A core-shell structure wear-resistant super-hydrophobic yarn and a preparation device and method thereof

Abstract

The application provides a kind of core-shell structure wear-resistant super-hydrophobic yarn and its preparation device and preparation method, and the super-hydrophobic functionalization treatment of yarn is completed in single bath at room temperature. The core-shell structure wear-resistant super-hydrophobic yarn includes fiber substrate A and super-hydrophobic shell B covalently bonded to the surface of fiber substrate, and the super-hydrophobic shell B is a core-shell structure. The preparation device of the core-shell structure wear-resistant super-hydrophobic yarn includes a pay-off end, a super-hydrophobic treatment liquid immersion tank, a humid air reaction chamber and a drying chamber. The application realizes continuous production, and the yarn passes through the treatment line at a stable speed, and the coating deposition and curing can be completed within a few seconds. The fiber-level core-shell super-hydrophobic coating forms a covalent interface between the fiber and the coating with high bonding force, significantly improving the durability and mechanical stability of the hydrophobic coating. Since the shell thickness is only on the order of nanometers and is distributed on the surface of the single fiber without blocking the fabric pores, the air permeability and softness of the treated fabric are basically not affected.

Description

Technical Field

[0001] This invention relates to the field of textile technology, specifically to a core-shell structure wear-resistant superhydrophobic yarn and its preparation apparatus and method. Background Technology

[0002] Superhydrophobic textiles have significant application needs in outdoor protection and other fields due to their waterproof and self-cleaning properties. However, achieving long-term durable superhydrophobicity under mechanical stress has remained a challenge for the industry. Traditional techniques often employ nanoparticle coatings or fluorinated chemical finishing to achieve hydrophobicity, but these methods suffer from weak adhesion and easy wear and tear. Nanoparticle coatings can clog the pores between fibers, increasing fabric weight and reducing breathability and hand feel. Furthermore, commonly used perfluorinated compounds (PFAS) hydrophobic finishing are subject to strict regulation due to their environmental persistence and potential toxicity.

[0003] Meanwhile, existing hydrophobic finishing processes for fabrics are often cumbersome and difficult to complete efficiently and continuously. Traditional processes typically involve applying water-repellent finishing to the finished fabric, requiring multiple steps of padding, drying, and curing. Several patents and documents have proposed various alternatives, such as the nano-alumina method (Chinese patent CN102277720A), the fiber surface hydrophobic coating treatment method (CN202510065076.0), and the layer-by-layer self-assembly method (CN202411259829.3). However, due to the limited interaction between the hydrophobic material and the fiber matrix, the superhydrophobic fabrics prepared by these methods exhibit poor durability, limiting their practical application. Some studies have also used high-energy radiation to graft hydrophobic polymers onto fabrics to improve abrasion and wash resistance (e.g., CN202310252382.6), but such processes require demanding equipment, are costly, and pose safety hazards. These multi-step methods are not only time-consuming and energy-intensive, but also increase process complexity and cost due to the need for high-temperature drying or special equipment (such as plasma treatment or radiation devices).

[0004] The existing process has the following problems: First, the multi-step processing leads to low production efficiency and makes it difficult to adapt to continuous industrial production; second, it requires high-temperature drying or high-energy equipment (such as...). γ Processes involving radiation and plasma have high energy consumption, may damage fiber properties, and pose safety hazards. Furthermore, post-processing coatings are prone to peeling off due to friction and other stresses when the fibers are woven into fabric, affecting durability. Therefore, the technical problem of this invention is to achieve continuous room-temperature superhydrophobic modification of yarns without the need for high temperatures or complex equipment, thereby obtaining robust and durable hydrophobic properties suitable for large-scale production.

[0005] Furthermore, techniques for functional finishing of yarns or single fibers before textile formation are even rarer. Most superhydrophobic finishing is done on the fabric width, which may cause the coating to be damaged during subsequent weaving.

[0006] Therefore, there is a lack of a method to perform hydrophobic modification on the yarn in a continuous one-bath manner and impart a durable and robust superhydrophobic coating to the fiber without the need for harmful reagents and complex processes. Summary of the Invention

[0007] This invention addresses the shortcomings of existing fabric hydrophobic treatment methods, such as poor durability, environmental hazards, and the tendency for superhydrophobic coatings to detach and fail under repeated friction, bending, and other mechanical stresses, failing to maintain long-term waterproof performance. Furthermore, these processes rely on fluorinated chemicals or large amounts of organic solvents, which do not meet current environmental and sustainable development requirements. Especially in lightweight, breathable textiles, traditional coatings can compromise the fabric's softness and breathability. This invention provides a core-shell structured abrasion-resistant superhydrophobic yarn, its preparation apparatus, and preparation method. This new technology enables a firmly bonded superhydrophobic coating at the fiber level, overcoming the deficiencies of existing technologies in terms of abrasion resistance, breathability, and environmental friendliness.

[0008] This invention provides a core-shell structured wear-resistant superhydrophobic yarn, comprising a fiber matrix and a superhydrophobic shell layer covalently bonded to the surface of the fiber matrix; The fiber matrix is ​​a yarn matrix; The superhydrophobic shell is a SiO2-hydrosilane core-shell coating covalently bonded to the surface of the fiber matrix, including a silica network formed by silane hydrolysis and condensation and an organic hydrophobic outer layer bonded to the outer surface of the silica network; the silica network is covalently connected to the hydroxyl groups on the surface of the fiber matrix through silicon-oxygen bonds, and the organic hydrophobic outer layer is a long-chain hydrocarbon group. Fabrics made from core-shell structure wear-resistant superhydrophobic yarns are superhydrophobic fabrics, and the contact angle of superhydrophobic fabrics is greater than or equal to 150°.

