Hydrophobic conductive yarn and preparation method thereof

Abstract

The invention discloses a hydrophobic conductive yarn and a preparation method thereof, and belongs to the technical field of textile materials, and the preparation method comprises the following steps: S1, dipping a polyester yarn in a first mixed aqueous solution, taking out, drying, transferring into an ethanol suspension containing modified conductive carbon black, carrying out ultrasonic-assisted dipping, taking out, and drying to obtain a first conductive yarn; s2, soaking the first conductive yarn in a second mixed aqueous solution, dropwise adding a ferric chloride solution, soaking for 5 hours, taking out, washing with water, and drying in vacuum to obtain a second conductive yarn; s3, soaking the second conductive yarn in the titanium carbide thin layer dispersion liquid, taking out the second conductive yarn, performing vacuum drying, soaking the second conductive yarn in a 1H, 1H, 2H, 2H-perfluorodecyl trichlorosilane ethanol solution, dropwise adding ammonia water, performing reaction at 60 DEG C for 2-4 hours, taking out the second conductive yarn, and drying the second conductive yarn to obtain hydrophobic conductive yarn; through material compounding and hierarchical structure design, collaborative optimization of conductivity, hydrophobicity and stability is realized.

Description

Technical Field

[0001] The invention belongs to the technical field of textile materials, and particularly relates to a hydrophobic conductive yarn and a preparation method thereof. Background Art

[0002] With the rapid development of smart wearable devices, flexible electronics and health monitoring technologies, conductive yarns, as core materials, need to meet the requirements of high conductivity, environmental tolerance (such as waterproof / sweat) and mechanical stability. Traditional conductive yarns mainly achieve conductive functions through chemically plated metal materials, in-situ polymerized conductive polymer materials or composite carbon-based materials, but there are still many problems: 1) Poor structural stability of the conductive layer: The conductive layer (silver plating, carbon black, graphene, etc.) has weak bonding strength with the substrate interface and is easily detached due to friction or bending; 2) Poor water resistance: The conductive layer is prone to failure after being wet or washed multiple times, making it difficult to meet the needs of wearable scenarios; 3) The contradiction between conductivity and hydrophobicity: Conventional hydrophobic coatings are mostly insulating materials, which significantly reduce the conductivity after being covered with a conductive layer;

[0003] While existing research has explored improving conductivity through electroless plating, in-situ polymerization, or nanomaterial composites, the coordinated design of hydrophobicity and conductivity has largely been overlooked. Therefore, there is an urgent need to develop a conductive yarn that combines excellent conductivity and hydrophobicity with stable properties, ensuring the integrity of the conductive pathway while imparting durable hydrophobicity. Summary of the Invention

[0004] The object of the present invention is to provide a hydrophobic conductive yarn and a preparation method thereof, so as to solve the problems in the background technology.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing a hydrophobic conductive yarn comprises the following steps:

[0007] Step S1, immersing the polyester yarn in a first mixed aqueous solution containing dopamine and tris(hydroxymethyl)aminomethane for 4 hours, taking it out and drying it in an oven at 60°C, then transferring it to an ethanol suspension containing modified conductive carbon black, ultrasonically immersing it for 10-20 minutes, taking it out and drying it to obtain a first conductive yarn;

[0008] Step S2: immersing the first conductive yarn in a second mixed aqueous solution containing pyrrole monomer and p-toluenesulfonic acid, then adding ferric chloride solution dropwise, immersing for 5 hours, and then taking it out to uniformly polymerize the pyrrole monomer doped with p-toluenesulfonic acid on the surface of the first conductive yarn. The yarn is repeatedly washed with a large amount of deionized water and vacuum dried at 70° C. for 12 hours to obtain a second conductive yarn.

[0009] Step S3: Place the second conductive yarn on the titanium carbide thin layer (Ti3C2T xThe obtained result was as follows: the hydrophobic conductive yarn was immersed in a MXene dispersion for 10-20 min, vacuum-dried at 60 ° C, and then immersed in a 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution. Ammonia water was added dropwise and the mixture was reacted at 60 ° C for 2-4 h. The hydrophobic conductive yarn was then taken out and dried at 70 ° C for 6 h to obtain the hydrophobic conductive yarn.

