WO2024041439A1 - Continuous sio2 aerogel composite fiber, and preparation method therefor and use thereof - Google Patents

Continuous sio2 aerogel composite fiber, and preparation method therefor and use thereof Download PDF

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WO2024041439A1
WO2024041439A1 PCT/CN2023/113474 CN2023113474W WO2024041439A1 WO 2024041439 A1 WO2024041439 A1 WO 2024041439A1 CN 2023113474 W CN2023113474 W CN 2023113474W WO 2024041439 A1 WO2024041439 A1 WO 2024041439A1
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preparation
solution
sio
composite fiber
phenolic resin
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PCT/CN2023/113474
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French (fr)
Chinese (zh)
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张伟
胡佳丽
魏发云
戴家木
王海楼
李大伟
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南通大学
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/12—Condensation polymers of aldehydes or ketones
    • C04B26/122—Phenol-formaldehyde condensation polymers
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D27/00—Details of garments or of their making
    • A41D27/02—Linings
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/06—Thermally protective, e.g. insulating
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/08—Heat resistant; Fire retardant
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2400/00—Functions or special features of garments
    • A41D2400/10—Heat retention or warming
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00—Materials for garments
    • A41D2500/50—Synthetic resins or rubbers

Definitions

  • the invention belongs to the technical field of composite material preparation and relates to a continuous SiO 2 airgel composite fiber and its preparation method and application.
  • SiO 2 aerogel has a very low thermal conductivity due to its porous, low density, and large specific surface area, and it decomposes without producing toxic gases, so it is considered an ideal thermal insulation material.
  • SiO 2 aerogel has low strength and is easily broken, which limits its application range.
  • it is necessary to go through the steps of hydrolysis, polymerization (gelation), solvent replacement, and hydrophobic modification before drying.
  • SiO 2 aerogel is not prepared at normal temperature and pressure, The machine requirements are high, the cost is increased and industrialization is difficult; however, if SiO 2 aerogel is prepared at normal temperature and pressure, the gelation speed will be very slow during the polymerization stage, which also increases the difficulty of SiO 2 aerogel preparation cycle.
  • SiO 2 aerogel is combined with other flexible materials, its application is not only limited by the form of the substrate that is combined with SiO 2 aerogel, but is also still limited by long preparation cycles or difficulties in industrialization due to high costs.
  • SiO 2 airgel has a certain degree of flexibility.
  • foldability morphological changes and industrialization potential, it can adapt to multiple application scenarios. This can expand the application scope of SiO2 airgel and provide a technical basis for its application in thermal insulation fillers, linings, thermal protective clothing, etc.
  • the present invention aims to provide a continuous SiO 2 airgel composite fiber and its preparation method and application.
  • the continuous SiO 2 airgel composite fiber has excellent thermal insulation properties and flame retardant properties, and is flexible and Good strength.
  • the invention provides a preparation method of continuous SiO 2 airgel composite fiber, which includes the following steps:
  • the silicon source is at least one of trimethoxymethylsilane, tetramethoxysilane, ethyl orthosilicate and water glass.
  • the acidic catalyst is one of oxalic acid, hydrochloric acid, hydrofluoric acid, nitric acid, formic acid and acetic acid;
  • the alkaline catalyst is one of sodium hydroxide, calcium hydroxide and ammonia water.
  • the average weight average molecular weight of the high molecular weight thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution is 600.
  • thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution is one of F-51B, F-52B and F-44B.
  • step S2 the concentration of the high molecular weight thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution is 40wt% to 50wt%, and the high molecular weight thermosetting phenolic resin solution and the SiO 2 airgel precursor solution The volume ratio is (1 ⁇ 2):3.
  • the coagulation bath of the wet spinning is specifically: under the temperature condition of 40°C to 60°C, the coagulation bath is first carried out in an anhydrous ethanol solution containing a silicon source, and then the coagulation is carried out in a sodium sulfate solution containing boric acid. bath.
  • the volume concentration of the silicon source is 10% to 30%; in the sodium sulfate solution containing boric acid, the volume concentration of boric acid is 0.5% to 2%.
  • the winding speed of the virgin silk after wet spinning is 5-50m/min.
  • the hydrophobic modification is specifically carried out by using a n-hexane solution of a hydrophobic modifier, and the hydrophobic modifier is trimethylchlorosilane, hexamethyldisiloxane and One of hexamethyldisilazane, the modification time is 8 to 12 hours.
  • the volume concentration of the hydrophobic modifier is 10% to 20%.
  • drying is using liquid CO 2 supercritical drying and then vacuum drying at 150°C to 180°C for 1 to 2 hours.
  • the invention also provides the above continuous SiO 2 airgel composite fiber or the continuous SiO 2 airgel composite prepared by the above preparation method. Application of fibers in thermal insulation materials or flame retardant materials.
  • the thermal insulation material is a protective clothing lining or thermal insulation felt.
  • the present invention has the following beneficial technical effects:
  • the preparation method provided by the present invention realizes rapid gelation of the precursor solution in the polymerization stage at normal temperature and pressure by adding a high molecular weight thermosetting phenolic resin to the precursor solution and adjusting the pH, and the added phenolic resin increases
  • the spinnability of SiO 2 aerogel has an enhanced and toughening effect, making the SiO 2 aerogel weavable and processable. It is then obtained through wet spinning processing and subsequent hydrophobic modification and supercritical drying.
  • Continuous SiO 2 airgel composite fiber not only has a simple preparation method, but also solves the problems of traditional SiO 2 airgel being easily broken and having low strength.
  • the continuous SiO 2 airgel composite fiber provided by the present invention not only has good thermal insulation properties, but also has certain toughness, strength, corrosion resistance, and no toxic gas is produced when burned.
  • SiO 2 aerogel Since SiO 2 aerogel has excellent thermal stability, and after carbonization of phenolics at high temperatures, it can also play a role in heat insulation and maintain the shape of SiO 2 aerogel fiber.
  • the fiber also has excellent flame retardant effect.
  • Figure 1 is a flow chart of a preparation method of continuous SiO 2 airgel composite fiber provided by the present invention
  • Figure 2 is a stress-elongation curve of the continuous SiO 2 airgel composite fiber prepared in Example 1;
  • Figure 3 is a physical diagram showing that the continuous SiO 2 airgel composite fiber prepared in Example 1 can still maintain fiber shape despite carbonization at high temperatures;
  • Figure 4 is a weight loss curve of the SiO 2 aerogel prepared in Comparative Example 1;
  • Figure 5 is a physical picture of the granular SiO 2 aerogel that cannot form fibers in Comparative Example 1.
  • the present invention provides a method for preparing continuous SiO 2 airgel composite fibers, which includes the following steps:
  • the acidic catalyst can be one of oxalic acid, hydrochloric acid, hydrofluoric acid, nitric acid, formic acid and acetic acid.
  • thermosetting phenolic resin solution Add the high molecular weight thermosetting phenolic resin solution to the SiO 2 airgel precursor solution, stir thoroughly and mix evenly, then add the alkaline catalyst dropwise while stirring at low speed until the pH is 6-7, and let it stand for 2- After 3 hours, use the spinning stock solution for wet spinning to obtain virgin silk;
  • the high molecular weight thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution can be one of F-51B, F-52B and F-44B.
  • the alkaline catalyst is one of sodium hydroxide, calcium hydroxide and ammonia.
  • the specific coagulation bath of wet spinning is: under the temperature condition of 40°C to 60°C, first conduct a coagulation bath in an absolute ethanol solution containing a silicon source, and then conduct a coagulation bath in a sodium sulfate solution containing boric acid.
  • the volume concentration of the silicon source is preferably 10% to 30%; in the sodium sulfate solution containing boric acid, the volume concentration of boric acid is preferably 0.5% to 2%.
  • the winding speed of the virgin silk after wet spinning is 5-50m/min.
  • Hydrophobic modification is specifically carried out by using a n-hexane solution of a hydrophobic modifier.
  • the hydrophobic modifier can be one of trimethylchlorosilane, hexamethyldisiloxane and hexamethyldisilazane.
  • the modification time is 8 to 12 hours.
  • the volume concentration of the hydrophobic modifier is 10% to 20%.
  • the drying method specifically uses liquid CO2 supercritical drying and then vacuum drying at 150°C to 180°C for 1 to 2 hours.
