A method for preparing functional textiles based on terpolymer as dispersant

Abstract

This invention discloses a method for preparing functional textiles based on terpolymers as dispersants, belonging to the field of functional fiber and nonwoven material preparation. The invention first uses a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer and functional fillers for blending and granulation; then it is mixed with a thermoplastic polymer for secondary granulation; finally, it undergoes melt spinning or spunbond nonwoven processing to prepare functional fibers or functional nonwoven materials. This invention uses tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant to disperse the functional fillers, omitting the need for small-molecule functional filler modification and the addition of small-molecule dispersants, thus imparting functionality to the fibers while maintaining their inherent physical and mechanical properties.

Description

Technical Field

[0001] This invention relates to a method for preparing functional textiles based on terpolymers as dispersants, belonging to the field of preparation of functional fibers and nonwoven materials. Background Technology

[0002] my country has a high output of chemical fibers, but these are still mainly conventional fibers, fine denier fibers, or profiled fibers, with the development of high-tech fibers lagging behind. my country ranks first in the world in the production of nonwoven materials, with spunbond nonwoven materials having the largest output, but their functionalization level is relatively low. Therefore, realizing the functionalization and high performance of chemical fibers and nonwoven materials to increase the added value of fibers and nonwoven materials and enhance market competitiveness is the current development direction.

[0003] However, functionalizing fibers and nonwoven materials requires the introduction of functional fillers. Functional fillers are generally inorganic nanoparticles, which are prone to agglomeration and difficult to disperse in polymer matrices; poor dispersion leads to spinning difficulties and decreased mechanical properties. Therefore, ensuring uniform dispersion of nanofillers in fibers and nonwoven materials is crucial for producing functional fibers and nonwoven materials.

[0004] Currently, the general approach to achieving uniform dispersion of inorganic nanofillers is through chemical modification of their surface. However, surface modification is time-consuming and requires organic solvents. Furthermore, if purification is insufficient, the surface of the inorganic nanoparticles may contain small-molecule modifiers, the introduction of which can lead to a decrease in fiber properties. In addition, adding dispersants can also achieve uniform dispersion of nanofillers; however, commercially available dispersants are generally amorphous, low-molecular-weight polymers with low softening points. Even slightly excessive amounts of these dispersants can cause a decrease in fiber properties. For example, the addition amount of polar functionalized polyether ester polymers should not exceed 1.0%.

[0005] Therefore, further simplifying the preparation process of functional fibers and nonwoven materials, and achieving uniform dispersion of nanoparticles in polymer matrices are goals that everyone is pursuing. Summary of the Invention

[0006] [Technical Issues]

[0007] Inorganic nanofillers, when used in spinning, can impart functionality to fibers, but they can also affect the physical and mechanical properties of the fibers themselves.

[0008] [Technical Solution]

[0009] To address the aforementioned problems, this invention first uses a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer and functional fillers for blending and granulation; then, it is mixed with a thermoplastic polymer for secondary granulation; finally, it undergoes melt spinning or spunbond nonwoven processing to prepare functional fibers or functional nonwoven materials. This invention uses the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant to disperse the functional fillers, omitting the need for small-molecule functional filler modification and the addition of small-molecule dispersants, thus imparting functionality to the fibers while maintaining their inherent physical and mechanical properties.

[0010] The first objective of this invention is to provide a method for preparing functional textiles based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant, comprising the following steps:

[0011] (1) Single granulation:

[0012] Functional filler and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer were melt-blended and granulated to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / functional filler chips.

[0013] (2) Secondary granulation:

[0014] The thermoplastic polymer and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / functional filler chips are melt-blended and granulated to obtain thermoplastic polymer / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / functional filler chips.

[0015] (3) Preparation of functional textiles:

[0016] Functional fibers were prepared by using thermoplastic polymer / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / functional filler chips as raw materials through melt spinning, stretching and heat setting.

[0017] Alternatively, functional spunbond nonwoven materials can be prepared by using thermoplastic polymer / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / functional filler chips as raw materials for spunbond nonwoven processing.

[0018] In one embodiment of the present invention, the weight percentages of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride structural units in the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer described in step (1) are 45.8%, 18.5% and 35.7%, respectively.

[0019] In one embodiment of the present invention, the functional filler in step (1) is a functional nanoparticle, specifically including one or a mixture of several of zirconium carbide, silver nanoparticles, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, zinc oxide and titanium dioxide.

