Colorful heat management fiber, preparation method thereof and heat management fabric

Abstract

The invention relates to the technical field of melt spinning and thermal management fibers, and discloses a colorful thermal management fiber, a preparation method of the colorful thermal management fiber and a thermal management fabric. And then respectively carrying out melt blending with a polymer to obtain a core layer master batch and a skin layer master batch, and respectively carrying out coaxial skin-core spinning on the skin layer master batch and the core layer master batch as a skin material and a core material to obtain the colorful heat management fiber. The prepared thermal management fiber is a structural thermal management fiber, compared with a thermal management fiber with the surface coated with a coating, the problem of interface bonding of a base material and inorganic filler is solved, and even if the thermal management fiber is subjected to external force friction or washing, the thermal management fiber does not lose the photo-thermal conversion capacity. Meanwhile, compared with a common photo-thermal conversion material, the photo-thermal conversion material has wider and stronger thermal regulation and control performance.

Description

Technical Field

[0001] The present invention relates to the technical fields of melt spinning and thermal management fibers, and particularly relates to a colorful thermal management fiber, a preparation method thereof, and a thermal management fabric. Background Art

[0002] In cold regions or high-altitude mountainous areas, traditional heating methods relying on fossil fuels such as coal and oil not only consume non-renewable energy but also cause environmental pollution. Therefore, a series of thermal management fabrics have been developed to maintain human thermal comfort in a sustainable manner. As one of the most abundant energy sources in nature, light energy can be used for heating and warming through photothermal conversion, becoming an effective thermal management technology.

[0003] Most photothermal conversion technologies use carbon-based materials with broad-spectrum absorption characteristics (such as graphene, carbon black, etc.) to achieve efficient photothermal conversion. However, their dark color and difficulty in dyeing, as well as the weak dyeability of inert substrates such as polypropylene and polyester, limit the colorful application of photothermal conversion fabrics. At the same time, the color display mechanism of traditional pigments relies on broad-spectrum absorption characteristics. In the visible light region (380 - 780 nm), colors are presented by selectively absorbing specific wavelengths. In the near-infrared wavelength range (780 - 2500 nm), the strong absorption of the specific chemical bonds of traditional pigment molecules will cause energy loss of infrared light in the solar spectrum, reducing the photothermal conversion efficiency of the fabric and resulting in incompatibility between photothermal conversion fabrics and colored fabrics. In addition, traditional pigments are prone to thermal degradation (such as the fading of organic dyes) or microstructural damage caused by thermal stress in a long-term photothermal coupling environment, further limiting their application in real scenarios. Summary of the Invention

[0004] In view of the problem that it is difficult to be compatible between the color display of traditional pigments in the visible light band and the photothermal management in the infrared band, in the present invention, inorganic fillers (such as zirconium carbide) and infrared transparent pigments (such as nano iron oxide, nano Prussian blue, and nano silicon powder, etc.) that exhibit significant photothermal conversion ability in the near-infrared band are selected to solve this technical problem. The infrared transparent pigments achieve high-saturation color display by selectively absorbing visible light. At the same time, due to the weak absorption and low scattering characteristics in the near-infrared band (780-2500 nm), most of the infrared light can efficiently penetrate. The infrared transparent pigments are combined with the broad-spectrum strong absorption and efficient photothermal conversion ability of inorganic fillers (such as zirconium carbide), and the two form a visible light-infrared spectrum synergistic system. The inorganic filler (such as zirconium carbide) can fully capture the near-infrared light penetrating the pigment layer and convert it into heat energy, avoiding the energy loss caused by the broad-spectrum absorption of traditional pigments; at the same time, the stable visible light color display function provided by the pigments breaks through the limitation of the single color of traditional photothermal materials. In addition, the high thermal conductivity of the inorganic filler (such as zirconium carbide) can accelerate the heat diffusion, avoiding the thermal degradation of the pigments caused by local overheating. The strong absorption of the pigment layer in the visible light region can ensure the color of the system and achieve an accurate balance between the color display and the photothermal function of the system. Through this synergistic effect, the compatibility between the visible light band and the infrared band can be achieved, thereby solving the incompatibility problem between the photothermal conversion fabric and the colored fabric.

[0005] Based on this, the present invention provides a method for preparing colorful thermally managed fibers by melt spinning and its product, to solve the incompatibility problem between the existing thermally managed fabrics and colored fabrics, and to improve the practicality of the thermally managed fabrics.