  • a phenolic resin reinforced continuous SiO 2 airgel fiber the preparation steps of which are as follows:
  • the spinning stock solution is extruded through the spinneret and passes through two coagulation baths.
  • the coagulation bath temperature is 55°C.
  • the solute is a silicon source and the solvent is anhydrous ethanol.
  • the solute volume concentration is 20%.
  • a sodium sulfate solution with a boric acid content of 1% after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
  • the drying process is divided into two steps.
  • the first step is supercritical drying with liquid CO2
  • the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
  • the continuous SiO 2 airgel composite fiber obtained in Example 1 can be formed and has a certain strength. Clamp the fiber on the upper and lower chucks of the tensile testing machine. The distance between the chucks is 10cm. Start the machine until the fiber breaks and stop the stretching movement. Export the data to make a stress-elongation curve.
  • the stress-elongation curve is shown in Figure 2. According to Figure 2, it can be seen that the breaking strength of the fiber is approximately 0.75N, indicating that the fiber has a certain strength and processability.
  • a phenolic resin reinforced continuous SiO 2 airgel fiber the preparation steps of which are as follows:
  • the spinning solution After the spinning solution is extruded through the spinneret, it passes through two coagulation baths.
  • the coagulation bath temperature is 55°C.
  • the solute is silicon source-trimethoxymethylsilane and the solvent is absolute ethanol.
  • the drying process is divided into two steps.
  • the first step is supercritical drying with liquid CO2
  • the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
  • Example 3 uses water glass as silicon source
  • the spinning solution After the spinning solution is extruded through the spinneret, it passes through two coagulation baths.
  • the coagulation bath temperature is 55°C. They are a mixture of silicon source-water glass and absolute ethanol. The volume concentration of water glass is 20 %, and a sodium sulfate solution with a boric acid content of 1%; after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
  • the drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour, that is Continuous SiO 2 airgel composite fibers were obtained.
  • Example 4 uses tetramethoxysilane as the silicon source
  • the drying process is divided into two steps.
  • the first step is supercritical drying with liquid CO2
  • the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
  • the spinning stock solution is extruded through the spinneret and passes through two coagulation baths.
  • the coagulation bath temperature is 55°C.
  • the solute is a silicon source and the solvent is anhydrous ethanol.
  • the solute volume concentration is 20%. and a sodium sulfate solution with a boric acid content of 1%; however, what is obtained after passing through the coagulation bath is not virgin silk, but a brittle wet gel that cannot be rolled, is not easy to collect, and is very easy to break;
  • the drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour to obtain are particles.
  • This comparative example provides a SiO 2 airgel fiber, which differs from Example 1 in that there is no backup in the preparation step (1).
  • F-52B type phenolic resin solution that is, in step (2), a certain volume of F-52B type phenolic resin solution is not added to the precursor solution.
  • the SiO 2 airgel fiber obtained in Comparative Example 1 has a low molding rate, very low strength, is brittle, and cannot be subjected to mechanical testing. It is granular and discontinuous as shown in Figure 5. However, its particles have excellent thermal stability.
  • the thermogravimetric curve is shown in Figure 4. According to Figure 4, it can be seen that its weight loss rate at 800°C is higher than 75%.
  • the spinning solution After the spinning solution is extruded through the spinneret, it passes through two coagulation baths.
  • the coagulation bath temperature is 55°C.
  • the solute is a silicon source and the solvent is anhydrous ethanol.
  • the solute volume concentration is 20%.
  • a sodium sulfate solution with a boric acid content of 1% after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
  • the drying process is divided into two steps.
  • the first step is supercritical drying with liquid CO2
  • the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
  • This comparative example provides a SiO 2 airgel fiber.
  • the difference from Example 1 is that the pH value range of the mixed sol in step (2) is not 6-7, that is, ammonia water is added in step (2). Finally, adjust the pH of the mixed solution to 4-5 to obtain a mixed sol.
  • the spinning stock solution is extruded through the spinneret and passes through two coagulation baths.
  • the coagulation bath temperature is 55°C.
  • the solute is a silicon source and the solvent is anhydrous ethanol.
  • the solute volume concentration is 20%.
  • a sodium sulfate solution with a boric acid content of 1% after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
  • the drying process is divided into two steps.
  • the first step is supercritical drying with liquid CO2
  • the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
  • This comparative example provides a SiO 2 airgel fiber.
  • the difference from Example 1 is that the pH value range of the mixed sol in step (2) is not 6-7, that is, ammonia water is added in step (2). Finally, adjust the pH of the mixed solution to 8-9 to obtain a mixed sol.
  • the preparation period of the SiO2 airgel fibers obtained in Comparative Examples 2 and 3 is 4-6 hours longer than that of Example 1. Because the gel speed is greatly reduced after the pH value changes, the resting time before wet spinning becomes longer, which extends preparation cycle.
  • the prepared phenolic resin-reinforced continuous SiO 2 aerogel fibers not only have good thermal insulation It also has certain toughness, strength, corrosion resistance, no toxic gas is produced when burned, the process is simple, and the cycle is short. Moreover, the fiber also has a flame-retardant effect and can be used in the field of thermal insulation, such as making thermal protective clothing linings and insulation felts, acting as thermal insulation fillers, etc.

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Abstract

The present invention belongs to the technical field of composite material preparation, and discloses a continuous SiO2 aerogel composite fiber, and a preparation method therefor and the use thereof. The preparation method comprises: S1, mixing a silicon source, ethanol and water until uniform, slowly adding, in a dropwise manner, an acidic catalyst until the pH is 3, stirring the resulting mixture for 1.5-2 h, and leaving same to stand for 2-3 h to obtain an SiO2 aerogel precursor solution; S2, adding a high-molecular-weight thermosetting phenolic resin solution, adding, in a dropwise manner, a basic catalyst while stirring at a low speed until the pH is 6-7, leaving same to stand for 2-3 h, and subjecting same as a spinning solution to wet spinning to obtain an as-spun filament; and S3, subjecting the as-spun filament to hydrophobic modification, then soaking same in n-hexane for 12-24 h, taking same out, and drying same to obtain a continuous SiO2 aerogel composite fiber. The continuous SiO2 aerogel composite fiber has good thermal insulation performance and flame retardant performance, also has good flexibility and strength, and can be applied to the preparation of heat preservation and thermal insulation materials or flame retardant materials.

Description

一种连续SiO2气凝胶复合纤维及其制备方法与应用A kind of continuous SiO2 airgel composite fiber and its preparation method and application 技术领域Technical field
本发明属于复合材料制备技术领域，涉及一种连续SiO2气凝胶复合纤维及其制备方法与应用。The invention belongs to the technical field of composite material preparation and relates to a continuous SiO 2 airgel composite fiber and its preparation method and application.
背景技术Background technique
SiO2气凝胶因多孔、密度小、比表面积大的原因而具有很低的导热率，而且它分解无有毒气体产生，因此被认为是一种理想的保温隔热材料。但是SiO2气凝胶强度很低，易碎裂，限制了它的应用范围。不仅如此，在制备SiO2气凝胶时，在干燥前需要经过水解、聚合(凝胶化)、溶剂置换、疏水改性的步骤，若不是在常温常压下制备SiO2气凝胶，则对机器要求较高，成本增加且产业化困难；但是，若在常温常压下制备SiO2气凝胶，则其在聚合阶段凝胶速度会很慢，这也增加了SiO2气凝胶的制备周期。并且将SiO2气凝胶与其他柔性材料复合，其应用场所不仅受与SiO2气凝胶复合的基材形态的限制，也仍然会受制备周期长或因成本高而产业化困难的限制。SiO 2 aerogel has a very low thermal conductivity due to its porous, low density, and large specific surface area, and it decomposes without producing toxic gases, so it is considered an ideal thermal insulation material. However, SiO 2 aerogel has low strength and is easily broken, which limits its application range. Not only that, when preparing SiO 2 aerogel, it is necessary to go through the steps of hydrolysis, polymerization (gelation), solvent replacement, and hydrophobic modification before drying. If SiO 2 aerogel is not prepared at normal temperature and pressure, The machine requirements are high, the cost is increased and industrialization is difficult; however, if SiO 2 aerogel is prepared at normal temperature and pressure, the gelation speed will be very slow during the polymerization stage, which also increases the difficulty of SiO 2 aerogel preparation cycle. Moreover, when SiO 2 aerogel is combined with other flexible materials, its application is not only limited by the form of the substrate that is combined with SiO 2 aerogel, but is also still limited by long preparation cycles or difficulties in industrialization due to high costs.