[0020] In one embodiment of the present invention, the particle size of the functional filler in step (1) is 1-500 nm.

[0021] In one embodiment of the present invention, the melt blending granulation in step (1) involves premixing the functional filler and the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and then melt blending and granulating them in a twin-screw mixer at a granulation temperature of 150-250°C and a screw speed of 100-500 rpm.

[0022] In one embodiment of the present invention, the melting point of the thermoplastic polymer in step (2) is 100-250°C.

[0023] In one embodiment of the present invention, the thermoplastic polymer in step (2) includes one of polylactic acid, polyethylene terephthalate, nylon 6, nylon 66, nylon 11, nylon 56, nylon 12, polypropylene terephthalate, polybutylene terephthalate, polypropylene, and polyethylene; wherein the polylactic acid has a viscosity-average molecular weight of 2.0 × 10⁻⁶. 5 The intrinsic viscosity of L-polylactic acid and polyethylene terephthalate is 0.65 dL / g.

[0024] In one embodiment of the present invention, the thermoplastic polymer blending granulation in step (2) needs to be dried in a vacuum oven at 60-150°C for 4-48 hours before granulation.

[0025] In one embodiment of the present invention, the mass ratio of the thermoplastic polymer and the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer is 98:2-50:50; the mass of the functional filler is 0.01%-3% of the sum of the masses of the thermoplastic polymer and the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer.

[0026] In one embodiment of the present invention, the melt blending granulation in step (2) involves premixing the thermoplastic polymer and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / functional filler chips, followed by melt blending and granulation in a twin-screw mixer at a granulation temperature of 150-300°C and a screw speed of 100-500 rpm.

[0027] In one embodiment of the present invention, after the melt blending and granulation in step (2), the prepared slices are vacuum dried at 60-150°C for 4-48 hours for later use.

[0028] In one embodiment of the present invention, the temperature for melt spinning to prepare multifilaments in step (3) is 150-300℃, the spinning speed is 1000-3000m / min; the drawing temperature is 25-100℃, and the drawing ratio is 1-20 times; the heat setting temperature is 80-240℃; the process for preparing monofilaments by melt spinning in step (3) includes melt extrusion (temperature 150-300℃), water bath cooling, first-stage hot steam drawing (drawing temperature 25-100℃, drawing ratio 5-10), second-stage hot air drawing (drawing temperature 50-200℃, drawing ratio 1-5), hot air setting (heat setting temperature 80-250℃), and winding (winding speed 100-300m / min).

[0029] In one embodiment of the present invention, the spunbond nonwoven processing in step (3) includes spinning and web formation and hot rolling reinforcement. In the spinning process, the spinning temperature is 150-350℃, the spinning speed is 1000-5000m / min, the web formation speed is 10-30m / min, and the pump supply is 40-200mL / min. In the hot rolling reinforcement process, the hot rolling linear pressure is 60-100N / mm, and the hot rolling mill temperature is 50-300℃.

[0030] The second objective of this invention is to obtain functional fibers or functional spunbond nonwoven materials prepared by the method described in this invention.

[0031] A third objective of this invention is to provide a functional textile fabric prepared using the functional fibers or functional spunbond nonwoven materials of this invention.

[0032] In one embodiment of the present invention, the preparation is carried out by one or more of the following methods: spinning, weaving, cutting, and bonding.

[0033] [Beneficial Effects]

[0034] (1) The present invention does not require any treatment of the nano-functional filler. The nano-filler can be uniformly dispersed in the polymer matrix by using tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer. Moreover, the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer is a fluorinated polymer and does not need to be dried before melt processing. The process is simple.

[0035] (2) The tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer used in this invention is a polymer with good spinnability. Its introduction will not reduce the spinnability and mechanical properties of the polymer matrix.

[0036] (3) The present invention can control the melting point by adjusting the proportion of each structural unit in the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer. The melting point of the commercially available tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer is as low as 115°C and as high as 225°C, which can almost meet the processing requirements of all commercially available thermoplastic fibers. The tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer can be selected according to the melting point of commercial thermoplastic fibers. Detailed Implementation

[0037] The preferred embodiments of the present invention are described below. It should be understood that the embodiments are for better explanation of the present invention and are not intended to limit the present invention.

[0038] Test method:

[0039] 1. Test method for fracture strength:

[0040] The tensile mechanical properties of high-efficiency photothermal responsive polylactic acid materials were tested in accordance with the national standard GB / T 14344-2022 "Test Method for Tensile Properties of Chemical Fiber Filaments".