[0010] The present invention first uses polydopamine as a strong adhesion interface layer, achieves tight anchoring of modified conductive carbon black through covalent bonds and hydrogen bonds, and uniformly and firmly self-assembles the modified conductive carbon black containing nano-nickel balls on the surface of the polyester yarn to obtain a first conductive yarn; then, the first conductive yarn loaded with the modified conductive carbon black is used as a base layer, and pyrrole monomer is doped with p-toluenesulfonic acid and in-situ polymerized into polypyrrole under the action of an oxidant to fill the gaps between the modified conductive carbon black particles to obtain a second conductive yarn; then, a titanium carbide thin layer is introduced onto the surface of the second conductive yarn for coverage, and finally, a perfluorosilane hydrophobic layer is directionally grafted onto the surface of the titanium carbide thin layer to obtain a hydrophobic conductive yarn.

[0011] Furthermore, the dosage ratio of the polyester yarn, the first mixed aqueous solution and the ethanol suspension is 6 g:300 mL:300 mL; wherein the concentration of dopamine in the first mixed aqueous solution is 2-4 g / L; the concentration of tris(hydroxymethyl)aminomethane in the first mixed aqueous solution is 1-2 g / L; and the concentration of modified conductive carbon black in the ethanol suspension is 1.5-3 g / L.

[0012] Furthermore, the modified conductive carbon black is prepared by the following steps:

[0013] Conductive carbon black, nickel nitrate and urea are added to deionized water and stirred to mix, and then a hydrothermal reaction is carried out in a hydrothermal reactor. After being taken out, the mixture is dried in a 60°C oven for 12 hours, and then transferred to a tube furnace. A mixed gas is first introduced to exclude air, and then the temperature is increased to 650-850°C at a heating rate of 5°C / min. After maintaining a constant temperature for 2 hours, the mixture is cooled to room temperature to obtain modified conductive carbon black. The present invention uses conductive carbon black as a framework, first uses a hydrothermal method to load nickel ions on the surface of the conductive carbon black, and then performs high-temperature reduction under a protective atmosphere to achieve uniform loading of nano-nickel balls on the surface of the conductive carbon black. Since the conductivity of metallic nickel is better than that of conductive carbon black, the conductivity of the modified conductive carbon black is significantly improved; at the same time, the modified conductive carbon black can also improve the dispersibility of the nano-nickel balls compared to nano-nickel powder, and can prevent nano-nickel agglomeration and inhibit nickel oxidation; in addition, the conductive carbon black buffers external forces through a porous structure, reducing the physical damage to the modified conductive carbon black caused by water washing.

[0014] Furthermore, the usage ratio of the conductive carbon black, nickel nitrate, urea and deionized water is 3g:7.25-9g:12-15g:1L.

[0015] Furthermore, the temperature of the hydrothermal reaction is 100-120° C., and the reaction time is 3 hours.

[0016] Furthermore, the mixed gas is composed of hydrogen and nitrogen in a volume ratio of 1:19.

[0017] Furthermore, the usage ratio of the first conductive yarn, the second mixed aqueous solution and the ferric chloride solution is 6g:300mL:300mL; wherein the concentration of the pyrrole monomer in the second mixed aqueous solution is 6-7mL / L; the concentration of p-toluenesulfonic acid in the second mixed aqueous solution is 15-18g / L; and the concentration of the ferric chloride solution is 3-4mol / L.

[0018] Furthermore, the dosage ratio of the second conductive yarn, titanium carbide thin layer dispersion, 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution and ammonia water is 6g:300mL:300mL:4-5mL; wherein the concentration of the titanium carbide thin layer dispersion is 5-6mg / mL, and the solvent is water; the volume concentration of the 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution is 0.8-1%.

[0019] A hydrophobic conductive yarn is prepared by the above preparation method.

[0020] Beneficial effects:

[0021] The present invention provides a hydrophobic conductive yarn, which innovatively achieves the coordinated optimization of conductivity, hydrophobicity and stability through material composite and hierarchical structure design. The present invention constructs a multiple conductive network: nano-nickel balls loaded on the surface of conductive carbon black, pyrrole monomers are in situ polymerized to fill the gaps in the modified conductive carbon black to form a continuous conductive film, and the introduction of a titanium carbide thin layer further reduces the contact resistance. The synergistic effect of the three significantly reduces the overall unit resistance of the conductive yarn; at the same time, by directionally grafting a perfluorosilane hydrophobic layer on the surface of the titanium carbide thin layer, a low surface energy super-hydrophobic interface is formed while maintaining the intrinsic conductivity of the titanium carbide thin layer, breaking through the problem of traditional insulating hydrophobic coatings blocking the conductive path; the titanium carbide thin layer combined with the hydrophobic layer can not only play a good barrier role in the penetration of water molecules, but also improve the wear resistance and durability of the conductive yarn, so that the resistance increase and contact angle attenuation of the conductive yarn are maintained at about 5% after 50 standard water washes, solving the industry pain points of easy shedding and poor stability of the conductive layer;

