Multifunctional moisture-absorbing and refrigeration fabric, and preparation method and application thereof

Abstract

The application discloses a multifunctional moisture-absorbing and refrigeration fabric and a preparation method thereof. The multifunctional moisture-absorbing and refrigeration clothing comprises a super-hydrophobic MOF fabric and a super-absorbing film material. The super-hydrophobic MOF fabric is obtained by growing a metal organic framework ZIF-8 coating on a carboxylated cotton fabric surface in situ and then hydrophobizing. The super-absorbing film material is formed by mixing and solidifying a hygroscopic inorganic metal salt ethanolamine aqueous solution and a polystyrene sulfonic acid sodium solution. The high polymer film material with excellent moisture absorption performance is arranged between the multifunctional super-hydrophobic MOF fabric layers to form the multifunctional moisture-absorbing and refrigeration clothing with a double-sided one-way moisture-guiding sandwich structure. The multifunctional moisture-absorbing and refrigeration clothing is prepared under mild conditions, and the production process is simple and safe to operate. The super-absorbing material has strong renewability, and the refrigeration and cooling effect is remarkable. The multifunctional moisture-absorbing and refrigeration clothing can be widely applied to personnel who need to wear protective clothing to work in a high-temperature environment, such as firefighters, medical staff, armed police, soldiers and doll performers.

Description

Technical Field

[0001] This invention relates to a multifunctional moisture-wicking and cooling garment and its preparation method, specifically to a multifunctional moisture-wicking and cooling garment with a "sandwich"-like structure having double-sided unidirectional moisture-wicking function, belonging to the field of high-end textile technology. Background Technology

[0002] In recent years, extreme weather events have become increasingly frequent globally, such as extreme cold or heat waves, posing a significant challenge to people's normal lives and work, especially those working in high-temperature environments. In particular, medical personnel involved in epidemic prevention must wear protective suits. While these suits isolate viruses, they also prevent the evaporation of sweat, cutting off the most effective way for the body to cool down. This exposes them to hot and humid environments, greatly increasing their risk of heatstroke and other heat-related illnesses. Firefighters face similar problems. To prevent burns during firefighting, firefighters must wear thick, specially designed fireproof clothing. Due to the high temperatures and prolonged, strenuous activity, they produce large amounts of sweat that cannot be expelled, also increasing their risk of heatstroke, fainting, and other heat-related illnesses. Many cases of heatstroke due to prolonged work in hot and humid environments have been reported in recent years. Studies have shown that the heat discomfort and physiological stress caused by personal protective equipment can lead to dehydration, impaired professional judgment, fatigue, heatstroke, and exercise-induced heat illness among medical staff or workers in high-temperature environments. Therefore, developing a moisture-wicking and cooling garment for use in high-temperature and high-humidity environments is of great practical significance.

[0003] Previously, various cooling devices have been developed to alleviate occupational heat stress experienced by workers in high-temperature environments. For example, air-cooled clothing with built-in fans can be worn to cool the body by enhancing air convection and sweat evaporation. Furthermore, the intake of ice slurry has been shown to lower core body temperature, primarily due to the large latent heat of melting during the endothermic phase transition. However, most existing methods are not effectively and widely applicable to personal thermal management due to factors such as high cost, high energy consumption, large size, heavy weight, and limited working time. Summary of the Invention

[0004] This invention employs a novel technical approach, growing and hydrophobically-enhancing metal-organic framework (MOF) materials on the surface of carboxylated fibers to obtain superhydrophobic fabrics. It also incorporates the unique properties of superabsorbent membrane materials, disclosing a multifunctional moisture-wicking and cooling fabric and its preparation method. The preparation involves grafting and polymerizing carboxyl-containing aromatic free radicals onto the fiber surface to obtain carboxylated fabrics. Then, MOF materials are grown in situ on the surface of the carboxylated fibers to obtain MOF fabrics. By controlling the processing technology, while ensuring that the strength, breathability, hand feel, and wearing performance of the fabric (or fiber) are not affected, the MOF fabrics are hydrophobically treated using thermal crosslinking technology to obtain superhydrophobic MOF fabrics. Furthermore, an inorganic metal salt ethanolamine solution is mixed with a polymer and thermosetting to obtain a superabsorbent membrane. Finally, the prepared superabsorbent membrane is composited into the interlayer of the superhydrophobic MOF fabric, successfully preparing a "sandwich"-like moisture-wicking and cooling fabric with unidirectional moisture-wicking, perspiration-wicking, and antibacterial functions.

