Conductive polyester elastic fiber as well as preparation method and application thereof
Conductive polyester elastic fibers were prepared by using composite spinning technology and enriching heterogeneously distributed carbon nanotubes, which solved the problem of difficulty in balancing conductivity and elasticity in existing technologies and achieved a good combination of conductivity and elasticity.
Patent Information
- Application Number
- CN202510773353.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-11
- Publication Date
- 2025-10-17
AI Technical Summary
Existing technologies struggle to impart good electrical conductivity to polyester fibers while maintaining their elasticity. Chemical plating or electroplating methods are prone to cracking, and adding conductive materials leads to interfacial instability and a decrease in elasticity.
Using composite spinning technology, conductive polyester elastic fibers are prepared by using polyethylene terephthalate with different molecular weights, hydroxyl-terminated hyperbranched polyester, and conductive carbon nanotube masterbatch as fiber components through melt spinning process. The hydroxyl-terminated hyperbranched polyester diffuses to the fiber surface in the high-temperature molten state to form a heterogeneous distribution, and the carbon nanotubes are enriched on the fiber surface to enhance conductivity and maintain elasticity.
This invention achieves the improvement of elastic properties in conductive polyester fibers while maintaining good conductivity, overcoming the problem of sacrificing one aspect for another in existing technologies.
Smart Images
Figure CN120797249A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of functional fibers, in particular to a conductive polyester elastic fiber and a preparation method and application thereof. BACKGROUND
[0002] Polyethylene terephthalate fibers (PET fibers, polyester fibers) have a wide range of applications in the clothing and decoration industries due to their high strength, light weight, easy washing and drying, good crispness (the ability of the fabric to maintain shape stability and resistance to deformation), and other characteristics. With the development of technology and people's pursuit of high-quality clothing, the multifunctional application of PET fibers has become a research hotspot. Among them, polyester fibers with both conductivity and elasticity have great application potential in the fields of smart textiles, flexible electronic devices, and wearable technology. Generally speaking, based on the difference in the viscoelasticity of the two-component melt, using composite spinning technology to design and develop side-by-side composite fibers is an effective means to give the fiber an elastic form. On this basis, in order to give the fiber good conductivity, method one is to build a conductive layer on the surface of the fiber by chemical plating or electroplating, etc. This method has good conductivity, but the conductive layer is prone to cracking or falling off, and the conductivity durability is poor. Method two is to add conductive materials in the components of the composite fiber. This method can give the fiber good conductivity durability to some extent, but the current polyester fiber will cause the interface of the composite fiber to be unstable and the elastic performance of the fiber to decrease significantly with the introduction of conductive materials. Therefore, how to give the fiber good conductivity while maintaining good elastic performance is a technical problem that needs to be solved. SUMMARY
[0003] The purpose of the present application is to overcome one or more of the deficiencies in the prior art, and to provide an improved conductive polyester elastic fiber that can maintain good elastic performance while having good conductivity, overcoming the problem of sacrificing one for the other in the prior art.
[0004] The present application also provides a preparation method of the conductive polyester elastic fiber and its application in the preparation of smart textiles or flexible electronic devices.
[0005] To achieve the above-mentioned purpose, one technical solution adopted by the present application is: A conductive polyester elastic fiber, the raw materials of the conductive polyester elastic fiber comprising a first component and a second component, the first component comprising a first polyethylene terephthalate, the second component comprising a second polyethylene terephthalate, a hydroxyl-terminated hyperbranched polyester, and a conductive carbon nanotube master batch, the raw materials of the conductive carbon nanotube master batch comprising a third polyethylene terephthalate and amino-functionalized carbon nanotubes; wherein the first polyethylene terephthalate has a different molecular weight than the second polyethylene terephthalate, and the molecular weight of the one of the first polyethylene terephthalate and the second polyethylene terephthalate that has a relatively small molecular weight is more than 2.5 times the molecular weight of the hydroxyl-terminated hyperbranched polyester.
[0006] In some embodiments of the present application, the first polyethylene terephthalate has a larger molecular weight than the second polyethylene terephthalate.