[0041] 2. Method for measuring the average diameter of fibers:

[0042] For samples prepared using the same experimental parameters, five monofilaments were randomly selected and photographed under an optical fiber microscope. For each optical microscope image, the diameter of the monofilament was measured at three randomly selected locations using ImageJ software, and the average value was taken as the average diameter of the monofilament under those parameters.

[0043] 3. Photothermal heating performance test method:

[0044] A solar simulator was used (simulating a solar radiation intensity of 1000 W / m²). 2 The photothermal material was irradiated, and the temperature change of the sample was recorded using an infrared thermal imager for 1 minute.

[0045] 4. Antibacterial performance test method:

[0046] The antibacterial properties of the material were tested according to the standard GB / T 20944.3-2008 Evaluation of antimicrobial properties of textiles - Part 3: Vibration method.

[0047] Raw materials used in the examples:

[0048] The weight percentages of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride structural units in the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer are 45.8%, 18.5%, and 35.7%, respectively.

[0049] Example 1

[0050] A method for preparing functional fibers based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant includes the following steps:

[0051] (1) Single granulation:

[0052] Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer with a melting point of 165℃ and zirconium carbide with a particle size of 50nm were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 180℃ and a screw speed of 400rpm to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano zirconium carbide chips.

[0053] (2) Secondary granulation:

[0054] With a viscosity-average molecular weight of 2.0 × 10⁻⁶ 5 L-co-lactic acid was dried in a vacuum oven at 75°C for 24 hours for later use. Then, L-co-lactic acid and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-zirconium carbide chips were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 190°C and a screw speed of 400 rpm to obtain polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-zirconium carbide chips. The obtained chips were then vacuum-dried at 75°C for 24 hours for later use.

[0055] (3) Preparation of functional fibers:

[0056] Photothermal polylactic acid (PLA) nascent multifilaments were obtained by melt spinning polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-zirconium carbide chips (spinning temperature 165℃, spinning speed 2000m / min); the nascent multifilaments were then drawn at 80℃ with a draw ratio of 3.0; finally, they were heat-set at 120℃ to obtain photothermal PLA multifilaments.

[0057] The mass ratio of L-polylactic acid, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide is 90:10:0.05.

[0058] The obtained photothermal polylactic acid multifilaments were subjected to performance testing, and the test results are as follows:

[0059] The intensity is 2.52 cN / dtex, and the temperature can rise from 22℃ to 26.3℃ after 1 minute of light exposure.

[0060] Comparative Example 1

[0061] Zirconium carbide in step (1) of Example 1 is omitted, and everything else remains the same as in Example 1 to obtain polylactic acid multifilament.

[0062] Comparative Example 2

[0063] The tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer in step (1) of Example 1 is omitted. Zirconium carbide is directly added to polylactic acid in step (2), and everything else is kept the same as in Example 1 to obtain polylactic acid multifilament.

[0064] The performance test results of the polylactic acid multifilaments obtained in Example 1 and Comparative Examples 1 and 2 are as follows:

[0065] Table 1 Test Results

[0066] example Strength (cN / dtex) Photothermal emission (1 min) Spinability Example 1 2.52 The temperature rose from 22℃ to 26.3℃. good Comparative Example 1 2.48 The temperature rose from 22℃ to 23.2℃. good Comparative Example 2 1.25 The temperature rose from 22℃ to 27.2℃. Poor spinnability, prone to yarn breakage

[0067] As can be seen from Table 1, omitting the addition of zirconium carbide does not affect the spinnability, that is, the addition of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer does not affect spinnability; however, after omitting the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, zirconium carbide cannot be well dispersed, thus affecting spinnability.

[0068] Example 2

[0069] A method for preparing functional fibers based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant includes the following steps:

[0070] (1) Single granulation:

[0071] Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer with a melting point of 165℃ and 100nm nano-silver were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 180℃ and a screw speed of 400rpm to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-silver chips.

[0072] (2) Secondary granulation:

[0073] With a viscosity-average molecular weight of 2.0 × 10⁻⁶ 5 L-co-lactic acid was dried in a vacuum oven at 75°C for 24 hours for later use. Then, L-co-lactic acid and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano silver chips were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 190°C and a screw speed of 400 rpm to obtain polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano silver chips. The obtained chips were then vacuum-dried at 75°C for 24 hours for later use.