[0006] To achieve the above object, on the one hand, the present invention provides a method for preparing colorful thermally managed fibers, which comprises the following steps:

[0007] (1) Modification of inorganic materials

[0008] Take two inorganic materials, namely inorganic fillers with photothermal conversion ability and near-infrared transparent inorganic pigments, and perform the following modification treatments respectively. The inorganic fillers are selected from carbides of transition metals, and the inorganic pigments are selected from at least one of silicon nanoparticles with a yellow surface color, nano iron oxide particles with a red surface color, and nano Prussian blue particles with a blue surface color;

[0009] Add a coupling agent to a mixed solvent of anhydrous ethanol and deionized water to prepare a coupling agent solution, and adjust the pH range to 3.0-4.0 with acetic acid to obtain a mixed solution; soak and wash the inorganic materials in acetone, wait for stratification, put the lower-layer nano solution into a vacuum oven and dry it to constant weight, then add it to the mixed solution, first ultrasonically oscillate and disperse, then perform constant-temperature stirring treatment at 70-80 °C, and finally perform vacuum filtration, acetone washing, and drying to obtain the modified inorganic materials;

[0010] (2) Preparation of Core Layer and Skin Layer Masterbatches

[0011] The core layer masterbatch is obtained by melt blending a polymer and modified inorganic fillers; the skin layer masterbatch is obtained by melt blending a polymer and modified inorganic pigments.

[0012] The polymer is selected from polyethylene terephthalate, polyamide, polyphenylene sulfide or polypropylene, and the polymers in the core layer masterbatch and the skin layer masterbatch are the same kind.

[0013] (3) Core-Sheath Spinning

[0014] The core-sheath spinning process is adopted, and coaxial melt spinning is carried out by using a core-sheath spinning component. The skin layer masterbatch and the core layer masterbatch are respectively extruded from the core-sheath spinning component as the skin material and the core material to obtain primary fibers, and then the primary fibers are stretched and heat-set to obtain heat management fibers.

[0015] In the present invention, silicon nanoparticles with a surface color of yellow, nano iron oxide particles with a surface color of red, and nano Prussian blue particles with a surface color of blue are used as inorganic pigments and doped into the skin layer of the fiber, so that the fiber presents colors according to the inorganic pigments. For example, color matching is carried out according to the silicon nanoparticles, nano iron oxide particles, and nano Prussian blue particles, so as to achieve the colorful effect of the fiber. Achieving the colorful effect of the fiber through color matching of the three primary colors belongs to the existing conventional technology and will not be elaborated here.

[0016] As a further preferred technical solution of the present invention, the carbide of the transition metal is selected from zirconium carbide or titanium carbide, and it is in the form of nanoparticles.

[0017] As a further preferred technical solution of the present invention, in step (1), the coupling agent is a silane coupling agent or a titanate coupling agent, and the mass fraction of the coupling agent is 20% - 50% of the mass fraction of the inorganic materials.

[0018] As a further preferred technical solution of the present invention, in step (2), before melt blending, it further includes a drying step of the polymer, and specifically:

[0019] The polymer is dried in a vacuum oven at 90 °C for 1 - 2 h, then dried at 110 °C and 130 °C for 1 - 2 h respectively, and the above operations are repeated multiple times. Finally, it is dried in a vacuum rotary drum oven at 160 °C for 4 - 6 h.

[0020] As a further preferred technical solution of the present invention, in step (2), on the premise of ensuring continuous core-sheath spinning in the subsequent process, the mass fraction ratio of the inorganic filler in the core layer masterbatch to the mass fraction of the polymer is 1:1000 - 1:10, and the mass fraction ratio of the inorganic pigment in the skin layer masterbatch to the mass fraction of the polymer is 1:1000 - 1:10.

[0021] As a further preferred technical solution of the present invention, in step (3), the spinning temperature during the melt spinning process is 180-280 °C, the cooling air blowing temperature is 20-30 °C, the wind speed is 0.3-0.5 m / s, and the spinning speed is 1500-3000 m / min.

[0022] As a further preferred technical solution of the present invention, in step (3), the drawing temperature is 80-120 °C, the drawing ratio is 3-5 times, and the heat setting temperature is 180-220 °C.

[0023] According to another aspect of the present invention, the present invention also provides a colorful thermal management fiber prepared by the above method.

[0024] According to yet another aspect of the present invention, the present invention also provides a thermal management fabric prepared by the above colorful thermal management fiber.

[0025] Compared with the prior art, the present invention can achieve the following beneficial effects:

[0026] 1) The thermal management fiber prepared by the present invention is a structural thermal management fiber. Compared with the thermal management fiber with a surface-coated coating, the problem of interfacial bonding between the substrate and the inorganic filler is solved. Even under external force friction or washing, the photothermal conversion ability will not be lost. At the same time, compared with ordinary photothermal conversion materials, it has a wider and stronger thermal regulation performance.