[0007] In some embodiments of the present application, the molecular weight of the one of the first polyethylene terephthalate and the second polyethylene terephthalate that has a relatively small molecular weight is 2.5-40 times, for example, 2.5-30 times, 2.5-20 times, 2.5-10 times, 5-40 times, 10-40 times, 15-40 times, 20-40 times, 25-40 times, etc. the molecular weight of the hydroxyl-terminated hyperbranched polyester.
[0008] According to some preferred and specific aspects of the present application, the first polyethylene terephthalate has a number average molecular weight of 25000-35000 g / mol, and the second polyethylene terephthalate has a molecular weight of 16000-20000 g / mol.
[0009] According to some preferred and specific aspects of the present application, the hydroxyl-terminated hyperbranched polyester has a hydroxyl value of 200-600 mgKOH / g, a molecular weight of 400-6000 g / mol, and contains 5-100 terminal hydroxyl groups per molecule.
[0010] In some embodiments of the present application, the hydroxyl-terminated hyperbranched polyester comprises a combination of one or more compounds selected from the group consisting of compounds represented by Formula (I); ; In Formula (I), R1, R4, R7are independently selected from H, OH, ; R2, R3, R5, R6, R8, R9are independently selected from OH, ; wherein: (i) R a , R b , R c , R d are independently selected from OH, ; (ii) R e , R f are independently selected from OH, ; (iii) R g , R hIndependently selected from OH, ; Define R according to the rules (i) to (iii) i 、R j and subsequent further substituent groups, for example, R i 、R j Independently selected from OH, ; R k 、R l Independently selected from OH, According to this rule, the molecular weight and the number of terminal hydroxyl groups of the terminal hydroxyl hyperbranched polyester can be amplified.
[0011] According to some specific aspects of the present invention, the terminal hydroxyl hyperbranched polyester comprises a combination of one or more compounds selected from the group consisting of compounds represented by formula (I-1) to compounds represented by formula (I-4); 、 .
[0012] In some specific cases of the present invention, the hydroxyl-terminated hyperbranched polyester can be commercially obtained, for example, the HyPer H20 series can be purchased from Wuhan Hyperbranched Resin Technology Co., Ltd., which can be HyPer H201, HyPer H202, HyPerH203, HyPer H204, etc.
[0013] According to some preferred aspects of the present invention, based on 100 parts of the total amount of raw materials of the conductive polyester elastic fiber, the first component accounts for 50-70 parts, and the second component accounts for 30-50 parts.
[0014] In some embodiments of the present invention, the conductive carbon nanotube masterbatch is made from the third polyethylene terephthalate and the amino-treated carbon nanotubes. Furthermore, the method for preparing the conductive carbon nanotube masterbatch includes extruding the third polyethylene terephthalate and the amino-treated carbon nanotubes at a temperature of 250-265°C, water-cooling, and pelletizing to obtain the conductive carbon nanotube masterbatch.
[0015] According to some preferred aspects of the present invention, the amino carbon nanotubes account for 13%-18% of the raw materials of the conductive carbon nanotube masterbatch in terms of mass percentage, for example, 13%, 14%, 15%, 16%, 17%, 18%, etc.
[0016] According to some preferred aspects of the present invention, the number average molecular weight of the third polyethylene terephthalate is 14,000-15,000 g / mol.
[0017] According to some preferred aspects of the present application, the diameter of the amino-functionalized carbon nanotube is 10-30 nm, and the length is 10-50 μm.
[0018] According to some preferred aspects of the present application, the second polyethylene terephthalate accounts for 50-70 parts, the hydroxyl-terminated hyperbranched polyester accounts for 10-20 parts, and the conductive carbon nanotube master batch accounts for 20-30 parts, based on the total amount of the second component being 100 parts.
[0019] In some embodiments of the present application, the conductive polyester elastic fiber has a fineness of 1-10 dtex, a volume specific resistance of 10-1 x 10 4 Ω·cm, a crimping rate of 60%-85%, a crimping elastic recovery rate of 50%-80%, and a breaking strength greater than 3.0 cN / dtex.