[0009] The core-shell structure wear-resistant superhydrophobic yarn of the present invention, as a preferred embodiment, has a fiber matrix that is a natural yarn, a chemically synthesized yarn, or a blended yarn, and may also be a staple fiber or a filament yarn, with the twist direction being either forward or reverse. The superhydrophobic shell has a core-shell structure. Multifunctional small-molecule silanes are covalently linked to hydroxyl groups on the surface of the fiber matrix (A), and then hydrolyze in humid water vapor to obtain a silica network. The organic hydrophobic outer layer consists of C6–C... 18 Hydrocarbon-based organosilanes condense with a silica network to form and cover the outer surface of the silica network; The superhydrophobic shell contains no fluorine and has a thickness of less than 1000 nm; The silica network is formed by multifunctional small-molecule silanes that hydrolyze in humid water vapor, and the organic hydrophobic outer layer is composed of C6–C6 groups.18 It is formed by the hydrolytic condensation of a hydrocarbon-based organosilane with a silica network.

[0010] This invention provides a device for preparing a core-shell structure wear-resistant superhydrophobic yarn, comprising a pay-off end, a superhydrophobic treatment liquid impregnation tank, a humid air reaction chamber, a drying chamber, and a take-up end arranged sequentially, wherein the humid air reaction chamber is connected between the superhydrophobic treatment liquid impregnation tank and the drying chamber. The superhydrophobic treatment solution impregnation tank includes an impregnation tank body, a yarn inlet connected to one end of the impregnation tank body, a yarn outlet connected to the other end of the impregnation tank body, a yarn immersion roller connected to the lower side of the impregnation tank body, a yarn introducer connected to the yarn inlet, and a yarn exporter connected to the yarn outlet. The impregnation tank body contains superhydrophobic treatment solution and immerses the yarn immersion roller for one-bath impregnation treatment of the fiber matrix. The yarn introducer introduces the fiber matrix into the impregnation tank body, and the yarn exporter exports the impregnated fiber matrix out of the impregnation tank body. The humid air reaction chamber includes a chamber body and a humid water vapor inlet connected to the upper end of the chamber body. The humid air reaction chamber provides humid water vapor to carry out silane hydrolysis and condensation. The fiber matrix undergoes organic solvent evaporation and discharge of excess superhydrophobic treatment liquid and water vapor in the drying chamber in order to solidify the superhydrophobic shell. Before hydrophobic treatment, the fiber matrix is ​​wound on the pay-off end. Under the traction of the take-up end, it passes through the yarn inlet and yarn immersion roller in sequence and comes into contact with the superhydrophobic treatment liquid. Then, it passes through the yarn outlet, the chamber body, and the drying chamber in sequence to obtain a superhydrophobic shell layer covalently bonded to the surface of the fiber matrix, forming a core-shell structure abrasion-resistant superhydrophobic yarn, which is collected at the take-up end. The preparation device for the shell structure abrasion-resistant superhydrophobic yarn is a room temperature continuous operation device.

[0011] In a preferred embodiment of the apparatus for preparing a core-shell structure wear-resistant superhydrophobic yarn according to the present invention, the opening of the impregnation tank body includes only a yarn inlet and a yarn outlet, and the yarn immersion roller is cylindrical. The superhydrophobic treatment solution is composed of multifunctional small molecule silanes SiX4, HSiX3 or CH3SiX3, C6–C 18 It consists of long-chain hydrocarbon groups and organic solvents.

[0012] The apparatus for preparing a core-shell structure wear-resistant superhydrophobic yarn according to the present invention, in a preferred embodiment, includes a humidifier connected to a humid water vapor inlet in the humid air reaction chamber, wherein the humidity inside the humid air reaction chamber is greater than or equal to 30%. The chamber body is a cylindrical pipe with one end connected to the yarn outlet and the other end sealed to the drying chamber.

[0013] The apparatus for preparing a core-shell structure wear-resistant superhydrophobic yarn according to the present invention, in a preferred embodiment, includes a drying chamber comprising a drying chamber body and at least two yarn guide rollers arranged alternately in the drying chamber body.

[0014] The apparatus for preparing a core-shell structure wear-resistant superhydrophobic yarn according to the present invention, in a preferred embodiment, further includes a waste gas treatment system connected to one end of the drying chamber; The drying chamber also includes an air extraction port connected to one end of the drying chamber body; The exhaust gas treatment system includes an exhaust gas guide pipe sealed to the exhaust port, an exhaust gas treatment device connected to the exhaust gas guide pipe, an exhaust pump pipe and an exhaust pump connected in sequence to the exhaust gas treatment device, an L-shaped exhaust gas guide pipe connected to the end of the exhaust gas guide pipe, and an L-shaped exhaust pipe connected to the inlet of the exhaust pump pipe. The waste gas treatment device is a closed cavity with an internal waste gas reaction liquid, which is a lime suspension. The end of the L-shaped exhaust gas guide pipe is below the liquid surface of the exhaust gas reaction liquid, while the inlet of the L-shaped exhaust gas extraction pipe is above the liquid surface of the exhaust gas reaction liquid.