[0027] 2) The preparation method of the present invention extrudes the modified core layer functional masterbatch and the cortical masterbatch with corresponding colors through a core-shell spinning assembly to obtain a nascent fiber, making it have the corresponding color and not losing the photothermal conversion ability of the material. This is more practical compared to traditional thermal management fibers. In contrast, the obtained thermal management fiber can exhibit a variety of colors without damaging the photothermal conversion ability, and the inorganic pigments used have the characteristics of being opaque to visible light and highly transmissive in the infrared band.

[0028] 3) The preparation method of the present invention realizes the colorful effect of the fiber through color matching, that is, by changing the content of the inorganic fillers of the three primary colors (red, yellow, blue), which provides an important reference path for the development of colorful thermal management fibers and fabrics with practical application value. Specific Embodiments

[0029] The following details the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only for the purpose of illustrating and explaining the present invention, and are not used to limit the present invention.

[0030] Unless otherwise defined, the technical terms used in the following examples have the same meanings as commonly understood by those skilled in the art to which this invention pertains. The test reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the experimental methods are all conventional methods unless otherwise specified.

[0031] The following raw material parameters are selected: the intrinsic viscosity of polyethylene terephthalate (PET) is 0.675 dL / g; the melt index of polypropylene chips is 26.2 g / min; the particle size of zirconium carbide is 500 nm; the particle size of inorganic pigments (nano-silicon particles, nano-prussian blue particles, nano-iron oxide particles) is 200 nm; the silane coupling agent is KBM-403.

[0032] The diameter of the fibers obtained by using a conventional spinning pack is 0.25 mm; the diameter of the fibers obtained by using a sheath-core spinning pack is 0.25 mm, and the core layer diameter is 0.10 mm.

[0033] Comparative Example 1: Preparation of pure PET fibers and fabrics

[0034] (1) Weigh 500 g of polyethylene terephthalate (PET) chips and place them in a vacuum rotary drum oven to dry the moisture for later use.

[0035] (2) Carry out melt spinning through a conventional spinning pack. The spinning temperature is 270 °C, the cold air blowing temperature during spinning is 20 °C, the wind speed is 0.3 m / s, and the spinning speed is 2500 m / min to obtain as-spun fibers; successively carry out stretching and heat setting on the as-spun fibers. The stretching temperature is 90 °C, the stretching ratio is 3 times, and the heat setting is 200 °C. Finally, obtain pure PET fibers with a surface color of grayish-white and a strength greater than 3.0 cN / dtex.

[0036] (3) Combine and twist the obtained PET fibers, and then weave them into a plain fabric by a loom with a warp and weft density of 200 per 10 cm. Then, test the thermal management performance of the fabric.

[0037] Simulate a standard sunlight to irradiate the fibers through a solar simulator. With the initial temperature of the fabric being -5.0 °C and the irradiation time being 300 s, record the surface temperature. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a grayish-white surface color can rise to 5.2 °C within 300 s of irradiation time. Table 2 shows the measured data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a grayish-white surface color are L: 92.5, a: -0.3, b: +1.2.

[0038] Comparative Example 2: Preparation of PET fibers and fabrics doped with (0.5%) unmodified inorganic fillers

[0039] (1)Weigh 500 g of polyethylene terephthalate (PET) chips and place them in a vacuum rotary drum oven to dry the moisture for later use.

[0040] (2)Weigh 2.5 g of zirconium carbide and mix it with PET evenly (the mass fraction ratio of the photothermal conversion inorganic filler to the mass fraction of polyethylene terephthalate is 1:200), and then melt-blend and pelletize it through a twin-screw extruder.

[0041] (3)Conduct melt spinning through a conventional spinning assembly. The spinning temperature is 270 °C, the cold blowing temperature during the spinning process is 20 °C, the wind speed is 0.3 m / s, and the spinning speed is 2,500 m / min to obtain nascent fibers. Stretch and heat-set the nascent fibers in sequence. The stretching temperature is 90 °C, the stretching ratio is 3 times, and the heat setting is 200 °C. Finally, obtain PET fibers doped with (0.5%) unmodified inorganic fillers with a light gray surface color and a strength greater than 3.0 cN / dtex.

[0042] (4)Merge and twist the obtained PET fibers, and then weave them into a plain fabric by a knitting machine with a warp and weft density of 200 threads / 10 cm. Then, conduct thermal management performance tests on the fabric.

