 2.5:1, the dispersant is polyethylene glycol-4000, and the cross-linking agent is glutaraldehyde.

[0055] S1. Mix the dispersant into the solvent, stir at 400 rpm for 20 min, add the aerogel, ultrasonicate for 30 min, add the tourmaline and the anti-radiation agent, stir at 500 rpm for 40 min, ultrasonicate for 20 min, add polyvinyl alcohol, stir at 300 rpm for 1 h, add the cross-linking agent, stir at 200 rpm for 40 min, and obtain the spinning solution; S2. The spinning solution is wet-spun with a spinneret extrusion speed of 10 m / min, coagulated in a coagulation bath (25% sodium sulfate by mass + 5% boric acid aqueous solution by mass), wound at a speed of 15 m / min, and dried at 60°C for 8 h to obtain a preliminarily solidified fiber; the preliminarily solidified fiber is vacuum-treated at a vacuum degree of 10-4 Pa and 100°C for 4 h to obtain an aerogel far-infrared vacuum fiber.

[0056] Example 12 Example 12 is based on Example 3. The only difference between Example 12 and Example 3 is that the anti-radiation agent in Example 12 further includes fullerene.

[0057] Preparation of aerogel far-infrared vacuum fibers Weigh 25 g aerogel, 12.5 g tourmaline, 6 g anti-radiation agent, 50 g polyvinyl alcohol, 4 g dispersant, 2 g cross-linking agent, and 90 mL solvent, where the solvent consists of water, dimethyl sulfoxide, and ethanol in a volume ratio of 6:3:1, the anti-radiation agent consists of a mixture of carbon nanotubes and fullerenes in a mass ratio of 2:1, the dispersant is polyethylene glycol-4000, and the cross-linking agent is glutaraldehyde.

[0058] S1. Mix the dispersant into the solvent, stir at 400 rpm for 20 min, add the aerogel, ultrasonicate for 30 min, add the tourmaline and the anti-radiation agent, stir at 500 rpm for 40 min, ultrasonicate for 20 min, add polyvinyl alcohol, stir at 300 rpm for 1 h, add the cross-linking agent, stir at 200 rpm for 40 min, and obtain the spinning solution; S2. The spinning solution is wet-spun with a spinneret extrusion speed of 10 m / min, coagulated in a coagulation bath (25% sodium sulfate by mass + 5% boric acid aqueous solution by mass), wound at a speed of 15 m / min, and dried at 60°C for 8 h to obtain a preliminarily solidified fiber; the preliminarily solidified fiber is vacuum-treated at a vacuum degree of 10-4 Pa and 100°C for 4 h to obtain an aerogel far-infrared vacuum fiber.

[0059] Example 13 Example 13 is based on Example 3. The only difference between Example 13 and Example 3 is that the anti-radiation agent in Example 13 is composed of a mixture of carbon nanotubes and fullerenes in a mass ratio of 1:1.

[0060] Example 14 Example 14 is based on Example 13. The only difference between Example 14 and Example 13 is that the anti-radiation agent in Example 14 is composed of a mixture of carbon nanotubes and fullerenes in a mass ratio of 3:1.

[0061] Example 15 Example 15 is based on Example 13. The only difference between Example 15 and Example 13 is that the carbon nanotubes in Example 15 are modified and prepared by the following steps: S1. Place carbon nanotubes in a 70% by mass aqueous nitric acid solution, mix at a solid-liquid ratio of 1:20 g / mL, and reflux at 80°C at a stirring speed of 500 rpm for 4 hours to perform purification treatment. After the reaction, cool to below 30°C, centrifuge and wash with deionized water until neutral, collect the precipitate and dry it in vacuum at 80°C to obtain purified carbon nanotubes; S2. Mix ferric nitrate and cerium nitrate in water with a molar ratio of ferric nitrate to cerium nitrate of 1:1 to obtain a metal salt solution with a total concentration of 0.2 mol / L; add purified carbon nanotubes to the metal salt solution, ultrasonicate for 40 minutes, stir and react at a speed of 300 rpm for 1 hour, adjust the pH to 10 with 1 mol / L ammonia water, stir and react at a speed of 300 rpm at 80°C for 2 hours, centrifuge and wash with deionized water until neutral, vacuum dry at 80°C, heat to 500°C at a speed of 10°C / min, calcine for 2 hours, cool to below 30°C, and grind to obtain modified carbon nanotubes.

