Preparation method of synthetic fiber containing composite carbon-based titanium material
By employing steps such as carbon nanotube pretreatment, TiO2 composite aerogel preparation, and high-temperature carbonization, the problems of poor dispersion and interfacial bonding of titanium carbide during spinning were solved, resulting in lightweight, warm, and heat-generating synthetic fibers with excellent photothermal conversion and far-infrared radiation properties.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-17
- Publication Date
- 2026-03-31
AI Technical Summary
Existing heating fibers suffer from problems during spinning, such as easy recombination of titanium carbide, poor dispersibility, insufficient compatibility with polymer matrices, and poor interfacial bonding, resulting in poor functionality and an inability to simultaneously achieve excellent photothermal conversion and far-infrared radiation.
A titanium carbide/nitrogen-containing carbon-based aerogel doped with Al2O3 was formed by carbon nanotube pretreatment, TiO2 composite aerogel preparation, high-temperature carbonization treatment and amine modification. The composite carbon-based titanium material was then blended with polymers and melt-spun to form synthetic fibers with good dispersibility and interfacial bonding.
The prepared synthetic fibers are lightweight, warm, and heat-generating, with efficient photothermal conversion and far-infrared radiation properties. They are also breathable, have strong bonding between the fibers and polymers, and exhibit minimal carbon content loss after washing.
Abstract
Description
Technical Field
[0001] This invention relates to the field of synthetic fiber technology, and more specifically, to a method for preparing synthetic fibers containing composite carbon-based titanium materials. Background Technology
[0002] With the improvement of people's living standards and the increasing demand for healthy and comfortable clothing, textile materials with active heating functions have become a research hotspot. Among them, heating fibers developed using the principles of photothermal conversion and far-infrared radiation can convert light energy in the environment (especially sunlight) and heat energy from the human body into far-infrared rays, which act on the human skin to produce a warm feeling, meeting consumers' demand for heating textiles.
[0003] Currently, the most common heating fibers on the market are mainly achieved by adding functional powders during the spinning process. These powders mainly include: (1) carbon-based materials, such as graphene and carbon nanotubes, which have good light absorption and heat conduction properties; (2) ceramic powders, such as zirconium oxide, zirconium carbide, and titanium dioxide, which can efficiently absorb and radiate far-infrared rays.
[0004] However, commercially available fibers have the following drawbacks: The functional additions of a single material are not good, and it is impossible to have excellent light absorption and heat generation and far-infrared heat generation functions at the same time. Existing technologies often employ physical blending to simply mix powders with different functions, resulting in a lack of effective structural and functional synergy among the components and an inability to construct an efficient energy conversion and transfer network.
[0005] Titanium carbide has promising applications in the photothermal field due to its excellent metallic conductivity and photothermal conversion properties. However, its direct application in fiber spinning faces two major challenges: First, titanium carbide is prone to recombination during spinning, reducing its specific surface area or active sites and thus its heating performance; second, it has poor dispersibility and insufficient compatibility with the polymer matrix, resulting in poor interfacial bonding; and third, its density is higher than that of the polymer matrix, making the fabric heavier. Summary of the Invention
[0006] To address the problems existing in the prior art, this invention proposes a method for preparing synthetic fibers containing composite carbon-based titanium materials, which achieves efficient photothermal conversion and far-infrared radiation, while ensuring excellent dispersibility in the polymer matrix, good interfacial bonding with the matrix, and maintaining good spinnability and mechanical properties of the fibers.
[0007] A method for preparing synthetic fibers containing composite carbon-based titanium materials, the method comprising the following steps: S1, Pretreatment of carbon nanotubes Carbon nanotubes were added to a mixed solution of concentrated sulfuric acid and concentrated nitric acid and refluxed at 70–80 °C for 3–4 h to modify carboxyl groups on the surface of the carbon nanotubes. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, and washed to obtain carboxylated carbon nanotubes. These were then added to an aluminum chloride solution, and the pH was adjusted to 4–6. The mixture was stirred at room temperature for 50–60 min to allow aluminum ions to coordinate with the carboxyl groups of the carboxylated carbon nanotubes. After centrifugation, washing, and drying at 60–70 °C for 6–8 h, pretreated carbon nanotubes were obtained.