[0043] Simulate a standard sunlight to irradiate the fabric through a solar simulator. The initial temperature of the fabric is -5.0 °C, the irradiation time is 300 s, and record the surface temperature. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a light gray surface color can rise to 41.7 °C within 300 s of irradiation time. Table 2 shows the measured data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a light gray surface color are L: 79.5, a: +0.4, b: -0.9.

[0044] By comparing Comparative Examples 1 and 2, it can be seen from the data in Table 1 that within the same irradiation time, the temperature difference between the two fabrics is 38.1 °C. Therefore, adding zirconium carbide as a photothermal conversion filler and melt-blending can significantly improve the photothermal conversion ability of the fabric.

[0045] Comparative Example 3: Preparation of PET fibers and fabrics doped with (0.5%) modified inorganic fillers

[0046] (1)Weigh 500 g of polyethylene terephthalate (PET) chips and place them in a vacuum rotary drum oven to dry the moisture for later use.

[0047] (2) Weigh 2.5 g of zirconium carbide and 0.5 g of silane coupling agent; soak and clean the inorganic filler zirconium carbide for photothermal conversion in acetone, let it stand still and wait for stratification, and put the lower-layer nano solution into a vacuum oven and dry it to a constant weight; then prepare a solution of absolute ethanol and deionized water in a mass ratio of 1:1, add the coupling agent to prepare a coupling agent solution, adjust the pH to 4 with acetic acid, add the inorganic filler, ultrasonically oscillate for 30 min, then keep the solution stirred at a constant temperature of 80 °C for 2 h, finally vacuum filter the solution, wash it with acetone 3 times, and dry it to a constant weight to obtain modified zirconium carbide.

[0048] (3) Mix the modified zirconium carbide with PET evenly (the mass fraction ratio of the inorganic filler for photothermal conversion to the mass fraction of polyethylene terephthalate is 1:200), and melt-blend and pelletize it via a twin-screw extruder.

[0049] (4) Conduct melt spinning through a conventional spinning assembly, with a spinning temperature of 270 °C, a cold blowing temperature of 20 °C, a wind speed of 0.3 m / s, and a spinning speed of 2500 m / min during the spinning process to obtain as-spun fibers; stretch and heat-set the as-spun fibers in sequence, with a stretching temperature of 90 °C, a stretching ratio of 3 times, and a heat setting of 200 °C, and finally obtain PET fibers doped with (0.5%) modified inorganic filler with a surface color of light gray and a strength greater than 3.0 cN / dtex.

[0050] (5) Combine and twist the obtained PET fibers, and then weave them into a plain fabric by a loom with a warp and weft density of 200 per 10 cm, and then test the thermal management performance of the fabric.

[0051] Simulate a standard sunlight to irradiate the fabric through a solar simulator, with the initial temperature of the fabric being -5.0 °C, the irradiation time being 300 s, and record the surface temperature. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a light gray surface color can rise to 43.3 °C within 300 s of irradiation time. Table 2 shows the measured data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a light gray surface color are L: 79.5, a: +0.4, b: -0.9.

[0052] Through the comparison between Comparative Example 2 and Comparative Example 3, it can be seen from the data in Table 1 that: within the same irradiation time, the temperature difference between the two fabrics is 1.6 °C, indicating that the modification treatment of the inorganic filler can improve the compatibility between the polymer substrate and the inorganic filler, thereby improving the overall photothermal conversion ability of the fiber material. Similarly, according to the methods of Comparative Example 2 and Comparative Example 3, the modification effect of the inorganic pigment was also verified, and it was found that the modification treatment of the inorganic pigment can also improve the compatibility between the polymer substrate and the inorganic pigment, thereby making the overall color distribution of the fiber material more uniform, and the photothermal conversion ability also has a certain improvement.

[0053] Comparative Examples 4 - 9: Preparation of PET Fibers and Fabrics with Doped and Modified Inorganic Fillers

[0054] Based on the preparation method of Comparative Example 2, a series of PET fibers and fabrics were prepared by only changing the doping amount ratio of the modified inorganic filler zirconium carbide to 0.02%, 0.05%, 0.1%, 0.2%, 0.8%, and 1.0%. The corresponding test results of thermal management performance are shown in Table 1 and Table 2.

[0055] Example 1: Preparation of Nano - Silicon / ZrC(0.5%) / PET Fibers and Fabrics

[0056] (1) Weigh 500 g of polyethylene terephthalate (PET) chips and place them in a vacuum rotary drum oven to dry the moisture for later use.