[0015] This invention provides a method for preparing a core-shell structured wear-resistant superhydrophobic yarn, comprising the following steps: S1. The fiber matrix enters the superhydrophobic treatment solution immersion tank from the unwinding end at a speed of 0.1 to 10 m / s. Under the guidance of the yarn immersion roller, it is immersed in the superhydrophobic treatment solution to carry out a one-bath immersion treatment of the yarn and is wetted by the superhydrophobic treatment solution to obtain superhydrophobic wetted yarn. The superhydrophobic treatment solution is composed of 0.5% to 10% by mass volume of a fast crosslinking agent, 0.5% to 10% by mass volume of a low surface energy functional agent, and 80% to 99% by mass volume of an organic solvent. In the mass volume ratio, the fast crosslinking agent and the low surface energy functional agent are mass ratios in grams, and the organic solvent is a volume ratio in liters. The rapid crosslinking agent is a multifunctional small molecule silane SiX4, HSiX3, or CH3SiX3, and the low surface energy functional agent is R-SiX3. The functional group X is one or more of acetoxy, butanone oxime, -H, -Cl, -Br, enol acetone, and methoxy groups, and the functional group R is C6–C. 18 The saturated alkyl chain or unsaturated hydrocarbon chain, the unsaturated hydrocarbon chain is phenyl or oleic acid, the low surface energy functional agent also has the same functional group as the fast crosslinking agent, and the boiling point of the organic solvent is 20 to 90℃. S2. After the superhydrophobic wetted yarn enters the humid air reaction chamber through the yarn outlet and comes into direct contact with the humid air. The multifunctional small molecule silane is rapidly hydrolyzed on the surface of the superhydrophobic wetted yarn and forms a silica cross-linked network through covalent bonding. The low surface energy functional agent is bonded to the surface of the silica cross-linked network to form a superhydrophobic coating, and the yarn after initial curing is obtained. S3. After initial curing, the yarn enters the drying chamber. The vacuum pump maintains negative pressure in the drying chamber to promote the evaporation of organic solvents and remove excess superhydrophobic treatment liquid and water vapor. The organosilane on the yarn surface is completely cured and dried to form a superhydrophobic shell layer with a core-shell structure, resulting in a core-shell structure wear-resistant superhydrophobic yarn. It is collected at the take-up end at a speed of 0.1 to 10 m / s. The waste gas generated in the drying chamber is directly recycled and treated by the waste gas treatment device through the L-shaped waste gas guide pipe.

[0016] In the preferred embodiment of the method for preparing a core-shell structure wear-resistant superhydrophobic yarn described in this invention, the multifunctional small molecule silane in step S2 is silicon tetrachloride. The low surface energy functional agent is any one of the following: phenyltrichlorosilane, dodecyltrichlorosilane, and octadecyltrichlorosilane; The organic solvent is any one of the following: dichloromethane, n-hexane, petroleum ether, cyclopentane, and R1336mzz.

[0017] The method for preparing a core-shell structured wear-resistant superhydrophobic yarn according to the present invention, as a preferred embodiment, further includes step S4: S4. Superhydrophobic fabrics are obtained by spinning core-shell structure wear-resistant superhydrophobic yarns. The breathability and softness of the superhydrophobic fabrics are the same as those of fabrics spun from fiber matrix.

[0018] One-bath process is a textile processing technology that completes multiple process steps simultaneously in a single bath.

[0019] The present invention has the following advantages: (1) The one-bath continuous yarn treatment process of the present invention significantly improves the production efficiency and applicability of superhydrophobic finishing. On the one hand, the process truly realizes continuous production, with the yarn passing through the treatment line at a stable speed, and the coating deposition and curing can be completed within seconds. Compared with the traditional multi-step intermittent process, this method simplifies the process into a single-step continuous operation, reducing intermediate drying and tank changing steps, and significantly reducing production time and energy consumption. The entire process is carried out at room temperature without additional heating, which greatly saves energy and avoids potential damage to the fibers from high temperatures. On the other hand, the one-bath method simultaneously completes the formation of the silica network and the introduction of hydrophobic groups, ensuring uniform coverage and firm adhesion of the coating on the fiber surface. Since hydrophobic properties are imparted at the yarn stage, the treated yarn has a wear-resistant hydrophobic coating on all sides during the subsequent weaving process, and the finished fabric still maintains excellent water repellency after being subjected to weaving stress.

[0020] (2) The fiber-grade core-shell superhydrophobic coating of the present invention forms a covalent interface with high bonding force between the fiber and the coating, which significantly improves the durability and mechanical stability of the hydrophobic coating. Yarns and fabrics treated with the present invention have permanently bonded superhydrophobic properties and can maintain excellent hydrophobic performance with high contact angle and low roll-off angle even under strong friction, high-pressure water impact, repeated bending and extreme temperature environments. Tests show that the coating can withstand tens of thousands of friction and wear cycles without peeling off, and maintains water repellency under harsh abrasion conditions such as sand impact, which is far superior to traditional nanoparticle coatings that mainly rely on physical adhesion; in standard abrasion resistance tests, the wear depth of fabrics using the shell layer of the present invention is reduced by about 46% compared with conventional superhydrophobic coatings.

[0021] (3) Simultaneously, since the shell layer thickness is only on the nanometer scale and is distributed on the surface of a single fiber without blocking the fabric pores, the breathability and softness of the treated fabric are basically unaffected. Furthermore, this invention completely avoids the use of fluorides such as PFAS, significantly reducing environmental risks and raw material consumption. In summary, the method for preparing fiber-level core-shell structured superhydrophobic yarns of this invention achieves both durability and breathability, lightness, and environmental safety in superhydrophobic fabrics. It combines biomimetic principles with practical and scalable preparation methods, meeting the current urgent need for high-performance waterproof fabrics. Attached Figure Description