[0005] Current refrigeration methods suffer from high cost, large size, heavy weight, limited operating time, and restricted application scenarios, hindering their effective and widespread application in personal thermal management. This invention utilizes a diazo radical method to carboxylate fabrics, followed by in-situ growth to obtain MOF fabrics. Thermal crosslinking then yields superhydrophobic MOF fabrics with antibacterial and stain-resistant properties. By combining this with a membrane material possessing excellent moisture absorption properties, a "sandwich" structure fabric with double-sided unidirectional moisture-wicking capabilities is created. This enhances the garment's superior moisture absorption and cooling effect while endowing the fabric with antibacterial and stain-resistant multifunctionality.

[0006] The technical solution to achieve the objective of this invention is:

[0007] A multifunctional moisture-absorbing and cooling fabric includes a superhydrophobic fabric and a superabsorbent membrane material; the superhydrophobic fabric includes a fabric and a hydrophobic coating; the raw materials for preparing the moisture-absorbing membrane material include metal salts and polymers; preferably, the superabsorbent membrane material is formed by thermosetting an inorganic metal salt and a polymer solution.

[0008] This invention discloses a method for preparing the above-mentioned multifunctional moisture-absorbing and cooling fabric, comprising the following steps: using metal ions and organic ligands as raw materials, in-situ growth is carried out on the surface of carboxylated fabric and then treated with hydrophobic substances to obtain a superhydrophobic fabric; using metal salts and polymers as raw materials, a super-hygroscopic membrane material is obtained by curing; and the super-hygroscopic membrane material and the superhydrophobic fabric are combined to obtain a multifunctional moisture-absorbing and cooling fabric.

[0009] In this invention, the fabric is a cellulose-based fabric; the hydrophobic coating is a metal-organic framework coating treated with hydrophobic substances; the metal salt is an inorganic metal salt; and the polymer is a polystyrene-based polymer or a polyethylene-based polymer.

[0010] Preferably, the fabric is cotton, linen, or a blend thereof; the hydrophobic substance is a silane coupling agent, such as one or more of n-octyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, n-octyltriethoxysilane, or tridecafluorooctyltriethoxysilane; the raw materials for preparing the metal-organic framework include metal ions and organic ligands; the metal salt is one or more of calcium chloride, cobalt chloride, copper chloride, and lithium chloride; and the polymer is sodium polystyrene sulfonate and / or polyvinyl alcohol.

[0011] In this invention, a carboxylated fabric is obtained by carboxylation modification of the fabric using a diazo chemical method. Preferably, the fabric is added to a solution containing carboxyl aromatic free radicals, and the fabric fibers are subjected to in-situ diazo free radical graft polymerization to obtain the carboxylated fabric.

[0012] In this invention, during the in-situ growth of the metal-organic framework, the reaction temperature is 15–50°C and the time is 4–20 h, preferably 25–35°C and 8–15 h; during the hydrophobic treatment, the temperature is 100–180°C and the time is 0.5–5 h. Specifically, the MOF fabric is impregnated in a silane coupling agent solution and then baked at high temperature to obtain the superhydrophobic MOF fabric. The baking temperature is 100–180°C and the time is 0.5–5 h, preferably 120–150°C and 1–3 h.

[0013] In this invention, the polymer used in preparing the superabsorbent membrane material is one or more of sodium polystyrene sulfonate and polyvinyl alcohol. Specifically, the superabsorbent membrane is obtained by mixing an inorganic metal salt ethanolamine solution with a polymer solution and then thermally curing it. The mass ratio of metal salt to polymer is 5:1 to 1:2; the curing temperature is 30 to 80°C, and the time is 3 to 15 hours; preferably, the mass ratio of metal salt to polymer is (1 to 3.5):1; the curing temperature is 40°C, and the time is 6 to 12 hours.