[0008] Preferably, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 3:1.
[0009] Preferably, the concentrated sulfuric acid has a mass fraction of 98% and the concentrated nitric acid has a mass fraction of 68%.
[0010] Preferably, the amount of carbon nanotubes added to the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 10-20 g / L.
[0011] Preferably, the concentration of the aluminum chloride solution is 1-3%.
[0012] Preferably, the amount of carboxylated carbon nanotubes added to the aluminum chloride solution is 2-5 g / L.
[0013] Preferably, the stirring rate is 200-300 r / min.
[0014] Preparation of S2, TiO2 composite aerogel Pretreated carbon nanotubes and glucose were added to deionized water and stirred for 15–30 min to obtain a carbon-based dispersion. Tetrabutyl titanate and polyetheramine D230 were dissolved in anhydrous ethanol to obtain a mixed alcohol solution. The carbon-based dispersion was added to the mixed alcohol solution and stirred for 10–20 min. The pH was adjusted to 2–4 with nitric acid solution, and the mixture was heated to 40–50 °C for hydrolysis and condensation for 5–6 h to finally form a wet gel. The wet gel was aged for 48–72 hours, and then replaced with anhydrous ethanol every 6–12 hours for 2–3 days. The gel was then dried using supercritical CO2 to obtain TiO2 composite aerogel.
[0015] Preferably, the mass ratio of pretreated carbon nanotubes, glucose, and deionized water in the carbon-based dispersion is 1:1-2:50-60.
[0016] Preferably, the volume ratio of tetrabutyl titanate to anhydrous ethanol is 1:3 to 6.
[0017] Preferably, the amount of polyetheramine D230 added is 6 to 10% of the mass of tetrabutyl titanate.
[0018] Preferably, the amount of carbon-based dispersion added is based on the content of pretreated carbon nanotubes in the carbon-based dispersion, and the mass ratio of pretreated carbon nanotubes to tetrabutyl titanate is 1:2 to 3.
[0019] Preferably, the concentration of the nitric acid solution is 0.1–0.2 mol / L.
[0020] Pretreated carbon nanotubes exhibit improved dispersibility after being coordinated with aluminum ions. During the hydrolysis-condensation process, tetrabutyl titanate hydrolyzes to generate Ti(OH)4. Under acidic conditions, the carboxyl groups in the pretreated carbon nanotubes dissociate, and aluminum ions form coordination bonds with the amino groups, titanium hydroxyl groups, and hydroxyl groups of glucose in polyetheramine, creating more crosslinking points and enhancing the bonding force between the organic and inorganic phases. This results in crosslinked network structures such as Ti-O-Ti and Ti-O-Al. Polyetheramine provides flexible segments, and carbon nanotubes serve as the framework, improving the mechanical properties of the aerogel and inhibiting the collapse or deformation of the porous structure of the aerogel.
[0021] S3, High-temperature carbonization treatment TiO2 composite aerogel was subjected to high-temperature carbonization under nitrogen conditions, cooled to room temperature, and then immersed in triethylenediamine alcohol solution for amine modification treatment for 8–12 h. After washing and drying at 60–70 °C for 7–8 h, a composite carbon-based titanium material was obtained with an average pore size of 14–19 nm, a porosity of over 90%, and a compressive strength of 2.7–3.2 MPa.
[0022] Preferably, the high-temperature carbonization treatment is carried out at a temperature of 1300–1500°C, a heating rate of 3–5°C / min, and a holding time of 6–10 h.
[0023] Preferably, the mass fraction of the triethylenediamine alcohol solution is 1-2%.
