Core-shell wave-absorbing yarn based on conjugated microporous polymer as well as preparation method and application of core-shell wave-absorbing yarn
By preparing magnetic carbon materials through conjugated microporous polymers and combining them with the yarn core layer, a core-shell structured absorbing yarn is prepared, which solves the problems of light weight, high strength and broadband electromagnetic wave absorption, and achieves the effect of light, thin, wide and strong absorbing yarn.
Patent Information
- Application Number
- CN202510852345.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-24
- Publication Date
- 2025-09-19
AI Technical Summary
Existing absorbing yarns are insufficient in terms of lightness, high strength and mechanical properties, making it difficult to meet the needs of wearable devices.
Magnetic carbon material derived from conjugated microporous polymer is used as the absorbing filler and combined with the yarn core layer through conjugated electrospinning technology to prepare the core-shell structured absorbing yarn.
It achieves light weight, high strength and broadband electromagnetic wave absorption performance, expands the application scope of absorbing yarn, and is suitable for the demand for light, thin, wide and strong absorbing yarn.
Smart Images
Figure CN120666478A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of wave-absorbing materials, and in particular relates to a core-shell wave-absorbing yarn based on a conjugated microporous polymer, and a preparation method and application thereof. Background Art
[0002] With the development and widespread adoption of various electronic devices, electromagnetic pollution is becoming increasingly serious. To reduce the threat of electromagnetic waves to human health, the development of wearable, absorbing yarns is crucial. With growing demand, absorbing materials must be thin, lightweight, wide, and strong, while also evolving towards fiberization and wearability. Therefore, the development of new absorbing yarns that combine lightweight, high strength, and excellent mechanical properties is crucial for our daily lives. Summary of the Invention
[0003] The technical problem to be solved by the present invention is to provide a core-shell absorbing yarn based on a conjugated microporous polymer and a preparation method and application thereof.
[0004] The invention provides a core-shell wave-absorbing yarn. The shell layer of the core-shell wave-absorbing yarn contains nanofibers of magnetic wave-absorbing material, and the core layer is yarn.
[0005] Furthermore, the magnetic absorbing material is obtained by pyrolysis treatment of raw materials containing conjugated microporous polymers, iron salts, and cobalt salts; and the core layer is one or more of cotton yarns, polyester yarns, and polyimide yarns.
[0006] The present invention uses magnetic carbon materials derived from conjugated microporous polymers as absorbing fillers, polyacrylonitrile as the polymer matrix, and yarns made of materials such as cotton, polyester or polyimide as the yarn core, and prepares core-shell structured yarns with electromagnetic wave absorption properties through conjugated electrospinning technology.
[0007] The present invention provides a method for preparing a core-shell absorbing yarn, comprising:
[0008] (1) mixing a conjugated microporous polymer, an iron salt, a cobalt salt, and a solvent, centrifugally drying the mixture to obtain a precursor, and then pyrolyzing the mixture to obtain a magnetic carbon material;
[0009] (2) mixing a magnetic carbon material, a polymer, and a solvent to obtain a spinning solution;
[0010] (3) Using the spinning solution of step (2) as the shell layer, electrospinning is performed to obtain a core-shell absorbing yarn.
[0011] Preferably, the conjugated microporous polymer in step (1) is polytriphenylamine; the iron salt includes one or more of ferric chloride and ferric chloride hexahydrate; and the cobalt salt includes one or more of cobalt acetylacetonate and cobalt chloride.
[0012] The conjugated microporous polymer polytriphenylamine is prepared from raw materials containing tri(4-bromophenyl)amine and p-phenylenediamine through a metal catalytic coupling reaction.
[0013] Tri(4-bromophenyl)amine and p-phenylenediamine were used as monomers.
[0014] The preparation system of the conjugated microporous polymer also includes a catalyst, a ligand, and an organic base; the catalyst includes bis(dibenzylideneacetone)palladium (0); the ligand includes 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl; and the organic base includes sodium tert-butoxide.
[0015] The temperature of the metal coupling reaction is 105-115° C., the reaction time is 24-48 h, and the ambient atmosphere is nitrogen.
[0016] Preferably, the ratio of the conjugated microporous polymer, iron salt and cobalt salt in step (1) is (0.1-0.3) g: (0.1-1.0)
[0017] mmol:(0.1-1.0)mmol.
[0018] The solvent in step (1) includes methanol.
[0019] Preferably, the pyrolysis treatment process parameters in step (1) are: under protective gas conditions, the heating rate is 3-8°C·min -1 , temperature 700-900℃, pyrolysis time is 1-3h.
[0020] The protective gas is nitrogen atmosphere.