[0057] (2) Weigh 2.5 g of zirconium carbide and 0.5 g of silane coupling agent; first, soak and clean the inorganic filler zirconium carbide (ZrC) for photothermal conversion in acetone, wait for stratification, and put the lower - layer nano - solution into a vacuum oven to dry to a constant weight; then prepare a solution of anhydrous ethanol and deionized water in a mass ratio of 1:1, add the coupling agent to prepare a coupling agent solution, adjust the pH = 4 with acetic acid, add the inorganic filler, ultrasonically oscillate for 30 min, then keep the solution stirring at a constant temperature of 80 °C for 2 h, finally perform vacuum filtration on the solution, wash it 3 times with acetone, and dry it to a constant weight to obtain the modified zirconium carbide.

[0058] Weigh 2.5 g of nano - silicon particles with a yellow surface color, and modify the nano - silicon particles in the same way as the modified zirconium carbide to obtain the modified nano - silicon.

[0059] (3) Mix the modified zirconium carbide with PET evenly (the mass fraction ratio of zirconium carbide to polyethylene terephthalate is 1:200), and melt - blend and pelletize it through a twin - screw extruder. After drying, obtain the core - layer masterbatch for later use.

[0060] Mix the modified nano - silicon with PET evenly (the mass fraction ratio of nano - silicon to polyethylene terephthalate is 1:200), and melt - blend and pelletize it through a twin - screw extruder. After drying, obtain the skin - layer masterbatch for later use.

[0061] (4) The sheath-core spinning process is adopted, and coaxial melt spinning is carried out by using a sheath-core spinning assembly. The sheath masterbatch and the core masterbatch are used as the sheath material and the core material respectively. With a spinning temperature of 270 °C, a cold blowing temperature of 20 °C, a wind speed of 0.3 m / s, and a spinning speed of 2500 m / min during the spinning process, the as-spun fibers are obtained; the as-spun fibers are successively drawn and heat-set. The drawing temperature is 90 °C, the drawing ratio is 3 times, and the heat setting is 200 °C. Finally, nano-silicon / ZrC(0.5%) / PET fibers with a surface color of yellow, a strength greater than 3.0 cN / dtex, and a sheath-core structure are obtained.

[0062] (5) The obtained PET fibers are drawn together and twisted, and then woven into a plain fabric by a loom with a warp density and a weft density of 200 per 10 cm. Then, the thermal management performance of the fabric is tested.

[0063] A standard sunlight is simulated by a solar simulator to irradiate the fibers. The initial temperature of the fabric is -5.0 °C, the irradiation time is 300 s, and the surface temperature is recorded. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a surface color of yellow can rise to 43.1 °C within 300 s of irradiation time. Table 2 shows the measured data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a surface color of yellow are L: 85.2, a: -5.3, b: +48.5.

[0064] Example 2: Preparation of nano Prussian blue / ZrC(0.5%) / PET fibers and fabrics

[0065] The same preparation method as in Example 1 is adopted, except that: 2.5 g of nano-silicon particles with a surface color of yellow in Example 1 are replaced with an equal amount of nano Prussian blue particles with a surface color of blue, and finally nano Prussian blue / ZrC(0.5%) / PET fibers with a surface color of blue and the corresponding fabrics are obtained.

[0066] A standard sunlight is simulated by a solar simulator to irradiate the fibers. The initial temperature of the fabric is -5.0 °C, the irradiation time is 300 s, and the surface temperature is recorded. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a surface color of blue can rise to 42.4 °C within 300 s of irradiation time. Table 2 shows the measured data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a surface color of blue are L: 62.7, a: -12.8, b: -35.2.

[0067] Example 3: Preparation of nano iron oxide / ZrC(0.5%) / PET fibers and fabrics

[0068] The same preparation method as in Example 1 was adopted, with the difference that: 2.5 g of nano-silicon particles with a yellow surface color in Example 1 were replaced with an equal amount of nano-iron oxide particles with a red surface color, and finally nano-iron oxide / ZrC(0.5%) / PET fibers with a red surface color and the corresponding fabric were obtained.

[0069] A standard sunlight was simulated by a solar simulator to irradiate the fabric. The initial temperature of the fabric was -5.0 °C, the illumination time was 300 s, and the surface temperature was recorded. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a red surface color could rise to 42.9 °C within 300 s of illumination time. Table 2 shows the measurement data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a red surface color were L: 55.4, a: +38.6, b: +15.3.

[0070] By comparing Comparative Example 3 with Examples 1, 2, and 3, it can be seen from the data in Table 1 that: within the same irradiation time, the temperature difference of the four different fabrics did not exceed 1 °C, indicating that the high absorption of zirconium carbide in the near-infrared band endows it with excellent photothermal conversion ability, and the added near-infrared transparent inorganic pigment does not affect the photothermal conversion ability of the fabric.