[0024] During the high-temperature carbonization process, aluminum in the TiO2 composite aerogel is converted into Al2O3, which serves as a rigid reinforcing phase; TiO2 is converted into titanium carbide; after high-temperature carbonization, polyetheramine and glucose form a nitrogen-doped porous carbon network, with carbon nanotubes serving as the framework structure, resulting in Al2O3-doped titanium carbide / nitrogen-containing carbon-based aerogel. After further amine modification, the amine groups are modified to obtain a composite carbon-based titanium material.
[0025] S4. Preparation of functional masterbatches The composite carbon-based titanium material and polyethylene wax were mixed and ground to 0.5-2 μm, then added to polymer chips for blending, and then added to a twin-screw extruder for granulation. The resulting product was then vacuum dried to obtain a functional masterbatch.
[0026] Preferably, the amount of polyethylene wax added is 2 to 3% of the mass of the composite carbon-based titanium material.
[0027] Preferably, the mass ratio of the composite carbon-based titanium material to the polymer chips is 4–7:93–96.
[0028] Preferably, the polymer chips are either PA6 or PET, with a particle size of 200-300 mesh.
[0029] During the granulation process, the temperature range of the twin-screw extruder is 230–280°C. At this temperature, the amine groups in the composite carbon-based titanium material and the ester groups of PET undergo transesterification or amidation with the terminal carboxyl groups of PA6 to graft or crosslink, thereby improving the interfacial bonding force between the composite carbon-based titanium material and the fiber.
[0030] S5, melt spinning Functional masterbatch and polymer chips are blended and melted, metered by a metering pump and fed into a spinning assembly. After being ejected by a spinneret, the fibers are cooled and shaped to obtain synthetic fibers containing composite carbon-based titanium materials.
[0031] Preferably, the polymer chips are either PA6 or PET, with a particle size of 200-300 mesh.
[0032] Preferably, the mass ratio of the functional masterbatch to the polymer chips is 3-5:95-97.
[0033] By adopting the above technical solution, the technical effect achieved by this invention is as follows: 1. The synthetic fiber containing composite carbon-based titanium material prepared by this invention has the characteristics of being lightweight, warm, and heat-generating. Taking polyester fiber as an example, the density of the fabric after being made is 0.8-0.9 g / cm³. 3 The thermal conductivity is 0.011~0.02W / m·K (measured using a thermal conductivity meter); the far-infrared emissivity is not less than 0.78, and the far-infrared radiation temperature rise is >3℃ (measured according to GB / T 30127-2013); its photothermal storage performance is tested, with a maximum temperature rise of 10~13℃ and an average temperature rise of 6~8℃ (measured according to GB / T18319-2019).
[0034] 2. The synthetic fiber containing composite carbon-based titanium material prepared by this invention has excellent mechanical properties. Due to the presence of porous aerogel, it has better air permeability, with an air permeability greater than 200 mm / s (measured according to GB / T5453-1997).
[0035] 3. The synthetic fiber containing composite carbon-based titanium material prepared by this invention has a stronger bonding force between the composite carbon-based titanium material and the fiber, and the carbon content loss is less than 5% after 50 water washes.
[0036] 4. The synthetic fiber prepared by this invention has good whiteness, with a whiteness greater than 80% (measured according to GB / T 17644-2008). Compared with gray / black heat-generating fibers on the market, the dyeing of subsequent fabrics is less restricted, and light-colored fabrics can be made, making it more widely used. Detailed Implementation
[0037] To further illustrate the technical means and effects of the present invention in achieving the intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention, in conjunction with preferred embodiments, is provided below.
[0038] Example 1: A method for preparing synthetic fibers containing composite carbon-based titanium materials, the method comprising the following steps: S1, Pretreatment of carbon nanotubes Carbon nanotubes were added to a mixed solution of concentrated sulfuric acid and concentrated nitric acid and refluxed at 75°C for 4 hours to modify carboxyl groups on the surface of the carbon nanotubes. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, and washed to obtain carboxylated carbon nanotubes. These were then added to an aluminum chloride solution, the pH was adjusted to 5, and the mixture was stirred at room temperature for 60 minutes to allow aluminum ions to coordinate with the carboxyl groups of the carboxylated carbon nanotubes. After centrifugation, washing, and drying at 65°C for 7 hours, pretreated carbon nanotubes were obtained.