所以，亟需一种物理或化学方法，在不影响SiO2气凝胶保温隔热性能的前提下，可以提高它的强度并加快其凝胶速度，使SiO2气凝胶具有一定的可弯折性、形态变化和产业化潜力，可以适应多个应用场景。这样就可以扩大SiO2气凝胶的应用范围，为其在保温隔热填料、衬里、热防护服等方面的应用提供技术基础。Therefore, there is an urgent need for a physical or chemical method that can improve the strength and accelerate the gelation speed of SiO 2 airgel without affecting its thermal insulation performance, so that SiO 2 airgel has a certain degree of flexibility. With its foldability, morphological changes and industrialization potential, it can adapt to multiple application scenarios. This can expand the application scope of SiO2 airgel and provide a technical basis for its application in thermal insulation fillers, linings, thermal protective clothing, etc.
发明内容Contents of the invention
有鉴于此，本发明旨在提供一种连续SiO2气凝胶复合纤维及其制备方法与应用，该连续SiO2气凝胶复合纤维具有优异的隔热性能和阻燃性能，且柔韧性和强度好。In view of this, the present invention aims to provide a continuous SiO 2 airgel composite fiber and its preparation method and application. The continuous SiO 2 airgel composite fiber has excellent thermal insulation properties and flame retardant properties, and is flexible and Good strength.
本发明提供了一种连续SiO2气凝胶复合纤维的制备方法，包括以下步骤：The invention provides a preparation method of continuous SiO 2 airgel composite fiber, which includes the following steps:
S1.将硅源、乙醇、水按摩尔比1:(7～8):(2～3)混合，充分搅拌使其混合均匀，搅拌条件下，缓慢滴加酸性催化剂至pH为3，继续搅拌1.5-2h，然后静置2-3h，得到SiO2气凝胶前驱体溶液；S1. Mix the silicon source, ethanol, and water in a molar ratio of 1:(7~8):(2~3), and stir thoroughly to mix evenly. Under stirring conditions, slowly add the acidic catalyst dropwise until the pH is 3, and continue stirring. 1.5-2h, then let it stand for 2-3h to obtain the SiO 2 airgel precursor solution;
S2.将高分子量热固性酚醛树脂溶液加入到所述SiO2气凝胶前驱体溶液中，并充分搅拌混合均匀，而后边低速搅拌边滴加碱性催化剂至pH为6-7，静置2-3h后作为纺丝原液进行湿法纺丝得到初生丝；S2. Add the high molecular weight thermosetting phenolic resin solution to the SiO 2 airgel precursor solution, stir thoroughly and mix evenly, then add the alkaline catalyst dropwise while stirring at low speed until the pH is 6-7, and let it stand for 2- After 3 hours, it is used as spinning solution for wet spinning to obtain virgin silk;
S3.对所述初生丝进行疏水改性后在正己烷中浸泡12～24h，取出后干燥，得到连续SiO2气凝胶复合纤维。S3. Perform hydrophobic modification on the virgin silk, soak it in n-hexane for 12 to 24 hours, take it out and dry it to obtain continuous SiO 2 airgel composite fiber.
进一步的，所述硅源为三甲氧基甲基硅烷、四甲氧基硅烷、正硅酸乙酯和水玻璃中的至少一种。Further, the silicon source is at least one of trimethoxymethylsilane, tetramethoxysilane, ethyl orthosilicate and water glass.
进一步的，所述酸性催化剂为草酸、盐酸、氢氟酸、硝酸、甲酸和乙酸中的一种；Further, the acidic catalyst is one of oxalic acid, hydrochloric acid, hydrofluoric acid, nitric acid, formic acid and acetic acid;
进一步的，所述碱性催化剂为氢氧化钠、氢氧化钙和氨水中的一种。Further, the alkaline catalyst is one of sodium hydroxide, calcium hydroxide and ammonia water.
进一步的，所述高分子量热固性酚醛树脂溶液中高分子量热固性酚醛树脂的平均重均分子量是600。Further, the average weight average molecular weight of the high molecular weight thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution is 600.
进一步的，所述高分子量热固性酚醛树脂溶液中高分子量热固性酚醛树脂为F-51B、F-52B和F-44B中的一种。Further, the high molecular weight thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution is one of F-51B, F-52B and F-44B.
进一步的，步骤S2中，所述高分子量热固性酚醛树脂溶液中，高分子量热固性酚醛树脂的浓度为40wt％～50wt％，所述高分子量热固性酚醛树脂溶液与所述SiO2气凝胶前驱体溶液的体积比为(1～2)：3。Further, in step S2, the concentration of the high molecular weight thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution is 40wt% to 50wt%, and the high molecular weight thermosetting phenolic resin solution and the SiO 2 airgel precursor solution The volume ratio is (1~2):3.
进一步的，所述湿法纺丝的凝固浴具体为：40℃～60℃温度条件下，先在含有硅源的无水乙醇溶液中进行凝固浴，然后在含有硼酸的硫酸钠溶液中进行凝固浴。Further, the coagulation bath of the wet spinning is specifically: under the temperature condition of 40°C to 60°C, the coagulation bath is first carried out in an anhydrous ethanol solution containing a silicon source, and then the coagulation is carried out in a sodium sulfate solution containing boric acid. bath.
进一步的，所述含有硅源的无水乙醇溶液中，硅源的体积浓度为10％～30％；所述含有硼酸的硫酸钠溶液中，硼酸的体积浓度为0.5％～2％。Further, in the absolute ethanol solution containing the silicon source, the volume concentration of the silicon source is 10% to 30%; in the sodium sulfate solution containing boric acid, the volume concentration of boric acid is 0.5% to 2%.
进一步的，所述湿法纺丝后初生丝卷绕速度在5～50m/min。Further, the winding speed of the virgin silk after wet spinning is 5-50m/min.
进一步的，所述疏水改性具体为采用疏水改性剂的正己烷溶液进行疏水改性，所述疏水改性剂为疏水改性剂为三甲基氯硅烷、六甲基二硅氧烷和六甲基二硅氮烷中的一种，改性时间为8～12h。Further, the hydrophobic modification is specifically carried out by using a n-hexane solution of a hydrophobic modifier, and the hydrophobic modifier is trimethylchlorosilane, hexamethyldisiloxane and One of hexamethyldisilazane, the modification time is 8 to 12 hours.
进一步的，所述疏水改性剂的正己烷溶液中，疏水改性剂的体积浓度为10％～20％。Further, in the n-hexane solution of the hydrophobic modifier, the volume concentration of the hydrophobic modifier is 10% to 20%.
进一步的，所述干燥为采用液态CO2超临界干燥后150℃～180℃真空干燥1～2h。Further, the drying is using liquid CO 2 supercritical drying and then vacuum drying at 150°C to 180°C for 1 to 2 hours.
本发明还提供了一种上述连续SiO2气凝胶复合纤维或上述制备方法制备得到的连续SiO2气凝胶复合 纤维在保温隔热材料或阻燃材料中的应用。The invention also provides the above continuous SiO 2 airgel composite fiber or the continuous SiO 2 airgel composite prepared by the above preparation method. Application of fibers in thermal insulation materials or flame retardant materials.
进一步的，所述保温隔热材料为防护服衬里或隔热毡。Further, the thermal insulation material is a protective clothing lining or thermal insulation felt.
与现有技术相比，本发明具有以下有益的技术效果：Compared with the existing technology, the present invention has the following beneficial technical effects:
(1)本发明提供的制备方法通过向前驱体溶液中添加高分子量热固性酚醛树脂并调节pH，实现在常温常压下实现前驱体溶液在聚合阶段的快速凝胶，且添加的酚醛树脂增加了SiO2气凝胶的可纺性，起到了增强增韧的效果，使SiO2气凝胶具有可织造和加工成形性能，进而通过湿法纺丝加工及后续疏水改性及超临界干燥处理得到连续SiO2气凝胶复合纤维，不仅制备方法简单，且解决了传统SiO2气凝胶容易碎裂和强度低的问题。(1) The preparation method provided by the present invention realizes rapid gelation of the precursor solution in the polymerization stage at normal temperature and pressure by adding a high molecular weight thermosetting phenolic resin to the precursor solution and adjusting the pH, and the added phenolic resin increases The spinnability of SiO 2 aerogel has an enhanced and toughening effect, making the SiO 2 aerogel weavable and processable. It is then obtained through wet spinning processing and subsequent hydrophobic modification and supercritical drying. Continuous SiO 2 airgel composite fiber not only has a simple preparation method, but also solves the problems of traditional SiO 2 airgel being easily broken and having low strength.