[0071] Comparative Example 10: Preparation of carbon black(0.5%) / PET fibers and fabric

[0072] Based on the preparation method of PET fibers and fabric doped with (0.5%) modified inorganic filler in Comparative Example 3, the difference in this comparative example was that: the inorganic filler zirconium carbide raw material was replaced with an equal amount of carbonization, and finally PET fibers with a black surface color and the corresponding fabric were obtained.

[0073] A standard sunlight was simulated by a solar simulator to irradiate the fabric. The initial temperature of the fabric was -5.0 °C, the illumination time was 300 s, and the surface temperature was recorded. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a black surface color could rise to 45.7 °C within 300 s of illumination time. Table 2 shows the measurement data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a black surface color were L: 55.2, a: +0.2, b: -0.5.

[0074] By comparing Comparative Example 3 with Comparative Example 10, from the data in Table 1: within the same irradiation time, the temperature difference between the two fabrics was 2.4 °C, indicating that the photothermal conversion ability of carbon black was stronger than that of zirconium carbide.

[0075] By comparing Comparative Example 3 with Comparative Example 10, from the data in Table 2 and Table 3: through the comparison of Lab values and color descriptions, it can be known that at the same ratio, the surface color of the fabric added with carbon black was darker and more difficult to dye.

[0076] Example 4: Preparation of Nano - Silicon / Carbon Black (0.5%) / PET Fibers and Fabrics

[0077] Based on the process of Comparative Example 10, this example regulates the addition of inorganic pigments to prepare core - sheath fibers, and verifies by comparison whether the addition of inorganic pigments has an impact on the photothermal conversion ability of carbon black / inorganic pigment / PET fibers and fabrics.

[0078] This example adopts the same preparation method as Example 1, with the only difference being that 2.5 g of zirconium carbide in Example 1 is replaced with an equal amount of carbon black, and finally nano - silicon / carbon black (0.5%) / PET fibers with a yellow surface color and the corresponding fabrics are obtained.

[0079] A standard sunlight is simulated by a solar simulator to irradiate the fibers. The initial temperature of the fabric is - 5.0 °C, the illumination time is 300 s, and the surface temperature is recorded. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a yellow surface color can rise to 33.2 °C within 300 s of illumination time. Table 2 shows the measured data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a yellow surface color are L: 68.3, a: - 4.5, b: + 40.7.

[0080] By comparing Example 4 with Comparative Example 10, it can be seen from the data in Table 1 that within the same irradiation time, the temperature difference between the two fabrics is 12.5 °C, indicating that the excellent photothermal conversion ability of carbon black stems from the absorption of a wide spectrum, but the surface color of the fabric will affect the visible - light absorption of carbon black, thereby affecting its photothermal conversion ability. Therefore, the effect of using carbon black as the inorganic filler is significantly worse than that of ZrC.

[0081] By comparing Example 1 with Example 4, from the data in Table 2 and Table 3: Through the comparison of Lab values and color descriptions, at the same ratio, carbon black as the inorganic filler in the core layer will have a certain impact on the color development of nano - silicon powder in the skin layer.

[0082] Comparative Example 11: Preparation of ZrC (1%) / PP Fibers and Fabrics

[0083] (1) Weigh 500 g of polypropylene (PP) chips and place them in a vacuum rotary drum oven to dry the moisture for later use.

[0084] (2) Weigh 5.0 g of zirconium carbide and 1.5 g of silane coupling agent. Soak and clean the inorganic filler zirconium carbide for photothermal conversion in acetone, let it stand still and wait for stratification, then put the lower-layer nano solution into a vacuum oven and dry it to constant weight. Then, prepare a solution of absolute ethanol and deionized water in a mass ratio of 1:1, add the coupling agent to prepare a coupling agent solution, adjust the pH to 4 with acetic acid, add the inorganic filler, ultrasonically oscillate for 30 min, then keep the solution stirring at a constant temperature of 80 °C for 2 h. Finally, vacuum filter the solution, wash it with acetone three times, and dry it to constant weight to obtain modified zirconium carbide.

[0085] (3) Mix the modified zirconium carbide with PET evenly (the mass fraction ratio of the inorganic filler for photothermal conversion to the mass fraction of polyethylene terephthalate is 1:100), and melt-blend and pelletize it through a twin-screw extruder.