[0021] Preferably, in step (2), the polymer comprises polyacrylonitrile; the solvent comprises N,N-dimethylformamide;
[0022] Preferably, in step (2), the mass ratio of the magnetic carbon material to the polymer is (1:9) to (3:7);
[0023] Preferably, the concentration of the magnetic carbon material in the spinning solution in step (2) is 10 wt% to 30 wt%; and the concentration of the polyacrylonitrile is 12% to 18 wt%.
[0024] Preferably, in step (3), the spinning solution of step (2) is used as the shell layer and the yarn core is used as the receiving device to perform electrostatic spinning; wherein the yarn core comprises one or more of cotton yarn, polyester yarn, and polyimide yarn.
[0025] Preferably, the electrospinning process parameters in step (3) include: spinning voltage of ±8kV to ±15kV, spinning solution extrusion rate of 0.8mL / h to 1.5mL / h, and collection device rotation speed of 30rpm to 300rpm.
[0026] Furthermore, the yarn core is fixed on the receiving drum, the yarn core pulling speed is set to 0.3-0.6 mm / s, the collecting device speed is 0.6-1.0 r / min, the spinning voltage is ±8 kV-±15 kV, and the spinning solution extrusion rate is 0.8 mL / h-1.5 mL / h.
[0027] The present invention provides a fabric, which is obtained by knitting the core-shell absorbing yarn or the core-shell absorbing yarn prepared by any of the methods.
[0028] The yarn is woven into a 3.5mm thick fabric using a plain weave method. When the spinning solution concentration is 10wt%, the maximum absorption intensity in the X-band is -10.8dB, and the effective absorption bandwidth is 2.7GHz. When the spinning solution concentration is 20wt%, the maximum absorption intensity in the X-band is -11.8dB, and the effective absorption bandwidth is 2.6GHz. When the spinning solution concentration is 30wt%, the maximum absorption intensity in the X-band is -18.3dB, and the effective absorption bandwidth is 2.2GHz.
[0029] The present invention provides an application of the core-shell absorbing yarn or the fabric in the fields of electromagnetic protection and flexible wearables.
[0030] Beneficial effects
[0031] The core-shell absorbing yarn of the present invention has excellent mechanical properties and broadband strong absorption performance.
[0032] The core-shell structured absorbing yarn of the present invention can utilize yarns of various materials as its core. The yarn exhibits excellent mechanical properties, overcoming the poor mechanical properties of conventional absorbing fibers. The yarn's core-shell structure provides excellent mechanical properties in the core layer and strong broadband absorption in the shell layer, expanding the yarn's applicability and offering a new method for assembling "light, thin, wide, and strong" absorbing yarns. BRIEF DESCRIPTION OF THE DRAWINGS
[0033] Figure 1 This is a graph showing the absorbing performance of a core-shell absorbing yarn based on a conjugated microporous polymer provided in Example 1 of the present invention;
[0034] Figure 2 This is a graph showing the absorbing performance of a core-shell absorbing yarn based on a conjugated microporous polymer provided in Example 2 of the present invention;
[0035] Figure 3This is a graph showing the absorbing performance of a core-shell absorbing yarn based on a conjugated microporous polymer provided in Example 3 of the present invention;
[0036] Figure 4 This is a graph showing the mechanical properties of a core-shell absorbing yarn based on a conjugated microporous polymer provided in Example 3 of the present invention;
[0037] Figure 5 This is a microscopic morphology of a core-shell absorbing yarn based on a conjugated microporous polymer provided in Example 3 of the present invention. DETAILED DESCRIPTION
[0038] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.
[0039] Example 1
[0040] A core-shell absorbing yarn based on a conjugated microporous polymer is prepared by the following method:
[0041] Tri(4-bromophenyl)amine (1.0 mmol), p-phenylenediamine (1.5 mmol), bis(dibenzylideneacetone)palladium(0) (Pd(dba)2, 0.06 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos, 0.09 mmol), sodium tert-butoxide (4 mmol), and N,N-dimethylformamide (DMF, 75 mL) were weighed and placed in a 100 mL reaction tube. The reaction was stirred at 110°C under nitrogen for 24 hours. After cooling the reaction system to room temperature, the solid product was isolated by filtration, washed sequentially with methanol, chloroform, and deionized water, and dried under vacuum at 40°C for 12 hours to obtain polytriphenylamine powder.
[0042] Ferric chloride hexahydrate (0.5 mmol) and cobalt acetylacetonate (0.5 mmol) were weighed and dissolved in methanol (100 mL). After stirring to dissolve, polytriphenylamine (0.2 g) was added and stirred continuously until uniformly dispersed. The mixture was centrifuged, and the resulting solid was washed with deionized water and ethanol, followed by drying to obtain a precursor powder. This powder was placed in a quartz crucible and heated to 700°C at a rate of 5°C / min under a nitrogen atmosphere. The temperature was maintained for 2 hours for carbonization, and finally cooled naturally to room temperature to obtain a magnetic absorbing filler.