[0062] Comparative Example 1 Comparative Example 1 is based on Example 3. The only difference between Comparative Example 1 and Example 3 is that cellulose nanowhiskers are not added when preparing the aerogel in Comparative Example 1.

[0063] Preparation of aerogel 25 g of ethyl orthosilicate was dispersed in 80 mL of ethanol aqueous solution (the volume ratio of ethanol to water was 1:1), and the mixture was stirred at 300 rpm for 30 min to obtain a mixed solution; the pH of the mixed solution was adjusted to 3 with 0.1 mol / L hydrochloric acid, and after stirring at 200 rpm for 20 min, the mixture was poured into a mold for gelation reaction, and the reaction was carried out at 45 ° C for 1.5 h and at 65 ° C for 3.5 h. After the gelation reaction was completed, it was aged at 25 ° C for 24 h, vacuum dried at 60 ° C, and ball milled at 500 rpm for 2 h to obtain aerogel.

[0064] Performance testing (1) The aerogel far-infrared vacuum fiber was made into a 100cm2 aerogel far-infrared vacuum fiber according to the GB / T30127-2013 Testing and Evaluation of Textile Far-Infrared Performance. 2 The far-infrared emissivity of the fabric sheet and the temperature rise of the sample surface after irradiation were tested. Each sample was tested three times and the average value was taken after measurement. The results are recorded in Table 1.

[0065] (2) Thermal insulation performance test: The aerogel far-infrared vacuum fiber was made into an area of ​​100 cm 2The thermal conductivity of the fabric sheet was measured by a thermal conductivity meter. Each sample was tested three times, and the average value was taken after measurement. The results are recorded in Table 1.

[0066] (3) Radiation performance test: The aerogel far-infrared vacuum fiber was made into an area of ​​100 cm 2 The electromagnetic radiation intensity before and after the sample was placed on the fabric sheet was measured using an electromagnetic shielding effectiveness tester to calculate the electromagnetic shielding effectiveness (dB). Each sample was tested three times and the average value was taken after measurement. The results are recorded in Table 1.

[0067] Table 1 Test results of far-infrared emission performance, thermal insulation performance and radiation resistance of fibers As can be seen from Table 1, the far-infrared emissivity of Examples 1-3 is greater than 86.5%, the temperature rise value is greater than 2.2°C, the thermal conductivity is less than 0.023W / (m·K), and the electromagnetic shielding effectiveness is greater than 33.2dB. It can be seen that the aerogel far-infrared vacuum fiber prepared in this application has good far-infrared emission performance, thermal insulation performance and radiation resistance, can promote human blood circulation, and has good functionality and comfort.

[0068] As can be seen from Table 1, the only difference between Example 4 and Example 3 is that Example 4 does not use segmented temperature control for the gelation reaction. Compared with Example 3, Example 4 has a lower performance. This is because the pore structure of the aerogel is affected by not using segmented temperature control for the gelation reaction, thereby affecting the thermal insulation performance and reducing the performance.

[0069] As can be seen from Table 1, the difference between Examples 5-9 and Example 3 is that: in Example 5, dopamine hydrochloride is used to modify the tourmaline to improve its dispersibility and compatibility, and the performance is improved compared with Example 3; in Examples 6-8, zirconium hydroxide is added to modify the tourmaline, and the performance of the tourmaline is further enhanced through synergistic effects; in Example 9, the optimal ratio is destroyed, and excessive zirconium hydroxide affects the surface structure and mechanical properties of the tourmaline, and the performance improvement effect is slightly reduced.

[0070] As can be seen from Table 1, the difference between Examples 10-15 and Example 3 is that fullerene is further added to the anti-radiation agent in Examples 10-12. Compared with Example 3, the performance of Examples 10-12 is improved. This is because the carbon nanotubes and fullerenes act synergistically to achieve performance improvement; Examples 13-14 destroy the optimal ratio and the performance decreases; Example 15 further modifies the carbon nanotubes, enhances the synergistic effect of the modified carbon nanotubes and fullerenes, and further improves the performance.

[0071] As can be seen from Table 1, the only difference between Comparative Example 1 and Example 3 is that no cellulose nanowhiskers were added when preparing the aerogel in Comparative Example 1. Compared with Example 3, the performance of Comparative Example 1 was significantly reduced. This is because the lack of the regulating effect of cellulose nanowhiskers deteriorated the pore structure of the aerogel, thereby affecting the performance.