[0074] (3) Preparation of functional fibers:

[0075] Antibacterial polylactic acid (PLA) nascent multifilaments were obtained by melt spinning polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano silver chips (spinning temperature 165℃, spinning speed 2000m / min); the nascent multifilaments were then drawn at 80℃ with a draw ratio of 3.0; finally, they were heat-set at 120℃ to obtain antibacterial PLA multifilaments.

[0076] The mass ratio of L-polylactic acid, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and nano-silver is 90:10:0.1.

[0077] The obtained antibacterial polylactic acid multifilaments were subjected to performance testing, and the test results are as follows:

[0078] The strength is 2.65 cN / dtex, and the inhibition rates against Staphylococcus aureus and Escherichia coli are 98.9% and 97.3%, respectively.

[0079] Example 3

[0080] A method for preparing functional fibers based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant includes the following steps:

[0081] (1) Single granulation:

[0082] Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer with a melting point of 165℃ and 50nm zirconium carbide were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 180℃ and a screw speed of 400rpm to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconium carbide chips.

[0083] (2) Secondary granulation:

[0084] With a viscosity-average molecular weight of 2.0 × 10⁻⁶ 5 L-co-lactic acid was dried in a vacuum oven at 75°C for 24 hours for later use. Then, L-co-lactic acid and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconia carbide chips were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 190°C and a screw speed of 400 rpm to obtain polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconia carbide chips. The obtained chips were then vacuum-dried at 75°C for 24 hours for later use.

[0085] (3) Preparation of functional fibers:

[0086] Photothermal polylactic acid (PLA) monofilaments were obtained by melt extrusion (195°C), water bath cooling, first hot steam stretching (95°C, stretching ratio 6.5), second hot air stretching (125°C, stretching ratio 1.2), hot air setting (130°C), and winding (150 m / min).

[0087] The mass ratio of L-polylactic acid, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide is 90:10:0.05.

[0088] The obtained photothermal polylactic acid monofilament was subjected to performance testing, and the test results are as follows:

[0089] With a diameter of 0.1 mm and an intensity of 4.2 cN / dtex, the temperature of the monofilament can rise from 22℃ to 26.1℃ after 1 minute of light exposure.

[0090] Example 4

[0091] A method for preparing functional fibers based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant includes the following steps:

[0092] (1) Single granulation:

[0093] Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer with a melting point of 225℃ and 50nm zirconium carbide were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 235℃ and a screw speed of 400rpm to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconium carbide chips.

[0094] (2) Secondary granulation:

[0095] Polyethylene terephthalate (PET) with an intrinsic viscosity of 0.65 dL / g was dried in a vacuum oven at 120°C for 24 h. Then, PET and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconia carbide chips were premixed in a high-speed mixer for 5 min, followed by melt blending and granulation in a twin-screw mixer at 270°C and a screw speed of 400 rpm to obtain PET / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconia carbide chips. The obtained chips were vacuum dried at 120°C for 24 h, followed by pre-crystallization at 150°C for 12 h for later use.

[0096] (3) Preparation of functional fibers:

[0097] Photothermal polyethylene terephthalate (PET) primordial multifilaments were obtained by melt spinning of polyethylene terephthalate / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconium carbide chips (spinning temperature 285℃, spinning speed 2500m / min); the primordial multifilaments were then drawn at 100℃ with a draw ratio of 3.0; finally, they were heat-set at 130℃ to obtain photothermal PET multifilaments.

[0098] The mass ratio of polyethylene terephthalate, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide is 90:10:0.05.

[0099] The obtained photothermal polyethylene terephthalate multifilaments were subjected to performance tests, and the test results are as follows:

[0100] The intensity is 3.2 cN / dtex, and the temperature can rise from 22℃ to 26.3℃ after 1 minute of light exposure.

[0101] Example 5

[0102] A method for preparing functional fibers based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant includes the following steps:

[0103] (1) Single granulation:

[0104] Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer with a melting point of 225℃ and 50nm zirconium carbide were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 235℃ and a screw speed of 400rpm to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconium carbide chips.

[0105] (2) Secondary granulation:

[0106] Polyethylene terephthalate (PET) with an intrinsic viscosity of 0.65 dL / g was dried in a vacuum oven at 120°C for 24 h. Then, PET and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconia carbide chips were premixed in a high-speed mixer for 5 min, followed by melt blending and granulation in a twin-screw mixer at 270°C and a screw speed of 400 rpm to obtain PET / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconia carbide chips. The obtained chips were vacuum dried at 120°C for 24 h, followed by pre-crystallization at 150°C for 12 h for later use.