[0039] The volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 3:1.
[0040] The concentrated sulfuric acid has a mass fraction of 98%, and the concentrated nitric acid has a mass fraction of 68%.
[0041] The amount of carbon nanotubes added to the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 15 g / L.
[0042] The concentration of the aluminum chloride solution is 3%.
[0043] The amount of carboxylated carbon nanotubes added to the aluminum chloride solution is 3 g / L.
[0044] The stirring rate is 250 r / min.
[0045] Preparation of S2, TiO2 composite aerogel Pretreated carbon nanotubes and glucose were added to deionized water and stirred for 25 min to obtain a carbon-based dispersion. Tetrabutyl titanate and polyetheramine D230 were dissolved in anhydrous ethanol to obtain a mixed alcohol solution. The carbon-based dispersion was added to the mixed alcohol solution and stirred for 15 min. The pH was adjusted to 3 with nitric acid solution, and the temperature was raised to 45℃ for hydrolysis and condensation for 5.5 h to finally form a wet gel. The wet gel was aged for 60 hours, and then solvent was replaced with anhydrous ethanol every 10 hours for 3 days. The TiO2 composite aerogel was obtained by supercritical CO2 drying.
[0046] The mass ratio of pretreated carbon nanotubes, glucose, and deionized water in the carbon-based dispersion is 1:1.5:55.
[0047] The volume ratio of tetrabutyl titanate to anhydrous ethanol is 1:5.
[0048] The amount of polyetheramine D230 added is 8% of the mass of tetrabutyl titanate.
[0049] The amount of carbon-based dispersion added is based on the content of pretreated carbon nanotubes in the carbon-based dispersion, and the mass ratio of pretreated carbon nanotubes to tetrabutyl titanate is 1:2.5.
[0050] The concentration of the nitric acid solution is 0.15 mol / L.
[0051] S3, High-temperature carbonization treatment TiO2 composite aerogel was subjected to high-temperature carbonization under nitrogen conditions, cooled to room temperature, and then immersed in triethylenediamine alcohol solution for amine modification treatment for 10 h. After washing and drying at 65 °C for 8 h, a composite carbon-based titanium material was obtained with an average pore size of 14 nm, a porosity of 94%, and a compressive strength of 3.2 MPa.
[0052] The high-temperature carbonization treatment is carried out at a temperature of 1400℃, a heating rate of 4℃ / min, and a holding time of 9h.
[0053] The mass fraction of the triethylenediamine alcohol solution is 1.5%.
[0054] S4. Preparation of functional masterbatches The composite carbon-based titanium material and polyethylene wax were mixed and ground to 1 μm, then added to PET chips for blending, and then added to a twin-screw extruder for granulation at 270°C. The mixture was then vacuum dried at 70°C for 8 hours to obtain the functional masterbatch.
[0055] The amount of polyethylene wax added is 2.5% of the mass of the composite carbon-based titanium material.
[0056] The mass ratio of the composite carbon-based titanium material to PET chips is 5:95.
[0057] The PET slices have a particle size of 300 mesh.
[0058] S5, melt spinning Functional masterbatch and PET chips are blended and melted, metered by a metering pump and fed into a spinning assembly. After being ejected by a spinneret, the fibers are cooled and shaped to obtain synthetic fibers containing composite carbon-based titanium materials.
[0059] The PET slices have a particle size of 300 mesh.
[0060] The mass ratio of the functional masterbatch to the polymer chips is 4:96.