[0020] The present application provides still another technical solution: a preparation method of the conductive polyester elastic fiber described above, which comprises: The first component and the second component are spun into the conductive polyester elastic fiber by using a melt spinning process; wherein the melt extrusion temperature of the first component is 285-300 ℃, the melt extrusion temperature of the second component is 275-290 ℃, the temperature of the spinning assembly is 280-295 ℃, the cooling mode is side blowing, the second component faces the blowing direction, the first component faces away from the blowing direction, the blowing temperature is 10-15 ℃, the heat drawing temperature is 140-150 ℃, and the heat drawing multiple is 4-7.
[0021] The present application provides still another technical solution: an application of the conductive polyester elastic fiber described above in the preparation of smart textiles or flexible electronic devices.
[0022] In the present application, the "first", "second", and "third" in the first polyethylene terephthalate, the second polyethylene terephthalate, and the third polyethylene terephthalate do not have a chronological order, and are only used to distinguish the polyethylene terephthalates used in different components.
[0023] Thanks to the above technical solutions, the present application has the following advantages compared with the prior art: Based on the problem of trade-off between high conductivity and good elasticity in the preparation of functional fibers, especially the fibers which need to have both high conductivity and good elasticity, the present application provides an improved conductive polyester elastic fiber, which uses a complex of polyethylene terephthalate, hydroxyl-terminated hyperbranched polyester and conductive carbon nanotube masterbatch (containing amino-functionalized carbon nanotubes) as one component of the fiber, and polyethylene terephthalate as another component, wherein the molecular weight of the hydroxyl-terminated hyperbranched polyester is significantly lower than that of the polyethylene terephthalate in any one component, and the hydroxyl-terminated hyperbranched polyester has a highly branched molecular structure and a low molecular weight, which makes its viscosity relatively small and has good flowability. When the viscosity of the hydroxyl-terminated hyperbranched polyester is significantly lower than the melt viscosity of the polyethylene terephthalate, the hydroxyl-terminated hyperbranched polyester is easy to diffuse to the surface of the fiber during the extrusion process (when melt spinning, the system is in a high temperature melting state, and the thermal motion of the molecules is intensified, so the hydroxyl-terminated hyperbranched polyester molecules with small viscosity are more likely to move in the melt. After extruding through the spinneret, the hydroxyl-terminated hyperbranched polyester is more likely to diffuse to the surface of the fiber due to the extrusion swelling effect, so it is enriched on the surface of the fiber). Further, the hydroxyl groups of the hydroxyl-terminated hyperbranched polyester and the amino groups of the amino-functionalized carbon nanotubes form a bond interaction, and the hydroxyl-terminated hyperbranched polyester drives the carbon nanotubes to be enriched on the surface of the fiber, significantly improving the conductivity of the fiber, and making the carbon nanotubes form a heterogeneous distribution in the component, so that the content of carbon nanotubes at the interface between the two components is low, the viscosity difference at the interface between the two components is small, which is beneficial to maintaining a good interface shape, and this heterogeneous distribution of carbon nanotubes induces a larger difference in microstructure in the radial direction of the fiber, resulting in a larger asymmetric stress in the radial direction of the fiber, which is beneficial to the improvement of the crimping form elasticity of the fiber.
[0024] In summary, the conductive polyester elastic fiber of the present application can have good conductivity while maintaining good elasticity, overcoming the trade-off problem in the prior art. BRIEF DESCRIPTION OF DRAWINGS
[0025] Figure 1 The optical microscope image of the conductive polyester elastic fiber prepared in Example 1 of the present application; Figure 2 The scanning electron microscope image of the cross-section of the conductive polyester elastic fiber prepared in Example 1 of the present application. DETAILED DESCRIPTION
[0026] The above scheme will be further described in combination with specific examples; it should be understood that these examples are used to illustrate the basic principles, main features and advantages of the present application, and the present application is not limited in scope by the following examples; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not specified are usually the conditions in conventional experiments.