[0107] (3) Preparation of functional fibers:

[0108] High-strength, high-diameter polyethylene terephthalate (PET) monofilaments were obtained by melt extrusion (285°C), water bath cooling, first hot steam stretching (95°C, stretching ratio 7.8), second hot air stretching (180°C, stretching ratio 1.2), hot air setting (230°C), and winding (180 m / min).

[0109] The mass ratio of polyethylene terephthalate, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide is 90:10:0.05.

[0110] The obtained high-strength, high-diameter photothermal polyethylene terephthalate monofilament was subjected to performance testing, and the test results are as follows:

[0111] The diameter of the monofilament is 0.1 mm, the strength is 4.8 cN / dtex, and the temperature of the monofilament can rise from 22℃ to 25.6℃ after 1 minute of light exposure.

[0112] Example 6

[0113] A method for preparing functional nonwoven materials based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant includes the following steps:

[0114] (1) Single granulation:

[0115] Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer with a melting point of 225℃ and 50nm zirconium carbide were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 235℃ and a screw speed of 400rpm to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconium carbide chips.

[0116] (2) Secondary granulation:

[0117] Polyethylene terephthalate (PET) with an intrinsic viscosity of 0.65 dL / g was dried in a vacuum oven at 120°C for 24 h. Then, PET and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconia carbide chips were premixed in a high-speed mixer for 5 min, followed by melt blending and granulation in a twin-screw mixer at 270°C and a screw speed of 400 rpm to obtain PET / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / zirconia carbide chips. The obtained chips were vacuum dried at 120°C for 24 h, followed by pre-crystallization at 150°C for 12 h for later use.

[0118] (3) Preparation of functional nonwoven materials:

[0119] Photothermal polyethylene terephthalate (PET) / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-zirconium carbide chips were used for spunbond nonwoven processing. The spunbond nonwoven material was prepared by spinning into a web (spinning temperature 280℃, spinning speed 3500m / min, web forming speed 24m / min, pump supply 48mL / min) and hot rolling reinforcement (hot rolling linear pressure 90N / mm, hot rolling mill temperature 240℃).

[0120] The mass ratio of polyethylene terephthalate, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide is 90:10:0.05.

[0121] The obtained photothermal polyethylene terephthalate spunbond nonwoven material was subjected to performance testing, and the test results are as follows:

[0122] The areal density of the photothermal polyethylene terephthalate spunbond nonwoven material is 36.5 g / m³. 2 The temperature can rise from 22℃ to 30.5℃ after 1 minute of light exposure.

[0123] Example 7

[0124] A method for preparing functional nonwoven materials based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant includes the following steps:

[0125] (1) Single granulation:

[0126] Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer with a melting point of 165℃ and 100nm nano-silver were premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 180℃ and a screw speed of 400rpm to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-silver chips.

[0127] (2) Secondary granulation:

[0128] With a viscosity-average molecular weight of 2.0 × 10⁻⁶ 5 L-type polylactic acid was dried in a vacuum oven at 75°C for 24 hours and set aside. Then, the raw materials were weighed according to the mass ratio of polylactic acid and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano silver chips of 90:10, premixed in a high-speed mixer for 5 minutes, and then melt-blended and granulated in a twin-screw mixer to obtain polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano silver chips. The granulation temperature was 190°C and the screw speed was 400 rpm. The obtained chips were then vacuum-dried at 75°C for 24 hours and set aside.

[0129] (3) Preparation of functional nonwoven materials:

[0130] Polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano silver chips were used for spunbond nonwoven processing. The process involved spinning into a web (spinning temperature 195℃, spinning speed 3500m / min, web forming speed 24m / min, pump supply 48mL / min) and hot rolling reinforcement (hot rolling linear pressure 70N / mm, hot rolling mill temperature 70℃) to prepare antibacterial polylactic acid spunbond nonwoven material.

[0131] The mass ratio of polylactic acid, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide is 90:10:0.1.

[0132] The obtained antibacterial polylactic acid spunbond nonwoven material was subjected to performance testing, and the test results are as follows:

[0133] The areal density of antibacterial polylactic acid spunbond nonwoven material is 35 g / m². 2 The inhibition rates against Staphylococcus aureus and Escherichia coli were 99.5% and 98.6%, respectively.