[0014] This invention loads a super-hygroscopic membrane material into a superhydrophobic MOF fabric interlayer to form a multifunctional moisture-absorbing and cooling fabric with a "sandwich" structure, which has a one-way moisture-wicking function.

[0015] This invention discloses a multifunctional moisture-wicking and cooling fabric, which is a functionalized modified fabric composite moisture-wicking membrane material. The fiber surface has a superhydrophobic MOF coating structure. This superhydrophobic MOF structure is formed by in-situ growth of metal ions and organic ligand solutions on the surface of carboxylated fibers, and is then hydrophobically treated with a silane coupling agent. The superhygroscopic membrane material is obtained by thermosetting an inorganic metal salt ethanolamine solution uniformly mixed in a polymer. This invention discloses the application of the above-mentioned multifunctional moisture-wicking and cooling fabric in the preparation of cooling clothing.

[0016] This invention involves adding carboxylated fabric to a solution of metal ions and organic ligands, and obtaining MOF fabric through in-situ growth. Then, the MOF fabric is added to an ethanol solution of a silane coupling agent, and thermally crosslinked to obtain the multifunctional MOF fabric. Alternatively, this invention involves uniformly mixing an inorganic metal salt ethanolamine solution with a polymer solution, and obtaining the super-hygroscopic membrane material through thermal curing. Preferably, calcium chloride, lithium chloride, and cobalt chloride are used as inorganic metal salts, and sodium polystyrene sulfonate and polyvinyl alcohol are used as polymer substrates. After uniform mixing and thermal curing, the super-hygroscopic membrane material is obtained. This invention also involves loading the super-hygroscopic membrane material onto a superhydrophobic MOF fabric to obtain the multifunctional moisture-wicking and cooling garment. Preferably, the super-hygroscopic membrane material is placed in the interlayer of the superhydrophobic MOF fabric to obtain the multifunctional moisture-wicking and cooling garment with a "sandwich" structure and double-sided unidirectional moisture-wicking function.

[0017] This invention utilizes a composite of superabsorbent membrane material and superhydrophobic MOF fabric to prepare a multifunctional moisture-absorbing and cooling garment with a one-way moisture-wicking "sandwich" structure.

[0018] This invention discloses a method for preparing the above-mentioned multifunctional moisture-absorbing and cooling garment, comprising the following steps:

[0019] (1) Carboxyl groups are introduced into the fiber surface by diazo radical covalent grafting modification to obtain carboxylated fabrics;

[0020] (2) The carboxylated fabric was immersed in a solution of metal ions and organic ligands and allowed to stand for reaction. The sample was taken out and washed several times to remove unreacted monomers, metal ions and MOF particles physically adsorbed on the fiber surface. Finally, it was dried to obtain MOF fabric. Then, the MOF fabric was immersed in an ethanol solution of silane coupling agent for hydrophobic treatment, and then baked to obtain superhydrophobic MOF fabric.

[0021] (3) Dissolve the inorganic metal salt in water by ultrasonication, then add ethanolamine solution and mix evenly by ultrasonication; then mix the above solution evenly with the polymer solution and obtain the super-hygroscopic membrane material by thermosetting.

[0022] (4) The super-hygroscopic membrane material prepared above is composited in the superhydrophobic MOF fabric interlayer. The excellent moisture absorption properties of the membrane material are combined with the anti-fouling and antibacterial properties of the superhydrophobic MOF fabric to prepare a multifunctional moisture-absorbing and cooling garment with a one-way moisture-wicking "sandwich" structure.

[0023] The reaction steps involved are as follows:

[0024] (1) Carboxylation of fiber surface:

[0025] First, aniline containing carboxyl groups is diazotized to form carboxyphenyl diazonium salt. Then, cotton fabric is added to the above carboxyphenyl diazonium salt solution, along with the reducing agent vitamin C (VC). The reaction solution is heated, and the aromatic diazonium salt is reduced to highly reactive free radicals, which induce the hydroxyl groups on the surface of cotton fibers to generate oxygen free radicals. Then, the carboxyphenyl free radicals and oxygen free radicals undergo covalent grafting to generate cotton fabric with carboxyl polymer molecular brushes.