[0027] All raw materials in the following examples are commercially available or prepared by conventional methods in the art. In the following, the amino-functionalized carbon nanotubes are purchased from Jiangsu Xianfeng Nanometer Material Technology Co., Ltd. with the code XFM62-1.
[0028] Example 1: This example provides a conductive polyester elastic fiber and a preparation method thereof. The raw materials of the conductive polyester elastic fiber comprise a first component and a second component, and the mass ratio of the first component to the second component is 50:50. The first component is a first polyethylene terephthalate, and the second component is composed of a second polyethylene terephthalate, a hydroxyl-terminated hyperbranched polyester, and a conductive carbon nanotube master batch. The mass ratio of the second polyethylene terephthalate, the hydroxyl-terminated hyperbranched polyester, and the conductive carbon nanotube master batch is 50:20:30. The hydroxyl-terminated hyperbranched polyester is HyPer H201 purchased from Wuhan Hyperbranched Resin Technology Co., Ltd. The raw materials of the conductive carbon nanotube master batch are composed of a third polyethylene terephthalate and amino-functionalized carbon nanotubes, and the mass ratio of the third polyethylene terephthalate to the amino-functionalized carbon nanotubes is 87:13. The first polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd. with a number average molecular weight of 25000 g / mol. The second polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd. with a number average molecular weight of 16000 g / mol. The third polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd. with a number average molecular weight of 15000 g / mol. The preparation method of the conductive carbon nanotube master batch comprises: drying the third polyethylene terephthalate at 120°C to a moisture content of less than 50 ppm, then pre-mixing with the amino-functionalized carbon nanotubes at high speed, and then melt blending and extruding through a twin-screw extruder, and then water-cooling and granulating to obtain the conductive carbon nanotube master batch. The temperatures of the I to VII zones of the twin-screw extruder are 250°C, 255°C, 255°C, 254°C, 253°C, 252°C, and 250°C, respectively.
[0029] The preparation method of the conductive polyester elastic fiber comprises: The first component and the second component are spun into the conductive polyester elastic fiber by using melt spinning process; wherein, the melt extrusion temperature of the first component: the temperature of I~IV area is 285℃, 288℃, 286℃, 286℃ respectively, and the first component is extruded by the metering pump I (the temperature of the metering pump is 286℃); the melt extrusion temperature of the second component: the temperature of I~IV area is 275℃, 278℃, 276℃, 276℃ respectively, and the second component is extruded by the metering pump II (the temperature of the metering pump is 276℃); the temperature of the spinning pack is 280℃; the cooling mode is side blowing, the second component faces the blowing direction, and the first component faces away from the blowing direction; the blowing temperature is 15℃; after the oiling by the bunching, the pre-drawing (the first hot roller temperature is 140℃, the speed is 1000m / min, and the second hot roller is 140℃, the speed is 1500m / min), the main drawing (the third hot roller temperature is 143℃, the speed is 4000m / min), the heat setting (the temperature is 140℃, the speed is 4000m / min) are sequentially performed, and finally the winding is performed at 3950m / min to obtain the conductive polyester elastic fiber.
[0030] In example 2, the raw material of the conductive polyester elastic fiber comprises a first component and a second component, and the mass ratio of the first component to the second component is 55:45. The first component is a first polyethylene terephthalate, and the second component is composed of a second polyethylene terephthalate, a hydroxyl-terminated hyperbranched polyester and a conductive carbon nanotube master batch; the mass ratio of the second polyethylene terephthalate, the hydroxyl-terminated hyperbranched polyester and the conductive carbon nanotube master batch is 56:17:27; the hydroxyl-terminated hyperbranched polyester is HyPer H202 purchased from Wuhan Hyperbranched Resin Technology Co., Ltd. The raw material of the conductive carbon nanotube master batch is composed of a third polyethylene terephthalate and an aminated carbon nanotube; the mass ratio of the third polyethylene terephthalate to the aminated carbon nanotube is 86:14. The first polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd., and the number average molecular weight is 28000g / mol; the second polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd., and the number average molecular weight is 17000g / mol; the third polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd., and the number average molecular weight is 14800g / mol. The preparation method of the conductive carbon nanotube master batch comprises: drying the third ethylene terephthalate at 120 DEG C to a moisture content of 50 ppm or less, then pre-high-speed mixing with the aminated carbon nanotubes, and then melt blending and extruding through a twin-screw extruder, and then water-cooling and pelletizing to obtain the conductive carbon nanotube master batch, wherein the temperatures of the I to VII zones of the twin-screw extruder are 250 DEG C, 256 DEG C, 256 DEG C, 254 DEG C, 253 DEG C, 252 DEG C, and 250 DEG C, respectively.