[0061] Example 2: A method for preparing synthetic fibers containing composite carbon-based titanium materials, the method comprising the following steps: S1, Pretreatment of carbon nanotubes Carbon nanotubes were added to a mixed solution of concentrated sulfuric acid and concentrated nitric acid and refluxed at 70°C for 3 hours to modify carboxyl groups on the surface of the carbon nanotubes. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, and washed to obtain carboxylated carbon nanotubes. These were then added to an aluminum chloride solution, the pH was adjusted to 4, and the mixture was stirred at room temperature for 50 minutes to allow aluminum ions to coordinate with the carboxyl groups of the carboxylated carbon nanotubes. After centrifugation, washing, and drying at 60°C for 8 hours, pretreated carbon nanotubes were obtained.
[0062] The volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 3:1.
[0063] The concentrated sulfuric acid has a mass fraction of 98%, and the concentrated nitric acid has a mass fraction of 68%.
[0064] The amount of carbon nanotubes added to the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 10 g / L.
[0065] The concentration of the aluminum chloride solution is 1%.
[0066] The amount of carboxylated carbon nanotubes added to the aluminum chloride solution is 2 g / L.
[0067] The stirring rate is 200 r / min.
[0068] Preparation of S2, TiO2 composite aerogel Pretreated carbon nanotubes and glucose were added to deionized water and stirred for 15 min to obtain a carbon-based dispersion. Tetrabutyl titanate and polyetheramine D230 were dissolved in anhydrous ethanol to obtain a mixed alcohol solution. The carbon-based dispersion was added to the mixed alcohol solution and stirred for 10 min. The pH was adjusted to 2 with nitric acid solution, and the temperature was raised to 40℃ for hydrolysis and condensation for 5 h to finally form a wet gel. The wet gel was aged for 48 hours, and then solvent was replaced with anhydrous ethanol every 6 hours for 3 days. The TiO2 composite aerogel was obtained by supercritical CO2 drying.
[0069] The mass ratio of pretreated carbon nanotubes, glucose, and deionized water in the carbon-based dispersion is 1:1:50.
[0070] The volume ratio of tetrabutyl titanate to anhydrous ethanol is 1:3.
[0071] The amount of polyetheramine D230 added is 6% of the mass of tetrabutyl titanate.
[0072] The amount of carbon-based dispersion added is based on the content of pretreated carbon nanotubes in the carbon-based dispersion, and the mass ratio of pretreated carbon nanotubes to tetrabutyl titanate is 1:2.
[0073] The concentration of the nitric acid solution is 0.1 mol / L.
[0074] S3, High-temperature carbonization treatment TiO2 composite aerogel was subjected to high-temperature carbonization under nitrogen conditions, cooled to room temperature, and then immersed in triethylenediamine alcohol solution for amine modification treatment for 8 hours. After washing and drying at 60°C for 7 hours, a composite carbon-based titanium material was obtained with an average pore size of 19 nm, a porosity of 91%, and a compressive strength of 2.7 MPa.
[0075] The high-temperature carbonization treatment is carried out at a temperature of 1300℃, a heating rate of 3℃ / min, and a holding time of 6h.
[0076] The mass fraction of the triethylenediamine alcohol solution is 1%.
[0077] S4. Preparation of functional masterbatches The composite carbon-based titanium material and polyethylene wax were mixed and ground to 0.5 μm, then added to PET chips for blending, and then added to a twin-screw extruder for granulation at 270°C. The mixture was then vacuum dried at 70°C for 8 hours to obtain the functional masterbatch.
[0078] The amount of polyethylene wax added is 2% of the mass of the composite carbon-based titanium material.
[0079] The mass ratio of the composite carbon-based titanium material to PET chips is 4:96.
[0080] The PET chips have a particle size of 200 mesh.
[0081] S5, melt spinning Functional masterbatch and PET chips are blended and melted, metered by a metering pump and fed into a spinning assembly. After being ejected by a spinneret, the fibers are cooled and shaped to obtain synthetic fibers containing composite carbon-based titanium materials.
[0082] The PET chips have a particle size of 200 mesh.
[0083] The mass ratio of the functional masterbatch to PET chips is 3:97.