[0022] The preparation method of the present invention is simple and easy, and can achieve precise construction of each functional layer under mild conditions; the environmentally friendly solvent system is compatible with existing textile production lines, and the low usage of titanium carbide thin layer and perfluorosilane makes the overall cost low. The conductive yarn produced shows outstanding advantages in the field of smart wearables and is suitable for scenarios such as electrocardiogram monitoring clothing and marine intelligent equipment, providing a high-performance material foundation for the deep integration of flexible electronic devices and textiles. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0024] Example 1

[0025] This embodiment provides a modified conductive carbon black, which is prepared by the following steps:

[0026] 3g of conductive carbon black, 7.25g of nickel nitrate and 12g of urea were added to 1L of deionized water and stirred, then transferred to a hydrothermal reactor and subjected to hydrothermal reaction at 100°C for 3h. After being taken out, they were dried in an oven at 60°C for 12h, then transferred to a tubular furnace, and a mixture of hydrogen and nitrogen in a volume ratio of 1:19 was first introduced to exclude the air, and then the temperature was increased to 650°C at a heating rate of 5°C / min, maintained at a constant temperature for 2h, and then cooled to room temperature to obtain modified conductive carbon black.

[0027] Example 2

[0028] This embodiment provides a modified conductive carbon black, which is prepared by the following steps:

[0029] 3 g of conductive carbon black, 8.2 g of nickel nitrate and 13.5 g of urea were added to 1 L of deionized water and stirred to mix. The mixture was then transferred to a hydrothermal reactor and subjected to a hydrothermal reaction at 110 ° C for 3 h. After being taken out, the mixture was dried in an oven at 60 ° C for 12 h. Then, the mixture was transferred to a tubular furnace. A mixture of hydrogen and nitrogen in a volume ratio of 1:19 was introduced to exclude the air. The temperature was then increased to 750 ° C at a heating rate of 5 ° C / min, and the temperature was maintained constant for 2 h before being cooled to room temperature to obtain modified conductive carbon black.

[0030] Example 3

[0031] This embodiment provides a modified conductive carbon black, which is prepared by the following steps:

[0032] 3g of conductive carbon black, 9g of nickel nitrate and 15g of urea were added to 1L of deionized water and stirred to mix. Then, the mixture was transferred to a hydrothermal reactor and subjected to a hydrothermal reaction at 120°C for 3h. After being taken out, the mixture was dried in an oven at 60°C for 12h. Then, the mixture was transferred to a tubular furnace. A mixture of hydrogen and nitrogen in a volume ratio of 1:19 was introduced to exclude the air. The temperature was then increased to 850°C at a heating rate of 5°C / min. The temperature was maintained constant for 2h and then cooled to room temperature to obtain modified conductive carbon black.

[0033] Example 4

[0034] A hydrophobic conductive yarn is prepared by the following steps:

[0035] Step S1: 6 g of polyester yarn was immersed in 300 mL of a first mixed aqueous solution containing 2 g / L dopamine and 1 g / L tris(hydroxymethyl)aminomethane for 4 h, removed and dried in a 60° C. oven, then transferred to 300 mL of an ethanol suspension containing 1.5 g / L of the modified conductive carbon black prepared in Example 1, ultrasonically immersed for 10 min, removed and dried to obtain a first conductive yarn;

[0036] Step S2: 6 g of the first conductive yarn was immersed in 300 mL of a second mixed aqueous solution containing 6 mL / L of pyrrole monomer and 15 g / L of p-toluenesulfonic acid, and then 300 mL of a 3 mol / L ferric chloride solution was added dropwise. After immersion for 5 hours, the yarn was removed, repeatedly rinsed with a large amount of deionized water, and vacuum dried at 70°C for 12 hours to produce a second conductive yarn.

[0037] Step S3, soak 6 g of the second conductive yarn in 300 mL of a 5 mg / mL titanium carbide thin layer dispersion for 10 minutes, take it out and vacuum dry it at 60°C, then immerse it in 300 mL of a 0.8% volume concentration of 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution, add 4 mL of ammonia water, react at 60°C for 2 hours, take it out and dry it at 70°C for 6 hours to obtain a hydrophobic conductive yarn.