[0031] The preparation method of the conductive polyester elastic fiber comprises: The first component and the second component are spun into the conductive polyester elastic fiber by using a melt spinning process; wherein the melt extrusion temperature of the first component is: the temperatures of the I to IV zones are 288 DEG C, 292 DEG C, 290 DEG C, and 290 DEG C, respectively, and the first component is extruded through a metering pump I (the temperature of the metering pump is 290 DEG C); the melt extrusion temperature of the second component is: the temperatures of the I to IV zones are 280 DEG C, 283 DEG C, 282 DEG C, and 282 DEG C, respectively, and the second component is extruded through a metering pump II (the temperature of the metering pump is 282 DEG C); the temperature of the spinning assembly is 287 DEG C; the cooling mode is side blowing; the second component faces the blowing direction, and the first component faces away from the blowing direction; the blowing temperature is 14 DEG C; after oiling through a bunching device, the conductive polyester elastic fiber is obtained by sequentially performing pre-drawing (the first hot roller temperature is 143 DEG C, and the speed is 900 m / min; the second hot roller temperature is 143 DEG C, and the speed is 1200 m / min), main drawing (the third hot roller temperature is 145 DEG C, and the speed is 4500 m / min), heat setting (the temperature is 143 DEG C, and the speed is 4500 m / min), and finally winding at 4400 m / min.
[0032] Embodiment 3: The embodiment provides a conductive polyester elastic fiber and a preparation method thereof, the raw material of the conductive polyester elastic fiber comprises a first component and a second component, and the mass ratio of the first component to the second component is 60:40; The first component is a first polyethylene terephthalate, and the second component is composed of a second polyethylene terephthalate, a hydroxyl-terminated hyperbranched polyester, and a conductive carbon nanotube master batch; the mass ratio of the second polyethylene terephthalate, the hydroxyl-terminated hyperbranched polyester, and the conductive carbon nanotube master batch is 63:14:23; the hydroxyl-terminated hyperbranched polyester is HyPer H203 purchased from Wuhan Hyperbranched Resin Technology Co., Ltd.; The raw material of the conductive carbon nanotube master batch is composed of a third polyethylene terephthalate and aminated carbon nanotubes; the mass ratio of the third polyethylene terephthalate to the aminated carbon nanotubes is 85:15; The first polyethylene terephthalate is produced by Jiangsu Zhongyu Technology Development Co., Ltd. and has a number average molecular weight of 33,000 g / mol; the second polyethylene terephthalate is produced by Jiangsu Zhongyu Technology Development Co., Ltd. and has a number average molecular weight of 18,000 g / mol; the third polyethylene terephthalate is produced by Jiangsu Zhongyu Technology Development Co., Ltd. and has a number average molecular weight of 14,500 g / mol; The preparation method of conductive carbon nanotube masterbatch includes: drying tertiary ethylene terephthalate at 120°C to a moisture content of less than 50 ppm, then pre-mixing it with amino-treated carbon nanotubes at high speed, then melt-blending and extruding it through a twin-screw extruder, and water-cooling and pelletizing to obtain conductive carbon nanotube masterbatch, wherein the temperatures of zones I to VII of the twin-screw extruder are 250°C, 257°C, 257°C, 254°C, 254°C, 253°C, and 251°C, respectively.