(2)本发明提供的连续SiO2气凝胶复合纤维不仅具有良好的保温隔热性能，而且它还具有一定的韧性和强度、耐腐蚀，并且燃烧时无有毒气体产生。(2) The continuous SiO 2 airgel composite fiber provided by the present invention not only has good thermal insulation properties, but also has certain toughness, strength, corrosion resistance, and no toxic gas is produced when burned.
(2)由于SiO2气凝胶具有优异的热稳定性，且酚醛高温下碳化后也还可以起到隔热和保持SiO2气凝胶纤维形态的作用，该纤维还具有优异的阻燃效果，可用于保温隔热领域，例如用来制作热防护服衬里和隔热毡，充当隔热填料等。(2) Since SiO 2 aerogel has excellent thermal stability, and after carbonization of phenolics at high temperatures, it can also play a role in heat insulation and maintain the shape of SiO 2 aerogel fiber. The fiber also has excellent flame retardant effect. , can be used in the field of thermal insulation, such as making thermal protective clothing linings and insulation felts, acting as thermal insulation fillers, etc.
附图说明Description of drawings
图1为本发明提供的一种连续SiO2气凝胶复合纤维的制备方法的流程图；Figure 1 is a flow chart of a preparation method of continuous SiO 2 airgel composite fiber provided by the present invention;
图2为实施例1制备得到的连续SiO2气凝胶复合纤维的应力-伸长曲线图；Figure 2 is a stress-elongation curve of the continuous SiO 2 airgel composite fiber prepared in Example 1;
图3为实施例1制备得到的连续SiO2气凝胶复合纤维高温下虽碳化仍可保持纤维形态的实物图；Figure 3 is a physical diagram showing that the continuous SiO 2 airgel composite fiber prepared in Example 1 can still maintain fiber shape despite carbonization at high temperatures;
图4为对比例1制备得到的SiO2气凝胶的失重曲线图；Figure 4 is a weight loss curve of the SiO 2 aerogel prepared in Comparative Example 1;
图5为对比例1无法成纤SiO2气凝胶呈颗粒状的实物图。Figure 5 is a physical picture of the granular SiO 2 aerogel that cannot form fibers in Comparative Example 1.
具体实施方式Detailed ways
下面是具体的实施例，通过具体的实施例对本发明作更详细的描述说明，但本发明的保护范围并不仅限于此。The following are specific examples through which the present invention will be described in more detail, but the protection scope of the present invention is not limited thereto.
如图1所示，本发明提供了一种连续SiO2气凝胶复合纤维的制备方法，包括以下步骤：As shown in Figure 1, the present invention provides a method for preparing continuous SiO 2 airgel composite fibers, which includes the following steps:
S1.将硅源、乙醇、水按摩尔比1:(7～8):(2～3)混合，充分搅拌使其混合均匀，搅拌条件下，缓慢滴加酸性催化剂至pH为3，继续搅拌1.5-2h，然后静置2-3h，得到SiO2气凝胶前驱体溶液；硅源可选用三甲氧基甲基硅烷、四甲氧基硅烷、正硅酸乙酯和水玻璃中的至少一种。酸性催化剂可选用草酸、盐酸、氢氟酸、硝酸、甲酸和乙酸中的一种。S1. Mix the silicon source, ethanol, and water in a molar ratio of 1:(7~8):(2~3), and stir thoroughly to mix evenly. Under stirring conditions, slowly add the acidic catalyst dropwise until the pH is 3, and continue stirring. 1.5-2h, then let it stand for 2-3h to obtain the SiO 2 airgel precursor solution; the silicon source can be at least one of trimethoxymethylsilane, tetramethoxysilane, ethyl orthosilicate and water glass. kind. The acidic catalyst can be one of oxalic acid, hydrochloric acid, hydrofluoric acid, nitric acid, formic acid and acetic acid.
S2.将高分子量热固性酚醛树脂溶液加入到所述SiO2气凝胶前驱体溶液中，并充分搅拌混合均匀，而后边低速搅拌边滴加碱性催化剂至pH为6-7，静置2-3h后作为纺丝原液进行湿法纺丝得到初生丝；高分子量热固性酚醛树脂溶液中高分子量热固性酚醛树脂可选用F-51B、F-52B和F-44B中的一种。碱性催化剂为氢氧化钠、氢氧化钙和氨水中的一种。湿法纺丝的凝固浴具体为：40℃～60℃温度条件下，先在含有硅源的无水乙醇溶液中进行凝固浴，然后在含有硼酸的硫酸钠溶液中进行凝固浴。其中，含有硅源的无水乙醇溶液中，硅源的体积浓度优选为10％～30％；含有硼酸的硫酸钠溶液中，硼酸的体积浓度优选为0.5％～2％。湿法纺丝后初生丝卷绕速度在5～50m/min。S2. Add the high molecular weight thermosetting phenolic resin solution to the SiO 2 airgel precursor solution, stir thoroughly and mix evenly, then add the alkaline catalyst dropwise while stirring at low speed until the pH is 6-7, and let it stand for 2- After 3 hours, use the spinning stock solution for wet spinning to obtain virgin silk; the high molecular weight thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution can be one of F-51B, F-52B and F-44B. The alkaline catalyst is one of sodium hydroxide, calcium hydroxide and ammonia. The specific coagulation bath of wet spinning is: under the temperature condition of 40°C to 60°C, first conduct a coagulation bath in an absolute ethanol solution containing a silicon source, and then conduct a coagulation bath in a sodium sulfate solution containing boric acid. Among them, in the absolute ethanol solution containing the silicon source, the volume concentration of the silicon source is preferably 10% to 30%; in the sodium sulfate solution containing boric acid, the volume concentration of boric acid is preferably 0.5% to 2%. The winding speed of the virgin silk after wet spinning is 5-50m/min.
S3.对所述初生丝进行疏水改性后在正己烷中浸泡12～24h，取出后干燥，得到连续SiO2气凝胶复合纤维。疏水改性具体为采用疏水改性剂的正己烷溶液进行疏水改性，疏水改性剂可选用三甲基氯硅烷、六甲基二硅氧烷和六甲基二硅氮烷中的一种，改性时间为8～12h。疏水改性剂的正己烷溶液中，疏水改性剂的体积浓度为10％～20％。干燥具体为采用液态CO2超临界干燥后150℃～180℃真空干燥1～2h。S3. Perform hydrophobic modification on the virgin silk, soak it in n-hexane for 12 to 24 hours, take it out and dry it to obtain continuous SiO 2 airgel composite fiber. Hydrophobic modification is specifically carried out by using a n-hexane solution of a hydrophobic modifier. The hydrophobic modifier can be one of trimethylchlorosilane, hexamethyldisiloxane and hexamethyldisilazane. , the modification time is 8 to 12 hours. In the n-hexane solution of the hydrophobic modifier, the volume concentration of the hydrophobic modifier is 10% to 20%. The drying method specifically uses liquid CO2 supercritical drying and then vacuum drying at 150°C to 180°C for 1 to 2 hours.
本发明实施例中使用的材料均为市售商品，如下表所示：

The materials used in the embodiments of the present invention are all commercially available products, as shown in the following table:

实施例1Example 1
一种酚醛树脂增强的连续SiO2气凝胶纤维，其制备步骤如下：A phenolic resin reinforced continuous SiO 2 airgel fiber, the preparation steps of which are as follows:
(1)按一定体积比取一定体积的F-52B型酚醛树脂溶液备用。(1) Take a certain volume of F-52B phenolic resin solution according to a certain volume ratio and set aside.