[0043] Magnetic absorbing filler (0.17 g) and polyacrylonitrile powder (1.5 g) were weighed and added to N,N-dimethylformamide (DMF, 8.5 mL). The mixture was magnetically stirred at 60°C for 6 hours to prepare a homogeneous spinning solution containing 10 wt% magnetic carbon material. A polyimide yarn was used as the yarn core, passed through the spinning nozzle, and fixed to a receiving roller. The yarn core pulling speed was set at 0.5 mm / s, the collection device speed was set at 0.8 rpm, the spinning voltage was set at ±12 kV, and the spinning solution extrusion rate was set at 1.2 mL / h to obtain a uniform core-shell absorbing yarn. The yarns were used as warp and weft threads, and every other yarn was interwoven up and down to form a fabric. The electromagnetic parameters of the fabric were measured using a vector network analyzer using the waveguide method. When the fabric thickness was 3.5 mm, the minimum reflection loss in the X-band was -10.8 dB, and the effective absorption bandwidth reached 2.7 GHz.
[0044] Example 2
[0045] A core-shell absorbing yarn based on a conjugated microporous polymer is prepared by the following method:
[0046] Tri(4-bromophenyl)amine (1.0 mmol), p-phenylenediamine (1.5 mmol), bis(dibenzylideneacetone)palladium(0) (Pd(dba)2, 0.06 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos, 0.09 mmol), sodium tert-butoxide (4 mmol), and N,N-dimethylformamide (DMF, 75 mL) were weighed and placed in a 100 mL reaction tube. The reaction was stirred at 110°C under nitrogen for 24 hours. After cooling the reaction system to room temperature, the solid product was isolated by filtration, washed sequentially with methanol, chloroform, and deionized water, and dried under vacuum at 40°C for 12 hours to obtain polytriphenylamine powder.
[0047] Ferric chloride hexahydrate (0.5 mmol) and cobalt acetylacetonate (0.5 mmol) were weighed and dissolved in methanol (100 mL). After stirring to dissolve, polytriphenylamine (0.2 g) was added and stirred continuously until uniformly dispersed. The mixture was centrifuged, and the resulting solid was washed with deionized water and ethanol, followed by drying to obtain a precursor powder. This powder was placed in a quartz crucible and heated to 700°C at a rate of 5°C / min under a nitrogen atmosphere. The temperature was maintained for 2 hours for carbonization, and finally cooled naturally to room temperature to obtain a magnetic absorbing filler.
[0048] Magnetic absorbent filler (0.38 g) and polyacrylonitrile powder (1.5 g) were weighed and added to N,N-dimethylformamide (DMF, 8.5 mL). The mixture was magnetically stirred at 60°C for 6 hours to prepare a homogeneous spinning solution containing 20 wt% magnetic carbon material. A polyimide yarn was used as the yarn core, passed through the spinning nozzle, and fixed to a receiving roller. The yarn core pulling speed was set at 0.5 mm / s, the collection device speed was set at 0.8 rpm, the spinning voltage was set at ±12 kV, and the spinning solution extrusion rate was set at 1.2 mL / h to obtain a uniform core-shell absorbent yarn. The mechanical properties of the yarn were tested using a tensile testing machine according to GB / T 3916-2013. Test conditions: a clamping distance of 500 mm and a tensile speed of 500 mm / min. Twenty valid samples were tested in each group, and abnormal data were eliminated. The core-shell absorbing yarn has a tensile strength of 323.4 MPa (calculated from the breaking strength and yarn cross-sectional area using the formula: σ = F / A, where A is the yarn cross-sectional area). The yarns are used as warp and weft threads, with alternate yarns interwoven vertically to form a fabric. The electromagnetic parameters of the fabric were measured using a vector network analyzer (VNA) using the waveguide method. When the fabric was 3.5 mm thick, the minimum reflection loss in the X-band was -11.8 dB, and the effective absorption bandwidth reached 2.6 GHz.
[0049] Example 3
[0050] A core-shell absorbing yarn based on a conjugated microporous polymer is prepared by the following method:
[0051] Tri(4-bromophenyl)amine (1.0 mmol), p-phenylenediamine (1.5 mmol), bis(dibenzylideneacetone)palladium(0) (Pd(dba)2, 0.06 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos, 0.09 mmol), sodium tert-butoxide (4 mmol), and N,N-dimethylformamide (DMF, 75 mL) were weighed and placed in a 100 mL reaction tube. The reaction was stirred at 110°C under nitrogen for 24 hours. After cooling the reaction system to room temperature, the solid product was isolated by filtration, washed sequentially with methanol, chloroform, and deionized water, and dried under vacuum at 40°C for 12 hours to obtain polytriphenylamine powder.