[0033] The preparation method of the conductive polyester elastic fiber comprises: The first component and the second component are spun into conductive polyester elastic fibers by a melt spinning process; wherein, the melt extrusion temperature of the first component: the temperatures of zones I to IV are 291°C, 295°C, 293°C, and 293°C, respectively, and are metered and extruded by metering pump I (the metering pump temperature is 293°C); the melt extrusion temperature of the second component: the temperatures of zones I to IV are 282°C, 286°C, 284°C, and 284°C, respectively, and are metered and extruded by metering pump II (the metering pump temperature is 284°C); the temperature of the spinning assembly is 290°C, and the cooling method is The second component faces the blowing direction, the first component faces the back of the blowing direction, the blowing temperature is 12°C, and after bundling and oiling, it is sequentially pre-stretched (the first hot roller temperature is 145°C, the speed is 800m / min, the second hot roller temperature is 145°C, the speed is 1100m / min), main stretching (the third hot roller temperature is 148°C, the speed is 4800m / min), heat setting (temperature is 145°C, speed is 4800m / min), and finally wound at 4700m / min to obtain conductive polyester elastic fiber.
[0034] Example 4: This example provides a conductive polyester elastic fiber and a preparation method thereof. The raw materials of the conductive polyester elastic fiber include a first component and a second component, and the mass ratio of the first component to the second component is 70:30; the first component is a first polyethylene terephthalate, and the second component is composed of a second polyethylene terephthalate, a hydroxyl-terminated hyperbranched polyester, and a conductive carbon nanotube masterbatch. The mass ratio of the second polyethylene terephthalate, the hydroxyl-terminated hyperbranched polyester, and the conductive carbon nanotube masterbatch is 70:10:20. The hydroxyl-terminated hyperbranched polyester is purchased from HyPer H204 of Wuhan Hyperbranched Resin Technology Co., Ltd. The raw material of the conductive carbon nanotube master batch is composed of the third polyethylene terephthalate and the aminated carbon nanotube, and the mass ratio of the third polyethylene terephthalate to the aminated carbon nanotube is 82:18. The first polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd., and has a number average molecular weight of 35000 g / mol; the second polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd., and has a number average molecular weight of 20000 g / mol; and the third polyethylene terephthalate is produced by Jiangsu Zhonglu Science and Technology Development Co., Ltd., and has a number average molecular weight of 14000 g / mol. The preparation method of the conductive carbon nanotube master batch comprises the following steps: drying the third polyethylene terephthalate at 120℃ to a moisture content of less than 50 ppm, then pre-mixing the third polyethylene terephthalate with the aminated carbon nanotube at a high speed, and then melt blending and extruding through a double-screw extruder, and then obtaining the conductive carbon nanotube master batch through water cooling and granulation, wherein the temperatures of the I zone to the VII zone of the double-screw extruder are 250℃, 257℃, 257℃, 255℃, 255℃, 254℃ and 252℃ respectively.
[0035] The preparation method of the conductive polyester elastic fiber comprises the following steps: The first component and the second component are spun into the conductive polyester elastic fiber by using a melt spinning process; wherein the melt extrusion temperature of the first component is: the temperatures of the I zone to the IV zone are 295℃, 300℃, 298℃ and 298℃ respectively, and the first component is extruded through a metering pump I (the temperature of the metering pump is 298℃); the melt extrusion temperature of the second component is: the temperatures of the I zone to the IV zone are 286℃, 290℃, 288℃ and 288℃ respectively, and the second component is extruded through a metering pump II (the temperature of the metering pump is 288℃); the temperature of the spinning assembly is 295℃; the cooling mode is side blowing; the second component faces the blowing direction, and the first component faces away from the blowing direction; the blowing temperature is 10℃; after oiling through bundling, the following processes are performed in sequence: pre-drawing (the first hot roller temperature is 148℃, and the speed is 700 m / min; the second hot roller temperature is 148℃, and the speed is 1000 m / min), main drawing (the third hot roller temperature is 150℃, and the speed is 4900 m / min), heat setting (the temperature is 148℃, and the speed is 4900 m / min), and finally winding at 4800 m / min to obtain the conductive polyester elastic fiber.