(2)将正硅酸乙酯与乙醇、水按摩尔比1:7:3混合于烧杯中，常温常压下搅拌30min，然后边搅拌边逐步滴入盐酸，调整混合溶液的pH至3左右，搅拌2h；而后静置3h，使其充分水解得到前驱体溶液。将备用的一定体积的F-52B型酚醛树脂溶液倒入前驱体溶液中，充分搅拌混合均匀，酚醛树脂溶液体积分数为10％。然后在低速搅拌下，缓慢加入氨水，调整混合溶液pH至6-7得到混合溶胶，静置2.5h得到纺丝原液，然后进行湿法纺丝。F-52B型酚醛树脂溶液(40wt％)与前驱体溶液体积比为2：3。(2) Mix ethyl orthosilicate, ethanol and water in a beaker at a molar ratio of 1:7:3, stir for 30 minutes at room temperature and pressure, then gradually drop in hydrochloric acid while stirring, and adjust the pH of the mixed solution to about 3 , stir for 2 hours; then let it stand for 3 hours to allow it to be fully hydrolyzed to obtain a precursor solution. Pour a certain volume of reserved F-52B phenolic resin solution into the precursor solution, stir thoroughly and mix evenly. The volume fraction of the phenolic resin solution is 10%. Then, under low-speed stirring, slowly add ammonia water, adjust the pH of the mixed solution to 6-7 to obtain a mixed sol, let it stand for 2.5 hours to obtain the spinning stock solution, and then perform wet spinning. The volume ratio of F-52B phenolic resin solution (40wt%) to precursor solution is 2:3.
(3)纺丝原液经喷丝孔挤出后前后经过两道凝固浴，凝固浴温度为55℃，分别为溶质为硅源，溶剂为无水乙醇的溶液，其溶质体积浓度为20％，以及硼酸含量为1％的硫酸钠溶液；经过凝固浴后得到初生丝，初生丝卷绕速度为20m/min；(3) The spinning stock solution is extruded through the spinneret and passes through two coagulation baths. The coagulation bath temperature is 55°C. The solute is a silicon source and the solvent is anhydrous ethanol. The solute volume concentration is 20%. And a sodium sulfate solution with a boric acid content of 1%; after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
(4)对初生丝进行疏水改性，采用三甲基氯硅烷为疏水改性剂，以疏水改性剂为溶质正己烷为溶剂的溶液对初生丝浸泡处理，其中疏水改性剂的体积浓度为10％，改性时间为8h，然后用正己烷浸泡12h。(4) Hydrophobic modification of the virgin silk, using trimethylsilyl chloride as the hydrophobic modifier, and soaking the virgin silk in a solution with the hydrophobic modifier as the solute and n-hexane as the solvent, in which the volume concentration of the hydrophobic modifier is 10%, the modification time is 8h, and then soaked in n-hexane for 12h.
(5)将改性后的初生丝进行干燥处理，干燥工序分为两步，第一步是用液态CO2超临界干燥，第二步是在160℃的温度下真空干燥1h，即得连续SiO2气凝胶复合纤维。(5) Dry the modified virgin silk. The drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
实施例1获得的连续SiO2气凝胶复合纤维可成型，且具有一定的强度。将纤维夹在拉伸试验机的上下两个夹头上，夹头隔距是10cm，启动机器直至纤维断裂停止拉伸运动，导出数据做出应力-伸长曲线图。其应力-伸长曲线图如图2所示，根据图2可知该纤维的断裂强力约为0.75N，说明该纤维具有一定的强度和可加工性。The continuous SiO 2 airgel composite fiber obtained in Example 1 can be formed and has a certain strength. Clamp the fiber on the upper and lower chucks of the tensile testing machine. The distance between the chucks is 10cm. Start the machine until the fiber breaks and stop the stretching movement. Export the data to make a stress-elongation curve. The stress-elongation curve is shown in Figure 2. According to Figure 2, it can be seen that the breaking strength of the fiber is approximately 0.75N, indicating that the fiber has a certain strength and processability.
将实施例1获得的连续SiO2气凝胶复合纤维在管式炉氮气气氛下350℃下碳化2h后，如图3所示，可见高温下哪怕碳化也可保持纤维形态。After the continuous SiO 2 airgel composite fiber obtained in Example 1 was carbonized at 350°C for 2 hours in a tube furnace nitrogen atmosphere, as shown in Figure 3, it can be seen that the fiber shape can be maintained even if carbonized at high temperature.
实施例2Example 2
一种酚醛树脂增强的连续SiO2气凝胶纤维，其制备步骤如下：A phenolic resin reinforced continuous SiO 2 airgel fiber, the preparation steps of which are as follows:
(1)按一定体积比取一定体积的F-52B型酚醛树脂溶液备用。(1) Take a certain volume of F-52B phenolic resin solution according to a certain volume ratio and set aside.
(2)将三甲氧基甲基硅烷与乙醇、水按摩尔比1:7:3混合于烧杯中，常温常压下搅拌30min，然后边搅拌边逐步滴入盐酸，调整混合溶液的pH至3左右，搅拌2h；而后静置3h，使其充分水解得到前驱体溶液。将备用的一定体积的F-52B型酚醛树脂溶液倒入前驱体溶液中，充分搅拌混合均匀，酚醛树脂溶液体积分数为10％。然后在低速搅拌下，缓慢加入氨水，调整混合溶液pH至6-7得到混合溶胶，静置2.5h得到纺丝原液，然后进行湿法纺丝。F-52B型酚醛树脂溶液(40wt％)与前驱体溶液体积比为2：3。(2) Mix trimethoxymethylsilane, ethanol, and water in a beaker at a molar ratio of 1:7:3, stir for 30 minutes at room temperature and pressure, then gradually drop in hydrochloric acid while stirring, and adjust the pH of the mixed solution to 3 Left and right, stir for 2 hours; then let it stand for 3 hours to allow it to be fully hydrolyzed to obtain a precursor solution. Pour a certain volume of reserved F-52B phenolic resin solution into the precursor solution, stir thoroughly and mix evenly. The volume fraction of the phenolic resin solution is 10%. Then, under low-speed stirring, slowly add ammonia water, adjust the pH of the mixed solution to 6-7 to obtain a mixed sol, let it stand for 2.5 hours to obtain the spinning stock solution, and then perform wet spinning. The volume ratio of F-52B phenolic resin solution (40wt%) to precursor solution is 2:3.
(3)纺丝原液经喷丝孔挤出后前后经过两道凝固浴，凝固浴温度为55℃，分别为溶质为硅源-三甲氧基甲基硅烷，溶剂为无水乙醇的溶液，其溶质体积浓度为20％，以及硼酸含量为1％的硫酸钠溶液；经过凝固浴后得到初生丝，初生丝卷绕速度为20m/min；(3) After the spinning solution is extruded through the spinneret, it passes through two coagulation baths. The coagulation bath temperature is 55°C. The solute is silicon source-trimethoxymethylsilane and the solvent is absolute ethanol. A sodium sulfate solution with a solute volume concentration of 20% and a boric acid content of 1%; after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
(4)对初生丝进行疏水改性，采用三甲基氯硅烷为疏水改性剂，以疏水改性剂为溶质正己烷为溶剂 的溶液对初生丝浸泡处理，其中疏水改性剂的体积浓度为10％，改性时间为8h，然后用正己烷浸泡12h。(4) Hydrophobic modification of virgin silk, using trimethylsilyl chloride as the hydrophobic modifier, and using the hydrophobic modifier as the solute and n-hexane as the solvent. The solution was used to soak the virgin silk, in which the volume concentration of the hydrophobic modifier was 10%, the modification time was 8 hours, and then soaked in n-hexane for 12 hours.
(5)将改性后的初生丝进行干燥处理，干燥工序分为两步，第一步是用液态CO2超临界干燥，第二步是在160℃的温度下真空干燥1h，即得连续SiO2气凝胶复合纤维。(5) Dry the modified virgin silk. The drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
实施例3以水玻璃为硅源Example 3 uses water glass as silicon source
(1)按一定体积比取一定体积的F-52B型酚醛树脂溶液备用。(1) Take a certain volume of F-52B phenolic resin solution according to a certain volume ratio and set aside.