[0052] Ferric chloride hexahydrate (0.5 mmol) and cobalt acetylacetonate (0.5 mmol) were weighed and dissolved in methanol (100 mL). After stirring to dissolve, polytriphenylamine (0.2 g) was added and stirred continuously until uniformly dispersed. The mixture was centrifuged, and the resulting solid was washed with deionized water and ethanol, followed by drying to obtain a precursor powder. This powder was placed in a quartz crucible and heated to 700°C at a rate of 5°C / min under a nitrogen atmosphere. The temperature was maintained for 2 hours for carbonization, and finally cooled naturally to room temperature to obtain a magnetic absorbing filler.
[0053] Magnetic absorbing filler (0.64 g) and polyacrylonitrile powder (1.5 g) were weighed and added to N,N-dimethylformamide (DMF, 8.5 mL). The mixture was magnetically stirred at 60°C for 6 hours to prepare a homogeneous spinning solution containing 30 wt% magnetic carbon material. A polyimide yarn was used as the yarn core, passed through the spinning nozzle, and fixed to a receiving roller. The yarn core pulling speed was set at 0.5 mm / s, the collection device speed was set at 0.8 rpm, the spinning voltage was set at ±12 kV, and the spinning solution extrusion rate was set at 1.2 mL / h, resulting in a uniform core-shell absorbing yarn. The yarns were used as warp and weft threads, interweaving every other yarn up and down to form a fabric. The electromagnetic parameters of the fabric were measured using a vector network analyzer using the waveguide method. When the fabric thickness was 3.5 mm, the minimum reflection loss in the X-band was -18.3 dB, and the effective absorption bandwidth reached 2.2 GHz.
Claims
1. A core-shell absorbing yarn, characterized in that: The shell layer of the core-shell absorbing yarn contains nanofibers of magnetic absorbing material, and the core layer is yarn.
2. A method for preparing a core-shell absorbing yarn, comprising: (1) mixing a conjugated microporous polymer, an iron salt, a cobalt salt, and a solvent, centrifugally drying the mixture to obtain a precursor, and then pyrolyzing the mixture to obtain a magnetic carbon material; (2) mixing a magnetic carbon material, a polymer, and a solvent to obtain a spinning solution; (3) Using the spinning solution of step (2) as the shell layer, electrospinning is performed to obtain a core-shell absorbing yarn.
3. The preparation method according to claim 2, characterized in that: In the step (1), the conjugated microporous polymer is polytriphenylamine; the iron salt includes one or more of ferric chloride and ferric chloride hexahydrate; and the cobalt salt includes one or more of cobalt acetylacetonate and cobalt chloride.
4. The preparation method according to claim 2, characterized in that In the step (1), the ratio of the conjugated microporous polymer, the iron salt and the cobalt salt is (0.1-0.3) g: (0.1-1.0) mmol: (0.1-1.0) mmol.
5. The preparation method according to claim 2, characterized in that: The pyrolysis treatment process parameters in step (1) are as follows: under protective gas conditions, the heating rate is 3-8°C·min -1 , temperature 700-900℃, pyrolysis time is 1-3h.
6. The preparation method according to claim 2, characterized in that: In the step (2), the polymer includes polyacrylonitrile; the solvent includes N,N-dimethylformamide; In the step (2), the mass ratio of the magnetic carbon material to the polymer is (1:9) to (3:7); The concentration of the magnetic carbon material in the spinning solution in step (2) is 10 wt% to 30 wt%.
7. The preparation method according to claim 2, characterized in that: In step (3), the spinning solution of step (2) is used as the shell layer and the yarn core is used as the receiving device to perform electrospinning; The yarn core includes one or more of cotton yarn, polyester yarn, and polyimide yarn.
8. The preparation method according to claim 2, characterized in that: The electrospinning process parameters in step (3) include: spinning voltage of ±8kV to ±15kV, spinning solution extrusion rate of 0.8mL / h to 1.5mL / h, and collection device rotation speed of 30rpm to 300rpm.
9. A fabric, characterized in that: The fabric is woven from the core-shell absorbing yarn according to claim 1 or the core-shell absorbing yarn prepared by any one of the methods according to claims 2-8.
10. Use of the core-shell absorbing yarn according to claim 1 or the fabric according to claim 9 in the fields of electromagnetic protection and flexible wearables.