[0022] Figure 1 A front view of an apparatus for preparing a core-shell structured wear-resistant superhydrophobic yarn; Figure 2 Top view of an apparatus for preparing a core-shell structured wear-resistant superhydrophobic yarn; Figure 3 A front view of a recycling device for a core-shell structured wear-resistant superhydrophobic yarn; Figure 4 A flowchart of a method for preparing a core-shell structured wear-resistant superhydrophobic yarn; Figure 5 Example 1 shows the surface morphology of the superhydrophobic fiber of a core-shell structure wear-resistant superhydrophobic yarn, its preparation device and method; Figure 6 Example 1: Schematic diagram of the hydrophobicity of the surface of the superhydrophobic fiber, showing the preparation device and method of a core-shell structure wear-resistant superhydrophobic yarn; Figure 7 Schematic diagram of the surface morphology and contact angle of a single yarn of different materials for a core-shell structure wear-resistant superhydrophobic yarn, its preparation device and preparation method, Example 1; Figure 8 Example 2 shows the surface morphology of fibers of different materials and the contact angle of a single yarn for a core-shell structure wear-resistant superhydrophobic yarn, its preparation device and preparation method; Figure 9 Example 1: Schematic diagrams of the surface morphology and superhydrophobicity of textiles with different weaving forms, illustrating a core-shell structure wear-resistant superhydrophobic yarn, its preparation device and method; Figure 10 A schematic diagram of the impact resistance of superhydrophobic treated textiles in Example 1 of a core-shell structure abrasion-resistant superhydrophobic yarn, its preparation device and method; Figure 11 Example 1: Schematic diagram of the wear resistance of a core-shell structured wear-resistant superhydrophobic yarn, its preparation device and method; Figure 12 Example 1: A schematic diagram of the abrasion resistance of superhydrophobic textiles (dual-wheel abrasion method) for a core-shell structure abrasion-resistant superhydrophobic yarn, its preparation device and method; Figure label: 1. Pay-off end; 2. Superhydrophobic treatment solution impregnation tank; 21. Impregnation tank body; 22. Yarn inlet; 23. Yarn outlet; 24. Yarn immersion roller; 25. Yarn inlet; 26. Yarn outlet; 3. Humid air reaction chamber; 31. Chamber body; 32. Moisture vapor inlet; 33. Humidifier; 4. Drying chamber; 41. Drying chamber body; 42. Yarn guide roller; 43. Air extraction port; 5. Take-up end; 6. Exhaust gas treatment system; 61. Exhaust gas guide pipe; 62. Exhaust gas treatment device; 63. Air extraction pump pipe; 64. Air extraction pump; 65. L-shaped exhaust gas guide pipe; 66. L-shaped air extraction duct; A. Fiber matrix; B. Superhydrophobic shell. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Example 1

[0024] like Figures 1-4 As shown, a core-shell structure wear-resistant superhydrophobic yarn and its preparation device and method are disclosed, wherein the superhydrophobic functionalization of the yarn is completed in one step using a single bath solution at room temperature.

[0025] The core-shell structured abrasion-resistant superhydrophobic yarn includes a fiber matrix A and a superhydrophobic shell B covalently bonded to the surface of the fiber matrix. The superhydrophobic shell B has a core-shell structure, comprising an inner layer of silica network formed by silane hydrolysis and condensation, and an outer layer of organic hydrophobicity bonded to the surface of the silica network. The silica network is covalently connected to the surface hydroxyl groups of the fiber matrix through silicon-oxygen bonds, and the organic hydrophobicity outer layer contains long-chain alkyl groups and covers the outer surface of the silica network.

[0026] In this embodiment, the silicon dioxide network is formed by the hydrolysis and condensation of silicon tetrachloride, and the long-chain alkyl groups are introduced by the hydrolysis reaction of dodecyltrichlorosilane, thereby constructing a covalently bonded SiO2-alkylsilane core-shell coating on the fiber surface.

[0027] This invention can treat yarns of various materials (e.g., natural yarns, chemically synthesized yarns, and blended yarns), yarns of various structures (staple fibers and filaments), yarns of various thicknesses (fixed weight and fixed length), and yarns of various twists and twist directions (reverse twist, forward twist, etc.). Fibers treated with the superhydrophobic shell B retain their superhydrophobic properties with a contact angle greater than 150° after being woven or knitted into fabrics, while also maintaining the fabric's original breathability and softness.

[0028] The apparatus for preparing core-shell structure wear-resistant superhydrophobic yarn includes: a yarn feeding end 1, a superhydrophobic treatment liquid impregnation tank 2 equipped with superhydrophobic treatment liquid, a humid air reaction chamber 3 located at the outlet of the superhydrophobic treatment liquid impregnation tank 2, a drying chamber 4, and a yarn import and export conveying mechanism between various devices, etc.

[0029] The specific structure of the apparatus for preparing core-shell structured wear-resistant superhydrophobic yarn is as follows: The impregnation tank body 21 of the superhydrophobic treatment solution impregnation tank 2 is relatively enclosed, with only a yarn inlet 22 and a yarn outlet 23. Inside the impregnation tank body 21 is a cylindrical yarn immersion roller 24 (yarn guide immersion roller), and inside the superhydrophobic treatment solution impregnation tank 2 is a superhydrophobic treatment solution. The entire superhydrophobic treatment solution impregnation tank 2 is operated at normal temperature and pressure. The size of the superhydrophobic treatment solution impregnation tank 2 can be freely adjusted according to the number of yarns being processed, ensuring that the yarn guide immersion roller is positioned slightly below the middle of the superhydrophobic treatment solution impregnation tank 2 to ensure that the yarn is completely immersed in the superhydrophobic treatment solution.

[0030] The superhydrophobic treatment solution inside the superhydrophobic treatment solution immersion tank 2 contains at least two organosilane components with different functions: one uses small molecule silanes as rapid crosslinking agents, such as one or more of SiX4, HSiX3, and CH3SiX3; the other has C6-C... 18 Hydrocarbon-based organosilanes R-SiX3 (such as phenyltrichlorosilane / dodecyltrichlorosilane or octadecyltrichlorosilane, single or mixed organosilanes with 6 or more carbon atoms) are low surface energy functional agents.