[0134] Comparative Example 3

[0135] Zirconium carbide in step (1) of Example 6 is omitted, while other steps remain the same as in Example 6, to obtain photothermal polyethylene terephthalate spunbond nonwoven material.

[0136] Comparative Example 4

[0137] The tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer in step (1) of Example 1 is omitted. Zirconium carbide is directly added to polyethylene terephthalate in step (2). Everything else is the same as in Example 1 to obtain polylactic acid multifilament and photothermal polyethylene terephthalate spunbond nonwoven material.

[0138] Comparative Example 5

[0139] In Example 6, the mass ratio of polyethylene terephthalate, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide was adjusted to 95:5:0.05, while other aspects remained the same as in Example 6, to obtain a photothermal polyethylene terephthalate spunbond nonwoven material.

[0140] Comparative Example 6

[0141] In Example 6, the mass ratio of polyethylene terephthalate, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide was adjusted to 90:10:0.5, while other aspects remained the same as in Example 6, to obtain a photothermal polyethylene terephthalate spunbond nonwoven material.

[0142] The performance test results of the polylactic acid multifilaments obtained in Example 6 and Comparative Examples 3-6 are as follows:

[0143] As shown in Table 2, omitting the addition of zirconium carbide did not affect the spinnability, meaning that the addition of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer did not affect spinnability. However, omitting the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resulted in poor dispersion of zirconium carbide, thus affecting spinnability. Insufficient addition of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer led to uneven dispersion of zirconium carbide, occasional filament breakage, and minor spinneret blockage. Excessive addition of zirconium carbide prevented airflow drafting, easily causing spinneret blockage.

[0144] Table 2 Test Results

[0145] example Photothermal emission (1 min) Spinability Example 6 The temperature rose from 22℃ to 30.5℃ Smooth airflow drafting, good spinnability Comparative Example 3 The temperature rose from 22℃ to 22.9℃. Smooth airflow drafting, good spinnability Comparative Example 4 The temperature rose from 22℃ to 28.3℃. The spinneret is prone to breakage and clogging. Comparative Example 5 The temperature rose from 22℃ to 28.5℃. Occasional filament breakage and minor spinneret blockage Comparative Example 6 / Unable to achieve airflow stretching, spinneret orifices are easily clogged.

[0146] Example 8

[0147] In Example 1, the mass ratios of L-polylactic acid, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide were adjusted to 90:10:0.1, 90:10:0.15, and 90:10:0.2, while other parameters remained the same as in Example 1, to obtain polylactic acid multifilaments.

[0148] The obtained polylactic acid multifilaments were subjected to performance testing, and the test results are as follows:

[0149] As can be seen from Table 3, excessive addition of zirconium carbide will affect spinnability and strength.

[0150] Table 3 Test Results

[0151]

[0152] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the claims.

Claims

1. A method for preparing functional fibers based on a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer as a dispersant, characterized in that, Includes the following steps: (1) Single granulation: A tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer with a melting point of 165℃ and zirconium carbide with a particle size of 50nm were premixed in a high-speed mixer for 5 min, and then melt-blended and granulated in a twin-screw mixer at a granulation temperature of 180℃ and a screw speed of 400 rpm to obtain tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-zirconium carbide chips; the weight percentages of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride structural units in the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer were 45.8%, 18.5%, and 35.7%, respectively. (2) Secondary granulation: With a viscosity-average molecular weight of 2.0 × 10⁻⁶ 5 L-co-lactic acid was dried in a vacuum oven at 75°C for 24 h for later use. Then, L-co-lactic acid and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-zirconium carbide chips were premixed in a high-speed mixer for 5 min, followed by melt blending and granulation in a twin-screw mixer at 190°C and a screw speed of 400 rpm to obtain polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-zirconium carbide chips. The obtained chips were then vacuum dried at 75°C for 24 h for later use. (3) Preparation of functional fibers: Photothermal polylactic acid (PLA) nascent multifilaments were obtained by melt spinning polylactic acid / tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer / nano-zirconium carbide chips. The nascent multifilaments were then drawn at 80°C with a draw ratio of 3.

0. Finally, they were heat-set at 120°C to obtain the photothermal PLA multifilaments. The melt spinning conditions were: spinning temperature 165°C and spinning speed 2000 m / min. The mass ratio of L-polylactic acid, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer, and zirconium carbide is 90:10:0.

1.

2. The functional fiber prepared by the method of claim 1.

3. A functional textile, characterized in that, It is prepared using the functional fiber described in claim 2.

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