[0072] This specific embodiment is merely an explanation of the present application and does not limit the present application. Based on the above description, relevant personnel can make various changes and modifications without departing from the technical scope of the present application. The technical scope of the present application is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. An aerogel far-infrared vacuum fiber, characterized by: The raw materials for preparation include the following components in parts by weight: 20-30 parts of aerogel 10-15 parts tourmaline 4-8 parts of anti-radiation agent 40-60 parts of polyvinyl alcohol 3-5 parts dispersant 1-3 parts crosslinking agent The raw materials for preparing the aerogel include tetraethyl orthosilicate and cellulose nano whiskers; The anti-radiation agent includes carbon nanotubes.

2. The aerogel far-infrared vacuum fiber according to claim 1, characterized in that: The tourmaline is modified and prepared by the following steps: S1, grinding and sieving the tourmaline, and drying it to obtain pretreated tourmaline; S2. The pretreated tourmaline is mixed into a dopamine hydrochloride buffer solution, and the pH is adjusted to alkaline. After the reaction, the mixture is filtered, washed, and dried to obtain the modified tourmaline.

3. The aerogel far-infrared vacuum fiber according to claim 2, characterized in that: The raw materials for preparing the modified tourmaline also include zirconium hydroxide, which is prepared by the following steps: S1, grinding and sieving the tourmaline, and drying it to obtain pretreated tourmaline; S2. Add citric acid to the zirconium hydroxide solution and stir to obtain a zirconium oxide precursor solution; The pretreated tourmaline is added to the zirconium oxide precursor solution, the pH is adjusted to alkaline after ultrasonic treatment, the mixture is heated and stirred for reaction, the mixture is centrifuged, washed, dried, calcined, cooled and ground to obtain a composite powder; S3. Add the composite powder to dopamine hydrochloride buffer, adjust the pH to alkaline, and after the reaction, filter, wash, and dry to obtain modified tourmaline.

4. The aerogel far-infrared vacuum fiber according to claim 3, characterized in that: The mass ratio of the pretreated tourmaline, zirconium hydroxide and dopamine hydrochloride is 1:(0.14-0.29):0.

1.

5. The aerogel far-infrared vacuum fiber according to claim 1, characterized in that: The anti-radiation agent also includes fullerene.

6. The aerogel far-infrared vacuum fiber according to claim 5, characterized in that: The mass ratio of carbon nanotubes to fullerenes in the anti-radiation agent is (1.5-2.5):

1.

7. The aerogel far-infrared vacuum fiber according to claim 6, characterized in that: The carbon nanotubes are modified and prepared by the following steps: S1, purifying the carbon nanotubes to obtain purified carbon nanotubes; S2. Mix ferric nitrate and cerium nitrate in a solvent to obtain a metal salt solution; add purified carbon nanotubes to the metal salt solution, ultrasonically stir, adjust the pH to alkaline, stir for reaction, centrifuge, wash, calcine and then grind to obtain modified carbon nanotubes.

8. The aerogel far-infrared vacuum fiber according to claim 1, characterized in that: The aerogel is prepared by the following steps: The method comprises mixing tetraethyl orthosilicate and cellulose nanowhiskers into an ethanol aqueous solution and stirring to obtain a mixed solution; adjusting the pH of the mixed solution to acidic, stirring, pouring the mixed solution into a mold, heating to perform a gelation reaction, and performing an aging treatment after gelation is completed. The mixed solution is dried and then ball-milled to obtain an aerogel.

9. The aerogel far-infrared vacuum fiber according to claim 8, characterized in that: The gelation reaction conditions are: react at 40-50° C. for 1-2 hours, then heat to 60-70° C. for 3-4 hours.

10. A method for preparing an aerogel far-infrared vacuum fiber according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Mix the dispersant into the solvent, add the aerogel after stirring, add tourmaline and anti-radiation agent after ultrasonication, add polyvinyl alcohol after stirring and ultrasonication, add the cross-linking agent after stirring, and stir to obtain a spinning solution after reaction; S2. Wet-spinning the spinning solution, coagulating it in a coagulation bath, winding it up, and drying it to obtain a preliminarily solidified fiber; vacuum-treating the preliminarily solidified fiber to obtain an aerogel far-infrared vacuum fiber.

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