[0031] Functional group X is one or more of acetoxy, butanone oxime, -H, -Cl, -Br, enol acetone, and methoxy, and functional group R is C6–C. 18 Saturated alkyl chains or unsaturated hydrocarbon chains, wherein the unsaturated hydrocarbon chains are phenyl or oleic acid; When the rapid crosslinking agent has multiple components, the mass ratio of each component is 0.5~1.5; The mass-to-volume ratio of the fast crosslinking agent to the low surface energy functional agent is 0.5%–10%: 0.5%–10%. The organic reagent can be an organic solvent with a low boiling point range of 20–90℃ (e.g., dichloromethane, n-hexane, petroleum ether, cyclopentane, R1336mzz, etc.) (where silicon tetrachloride and long-chain alkyl organosilanes are by mass, and the organic solvent is by volume). The humid air reaction chamber 3 consists of a cylindrical pipe (chamber body 31) and a humidifier 33 connected to it. The cylindrical pipe is 30-100cm long and has a radius of 2-10cm. The humidifier 33 continuously introduces water vapor through the humid water vapor inlet 32 ​​to ensure that the humidity inside the chamber body 31 is maintained above 30%. The entire humid air reaction chamber 3 is at normal temperature and pressure. The drying chamber 4 has three yarn guide rollers 42 arranged in an alternating pattern, and this area is connected to the exhaust gas treatment system 6 via an exhaust port 43. The exhaust gas treatment system 6 has an exhaust pump 64 that maintains a low pressure throughout the drying chamber 4 and accelerates the vaporization of solvent on the yarn surface, thereby removing excess superhydrophobic treatment liquid and water. As the yarn passes through the yarn guide rollers 42, the yarn changes from a wet state to a dry state. The exhaust gas treatment system 6 includes an exhaust gas treatment device 62 containing an exhaust gas reaction liquid (lime suspension) and an air pump 64 that keeps the entire system under negative pressure. The exhaust gas generated during the reaction process in the humid air reaction chamber 3 enters the exhaust gas treatment device 62 through the exhaust gas guide pipe 61 to react with the reaction liquid. The air pump 64 continuously ensures that the generated exhaust gas continuously enters the exhaust gas treatment device 62. Yarns pass through a superhydrophobic treatment liquid at a speed of 0.1 to 10 m / s. Yarns of various materials (e.g., natural yarns, chemically synthesized yarns, and blended yarns), various structures (short fiber and filament yarns), various thicknesses (fixed weight and fixed length), and various twists and twist directions (reverse twist, forward twist, etc.) can all be treated.

[0032] The preparation method of core-shell structure wear-resistant superhydrophobic yarn includes: continuously passing the yarn to be treated (fiber matrix A) through a treatment solution containing an organosilane modifier at a constant speed to achieve one-bath impregnation treatment of the yarn; subsequently, the impregnated yarn is placed in a drying chamber 4 for drying, where the moisture causes the silane to rapidly hydrolyze and condense, forming a covalently bonded superhydrophobic coating in situ on the fiber surface. The superhydrophobic treatment solution contains at least two organosilane components with different functions: one is a small-molecule multifunctional silane, used to rapidly form a silica crosslinking network, and the other is a silane with long-chain hydrophobic groups, used to provide low surface energy hydrophobic groups.

[0033] Existing superhydrophobic fabric treatment technologies are generally limited to finished textile products. This is because superhydrophobic agents require long processing and drying times, necessitating intermittent processing and failing to meet industrial efficiency requirements. Furthermore, existing superhydrophobic agents exhibit poor abrasion resistance; direct fiber treatment leads to significant degradation of superhydrophobic properties during subsequent textile processes. However, the superhydrophobic treatment liquid based on this invention can rapidly treat yarns while maintaining excellent abrasion resistance, thus enabling mass production of superhydrophobic treatments for yarn surfaces.

[0034] Regarding the organosilane superhydrophobic treatment solution used in this invention, the present invention proposes a method for preparing a dedicated device for this treatment solution, comprising the following steps: S1. First, the yarn enters the core-shell structure wear-resistant superhydrophobic yarn preparation device and is immersed in the superhydrophobic treatment liquid inside the superhydrophobic treatment liquid impregnation tank 2 and will be quickly wetted (because the surface tension of the superhydrophobic treatment liquid is very low, the complete wetting time of the yarn can reach less than 10s). Therefore, when the immersion depth reaches 10cm, the yarn speed can reach 5m / s.

[0035] Untreated yarn enters the superhydrophobic treatment solution impregnation tank 2 through the yarn inlet 25. The tank contains a petroleum ether solution of approximately 4% (by mass / volume) small molecule silane and 2% dodecyltrichlorosilane as the superhydrophobic treatment solution. The impregnation tank body 21 is relatively enclosed, with only a yarn inlet 22 and a yarn outlet 23. The untreated yarn is guided by the yarn immersion roller 24 to be completely immersed in the superhydrophobic treatment solution. After exiting the superhydrophobic treatment solution impregnation tank 2, the yarn enters the humid air reaction chamber 3 located at the outlet of the impregnation tank.

[0036] S2. The yarn, fully wetted by the superhydrophobic treatment solution, then enters the humid air reaction chamber 3. Water vapor needs to be continuously introduced into the humid air reaction chamber 3 to solidify the organosilane in the superhydrophobic treatment solution. Experimental tests showed that under 60% humidity and 25℃ conditions, the initial curing time of the organosilane could be controlled within 10 seconds. Therefore, a water vapor inlet is needed at the yarn inlet in the humid air reaction chamber 3 to continuously replenish the reaction chamber with water vapor.

[0037] The yarn, after being impregnated with the superhydrophobic treatment solution, enters the humid air reaction chamber 3. In the humid air reaction chamber 3, the yarn can directly contact the humid air, immediately triggering a chemical reaction. This causes the solvent to evaporate rapidly and the silane to complete hydrolysis and curing, forming a covalently bonded superhydrophobic coating on the yarn surface in situ.

[0038] S3. Next, the yarn enters the drying chamber 4. This area needs to be connected to an air extraction device to maintain negative pressure, promoting the evaporation of organic solvents and expelling excess superhydrophobic treatment liquid and water vapor. After the excess organic solvents and water vapor are expelled, the organosilane on the yarn surface will be completely cured and dried to form a superhydrophobic nanolayer with a core-shell structure (superhydrophobic shell B), and then enter the yarn collection device to obtain the treated superhydrophobic yarn.

[0039] The yarn that triggers the reaction then enters the drying area. In this embodiment, three yarn guide rollers 42 guide the yarn forward at a uniform speed. At the same time, this stage helps the silicon crosslinking network on the yarn to bond further, which is beneficial to the formation of multi-level hydrophobic coating.

[0040] Finally, the treated yarn is collected at the take-up end 5 at a speed of 0.1 to 10 m / s. The waste gas generated in the drying chamber 4 is directly treated by the waste gas treatment device 62 through the L-shaped waste gas guide pipe 65.