[0038] Example 5

[0039] Step S1: 6 g of polyester yarn was immersed in 300 mL of a first mixed aqueous solution containing 3 g / L dopamine and 1.5 g / L tris(hydroxymethyl)aminomethane for 4 h, removed and dried in a 60° C. oven, then transferred to 300 mL of an ethanol suspension containing 2.2 g / L of the modified conductive carbon black prepared in Example 2, and ultrasonically immersed for 15 min. The yarn was removed and dried to obtain a first conductive yarn;

[0040] Step S2: 6 g of the first conductive yarn was immersed in 300 mL of a second mixed aqueous solution containing 6.5 mL / L of pyrrole monomer and 16.5 g / L of p-toluenesulfonic acid, and then 300 mL of a 3.5 mol / L ferric chloride solution was added dropwise. After immersion for 5 hours, the yarn was removed, repeatedly rinsed with a large amount of deionized water, and vacuum dried at 70°C for 12 hours to produce a second conductive yarn.

[0041] Step S3, soak 6 g of the second conductive yarn in 300 mL of a 5.5 mg / mL titanium carbide thin layer dispersion for 15 minutes, take it out and vacuum dry it at 60°C, then immerse it in 300 mL of a 0.9% volume concentration of 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution, add 4.5 mL of ammonia water, react at 60°C for 3 hours, take it out and dry it at 70°C for 6 hours to obtain a hydrophobic conductive yarn.

[0042] Example 6

[0043] Step S1: 6 g of polyester yarn was immersed in 300 mL of a first mixed aqueous solution containing 4 g / L dopamine and 2 g / L tris(hydroxymethyl)aminomethane for 4 h, removed and dried in a 60° C. oven, then transferred to 300 mL of an ethanol suspension containing 3 g / L of the modified conductive carbon black prepared in Example 1, and ultrasonically immersed for 20 min. The yarn was removed and dried to obtain a first conductive yarn;

[0044] Step S2: 6 g of the first conductive yarn was immersed in 300 mL of a second mixed aqueous solution containing 7 mL / L of pyrrole monomer and 18 g / L of p-toluenesulfonic acid, and then 300 mL of a 4 mol / L ferric chloride solution was added dropwise. After immersion for 5 hours, the yarn was removed and the pyrrole monomer doped with p-toluenesulfonic acid was uniformly polymerized on the surface of the first conductive yarn. The yarn was repeatedly washed with a large amount of deionized water and vacuum dried at 70°C for 12 hours to obtain a second conductive yarn.

[0045] Step S3, soak 6 g of the second conductive yarn in 300 mL of a 6 mg / mL titanium carbide thin layer dispersion for 20 minutes, take it out and vacuum dry it at 60°C, then immerse it in 300 mL of a 1% volume concentration of 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution, add 5 mL of ammonia water, react at 60°C for 4 hours, take it out and dry it at 70°C for 6 hours to obtain a hydrophobic conductive yarn.

[0046] Comparative Example 1

[0047] Compared with Example 6, this comparative example is different in that in step S1, the process of immersing the polyester yarn in the first mixed aqueous solution is omitted, and the polyester yarn is directly immersed in the ethanol suspension. The remaining steps are the same.

[0048] Comparative Example 2

[0049] Compared with Example 6, this comparative example differs in that in step S1, an equal amount of the modified conductive carbon black prepared in Example 1 is replaced by conductive carbon black that has not been modified, and the remaining steps are the same.

[0050] Comparative Example 3

[0051] Compared with Example 6, this comparative example differs in that in step S1, an equal amount of the modified conductive carbon black prepared in Example 1 is replaced by nano-nickel balls, and the remaining steps are the same.

[0052] Comparative Example 4

[0053] Compared with Example 6, this comparative example is different in that step S2 is not performed, and the first conductive yarn is directly subjected to step S3, and the remaining steps are the same.

[0054] Comparative Example 5

[0055] Compared with Example 6, this comparative example is different in that in step S3, the operation of immersing the second conductive yarn in the titanium carbide thin layer dispersion is omitted, and the remaining steps are the same.

[0056] The conductive yarns prepared in Examples 4 to 6 and Comparative Examples 1 to 5 were subjected to performance tests. The unit resistance of the conductive yarns was measured according to the DB41 / T 1790-2019 standard. The contact angle of the conductive yarns was measured using a contact angle meter. The conductive yarns were washed 50 times according to the AATCC 61-2013 standard, and the unit resistance and contact angle of the conductive yarns were measured again. The results are shown in Table 1.