[0026] (2) MOF in situ growth:

[0027] Organic ligands and metal salts were dissolved in anhydrous methanol and stirred to prepare ligand precursor solution and metal ion precursor solution, respectively. Then, carboxylated cotton fabric was immersed in the above mixed solution and allowed to react. The sample was taken out and washed multiple times to remove unreacted monomers, metal ions and MOF particles physically adsorbed on the fiber surface. Finally, it was dried to obtain MOF fabric.

[0028] (3) Hydrophobic finishing:

[0029] MOF fabric is immersed in an ethanol solution of silane coupling agent for hydrophobic treatment, and then taken out and baked at high temperature to obtain superhydrophobic MOF fabric.

[0030] (4) Preparation of superabsorbent membrane material:

[0031] Inorganic metal salts are ultrasonically dissolved in water, then ethanolamine solution is added and ultrasonically mixed evenly; the above solution is then mixed evenly with a polymer solution, and the superabsorbent membrane material is obtained by thermosetting.

[0032] The super-hygroscopic membrane material prepared above is composited into the interlayer of superhydrophobic MOF fabric. By utilizing the excellent moisture absorption properties of the membrane material in conjunction with the anti-fouling and antibacterial properties of the superhydrophobic MOF fabric, a multifunctional moisture-absorbing and cooling garment with a one-way moisture-wicking "sandwich" structure is prepared.

[0033] As an example, the preparation method of the multifunctional moisture-absorbing and cooling garment of the present invention includes the following steps:

[0034] (1) Carboxyl groups are introduced into the surface of cotton fabric by diazonium free radical covalent grafting modification to obtain carboxylated cotton fabric; the carboxyl aniline is 4-aminoaniline, m-aminoaniline or 5-aminoisophthalic acid;

[0035] (2) The carboxylated fabric is immersed in a solution of metal ions and organic ligands and MOF fabric is obtained by in-situ growth. The MOF is ZIF-8 or ZIF-67. The MOF fabric is immersed in an ethanol solution of silane coupling agent for hydrophobic treatment and baked to obtain superhydrophobic MOF fabric. The silane coupling agent is n-octyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, n-octyltriethoxysilane or tridecafluorooctyltriethoxysilane.

[0036] (3) The ethanolamine solution of inorganic metal salt is mixed evenly with the polymer solution and then heat-cured to obtain the super-hygroscopic membrane material; the inorganic metal salt is calcium chloride, copper chloride, cobalt chloride or lithium chloride; the polymer is sodium polystyrene sulfonate or polyvinyl alcohol solution;

[0037] (4) The super-hygroscopic membrane material prepared above is composited in the superhydrophobic MOF fabric interlayer to obtain a multifunctional moisture-absorbing and cooling garment with a one-way moisture-wicking "sandwich" structure.

[0038] In the above technical solution, in step (1), the mass concentration of the hydrochloric acid solution is 3.7%; the diazo radical grafting polymerization temperature is 30℃; the grafting reaction time is 12h; and the reducing agent is vitamin C (VC).

[0039] In the above technical solution, the in-situ growth temperature in step (2) is 30℃.

[0040] In the above technical solution, in step (3), the temperature at which the inorganic metal salt ethanolamine solution and the polymer solution are mixed is room temperature.

[0041] Compared with the prior art, the technical solution provided by the present invention has the following advantages:

[0042] 1. This invention loads the prepared superabsorbent membrane material into a superhydrophobic MOF fabric interlayer to obtain a "sandwich" structure moisture-absorbing and cooling garment with a superhydrophobic outer layer and a superhydrophilic inner layer, possessing unidirectional moisture-wicking, perspiration-wicking, and antibacterial functions. This garment has a significant dehumidification and cooling effect, which can significantly reduce the relative humidity and temperature in the human body's microenvironment, thereby reducing the human body's heat index, decreasing the risk of heatstroke, fainting, dehydration, and other "heat-related illnesses," and improving human thermal comfort. Therefore, it has good application prospects in the field of moisture-absorbing and cooling special protective clothing for human thermal management. At the same time, the preparation process is simple and easy to industrialize and promote.