[0041] like Figure 3 As shown, for the waste gas treatment device 62, the waste gas generated in the reaction chamber enters the waste gas treatment device 62 through the L-shaped waste gas guide pipe 65. The waste gas treatment device 62 contains lime suspension. The other end of the waste gas treatment device 62 is connected to a continuously pumping air pump 64. The pumping air pump 64 ensures that the waste gas treatment device 62 and the drying chamber 4 are always under negative pressure, thereby ensuring that the waste gas can always be drawn into the waste gas treatment reaction liquid (lime suspension).

[0042] S4. Use the treated superhydrophobic yarn to weave superhydrophobic textiles.

[0043] In this embodiment, the method for preparing the superhydrophobic solution during the superhydrophobic treatment of the yarn is as follows: Add 2% trichlorosilane, 2% silicon tetrachloride, and 1% octadecyltrichlorosilane (by weight / volume) to the organic solvent petroleum ether (40g trichlorosilane, 40g silicon tetrachloride, 10g dodecyltrichlorosilane, 2L petroleum ether), and mix at room temperature for 30 minutes. The resulting solution is the MARS superhydrophobic solution.

[0044] During the superhydrophobic aqueous solution treatment, the yarn to be treated is modified using a continuous yarn one-bath silane modification treatment device.

[0045] Comparative Example 1 is as follows: Preparation of superhydrophobic solution for superhydrophobic treatment of yarn: Capstone ST-200 (DuPont) and silica nanoparticles were mixed in a 1:1 ratio and stirred at room temperature for 24 hours. The resulting solution is the Capstone-FS superphobic water solution.

[0046] The superhydrophobic water treatment method of Comparative Example 1: The yarn to be treated was modified using a continuous yarn one-bath silane modification treatment device. Example 2

[0047] like Figures 1-4 As shown, a core-shell structured wear-resistant superhydrophobic yarn and its preparation apparatus and method are the same as those in Example 1, except for the composition of the superhydrophobic aqueous solution. In this example, when preparing the superhydrophobic aqueous solution, 2% trichlorosilane, 2% silicon tetrachloride, and 1% octadecyltrichlorosilane (by mass / volume ratio) are added to the organic solvent petroleum ether (40g trichlorosilane, 40g silicon tetrachloride, 10g dodecyltrichlorosilane, 2L petroleum ether), and mixed at room temperature for 30 minutes. The prepared solution is the MARS superhydrophobic aqueous solution.

[0048] ; Reaction Explanation: Some small-molecule silanes containing Si-H remain unchanged during the initial condensation, thus avoiding excessive cross-linking that could affect the density during the initial condensation process. During the subsequent air-drying process, most of the Si-H is oxidized by oxygen in the air to form Si-OH, which then condenses with other Si-OH molecules to form Si-O-Si (over several hours), improving the internal bonding strength of the superhydrophobic layer.

[0049] Treatment of superhydrophobic water solutions: The yarn to be treated was modified using a continuous yarn one-bath silane modification treatment device.

[0050] The performance evaluation results for Example 1, Example 2, and Comparative Example 1 are as follows: The impact resistance of superhydrophobic textiles is evaluated as follows: Textiles treated with the MARS superhydrophobic coating of Example 1 were fixed at a 45° angle, and droplets were dropped from heights of 29.4 cm, 38 cm, and 46.6 cm at intervals of 2.4 ms. -1 2.7ms -1 and 3.0ms -1 The speed of the impact of raindrops was simulated, and the number of impacting droplets was counted until the wettability of the superhydrophobic textile changed.

[0051] The abrasion resistance of superhydrophobic textiles is evaluated as follows: [1] Martindale method for determining the abrasion resistance of fabrics: The textiles treated with the MARS superhydrophobic coating of Example 1 were subjected to abrasion resistance testing according to the national standard GB / T21196.1-2007 "Textiles - Martindale Method - Determination of Abrasion Resistance of Fabrics - Part 1: Martindale Abrasion Tester". The fabric sample was fixed on the Martindale head and rubbed against a standard wool felt 80,000 times in a Lissajous pattern under a pressure of 9 kPa.

[0052] [2] Determination of fabric abrasion resistance using the double-wheel abrasion method: The textiles treated with the MARS superhydrophobic coating of Example 1 were subjected to abrasion resistance testing according to the national standard FZ / T01128-2014 "Determination of Abrasion Resistance of Textiles - Two-Wheel Abrasion Method". A circular fabric sample with a diameter of 100 mm was mounted on a rotating platform, and two counter-rotating CS-10 grinding wheels (each with a load of 250 g) rubbed the sample up to 20,000 times, producing inward and outward abrasion tracks.

[0053] [3] Abrasion resistance test of fabrics by sand removal method: Textiles treated with the MARS superhydrophobic coating of Example 1 were subjected to abrasion resistance testing according to the national standard GB / T23988-2009 "Determination of Abrasion Resistance of Coatings - Falling Sand Method". Quartz sand (400~700μm) was released from 91.4cm above the fabric and impacted at a 45° angle with an impact velocity of ~4.2m / s.

[0054] The surface morphology of the yarn treated with the MARS superhydrophobic coating obtained in Example 1 was observed, such as... Figure 5As shown, part a on the left is a SEM image of the superhydrophobic fiber surface of Example 1, part b on the right is a TEM image of the superhydrophobic fiber surface of Example 1, and part c on the bottom is a core-shell structure morphology diagram of the superhydrophobic fiber surface. As can be seen from the figure, the coating surface has mushroom-shaped silica aggregates (diameter 130~170nm) and tightly adhered silica shells (feature size 20~50nm), demonstrating a multi-level superhydrophobic coating structure. Further environmental scanning electron microscopy revealed that at 3.7°C and 100% relative humidity, condensed droplets (diameter <2μm, ~6fL) on a single fiber of Example 1 would roll off once they reached a size of ~2μm, exhibiting excellent hydrophobicity (e.g., ...). Figure 6 As shown). Superhydrophobic treatment was applied to fiber samples (wool, polyester, and nylon) of different materials in Example 1, and the results are as follows. Figure 7 As shown, the contact angles of the treated fiber monofilaments are all above 155°, with the polyester monofilament contact angle even reaching 163.0°, exhibiting excellent hydrophobic properties. Meanwhile, superhydrophobic coatings with different formulations (Example 2) also possess excellent superhydrophobic properties (such as...). Figure 8 (As shown).