[0086] (4) Perform melt spinning through a conventional spinning assembly. The spinning temperature is 180 °C, the cold blowing temperature during the spinning process is 25 °C, the wind speed is 0.4 m / s, and the spinning speed is 1500 m / min to obtain as-spun fibers. Stretch and heat-set the as-spun fibers successively. The stretching temperature is 130 °C, the stretching ratio is 3 times, and the heat setting is 180 °C. Finally, obtain PP fibers doped with 1% modified inorganic filler with a light gray surface color and a strength greater than 3.0 cN / dtex.

[0087] (5) Combine and twist the obtained PP fibers, and then weave them into a plain fabric by a loom with a warp and weft density of 200 per 10 cm, and then test the thermal management performance of the fabric.

[0088] Simulate a standard sunlight to irradiate the fibers through a solar simulator. The initial temperature of the fabric is -5.0 °C, the illumination time is 300 s, and record the surface temperature. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a light gray surface color can rise to 49.8 °C within 300 s of illumination time. Table 2 shows the measured data of the Lab values of the surface color of the fabric. The Lab values of the fabric with a light gray surface color are L: 53.6, a: +0.3, b: -0.8.

[0089] Example 5: Preparation of Prussian blue / ZrC (1%) / PP fibers and fabrics

[0090] This example is based on the process of Comparative Example 11, and the addition of inorganic pigments is regulated to prepare core-shell fibers, and compare and verify whether the addition of inorganic pigments has an impact on the photothermal conversion ability of carbon black / inorganic pigment / PP fibers and fabrics.

[0091] (1) Weigh 500 g of polypropylene (PP) chips, place them in a vacuum rotary drum oven, and dry the moisture for later use.

[0092] (2) Weigh 5.0 g of zirconium carbide and 1.5 g of silane coupling agent. First, soak and clean the inorganic filler zirconium carbide (ZrC) with photothermal conversion in acetone, let it stand still and wait for stratification, then put the lower-layer nano-solution into a vacuum oven and dry it to constant weight. Then, prepare a solution of absolute ethanol and deionized water in a mass ratio of 1:1, add the coupling agent to prepare a coupling agent solution, adjust the pH to 4 with acetic acid, add the inorganic filler, ultrasonically oscillate for 30 min, then keep the solution stirred at a constant temperature of 80 °C for 2 h, finally perform vacuum filtration on the solution, wash it 3 times with acetone, and dry it to constant weight to obtain modified zirconium carbide;

[0093] Weigh 5.0 g of nano Prussian blue particles with a blue surface color, and modify the nano Prussian blue particles in the same way as the modified zirconium carbide to obtain modified nano Prussian blue.

[0094] (3) Mix the modified zirconium carbide with PP evenly (the mass fraction ratio of zirconium carbide to polyethylene terephthalate is 1:200), and melt-blend and pelletize it through a twin-screw extruder. After drying, obtain the core-layer masterbatch for standby;

[0095] Mix the modified nano Prussian blue with PP evenly (the mass fraction ratio of nano-silicon to polyethylene terephthalate is 1:200), and melt-blend and pelletize it through a twin-screw extruder. After drying, obtain the skin-layer masterbatch for standby.

[0096] (4) Adopt the core-sheath spinning process and use a core-sheath spinning component for coaxial melt spinning. Take the skin-layer masterbatch and the core-layer masterbatch as the skin material and the core material respectively. With a spinning temperature of 180 °C, a cold blowing temperature of 25 °C, a wind speed of 0.4 m / s, and a spinning speed of 1500 m / min during the spinning process, obtain the nascent fiber; Stretch and heat-set the nascent fiber in sequence. The stretching temperature is 130 °C, the stretching ratio is 3 times, and the heat setting is 180 °C. Finally, obtain nano Prussian blue / ZrC(1%) / PP fibers with a blue surface color, a strength greater than 3.0 cN / dtex, and a core-sheath structure.

[0097] (5) Combine and twist the obtained PP fibers, then weave them into a plain fabric on a loom with a warp and weft density of 200 threads / 10 cm, and then test the thermal management performance of the fabric.

[0098] A standard sunlight is simulated by a sunlight simulator to irradiate the fiber. The initial temperature of the fabric is -5.0 °C, the irradiation time is 300 s, and the surface temperature is recorded. Table 1 shows the photothermal conversion data of the fabric. The surface temperature of the fabric with a blue surface color can rise to 49.4 °C within 300 s of irradiation time. Table 2 shows the measured Lab value data of the surface color of the fabric. The Lab value of the fabric with a blue surface color is L: 59.3, a: -14.4, b: -40.1.

[0099] By comparing Example 5 with Comparative Example 11, from the data in Table 1: within the same irradiation time, the temperature difference between the two fabrics does not exceed 1 °C, indicating that the high absorption of zirconium carbide in the near-infrared band endows it with excellent photothermal conversion ability, and the added near-infrared transparent inorganic pigment (ZrC) does not affect the photothermal conversion ability of the fabric.