[0043] 2. In this invention, an aqueous solution of inorganic metal salt and an ethanolamine solution are mixed to form coordinate bonds and crosslinked in a polymer solution. The mixture is then thermosetting to form a film, resulting in a moisture-absorbing membrane material with excellent moisture absorption properties. This moisture-absorbing membrane has a simple preparation process, excellent moisture absorption performance, large water absorption capacity, and significant dehumidification effect. It also has excellent recyclability, the absorbed water is easily desorbed, it is regenerable with low energy consumption, and it is easy to mass-produce.

[0044] 3. This invention utilizes metal-organic frameworks (MOFs) with extremely high specific surface area, diverse structures, and tunable micropores, loaded onto soft, flexible, renewable, and easily processed fibrous substrates to obtain functional textiles with MOF coatings on the surface. This endows the textiles with porous high specific surface area, thereby expanding the functional applications of fiber materials. Firstly, this invention introduces carboxyl aromatic polymer chains onto the fiber surface using a diazo radical grafting method. The reactive aromatic organic polymer graft layer serves as a "secondary reaction platform" for fiber functional modification, allowing MOF crystals to grow in situ on the fiber surface to prepare MOF fabrics. Then, thermal crosslinking and hydrophobic finishing are used to obtain superhydrophobic MOF fabrics. This solves the problem of poor fastness associated with direct coating or coatings containing powdered MOFs in traditional methods, providing a new solution for preparing durable flexible film composite MOF fabrics and a new approach for the preparation of functional specialty textiles. Attached Figure Description

[0045] Figure 1 This is a scanning electron microscope (SEM) image of the ZIF-8 type MOF fabric prepared in Example 1, showing that the fiber surface is loaded with a large number of nano-sized MOF particles.

[0046] Figure 2 This is a water contact angle test diagram of the surface of the hydrophobic MOF fabric prepared in Example 1.

[0047] Figure 3 This is a test image of the water adhesion force on the surface of the superhydrophobic MOF fabric prepared in Example 1.

[0048] Figure 4 This is an optical photograph of the superhygroscopic Ca-PSS membrane prepared in Example 1.

[0049] Figure 5 The amount of water adsorbed by the superhygroscopic Ca-PSS membrane prepared in Example 1 at 35°C under different relative humidities is shown.

[0050] Figure 6 This is a test diagram of the antibacterial performance of the superhydrophobic MOF fabric prepared in Example 1 against Escherichia coli.

[0051] Figure 7 This is a test diagram of the antibacterial performance of the superhydrophobic MOF fabric prepared in Example 1 against Staphylococcus aureus.

[0052] Figure 8 This is a temperature change graph showing the cooling effect of the multifunctional moisture-absorbing and cooling garment prepared in Example 1 during practical application.

[0053] Figure 9 This is a graph showing the relative humidity change during the practical application of the multifunctional moisture-absorbing and cooling garment prepared in Example 1, demonstrating its cooling effect.

[0054] Figure 10 This is a graph showing the change in the thermal index of the multifunctional moisture-absorbing and cooling garment prepared in Example 1 during its actual application.

[0055] Figure 11 This is a test diagram of the antibacterial performance of the unmodified fabric against Escherichia coli in Comparative Example 2.

[0056] Figure 12 This is a test chart showing the antibacterial performance of the unmodified fabric against Staphylococcus aureus in Comparative Example 2.

[0057] Figure 13 This is a schematic diagram illustrating the structure and function of the "sandwich" structure moisture-wicking and cooling garment with unidirectional moisture-wicking, perspiration-absorbing, and antibacterial functions of the present invention. Detailed Implementation

[0058] This invention relates to a multifunctional moisture-absorbing and cooling garment and its preparation method, specifically to a method for in-situ growth of superhydrophobic MOF fabric and thermosetting of superhygroscopic material into a film, wherein a superhygroscopic film is loaded into a superhydrophobic MOF fabric interlayer to prepare a multifunctional moisture-absorbing and cooling garment with a "sandwich" structure having double-sided unidirectional moisture-wicking function.