(2)将水玻璃与乙醇、水按摩尔比1:7:3混合于烧杯中，常温常压下搅拌30min，然后边搅拌边逐步滴入盐酸，直至混合溶液的pH至3左右，搅拌2h；而后静置3h，使其充分水解得到前驱体溶液。将备用的一定体积的F-52B型酚醛树脂溶液倒入前驱体溶液中，充分搅拌混合均匀，酚醛树脂溶液体积分数为10％。然后在低速搅拌下，缓慢加入氨水，直至混合溶液的pH在6-7之间，这样就得到了混合溶胶，静置2.5h得到纺丝原液，然后进行湿法纺丝。其中，F-52B型酚醛树脂溶液(40wt％)与前驱体溶液的体积比为2：3。(2) Mix water glass, ethanol and water in a beaker at a molar ratio of 1:7:3, stir for 30 minutes at room temperature and pressure, then gradually drop in hydrochloric acid while stirring until the pH of the mixed solution reaches about 3, stir for 2 hours ; and then let it stand for 3 hours to allow it to be fully hydrolyzed to obtain the precursor solution. Pour a certain volume of reserved F-52B phenolic resin solution into the precursor solution, stir thoroughly and mix evenly. The volume fraction of the phenolic resin solution is 10%. Then, under low-speed stirring, slowly add ammonia water until the pH of the mixed solution is between 6 and 7, thus obtaining a mixed sol. Let it stand for 2.5 hours to obtain the spinning stock solution, and then perform wet spinning. Among them, the volume ratio of F-52B phenolic resin solution (40wt%) and precursor solution is 2:3.
(3)纺丝原液经喷丝孔挤出后前后经过两道凝固浴，凝固浴温度为55℃，分别为硅源-水玻璃与无水乙醇的混合液，其中水玻璃的体积浓度为20％，以及硼酸含量为1％的硫酸钠溶液；经过凝固浴后得到初生丝，初生丝卷绕速度为20m/min；(3) After the spinning solution is extruded through the spinneret, it passes through two coagulation baths. The coagulation bath temperature is 55°C. They are a mixture of silicon source-water glass and absolute ethanol. The volume concentration of water glass is 20 %, and a sodium sulfate solution with a boric acid content of 1%; after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
(4)对初生丝进行疏水改性，采用三甲基氯硅烷为疏水改性剂，以疏水改性剂为溶质正己烷为溶剂的溶液对初生丝浸泡处理，其中疏水改性剂的体积浓度为10％，改性时间为8h，然后用正己烷浸泡12h。(4) Hydrophobic modification of the virgin silk, using trimethylsilyl chloride as the hydrophobic modifier, and soaking the virgin silk in a solution with the hydrophobic modifier as the solute and n-hexane as the solvent, in which the volume concentration of the hydrophobic modifier is 10%, the modification time is 8h, and then soaked in n-hexane for 12h.
(5)将经过疏水改性后的初生丝进行干燥处理，干燥工序分为两步，第一步是用液态CO2超临界干燥，第二步是在160℃的温度下真空干燥1h，即得连续SiO2气凝胶复合纤维。(5) Dry the hydrophobically modified virgin silk. The drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour, that is Continuous SiO 2 airgel composite fibers were obtained.
实施例4以四甲氧基硅烷为硅源Example 4 uses tetramethoxysilane as the silicon source
(1)按一定体积比取一定体积的F-52B型酚醛树脂溶液以备用。(1) Take a certain volume of F-52B phenolic resin solution according to a certain volume ratio for later use.
(2)将四甲氧基硅烷与乙醇、水按摩尔比1:7:3混合于烧杯中，先在常温常压下搅拌30min，然后边搅拌边逐步滴入盐酸，直至混合溶液的pH至3左右，搅拌2h；而后静置3h，使其充分水解从而得到前驱体溶液。将备用的一定体积的F-52B型酚醛树脂溶液倒入前驱体溶液中，充分搅拌使其混合均匀，其中，酚醛树脂溶液体积分数为10％。然后在低速搅拌下，缓慢的加入氨水，调整混合溶液pH至6-7，便得到了混合溶胶，静置2.5h后得到纺丝原液，然后进行湿法纺丝。F-52B型酚醛树脂溶液(40wt％)与前驱体溶液体积比为2：3。(2) Mix tetramethoxysilane, ethanol, and water in a beaker at a molar ratio of 1:7:3. Stir at room temperature and pressure for 30 minutes. Then gradually add hydrochloric acid while stirring until the pH of the mixed solution reaches About 3, stir for 2 hours; then let it stand for 3 hours to fully hydrolyze it to obtain the precursor solution. Pour a certain volume of reserved F-52B phenolic resin solution into the precursor solution, and stir thoroughly to mix evenly. The volume fraction of the phenolic resin solution is 10%. Then, under low-speed stirring, slowly add ammonia water, adjust the pH of the mixed solution to 6-7, and obtain a mixed sol. After standing for 2.5 hours, the spinning stock solution is obtained, and then wet spinning is performed. The volume ratio of F-52B phenolic resin solution (40wt%) to precursor solution is 2:3.
(3)纺丝原液经喷丝孔挤出后前后经过两道凝固浴，凝固浴温度为55℃，分别为溶质为硅源-四甲氧基硅烷，溶剂为无水乙醇的溶液，其中四甲氧基硅烷体积浓度为20％，以及硼酸含量为1％的硫酸钠溶液；经过凝固浴后得到初生丝，初生丝卷绕速度为20m/min；(3) After the spinning solution is extruded through the spinneret, it passes through two coagulation baths. The coagulation bath temperature is 55°C. The solute is silicon source-tetramethoxysilane and the solvent is absolute ethanol. Four of them The volume concentration of methoxysilane is 20%, and the sodium sulfate solution with boric acid content is 1%; after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
(4)采用三甲基氯硅烷为疏水改性剂对初生丝进行疏水改性，以疏水改性剂为溶质正己烷为溶剂的溶液对初生丝浸泡处理，其中疏水改性剂的体积浓度为10％，改性时间为8h，然后用正己烷浸泡12h。(4) Use trimethylchlorosilane as the hydrophobic modifier to hydrophobically modify the virgin silk, and soak the virgin silk in a solution using the hydrophobic modifier as the solute and n-hexane as the solvent. The volume concentration of the hydrophobic modifier is 10%, the modification time is 8h, and then soaked in n-hexane for 12h.
(5)将改性后的初生丝进行干燥处理，干燥工序分为两步，第一步是用液态CO2超临界干燥，第二步是在160℃的温度下真空干燥1h，即得连续SiO2气凝胶复合纤维。(5) Dry the modified virgin silk. The drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
对比例1Comparative example 1
(1)将TEOS与乙醇、水按摩尔比1:7:3混合于烧杯中，常温常压下搅拌30min，然后边搅拌边逐步滴入盐酸，调整混合溶液的pH至3左右，搅拌2h；而后静置3h，使其充分水解得到前驱体溶液。然后在低速搅拌下，缓慢加入氨水，调整混合溶液pH至6-7得到混合溶胶，静置2.5h得到纺丝原液，然后进行湿法纺丝。(1) Mix TEOS, ethanol and water in a beaker at a molar ratio of 1:7:3, stir for 30 minutes at room temperature and pressure, then gradually drop in hydrochloric acid while stirring, adjust the pH of the mixed solution to about 3, and stir for 2 hours; Then let it stand for 3 hours to allow it to be fully hydrolyzed to obtain a precursor solution. Then, under low-speed stirring, slowly add ammonia water, adjust the pH of the mixed solution to 6-7 to obtain a mixed sol, let it stand for 2.5 hours to obtain the spinning stock solution, and then perform wet spinning.
(2)纺丝原液经喷丝孔挤出后前后经过两道凝固浴，凝固浴温度为55℃，分别为溶质为硅源，溶剂为无水乙醇的溶液，其溶质体积浓度为20％，以及硼酸含量为1％的硫酸钠溶液；但是经过凝固浴后得到的并非初生丝，而是易碎的湿凝胶，不可卷绕不易收集，非常容易碎裂；(2) The spinning stock solution is extruded through the spinneret and passes through two coagulation baths. The coagulation bath temperature is 55°C. The solute is a silicon source and the solvent is anhydrous ethanol. The solute volume concentration is 20%. and a sodium sulfate solution with a boric acid content of 1%; however, what is obtained after passing through the coagulation bath is not virgin silk, but a brittle wet gel that cannot be rolled, is not easy to collect, and is very easy to break;
(3)然后进行疏水改性，采用三甲基氯硅烷为疏水改性剂，以疏水改性剂为溶质正己烷为溶剂的溶液对初生丝浸泡处理，其中疏水改性剂的体积浓度为10％，改性时间为8h，然后用正己烷浸泡12h。(3) Then carry out hydrophobic modification, using trimethylsilyl chloride as the hydrophobic modifier, using the hydrophobic modifier as the solute and n-hexane as the solvent to soak the virgin silk, in which the volume concentration of the hydrophobic modifier is 10 %, the modification time is 8h, and then soaked in n-hexane for 12h.