[0036] Comparative Example 1: This example provides a conductive polyester elastic fiber and a preparation method thereof, which are basically the same as those of Example 1, and the only difference is that no hydroxyl-terminated hyperbranched polyester is added in the second component, and the mass ratio of the second polyethylene terephthalate to the conductive carbon nanotube master batch is 70:30.
[0037] Comparative Example 2: This example provides a conductive polyester elastic fiber and a preparation method thereof, which is basically the same as Example 1, and the only difference is that the amino-functionalized carbon nanotubes are replaced with the same mass of carbon nanotubes without amino groups.
[0038] Performance test: (1) The following performance tests were performed on Examples 1-4 and Comparative Examples 1-2 above, and the specific test results are shown in Table 1.
[0039] The test standard for fineness (dtex) is GB / T 14343-2008 "Chemical Fiber Filament Linear Density Test Method"; The test standard for volume specific resistance (Ω·cm) is FZ / T 50035-2016 "Synthetic Fiber Filament Resistance Test Method"; The test standard for crimping rate (%) is GB / T 14338 "Chemical Fiber Filament Crimping Performance Test Method"; The test standard for crimping elastic recovery rate (%) is GB / T 14338 "Chemical Fiber Filament Crimping Performance Test Method"; The test standard for breaking strength (cN / dtex) is GB / T 14344-2022 "Chemical Fiber Filament Tensile Property Test Method".
[0040]
[0041] As can be seen from Table 1, the inventive examples have good electrical conductivity and good elastic properties; Compared with Example 1, Comparative Example 1 does not add the hydroxyl-terminated hyperbranched polyester, and the results show that the volume specific resistance is significantly improved (i.e., the electrical conductivity is severely decreased). It is analyzed that this is due to the lack of migration of low-viscosity hydroxyl-terminated hyperbranched resin to the surface of the fiber, which results in the inability to drive the enrichment of carbon nanotubes on the surface of the fiber, leading to a decrease in electrical conductivity.
[0042] Compared with Example 1, the carbon nanotubes added in Comparative Example 2 do not contain amino groups, and the results show that the volume specific resistance is significantly improved. It is analyzed that due to the lack of amino groups on the carbon nanotubes, they cannot form an interaction with the hydroxyl groups of the hyperbranched polyester. During the extrusion process, the ability of the hyperbranched polyester to drive the migration of carbon nanotubes on the surface of the fiber is weakened when it diffuses to the surface of the fiber, thereby leading to a decrease in the electrical conductivity of the fiber.
[0043] (2) Figure 1 is a microscope image of the conductive polyester elastic fiber prepared in Example 1 of the present application, which can be seen to have obvious crimping elastic properties, Figure 2It is a scanning electron microscope graph of the cross section part, the fiber cross section appearance analysis indicates that the carbon nanotube is embedded in the fiber matrix, and presents discrete point distribution, thanks to its high aspect ratio characteristics, the carbon nanotube can form a bridging network structure in the fiber axial direction, and significantly improve the conductivity of the fiber through the contact conduction mechanism.
[0044] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application shall be covered within the protection scope of the present application.
[0045] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not, in some cases, critical to the present application. Any numerical value, however, can be expressed as a range to include any and all expressed values between the two endpoints, whether or not modifier words are used. Such a range format is also used in the claims, specifying the approximate dimensions of the compositions and methods claimed.
Claims
1. A conductive polyester elastic fiber, characterized in that: The raw materials of the conductive polyester elastic fiber include a first component and a second component, the first component includes a first polyethylene terephthalate, the second component includes a second polyethylene terephthalate, a terminal hydroxyl hyperbranched polyester, and a conductive carbon nanotube masterbatch, and the raw materials of the conductive carbon nanotube masterbatch include a third polyethylene terephthalate and amino-treated carbon nanotubes; The molecular weight of the first polyethylene terephthalate is different from that of the second polyethylene terephthalate, and the molecular weight of the first polyethylene terephthalate or the second polyethylene terephthalate with a relatively smaller molecular weight is more than 2.5 times the molecular weight of the terminal hydroxyl hyperbranched polyester.