[0059] This invention proposes a novel protective strategy: utilizing a superabsorbent membrane material combined with a superhydrophobic MOF fabric to prepare a "sandwich"-like structure moisture-wicking and antibacterial garment. This reduces the humidity and perceived temperature of the human body's microenvironment and alleviates thermal stress through moisture absorption and cooling, improving comfort when working in high-temperature environments. The preparation process of this multifunctional moisture-wicking and cooling garment mainly involves: adding the fabric to a solution containing carboxyl aromatic diazonium salts, then adding a chemical reducing agent, and undergoing an in-situ polymerization reaction to obtain a fabric with surface covalently grafted carboxyl aromatic polymer chains; then, growing the fabric with surface-grafted carboxyl aromatic polymer chains in a solution containing metal ions and organic ligands to obtain MOF fabric, and then hydrophobically finishing the MOF fabric through thermal crosslinking to obtain a superhydrophobic MOF fabric; finally, incorporating the prepared moisture-wicking membrane Ca-PSS into the interlayer of the superhydrophobic MOF fabric, successfully preparing a "sandwich"-like structure moisture-wicking and cooling garment with unidirectional moisture-wicking and antibacterial functions. The "sandwich" structure multifunctional moisture-wicking and cooling garment features double-sided unidirectional moisture wicking, excellent moisture absorption and cooling performance, and anti-fouling and antibacterial functions. Furthermore, the preparation method boasts advantages such as simple process, mild conditions, abundant and inexpensive raw materials, and ease of large-scale production. The resulting moisture-wicking and cooling garment plays a crucial role in reducing the risk of heatstroke and even heat exhaustion, and has broad application prospects among those working in high-temperature and high-humidity environments, such as medical personnel, firefighters, police officers, and outdoor construction workers.

[0060] The multifunctional moisture-absorbing and cooling fabric disclosed in this invention consists of a superhydrophobic MOF fabric and a superhygroscopic membrane material sandwiched between it. Specifically, the superhydrophobic fabric is located on both sides of the superhygroscopic membrane material, or two layers of superhydrophobic fabric sandwich a layer of superhygroscopic membrane material. The composite method of the superhydrophobic fabric and the superhygroscopic membrane material is a conventional technique, employing common textile sewing methods. The superhydrophobic MOF fabric is obtained by in-situ growth of MOF on the surface of carboxylated fibers and followed by hydrophobic finishing. The superhygroscopic membrane material is obtained by thermosetting an inorganic metal salt ethanolamine solution mixed with a polymer.

[0061] This invention modifies the fibers of fabrics such as cotton and linen by carboxylation, and uses MOF materials to grow in situ on the surface of carboxylated fibers to obtain MOF-coated fabrics. Then, hydrophobic finishing is performed to obtain superhydrophobic MOF fabrics.

[0062] In this invention, the fabric is cotton and / or linen; the MOF is one or more of ZIF-8 and ZIF-67; the hydrophobic substance is one or more of n-octyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, n-octyltriethoxysilane, or tridecafluorooctyltriethoxysilane. Preferably, a methanol solution of zinc ions and dimethylimidazole is used as the metal ion solution and ligand solution, respectively, to obtain the ZIF-8 type MOF fabric.

[0063] In this invention, the inorganic metal salt is one or more of calcium chloride, cobalt chloride, copper chloride, and lithium chloride.

[0064] In this invention, the polymer solution is one or more of sodium polystyrene sulfonate and polyvinyl alcohol.

[0065] In this invention, cotton fabric is added to a solution containing carboxyl aromatic free radicals to perform in-situ diazo radical grafting polymerization on the cotton fibers to obtain the carboxylated fabric. The carboxylated fabric is then added to a metal ion solution and an organic ligand solution, and the MOF fabric is obtained through in-situ growth. The reaction temperature is 15~50℃, preferably 25~35℃; the reaction time is 4~20h, preferably 8~15h.

[0066] In this invention, MOF fabric is impregnated in an ethanol solution of silane coupling agent, and then the superhydrophobic MOF fabric is obtained by high-temperature baking. The baking temperature is 100~180℃, preferably 120~150℃, and the baking time is 0.5~5h, preferably 1~3h.