[0084] Example 3: A method for preparing synthetic fibers containing composite carbon-based titanium materials, the method comprising the following steps: S1, Pretreatment of carbon nanotubes Carbon nanotubes were added to a mixed solution of concentrated sulfuric acid and concentrated nitric acid and refluxed at 80°C for 3.5 h to modify carboxyl groups on the surface of the carbon nanotubes. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, and washed to obtain carboxylated carbon nanotubes. These were then added to an aluminum chloride solution, the pH was adjusted to 6, and the mixture was stirred at room temperature for 55 min to allow aluminum ions to coordinate with the carboxyl groups of the carboxylated carbon nanotubes. After centrifugation, washing, and drying at 70°C for 6 h, pretreated carbon nanotubes were obtained.
[0085] The volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 3:1.
[0086] The concentrated sulfuric acid has a mass fraction of 98%, and the concentrated nitric acid has a mass fraction of 68%.
[0087] The amount of carbon nanotubes added to the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 20 g / L.
[0088] The concentration of the aluminum chloride solution is 2%.
[0089] The amount of carboxylated carbon nanotubes added to the aluminum chloride solution is 5 g / L.
[0090] The stirring rate is 300 r / min.
[0091] Preparation of S2, TiO2 composite aerogel Pretreated carbon nanotubes and glucose were added to deionized water and stirred for 30 min to obtain a carbon-based dispersion. Tetrabutyl titanate and polyetheramine D230 were dissolved in anhydrous ethanol to obtain a mixed alcohol solution. The carbon-based dispersion was added to the mixed alcohol solution and stirred for 20 min. The pH was adjusted to 4 with nitric acid solution, and the mixture was heated to 50 °C for 6 h to hydrolyze and condense, eventually forming a wet gel. The wet gel was aged for 72 hours, and then solvent was replaced with anhydrous ethanol every 12 hours for 3 days. The TiO2 composite aerogel was obtained by supercritical CO2 drying.
[0092] The mass ratio of pretreated carbon nanotubes, glucose, and deionized water in the carbon-based dispersion is 1:2:60.
[0093] The volume ratio of tetrabutyl titanate to anhydrous ethanol is 1:6.
[0094] The amount of polyetheramine D230 added is 10% of the mass of tetrabutyl titanate.
[0095] The amount of carbon-based dispersion added is based on the content of pretreated carbon nanotubes in the carbon-based dispersion, and the mass ratio of pretreated carbon nanotubes to tetrabutyl titanate is 1:3.
[0096] The concentration of the nitric acid solution is 0.2 mol / L.
[0097] S3, High-temperature carbonization treatment TiO2 composite aerogel was subjected to high-temperature carbonization under nitrogen conditions, cooled to room temperature, and then immersed in triethylenediamine alcohol solution for amine modification treatment for 12 h. After washing and drying at 70 °C for 7.5 h, a composite carbon-based titanium material was obtained with an average pore size of 17 nm, a porosity of 92%, and a compressive strength of 2.8 MPa.
[0098] The high-temperature carbonization treatment is carried out at a temperature of 1500℃, a heating rate of 5℃ / min, and a holding time of 10h.
[0099] The mass fraction of the triethylenediamine alcohol solution is 2%.
[0100] S4. Preparation of functional masterbatches The composite carbon-based titanium material and polyethylene wax were mixed and ground to 2μm, then added to PET chips for blending, and then added to a twin-screw extruder for granulation at 270℃. After vacuum drying at 70℃ for 8 hours, functional masterbatch was obtained.
[0101] The amount of polyethylene wax added is 3% of the mass of the composite carbon-based titanium material.
[0102] The mass ratio of the composite carbon-based titanium material to PET chips is 7:93.
[0103] The PET slices have a particle size of 300 mesh.
[0104] S5, melt spinning Functional masterbatch and polymer chips are blended and melted, metered by a metering pump and fed into a spinning assembly. After being ejected by a spinneret, the fibers are cooled and shaped to obtain synthetic fibers containing composite carbon-based titanium materials.