[0057] Table 1

[0058]

[0059] As shown in Table 1, the conductive yarns produced in Examples 4-6 of the present invention exhibit excellent conductivity and hydrophobicity. After 50 standard washes, both the resistance increase and contact angle decay remained around 5%, demonstrating the stability of the multilayer structure. Through material synergy and structural optimization, the contradiction between conductivity, hydrophobicity, and durability was effectively resolved, providing a reliable material foundation for smart textiles. The data from Comparative Example 1 show that the polydopamine layer significantly impacts the conductivity and stability of the conductive yarn. The conductivity of Comparative Examples 2 and 3 decreased somewhat, demonstrating that modified conductive carbon black can comprehensively improve the conductivity and stability of the conductive yarn. The higher initial unit resistance of Comparative Example 4 demonstrates the necessity of polypyrrole to fill the gaps in the modified conductive carbon black for a continuous conductive path. Furthermore, the lack of the adhesive effect of polypyrrole weakens the adhesion of the titanium carbide layer, leading to a more significant decrease in contact angle after washing. Comparative Example 5 lacks the conductive contribution of the titanium carbide layer, resulting in decreased conductivity. Furthermore, the perfluorosilane may not be able to effectively adhere, resulting in poor hydrophobicity and a lower contact angle. Furthermore, the lack of the barrier effect of the titanium carbide layer reduces water repellency.

[0060] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0061] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a hydrophobic conductive yarn, characterized in that: The following steps are involved: Step S1, immersing the polyester yarn in a first mixed aqueous solution containing dopamine and tris(hydroxymethyl)aminomethane for 4 hours, removing the yarn and drying it, then transferring the yarn to an ethanol suspension containing modified conductive carbon black, ultrasonically immersing the yarn for 10-20 minutes, removing the yarn and drying it to obtain a first conductive yarn; Step S2, immersing the first conductive yarn in a second mixed aqueous solution containing pyrrole monomer and p-toluenesulfonic acid, then adding ferric chloride solution dropwise, immersing for 5 hours, taking out, washing, and vacuum drying to obtain a second conductive yarn; Step S3, soaking the second conductive yarn in the titanium carbide thin layer dispersion for 10-20 minutes, taking it out and vacuum drying it, then immersing it in 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution, adding ammonia water dropwise and reacting it at 60°C for 2-4 hours, taking it out and drying it to obtain a hydrophobic conductive yarn.

2. The method for preparing a hydrophobic conductive yarn according to claim 1, wherein: The dosage ratio of the polyester yarn, the first mixed aqueous solution and the ethanol suspension is 6g:300mL:300mL; wherein the concentration of dopamine in the first mixed aqueous solution is 2-4g / L; the concentration of tris(hydroxymethyl)aminomethane in the first mixed aqueous solution is 1-2g / L; and the concentration of modified conductive carbon black in the ethanol suspension is 1.5-3g / L.

3. The method for preparing a hydrophobic conductive yarn according to claim 1, wherein: The modified conductive carbon black is prepared by the following steps: Conductive carbon black, nickel nitrate and urea are added to deionized water and stirred and mixed, and then a hydrothermal reaction is carried out in a hydrothermal reactor. After being taken out and dried, the mixture is transferred to a tubular furnace, and a mixed gas is first introduced to exclude air, and then the temperature is increased to 650-850°C at a heating rate of 5°C / min, and the temperature is maintained constant for 2 hours and then cooled to room temperature to obtain modified conductive carbon black.

4. The method for preparing a hydrophobic conductive yarn according to claim 3, wherein: The amount ratio of the conductive carbon black, nickel nitrate, urea and deionized water is 3g: 7.25-9g:12-15g:1L.

5. The method for preparing a hydrophobic conductive yarn according to claim 3, wherein: The temperature of the hydrothermal reaction is 100-120° C., and the reaction time is 3 hours.

6. The method for preparing a hydrophobic conductive yarn according to claim 3, wherein: The mixed gas is composed of hydrogen and nitrogen in a volume ratio of 1:

19.

7. The method for preparing a hydrophobic conductive yarn according to claim 1, wherein: The usage ratio of the first conductive yarn, the second mixed aqueous solution and the ferric chloride solution is 6g:300mL:300mL; wherein the concentration of the pyrrole monomer in the second mixed aqueous solution is 6-7mL / L; the concentration of p-toluenesulfonic acid in the second mixed aqueous solution is 15-18g / L; and the concentration of the ferric chloride solution is 3-4mol / L.

8. The method for preparing a hydrophobic conductive yarn according to claim 1, wherein: The dosage ratio of the second conductive yarn, titanium carbide thin layer dispersion, 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution and ammonia water is 6g:300mL:300mL:4-5mL; wherein the concentration of the titanium carbide thin layer dispersion is 5-6mg / mL, and the solvent is water; the volume concentration of the 1H,1H,2H,2H-perfluorodecyltrichlorosilane ethanol solution is 0.8-1%.

9. A hydrophobic conductive yarn, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 8.

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