(4)将改性后的湿凝胶颗粒进行干燥处理，干燥工序分为两步，第一步是用液态CO2超临界干燥，第二步是在160℃的温度下真空干燥1h，得到的是颗粒。(4) Dry the modified wet gel particles. The drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour to obtain are particles.
本对比例中提供了一种SiO2气凝胶纤维，其与实施例1的区别之处在于：没有准备步骤(1)中备用 的F-52B型酚醛树脂溶液，即步骤(2)中并没有再前驱体溶液中加入一定体积的F-52B型酚醛树脂溶液。This comparative example provides a SiO 2 airgel fiber, which differs from Example 1 in that there is no backup in the preparation step (1). F-52B type phenolic resin solution, that is, in step (2), a certain volume of F-52B type phenolic resin solution is not added to the precursor solution.
对比例1获得的SiO2气凝胶纤维成型率低，强度很低，易碎，无法进行力学测试，如图5所示呈颗粒状不连续。但是其颗粒具有优异的热稳定性，热重曲线图如图4所示，根据图4可知，其在800℃下失重率还高于75％。The SiO 2 airgel fiber obtained in Comparative Example 1 has a low molding rate, very low strength, is brittle, and cannot be subjected to mechanical testing. It is granular and discontinuous as shown in Figure 5. However, its particles have excellent thermal stability. The thermogravimetric curve is shown in Figure 4. According to Figure 4, it can be seen that its weight loss rate at 800°C is higher than 75%.
对比例2Comparative example 2
(1)按一定体积比取一定体积的F-52B型酚醛树脂溶液备用。(1) Take a certain volume of F-52B phenolic resin solution according to a certain volume ratio and set aside.
(2)将TEOS与乙醇、水按摩尔比1:7:3混合于烧杯中，常温常压下搅拌30min，然后边搅拌边逐步滴入盐酸，调整混合溶液的pH至3左右，搅拌2h；而后静置3h，使其充分水解得到前驱体溶液。将备用的一定体积的F-52B型酚醛树脂溶液倒入前驱体溶液中，充分搅拌混合均匀，酚醛树脂溶液体积分数为10％。然后在低速搅拌下，缓慢加入氨水，调整混合溶液pH至4-5得到混合溶胶，静置6.5h得到纺丝原液，然后进行湿法纺丝。F-52B型酚醛树脂溶液(40wt％)与前驱体溶液体积比为2：3。(2) Mix TEOS, ethanol, and water in a beaker at a molar ratio of 1:7:3, stir for 30 minutes at room temperature and pressure, then gradually drop in hydrochloric acid while stirring, adjust the pH of the mixed solution to about 3, and stir for 2 hours; Then let it stand for 3 hours to allow it to be fully hydrolyzed to obtain a precursor solution. Pour a certain volume of reserved F-52B phenolic resin solution into the precursor solution, stir thoroughly and mix evenly. The volume fraction of the phenolic resin solution is 10%. Then, under low-speed stirring, slowly add ammonia water, adjust the pH of the mixed solution to 4-5 to obtain a mixed sol, let it stand for 6.5 hours to obtain the spinning stock solution, and then perform wet spinning. The volume ratio of F-52B phenolic resin solution (40wt%) to precursor solution is 2:3.
(3)纺丝原液经喷丝孔挤出后前后经过两道凝固浴，凝固浴温度为55℃，分别为溶质为硅源，溶剂为无水乙醇的溶液，其溶质体积浓度为20％，以及硼酸含量为1％的硫酸钠溶液；经过凝固浴后得到初生丝，初生丝卷绕速度为20m/min；(3) After the spinning solution is extruded through the spinneret, it passes through two coagulation baths. The coagulation bath temperature is 55°C. The solute is a silicon source and the solvent is anhydrous ethanol. The solute volume concentration is 20%. And a sodium sulfate solution with a boric acid content of 1%; after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
(4)对初生丝进行疏水改性，采用三甲基氯硅烷为疏水改性剂，以疏水改性剂为溶质正己烷为溶剂的溶液对初生丝浸泡处理，其中疏水改性剂的体积浓度为10％，改性时间为8h，然后用正己烷浸泡12h。(4) Hydrophobic modification of the virgin silk, using trimethylsilyl chloride as the hydrophobic modifier, and soaking the virgin silk in a solution with the hydrophobic modifier as the solute and n-hexane as the solvent, in which the volume concentration of the hydrophobic modifier is 10%, the modification time is 8h, and then soaked in n-hexane for 12h.
(5)将改性后的初生丝进行干燥处理，干燥工序分为两步，第一步是用液态CO2超临界干燥，第二步是在160℃的温度下真空干燥1h，即得连续SiO2气凝胶复合纤维。(5) Dry the modified virgin silk. The drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
本对比例中提供了一种SiO2气凝胶纤维，其与实施例1的区别之处在于：步骤(2)中混合溶胶的pH值范围不是6-7，即步骤(2)中加入氨水后，调整混合溶液pH至4-5得到混合溶胶。This comparative example provides a SiO 2 airgel fiber. The difference from Example 1 is that the pH value range of the mixed sol in step (2) is not 6-7, that is, ammonia water is added in step (2). Finally, adjust the pH of the mixed solution to 4-5 to obtain a mixed sol.
对比例3Comparative example 3
(1)按一定体积比取一定体积的F-52B型酚醛树脂溶液备用。(1) Take a certain volume of F-52B phenolic resin solution according to a certain volume ratio and set aside.
(2)将TEOS与乙醇、水按摩尔比1:7:3混合于烧杯中，常温常压下搅拌30min，然后边搅拌边逐步滴入盐酸，调整混合溶液的pH至3左右，搅拌2h；而后静置3h，使其充分水解得到前驱体溶液。将备用的一定体积的F-52B型酚醛树脂溶液倒入前驱体溶液中，充分搅拌混合均匀，酚醛树脂溶液体积分数为10％。然后在低速搅拌下，缓慢加入氨水，调整混合溶液pH至8-9得到混合溶胶，静置8h得到纺丝原液，然后进行湿法纺丝。F-52B型酚醛树脂溶液(40wt％)与前驱体溶液体积比为2：3。(2) Mix TEOS, ethanol, and water in a beaker at a molar ratio of 1:7:3, stir for 30 minutes at room temperature and pressure, then gradually drop in hydrochloric acid while stirring, adjust the pH of the mixed solution to about 3, and stir for 2 hours; Then let it stand for 3 hours to allow it to be fully hydrolyzed to obtain a precursor solution. Pour a certain volume of reserved F-52B phenolic resin solution into the precursor solution, stir thoroughly and mix evenly. The volume fraction of the phenolic resin solution is 10%. Then, under low-speed stirring, slowly add ammonia water, adjust the pH of the mixed solution to 8-9 to obtain a mixed sol, let it stand for 8 hours to obtain the spinning stock solution, and then perform wet spinning. The volume ratio of F-52B phenolic resin solution (40wt%) to precursor solution is 2:3.
(3)纺丝原液经喷丝孔挤出后前后经过两道凝固浴，凝固浴温度为55℃，分别为溶质为硅源，溶剂为无水乙醇的溶液，其溶质体积浓度为20％，以及硼酸含量为1％的硫酸钠溶液；经过凝固浴后得到初生丝，初生丝卷绕速度为20m/min；(3) The spinning stock solution is extruded through the spinneret and passes through two coagulation baths. The coagulation bath temperature is 55°C. The solute is a silicon source and the solvent is anhydrous ethanol. The solute volume concentration is 20%. And a sodium sulfate solution with a boric acid content of 1%; after passing through the coagulation bath, virgin silk is obtained, and the winding speed of the virgin silk is 20m/min;
(4)对初生丝进行疏水改性，采用三甲基氯硅烷为疏水改性剂，以疏水改性剂为溶质正己烷为溶剂的溶液对初生丝浸泡处理，其中疏水改性剂的体积浓度为10％，改性时间为8h，然后用正己烷浸泡12h。(4) Hydrophobic modification of the virgin silk, using trimethylsilyl chloride as the hydrophobic modifier, and soaking the virgin silk in a solution with the hydrophobic modifier as the solute and n-hexane as the solvent, in which the volume concentration of the hydrophobic modifier is 10%, the modification time is 8h, and then soaked in n-hexane for 12h.