[0105] The PET slices have a particle size of 300 mesh.
[0106] The mass ratio of the functional masterbatch to PET chips is 5:95.
[0107] Example 4: The difference between this example and Example 1 is that the polymer chips are PA6, while the rest are the same as in Example 1.
[0108] Comparative Example 1: A representative example, Example 1, was selected. In step S1, the carboxylated carbon nanotubes were not added to the aluminum chloride solution and were directly dried. The remaining steps were the same as in Example 1. The resulting composite carbon-based titanium material had an average pore size of 33 nm, a porosity of 86%, and a compressive strength of 1.7 MPa.
[0109] Comparative Example 2: A representative example, Example 1, was selected. In step S2, polyetheramine D230 was not added. All other steps were the same as in Example 1. The resulting composite carbon-based titanium material had an average pore size of 28 nm, a porosity of 88%, and a compressive strength of 2.2 MPa.
[0110] Comparative Example 3: A representative example 1 was selected. In step S3, no amine modification was performed, and the remaining steps were the same as in Example 1.
[0111] The synthetic fibers prepared in Examples 1-3 were tested for density, thermal conductivity, and heating performance, as detailed in Table 1.
[0112] Table 1 Testing items Example 1 Example 2 Example 3 <![CDATA[Density (g / cm 3 )]]> 0.864 0.892 0.835 Thermal conductivity (W / m▪K) 0.015 0.02 0.011 Far-infrared emissivity 0.8 0.78 0.83 Far-infrared radiation temperature rise (°C) 3.5 3.2 4 Maximum temperature rise (°C) 11 10 13 Average temperature rise (°C) 7 6 8 As can be seen from Table 1, the synthetic fibers prepared using Examples 1-3 have low density, low thermal conductivity, and good heating performance, indicating that the synthetic fibers of composite carbon-based titanium materials have the characteristics of being lightweight, warm, and generating heat.
[0113] The mechanical properties of the synthetic fibers prepared in Examples 1-3 were tested, as detailed in Table 2.
[0114] Table 2 Testing items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Fracture strength (cN / dtex) 3.7 3.62 3.58 3.42 3.48 3.56 Air permeability (mm / s) 237 214 261 154 178 231 As can be seen from Table 2, the composite carbon-based titanium materials of Comparative Examples 1 and 2 have worse performance than those of the Examples. During the grinding process, some of the porous structures collapsed, resulting in a decrease in fiber strength and air permeability. Comparative Example 3 was not modified with amine groups, so it did not react with PET chips or PA6 chips, nor did it produce a small amount of cross-linked structures. Since the amount of composite carbon-based titanium material added was small, the fiber strength decreased less, but the air permeability remained basically unchanged.
[0115] The synthetic fibers prepared in Examples 1-4 and Comparative Examples 1-3 were tested for titanium content loss rate during water washing, as detailed in Table 3.
[0116] Table 3 Testing items Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Titanium content loss rate (%) after 50 water washes 3.3 3.8 3.5 3.6 10.9 8.7 24 As can be seen from Table 3, the titanium loss after 50 washes in Comparative Examples 1-3 was greater than that in the Example. This is because the composite carbon-based titanium material prepared in Comparative Examples 1-2 had insufficient strength, and the structural collapse during the washing process caused the loss of titanium. In contrast, the composite carbon-based titanium material prepared in Comparative Example 3 had weak bonding force with the fiber, resulting in greater loss during washing.
[0117] Unless otherwise specified, all proportions and percentages mentioned in this invention are mass proportions and mass percentages; all raw materials are commercially available.
[0118] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. 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 some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.
Claims
1. A method for producing a synthetic fiber containing a composite carbon-based titanium material, characterized by, The preparation method comprises pretreatment of carbon nanotubes, preparation of TiO2 composite aerogel, high-temperature carbonization treatment, preparation of functional master batch and melt spinning.
2. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 1, characterized in that, The pretreatment of the carbon nanotubes comprises adding the carbon nanotubes to a mixed solution of concentrated sulfuric acid and concentrated nitric acid, refluxing at 70-80 DEG C for 3-4 hours to modify the surface of the carbon nanotubes with carboxyl groups, cooling to room temperature, centrifuging, washing and then adding the carbon nanotubes to an aluminum chloride solution, adjusting the pH to 4-6, stirring at room temperature for 50-60 minutes, centrifuging, washing, drying at 60-70 DEG C for 6-8 hours to obtain pretreated carbon nanotubes.
3. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 2, characterized in that, The carbon nanotubes are added to the mixed solution of concentrated sulfuric acid and concentrated nitric acid in an amount of 10-20 g / L. The concentration of the aluminum chloride solution is 1-3%. The carboxylated carbon nanotubes are added to the aluminum chloride solution in an amount of 2-5 g / L.
4. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 1, characterized in that, The preparation of the TiO2 composite aerogel comprises adding the pretreated carbon nanotubes and glucose to deionized water and stirring for 15-30 minutes to obtain a carbon-based dispersion; dissolving tetrabutyl titanate and polyetheramine D230 in anhydrous ethanol to obtain a mixed alcohol solution; adding the carbon-based dispersion to the mixed alcohol solution and stirring for 10-20 minutes, adjusting the pH to 2-4 with a nitric acid solution, and hydrolyzing and condensing at a temperature of 40-50 DEG C for 5-6 hours to finally form a wet gel; The wet gel is aged for 48-72 hours, solvent replacement is performed with anhydrous ethanol every 6-12 hours for 2-3 days, and CO2 supercritical drying is adopted to obtain the TiO2 composite aerogel.
5. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 4, characterized in that, The mass ratio of the pretreated carbon nanotubes, glucose and deionized water in the carbon-based dispersion is 1:1-2:50-60. The volume ratio of the tetrabutyl titanate and anhydrous ethanol is 1:3-6. The amount of the polyetheramine D230 added is 6-10% of the mass of the tetrabutyl titanate. The mass ratio of the pretreated carbon nanotubes to the tetrabutyl titanate is 1:2-3, based on the content of the pretreated carbon nanotubes in the carbon-based dispersion. The concentration of the nitric acid solution is 0.1-0.2 mol / L.
6. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 1, characterized in that, The high-temperature carbonization treatment comprises high-temperature carbonization treatment of the TiO2 composite aerogel under nitrogen, amine modification treatment of the TiO2 composite aerogel by immersing the TiO2 composite aerogel in a triethylenediamine alcohol solution for 8-12 hours after cooling to room temperature, and drying at 60-70 DEG C for 7-8 hours after washing to obtain a composite carbon-based titanium material.
7. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 6, characterized in that, The temperature of the high-temperature carbonization treatment is 1300-1500 DEG C, the temperature rising rate is 3-5 DEG C / min, and the holding time is 6-10 hours. The mass fraction of the triethylenediamine alcohol solution is 1-2%.
8. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 1, characterized in that, The preparation of the functional master batch comprises mixing and grinding the composite carbon-based titanium material and polyethylene wax to a particle size of 0.5-2 μm, adding the mixture to polymer chips for blending, adding the blend to a twin-screw extruder for granulation, and vacuum drying to obtain the functional master batch.
9. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 8, characterized in that, The amount of the polyethylene wax added is 2-3% of the mass of the composite carbon-based titanium material. The mass ratio of the composite carbon-based titanium material to the polymer chips is 4-7:93-96. The polymer chips are one of PA6 and PET, and the particle size is 200-300 mesh.
10. The method for preparing synthetic fibers containing composite carbon-based titanium materials according to claim 1, characterized in that, The melt spinning is that the functional master batch and polymer chips are blended, melt, metered by a metering pump, sprayed by a spinneret and cooled to form a synthetic fiber containing the composite carbon-based titanium material; The polymer chips are one of PA6 or PET, and the particle size is 200-300 mesh; The mass ratio of the functional master batch and the polymer chips is 3-5:95-97.