[0055] like Figure 9 As shown, the fibers treated in Example 1 were woven in different ways, and the contact angles of the woven textiles were all above 155°, namely 158.8° (warp and weft weaving), 156.1° (circular weft weaving) and 159.5° (integrated weaving machine), achieving excellent superhydrophobicity from monofilament to textile.

[0056] In simulated rainstorm tests, the fabric modified in Example 1 could withstand 12 hours of continuous raindrop impact, with a single point withstanding 10... 4 More than one impact (2.5 drops / second, impact velocity 2.4-3.0 m / s) −1 )(like Figure 10 (As shown). In addition, as... Figure 11 , Figure 12 As shown, the fabric modified in Example 1 exhibits significantly greater abrasion resistance compared to Comparative Example 1. In the Martindale test, the canvas fabric modified in Example 1 withstood up to 80,000 abrasion cycles under a pressure of 9 kPa, compared to a standard wool fabric, while maintaining θ > 150° and minimal contact angle change (Δθ < 5°). Unlike conventional coatings that degrade after a few hundred cycles, the MARS-modified fabric demonstrated superior durability. In the more stringent dual-wheel abrasion test (250 g load, 20,000 cycles), the fabric treated in Example 1 maintained its superhydrophobicity (θa ≈ 156.7°) and exhibited a decrease in contact angle (Δθ ≈ 8.8°). Figure 12SEM images confirmed that even after 20,000 abrasion cycles, the nanostructured MARS shell remained intact on the fiber surface, providing direct evidence of the coating's robustness. The nanostructured silica shell was securely embedded in the fiber matrix, significantly outperforming traditional nanoparticle-based coatings, reducing abrasion depth by 46.2%. In a sand-drop test, the sample modified in Example 1 withstood 100 impacts from a total of 320 kg of quartz sand while maintaining its water-repellent properties (e.g., ...). Figure 11 (As shown).

[0057] In summary, this invention provides a fiber-grade core-shell structured superhydrophobic shell yarn that can achieve excellent superhydrophobicity and abrasion resistance from yarn to woven textiles.

[0058] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A core-shell structured wear-resistant superhydrophobic yarn, characterized in that: It includes a fiber matrix (A) and a superhydrophobic shell (B) covalently bonded to the surface of the fiber matrix (A); The fiber matrix (A) is a yarn matrix; The superhydrophobic shell (B) is a SiO2-hydrosilane core-shell coating covalently bonded to the surface of the fiber matrix (A), comprising a silica network formed by silane hydrolysis and condensation and an organic hydrophobic outer layer bonded to the surface of the silica network; the silica network is covalently connected to the hydroxyl groups on the surface of the fiber matrix (A) through silicon-oxygen bonds, and the organic hydrophobic outer layer is a long-chain hydrocarbon group; The fabric prepared from the core-shell structure wear-resistant superhydrophobic yarn is a superhydrophobic fabric, and the contact angle of the superhydrophobic fabric is greater than or equal to 150°.

2. The core-shell structure wear-resistant superhydrophobic yarn according to claim 1, characterized in that: The fiber matrix (A) can be natural yarn, chemically synthesized yarn, or blended yarn, or it can be staple fiber or filament yarn, and the twist direction can be forward or reverse. The superhydrophobic shell (B) has a core-shell structure. A multifunctional small-molecule silane is covalently linked to hydroxyl groups on the surface of the fiber matrix (A), and then hydrolyzes in humid water vapor to obtain the silica network. The organic hydrophobic outer layer is composed of C6–C... 18 A hydrocarbon-based organosilane is condensed with the silica network to form and cover the outer surface of the silica network; The superhydrophobic shell (B) is fluorine-free and has a thickness of less than 1000 nm.

3. A device for preparing core-shell structured wear-resistant superhydrophobic yarn, characterized in that: It includes a wire feeding end (1), a superhydrophobic treatment liquid immersion tank (2), a humid air reaction chamber (3), a drying chamber (4) and a wire taking end (5) arranged in sequence. The humid air reaction chamber (3) is connected between the superhydrophobic treatment liquid immersion tank (2) and the drying chamber (4). The superhydrophobic treatment liquid impregnation tank (2) includes an impregnation tank body (21), a yarn inlet (22) connected to one end of the impregnation tank body (21), a yarn outlet (23) connected to the other end of the impregnation tank body (21), a yarn immersion roller (24) connected to the lower side inside the impregnation tank body (21), a yarn introducer (25) connected to the yarn inlet (22), and a yarn exporter (26) connected to the yarn outlet (23). The impregnation tank body (21) contains superhydrophobic treatment liquid and immerses the yarn immersion roller (24) to perform a one-bath impregnation treatment of the fiber matrix (A). The yarn introducer (25) introduces the fiber matrix (A) into the impregnation tank body (21), and the yarn exporter (26) exports the impregnated fiber matrix (A) from the impregnation tank body (21). The humid air reaction chamber (3) includes a chamber body (31) and a humid water vapor inlet (32) connected to the upper end of the chamber body (31). The humid air reaction chamber (3) provides humid water vapor for silane hydrolysis and condensation. The fiber matrix (A) undergoes the evaporation of organic solvents and discharge of excess superhydrophobic treatment liquid and water vapor in the drying chamber (4) to solidify the superhydrophobic shell (B); Before hydrophobic treatment, the fiber matrix (A) is wound on the pay-off end (1). Under the traction of the take-up end (5), it passes through the yarn inlet (22), the yarn immersion roller (24) and is wetted by the superhydrophobic treatment liquid. Then, it passes through the yarn outlet (23), the chamber body (31), and the drying chamber (4) to obtain a superhydrophobic shell layer (B) covalently bonded to the surface of the fiber matrix (A), forming a core-shell structure abrasion-resistant superhydrophobic yarn and collecting it at the take-up end (5). The preparation device of the shell structure abrasion-resistant superhydrophobic yarn is a room temperature continuous operation device.