2. The conductive polyester elastic fiber according to claim 1, characterized in that The molecular weight of the first polyethylene terephthalate is greater than that of the second polyethylene terephthalate.
3. The conductive polyester elastic fiber according to claim 2, characterized in that: The number average molecular weight of the first polyethylene terephthalate is 25,000-35,000 g / mol, and the molecular weight of the second polyethylene terephthalate is 16,000-20,000 g / mol.
4. The conductive polyester elastic fiber according to claim 1, characterized in that The hydroxyl-terminated hyperbranched polyester has a hydroxyl value of 200-600 mgKOH / g, a molecular weight of 400-6000 g / mol, and contains 5-100 terminal hydroxyl groups per molecule; and / or the molecular weight of the first polyethylene terephthalate or the second polyethylene terephthalate with a relatively smaller molecular weight is 2.5-40 times the molecular weight of the hydroxyl-terminated hyperbranched polyester.
5. The conductive polyester elastic fiber according to claim 1, characterized in that: The terminal hydroxyl hyperbranched polyester comprises a combination of one or more compounds selected from the group consisting of compounds represented by formula (I); ； In formula (I), R1, R4, and R7 are independently selected from H, OH, ; R2, R3, R5, R6, R8, R9 are independently selected from OH, ; in: (i) R a 、R b 、R c 、R d Independently selected from OH, ; (ii) R e 、R f Independently selected from OH, ; (iii) R g 、R h Independently selected from OH, ; Define R according to the rules (i) to (iii) i 、R j and subsequent further substituent groups.
6. The conductive polyester elastic fiber according to claim 1, characterized in that The terminal hydroxyl hyperbranched polyester comprises one or more combinations selected from the compounds represented by formula (I-1) to the compounds represented by formula (I-4); 、 。 7. The conductive polyester elastic fiber according to claim 1, characterized in that Based on 100 parts of the total amount of the raw materials of the conductive polyester elastic fiber, the first component accounts for 50-70 parts, and the second component accounts for 30-50 parts.
8. The conductive polyester elastic fiber according to claim 1, characterized in that The conductive carbon nanotube masterbatch is made of the third polyethylene terephthalate and the amino carbon nanotubes; and / or, in terms of mass percentage, the amino carbon nanotubes account for 13%-18% of the raw materials of the conductive carbon nanotube masterbatch.
9. The conductive polyester elastic fiber according to claim 1 or 8, characterized in that: The number average molecular weight of the third polyethylene terephthalate is 14000-15000 g / mol.
10. The conductive polyester elastic fiber according to claim 1 or 8, characterized in that: The diameter of the amino-modified carbon nanotubes is 10-30 nm, and the length is 10-50 μm.
11. The conductive polyester elastic fiber according to claim 1, characterized in that: Based on 100 parts of the total amount of the second component, the second polyethylene terephthalate accounts for 50-70 parts, the terminal hydroxyl hyperbranched polyester accounts for 10-20 parts, and the conductive carbon nanotube masterbatch accounts for 20-30 parts.
12. The conductive polyester elastic fiber according to claim 1, characterized in that: The conductive polyester elastic fiber has a fineness of 1-10 dtex and a volume resistivity of 10-1×10 4 Ω·cm, curl rate is 60%~85%, curl elastic recovery rate is 50%~80%, and breaking strength is greater than 3.0cN / dtex.
13. A method for preparing the conductive polyester elastic fiber according to any one of claims 1 to 12, characterized in that: The preparation method comprises: The first component and the second component are spun into conductive polyester elastic fibers using a melt spinning process; wherein, the melt extrusion temperature of the first component is 285~300°C, the melt extrusion temperature of the second component is 275~290°C, the temperature of the spinning assembly is 280~295°C, the cooling method is side blowing, the second component faces the blowing direction, the first component faces away from the blowing direction, the blowing temperature is 10~15°C, the hot stretching temperature is 140~150°C, and the hot stretching multiple is 4~7 times.
14. Use of the conductive polyester elastic fiber according to any one of claims 1 to 12 in the preparation of smart textiles or flexible electronic devices.