[0067] In this invention, aqueous solutions of inorganic metal salt ethanolamine of different concentrations are mixed with polymer solutions in different proportions, and then cured to obtain the superhygroscopic membrane material. The concentration of the inorganic metal salt is 1 mol / L to 8 mol / L, preferably 3 to 5 mol / L; the curing temperature is 30 to 80℃, preferably 40 to 50℃.

[0068] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments. The raw material involved is a conventional commodity, specifically a hydrophilic cotton fabric (5×5 cm). 2 (or 100% cotton T-shirt (size L); the specific preparation and testing procedures are standard techniques, and unless otherwise specified, the experiment is conducted in air.) Example 1

[0069] (1) Preparation of carboxylated cotton fabrics

[0070] A round-bottom flask equipped with a thermometer and a magnetic stirrer was used. 60 ml of 1 mol / L hydrochloric acid solution was added, followed by 227.7 mg of sodium nitrite, and the mixture was stirred until dissolved to form a sodium nitrite hydrochloric acid solution. 411.4 mg of 3-aminobenzoic acid was added and the mixture was incubated at 0°C for 1 hour to generate a 0.05 mol / L diazonium salt of 3-aminobenzoic acid. A piece of cotton fabric was then immersed in the reaction solution, followed by the addition of 53 mg of vitamin C as a reducing agent. The temperature was raised to 30°C and the reaction was maintained for 12 hours. The sample was then removed, washed with ethanol and water, and dried at 50°C to obtain the carboxylated cotton fabric.

[0071] (2) Preparation of superhydrophobic MOF fabrics

[0072] First, 1.25 mmol of Zn(NO3)2.6(H2O) and 5.05 mmol of 2-methylimidazole were ultrasonically dissolved in 25 mL of methanol solution to obtain metal ion solution and organic ligand solution, respectively. Then, carboxylated cotton fabric was immersed in the metal ion solution and ultrasonically sonicated for 0.5 h. Next, the organic ligand solution was added to the above reaction solution and ultrasonicated for another 0.5 h. The reaction was then carried out at room temperature for 10 h. The sample was removed, washed with methanol, and dried at 50 °C to obtain ZIF-8 type MOF cotton fabric. The MOF fabric was then immersed in a 5 wt% n-octyltriethoxysilane ethanol solution for 1 h, and then transferred to a 120 °C oven for baking for 1.5 h to obtain superhydrophobic MOF fabric.

[0073] Figure 1 The image shows a scanning electron microscope (SEM) image of the ZIF-8 type MOF fabric prepared above, with a large number of nanoscale MOF particles loaded on the fiber surface.

[0074] (3) Preparation of superabsorbent membrane

[0075] 0.6 mol of CaCl2·2H2O was ultrasonically dissolved in 150 mL of water, and then 3.6 mL of ethanolamine was added to obtain a 4 mol / L Ca complex solution. The Ca complex solution was mixed with sodium polystyrene sulfonate solution (PSS, Mw~200000, 30 wt%) at a volume ratio of 1:1 and stirred for 3 h to obtain a Ca-PSS dispersion solution. The Ca-PSS dispersion solution was then poured into a petri dish mold and dried at 40 °C for 6 h to prepare a superhygroscopic Ca-PSS membrane.

[0076] (4) The super-hygroscopic membrane Ca-PSS prepared above is composited in the sandwich of two layers of superhydrophobic MOF fabric to prepare a multifunctional moisture-absorbing and cooling clothing fabric with a one-way moisture-wicking "sandwich" structure, which has excellent moisture absorption performance and synergistic anti-fouling and antibacterial properties.

[0077] (5) Contact angle test

[0078] The wetting properties of superhydrophobic MOF fabrics were tested using a fully automated micro-droplet wettability measuring instrument from Krüss GmbH, Germany. Deionized water was selected as the test droplet, with a droplet volume of 5 μL. Five tests were performed, and the average value was taken. The contact angle of the MOF fabric surface after hydrophobic treatment was measured to be 162.7°, indicating that it has excellent superhydrophobic properties.