4. The apparatus for preparing a core-shell structured wear-resistant superhydrophobic yarn according to claim 3, characterized in that: The opening of the impregnation tank body (21) includes only the yarn inlet (22) and the yarn outlet (23), and the yarn immersion roller (24) is cylindrical; The superhydrophobic treatment solution is composed of 0.5% to 10% by mass volume of a rapid crosslinking agent, 0.5% to 10% by mass volume of a low surface energy functional agent, and 80% to 99% by mass volume of an organic solvent.

5. The apparatus for preparing a core-shell structured wear-resistant superhydrophobic yarn according to claim 3, characterized in that: The humid air reaction chamber (3) also includes a humidifier (33) connected to the humid water vapor inlet (32), and the humidity inside the humid air reaction chamber (3) is greater than or equal to 30%. The chamber body (31) is a cylindrical pipe with one end connected to the yarn outlet (23) and the other end sealed to the drying chamber (4).

6. The apparatus for preparing a core-shell structured wear-resistant superhydrophobic yarn according to claim 3, characterized in that: The drying chamber (4) includes a drying chamber body (41) and at least two yarn guide rollers (42) arranged alternately in the drying chamber body (41).

7. The apparatus for preparing a core-shell structured wear-resistant superhydrophobic yarn according to claim 3, characterized in that: It also includes an exhaust gas treatment system (6) connected to one end of the drying chamber (4); The drying chamber (4) also includes an air extraction port (43) connected to one end of the drying chamber body (41). The exhaust gas treatment system (6) includes an exhaust gas guide pipe (61) sealed to the exhaust port (43), an exhaust gas treatment device (62) connected to the exhaust gas guide pipe (61), an exhaust pump pipe (63) and an exhaust pump (64) connected in sequence to the exhaust gas treatment device (62), an L-shaped exhaust gas guide pipe (65) connected to the end of the exhaust gas guide pipe (61), and an L-shaped exhaust pipe (66) connected to the inlet of the exhaust pump pipe (63). The waste gas treatment device (62) is a closed cavity with waste gas reaction liquid inside, and the waste gas reaction liquid is a lime suspension; The end of the L-shaped exhaust gas guide pipe (65) is located below the liquid surface of the exhaust gas reaction liquid, and the inlet of the L-shaped exhaust gas duct (66) is located above the liquid surface of the exhaust gas reaction liquid.

8. A method for preparing a core-shell structured wear-resistant superhydrophobic yarn according to any one of claims 1 to 7, characterized in that: Includes the following steps: S1. The fiber matrix (A) enters the superhydrophobic treatment liquid immersion tank (2) from the unwinding end (1) at a speed of 0.1 to 10 m / s. Under the guidance of the yarn immersion roller (24), the yarn is immersed in the superhydrophobic treatment liquid for one-bath immersion treatment and is wetted by the superhydrophobic treatment liquid to obtain superhydrophobic wetted yarn. The superhydrophobic treatment solution is composed of 0.5% to 10% by mass volume of a fast crosslinking agent, 0.5% to 10% by mass volume of a low surface energy functional agent, and 80% to 99% by mass volume of an organic solvent. In the mass volume ratio, the fast crosslinking agent and the low surface energy functional agent are mass ratios in grams, and the organic solvent is a volume ratio in liters. The rapid crosslinking agent is one or more of the multifunctional small molecule silanes SiX4, HSiX3, and CH3SiX3, and the low surface energy functional agent is R-SiX3. The functional group X is one or more of acetoxy, butanone oxime, -H, -Cl, -Br, enol acetone, and methoxy, and the functional group R is C6–C. 18 The saturated alkyl chain or unsaturated hydrocarbon chain, wherein the unsaturated hydrocarbon chain is phenyl or oleic acid; The boiling point of the organic solvent is 20–90°C; S2. The superhydrophobic wetted yarn enters the humid air reaction chamber (3) through the yarn outlet (26) and comes into direct contact with the humid air. The multifunctional small molecule silane is rapidly hydrolyzed on the surface of the superhydrophobic wetted yarn and forms a silica crosslinking network through covalent bonds. The low surface energy functional agent is bonded to the surface of the silica crosslinking network to form a superhydrophobic coating, and the yarn is obtained after initial curing. S3. After initial curing, the yarn enters the drying chamber (4). The vacuum pump (64) keeps the drying chamber (4) under negative pressure to promote the evaporation of organic solvent and discharge excess superhydrophobic treatment liquid and water vapor. The organosilane on the surface of the yarn is completely cured and dried to form a superhydrophobic shell layer (B) with a core-shell structure, thus obtaining the wear-resistant superhydrophobic yarn with the core-shell structure. The yarn is collected at the take-up end (5) at a speed of 0.1 to 10 m / s. The waste gas generated in the drying chamber (4) is directly recycled and treated by the waste gas treatment device (62) through the L-shaped waste gas guide pipe (65).

9. The method for preparing a core-shell structured wear-resistant superhydrophobic yarn according to claim 8, characterized in that: In step S2, the low surface energy functional agent is any one of the following: phenyltrichlorosilane, dodecatrichlorosilane, and octadecyltrichlorosilane; The organic solvent is any one of the following: dichloromethane, n-hexane, petroleum ether, cyclopentane, and R1336mzz.

10. The method for preparing a core-shell structured wear-resistant superhydrophobic yarn according to claim 8, characterized in that: It also includes step S4: S4. The core-shell structure wear-resistant superhydrophobic yarn is spun to obtain a superhydrophobic fabric. The air permeability and softness of the superhydrophobic fabric are the same as those of the fabric spun from the fiber matrix (A).

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