[0100] The photothermal conversion data, Lab values, and RGB color values of the thermal management fabrics with different component ratios obtained from the above examples and comparative examples are summarized in Table 1, Table 2, and Table 3.

[0101] Table 1: Photothermal conversion data of thermal management fabrics with different component ratios

[0102]

[0103] Table 2: Lab values of thermal management fabrics with different component ratios

[0104]

[0105] Table 3: RGB values of thermal management fabrics with different component ratios

[0106]

[0107] Although the specific embodiments of the present invention have been described above, those skilled in the art should understand that these are only examples, and various changes or modifications can be made to these embodiments without departing from the principles and essence of the present invention. The protection scope of the present invention is only defined by the appended claims.

Claims

1. A preparation method of a colorful thermal management fiber, characterized in that, It includes the following steps: (1) Modification of inorganic materials Take two inorganic materials, inorganic filler and inorganic pigment, and perform the following modification treatments respectively. The inorganic filler is selected from transition metal carbides with photothermal conversion ability, and the inorganic pigment is selected from at least one of silicon nanoparticles with a yellow surface color, nano-iron oxide particles with a red surface color, and nano-prussian blue particles with a blue surface color; Add a coupling agent to a mixed solvent of anhydrous ethanol and deionized water to prepare a coupling agent solution, and adjust the pH range to 3.0 - 4.0 with acetic acid to obtain a mixed solution; soak and wash the inorganic materials in acetone, wait for stratification, put the lower-layer nano solution into a vacuum oven and dry it to constant weight, then add it to the mixed solution, first disperse it by ultrasonic oscillation, then perform constant-temperature stirring treatment at 70 - 80 °C, and finally perform vacuum filtration, wash with acetone, and dry to obtain the modified inorganic materials; (2) Preparation of core layer and skin layer masterbatches Take a polymer and the modified inorganic filler and obtain the core layer masterbatch by melt blending; take a polymer and the modified inorganic pigment and obtain the skin layer masterbatch by melt blending; The polymer is selected from polyethylene terephthalate, polyamide, polyphenylene sulfide, or polypropylene, and the polymers in the core layer masterbatch and the skin layer masterbatch are the same; (3) Skin-core spinning Use a skin-core spinning assembly for coaxial melt spinning, extrude the skin layer masterbatch and the core layer masterbatch as the skin material and the core material from the skin-core spinning assembly respectively to obtain primary fibers, and then stretch and heat-set the primary fibers to obtain thermal management fibers.

2. The preparation method of the colorful thermal management fiber according to claim 1, wherein, The inorganic filler is selected from zirconium carbide or titanium carbide.

3. The preparation method of the colorful thermal management fiber according to claim 1, characterized in that, In step (1), the coupling agent is a silane coupling agent or a titanate coupling agent, and the mass fraction of the coupling agent is 20 - 50% of the mass fraction of the inorganic materials.

4. The preparation method of the colorful thermal management fiber according to claim 1, characterized in that, In step (2), before melt blending, it also includes the drying step of the polymer, and specifically: The polymer is dried in a vacuum oven at 90 °C for 1 - 2 h, then dried at 110 °C and 130 °C for 1 - 2 h respectively, repeat the above operations multiple times, and finally dry at 160 °C in a vacuum rotary drum oven for 4 - 6 h.

5. The preparation method of the colorful thermal management fiber according to claim 1, wherein In step (2), the mass fraction ratio of the inorganic filler in the core layer masterbatch to the mass fraction of the polymer is 1:1000 - 1:10, and the mass fraction ratio of the inorganic pigment in the skin layer masterbatch to the mass fraction of the polymer is 1:1000 - 1:

10.

6. The preparation method of the colorful thermal management fiber according to claim 1, characterized in that, In step (3), the spinning temperature during the melt spinning process is 180 - 280 °C, the cooling air blowing temperature is 20 - 30 °C, the wind speed is 0.3 - 0.5 m / s, and the spinning speed is 1500 - 3000 m / min.

7. The preparation method of the colorful thermal management fiber according to claim 1, characterized in that, In step (3), the stretching temperature is 80 - 120 °C, the stretching ratio is 3 - 5 times, and the heat setting temperature is 180 - 220 °C.

8. A colorful thermal management fiber, characterized in that, Prepared by using the preparation method described in any one of claims 1 - 7.

9. A thermal management fabric, characterized in that, Using the colorful thermal management fiber described in claim 8.

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