(5)将改性后的初生丝进行干燥处理，干燥工序分为两步，第一步是用液态CO2超临界干燥，第二步是在160℃的温度下真空干燥1h，即得连续SiO2气凝胶复合纤维。(5) Dry the modified virgin silk. The drying process is divided into two steps. The first step is supercritical drying with liquid CO2 , and the second step is vacuum drying at 160°C for 1 hour, that is, continuous SiO2 airgel composite fiber.
本对比例中提供了一种SiO2气凝胶纤维，其与实施例1的区别之处在于：步骤(2)中混合溶胶的pH值范围不是6-7，即步骤(2)中加入氨水后，调整混合溶液pH至8-9得到混合溶胶。This comparative example provides a SiO 2 airgel fiber. The difference from Example 1 is that the pH value range of the mixed sol in step (2) is not 6-7, that is, ammonia water is added in step (2). Finally, adjust the pH of the mixed solution to 8-9 to obtain a mixed sol.
对比例2和3中获得的SiO2气凝胶纤维制备周期比实施例1长4-6h，因为pH值变化后凝胶速度大大降低，所以湿法纺丝前静置时间变长，延长了制备周期。The preparation period of the SiO2 airgel fibers obtained in Comparative Examples 2 and 3 is 4-6 hours longer than that of Example 1. Because the gel speed is greatly reduced after the pH value changes, the resting time before wet spinning becomes longer, which extends preparation cycle.
以上所述为本发明的较佳实施例。应该理解，以上实施例是对本发明的详细说明，并非对本发明保护范围的限制，本领域的技术人员对本发明所述内容在现有技术的基础上作出的一些非本质的改进和调整均属于本发明的保护范围。The above are the preferred embodiments of the present invention. It should be understood that the above embodiments are detailed descriptions of the present invention and do not limit the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art on the basis of the prior art belong to this invention. protection scope of the invention.
本发明解决了传统SiO2气凝胶容易碎裂和强度低、制取周期长、溶剂消耗大的问题，所制备的酚醛树脂增强的连续SiO2气凝胶纤维，不仅具有良好的保温隔热性能，而且它还具有一定的韧性和强度、耐腐蚀，并且燃烧时无有毒气体产生，工艺简单，周期较短。而且该纤维还具有阻燃的效果可用于保温隔热领域，例如用来制作热防护服衬里和隔热毡，充当隔热填料等。 This invention solves the problems of traditional SiO 2 aerogels being easily broken, having low strength, long preparation cycle, and large solvent consumption. The prepared phenolic resin-reinforced continuous SiO 2 aerogel fibers not only have good thermal insulation It also has certain toughness, strength, corrosion resistance, no toxic gas is produced when burned, the process is simple, and the cycle is short. Moreover, the fiber also has a flame-retardant effect and can be used in the field of thermal insulation, such as making thermal protective clothing linings and insulation felts, acting as thermal insulation fillers, etc.

Claims (10)

  1. 一种连续SiO2气凝胶复合纤维的制备方法，其特征在于，包括以下步骤：A method for preparing continuous SiO 2 airgel composite fibers, which is characterized by including the following steps:
    S1.将硅源、乙醇、水按摩尔比1：(7～8)：(2～3)混合，充分搅拌使其混合均匀，搅拌条件下，缓慢滴加酸性催化剂至pH为3，继续搅拌1.5-2h，然后静置2-3h，得到前驱体溶液；S1. Mix the silicon source, ethanol, and water at a molar ratio of 1: (7~8): (2~3), and stir thoroughly to mix evenly. Under stirring conditions, slowly add the acidic catalyst dropwise until the pH is 3, and continue stirring. 1.5-2h, then let it stand for 2-3h to obtain the precursor solution;
    S2.将高分子量热固性酚醛树脂溶液加入到所述前驱体溶液中，并充分搅拌混合均匀，而后边低速搅拌边滴加碱性催化剂至pH为6-7，静置2-3h后作为纺丝原液进行湿法纺丝得到初生丝；S2. Add the high molecular weight thermosetting phenolic resin solution to the precursor solution, stir thoroughly and mix evenly, then add the alkaline catalyst dropwise while stirring at low speed until the pH is 6-7, and let it stand for 2-3 hours before spinning. The raw solution is wet-spun to obtain virgin silk;
    S3.对所述初生丝进行疏水改性后在正己烷中浸泡12～24h，取出后干燥，得到连续SiO2气凝胶复合纤维。S3. Perform hydrophobic modification on the virgin silk, soak it in n-hexane for 12 to 24 hours, take it out and dry it to obtain continuous SiO 2 airgel composite fiber.
  2. 如权利要求1所述的制备方法，其特征在于，所述硅源为三甲氧基甲基硅烷、四甲氧基硅烷、正硅酸乙酯和水玻璃中的至少一种。The preparation method according to claim 1, wherein the silicon source is at least one of trimethoxymethylsilane, tetramethoxysilane, ethyl orthosilicate and water glass.
  3. 如权利要求1所述的制备方法，其特征在于，所述酸性催化剂为草酸、盐酸、氢氟酸、硝酸、甲酸和乙酸中的一种。The preparation method according to claim 1, wherein the acidic catalyst is one of oxalic acid, hydrochloric acid, hydrofluoric acid, nitric acid, formic acid and acetic acid.
  4. 如权利要求1所述的制备方法，其特征在于，所述碱性催化剂为氢氧化钠、氢氧化钙和氨水中的一种。The preparation method according to claim 1, characterized in that the alkaline catalyst is one of sodium hydroxide, calcium hydroxide and ammonia water.
  5. 如权利要求1所述的制备方法，其特征在于，所述高分子量热固性酚醛树脂溶液中高分子量热固性酚醛树脂为F-51B、F-52B和F-44B中的一种。The preparation method according to claim 1, characterized in that the high molecular weight thermosetting phenolic resin in the high molecular weight thermosetting phenolic resin solution is one of F-51B, F-52B and F-44B.
  6. 如权利要求1所述的制备方法，其特征在于，所述湿法纺丝的凝固浴具体为：40℃～60℃温度条件下，先在含有所述硅源的无水乙醇溶液中进行凝固浴，然后在含有硼酸的硫酸钠溶液中进行凝固浴。The preparation method according to claim 1, wherein the wet spinning coagulation bath is specifically: coagulated in an anhydrous ethanol solution containing the silicon source at a temperature of 40°C to 60°C. bath, followed by a coagulation bath in a sodium sulfate solution containing boric acid.
  7. 如权利要求1所述的制备方法，其特征在于，所述疏水改性具体为采用疏水改性剂的正己烷溶液进行疏水改性，所述疏水改性剂为三甲基氯硅烷、六甲基二硅氧烷和六甲基二硅氮烷中的一种。The preparation method according to claim 1, characterized in that the hydrophobic modification is specifically carried out by using a n-hexane solution of a hydrophobic modifier, and the hydrophobic modifier is trimethylsilyl chloride, hexane One of methyldisiloxane and hexamethyldisilazane.
  8. 如权利要求1所述的制备方法，其特征在于，所述干燥为采用液态CO2超临界干燥后150℃～180℃真空干燥1～2h。The preparation method according to claim 1, characterized in that the drying is supercritical drying with liquid CO2 followed by vacuum drying at 150°C to 180°C for 1 to 2 hours.
  9. 权利要求1-8所述的制备方法制备得到的连续SiO2气凝胶复合纤维。Continuous SiO 2 airgel composite fiber prepared by the preparation method described in claims 1-8.
  10. 权利要求9所述的连续SiO2气凝胶复合纤维在保温隔热材料或阻燃材料中的应用。 The application of the continuous SiO 2 airgel composite fiber described in claim 9 in thermal insulation materials or flame retardant materials.
PCT/CN2023/113474 2022-08-24 2023-08-17 Continuous sio2 aerogel composite fiber, and preparation method therefor and use thereof WO2024041439A1 (en)

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