[0079] (6) Water adhesion test

[0080] The adhesion force of water to the surface of superhydrophobic MOF fabric was tested using a DCAT 11 micro-sensor. Deionized water was selected as the test droplet with a droplet volume of 4 μL. The measured water adhesion force of the fabric was 27.05 μN, indicating that the interaction force between the surface of the superhydrophobic MOF fabric and water is very weak, and it can exhibit excellent self-cleaning and anti-fouling properties.

[0081] Figure 2 The image shows the water contact angle test results of the hydrophobic MOF fabric surface prepared above. The measured water contact angle of the fabric is 162.7°, indicating that the treated MOF fabric has superhydrophobic properties.

[0082] Figure 3 The above-prepared superhydrophobic MOF fabric surface water adhesion force test diagram shows that the water adhesion force of the fabric is 27.05μN, indicating that the interaction force between the superhydrophobic MOF fabric surface and water is very weak, thus exhibiting excellent anti-fouling and self-cleaning properties.

[0083] (7) Moisture absorption belt water volume test

[0084] The amount of water adsorbed by the Ca-PSS membrane at different relative humidities in an environment of 35℃ was determined using an AquaLab vapor adsorption analyzer, and the amount of water adsorbed per unit mass of the Ca-PSS membrane (gg) was calculated. -1 The saturated water absorption rates of the Ca-PSS membrane were measured to be 0.71, 1.22, 1.65, 2.52, and 3.58 g / L at relative humidity levels of 60%, 70%, 80%, 90%, and 95%, respectively. −1 It exhibits excellent moisture absorption and water-carrying capacity.

[0085] Figure 4 This is an optical photograph of the superhygroscopic Ca-PSS membrane prepared above. Figure 5 The water adsorption capacity of the super-hygroscopic Ca-PSS membrane prepared above at 35℃ under different relative humidities was measured. The saturated water absorption rate of the Ca-PSS membrane at relative humidities of 60%, 70%, 80%, 90% and 95% was measured, showing that it has excellent moisture absorption and water carrying capacity.

[0086] (8) Antibacterial test

[0087] The antibacterial properties of MOF fabric against Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 29213) were tested using a plate coating method. The inhibition rates of MOF fabric against Escherichia coli and Staphylococcus aureus were measured to be 99.99% and 98.99%, respectively, indicating that MOF fabric has excellent antibacterial properties.

[0088] Figure 6The above-prepared superhydrophobic MOF fabric exhibits excellent antibacterial properties against Escherichia coli. The measured antibacterial rate against Escherichia coli is 99.99%, indicating that the superhydrophobic MOF fabric has excellent antibacterial properties against Escherichia coli.

[0089] Figure 7 This is a test image showing the antibacterial performance of the superhydrophobic MOF fabric prepared above against Staphylococcus aureus. The measured antibacterial rate against Staphylococcus aureus was 98.99%, indicating that the superhydrophobic MOF fabric possesses excellent antibacterial properties against Staphylococcus aureus.

[0090] (9) Following the above method, process the all-cotton T-shirt (size L) and prepare the super-absorbent Ca-PSS membrane. Sew the super-absorbent Ca-PSS membrane onto the inner walls of the front and back of the T-shirt. The inner layer (skin-contact layer) is also processed all-cotton T-shirt fabric. Conduct temperature, relative humidity, and heat index tests in the human body microenvironment, using an unprocessed all-cotton T-shirt (size L) as a control.

[0091] The temperature, relative humidity, and heat index changes inside the special protective suit were monitored and recorded using a Kestrel D3 temperature and humidity meter during 20 minutes of running and 110 minutes of sitting to evaluate its moisture absorption and cooling effect. When the ambient temperature, relative humidity, and heat index were approximately 28.3℃, 77.0%, and 31.8℃, respectively, the temperature, relative humidity, and heat index of the control group increased to 36.5℃, 91.0%, and 65.0℃, respectively, while those of the experimental group were 31.6℃, 60%, and 39.5℃, respectively. These results indicate that the Ca-PSS composite superhydrophobic MOF fabric garment has excellent moisture absorption and cooling effects.

[0092] Figure 8 This is a temperature change graph showing the cooling effect of the multifunctional moisture-absorbing and cooling garment prepared above in practical applications. The test results show that, compared with the control group, the temperature in the human body microenvironment inside the special protective clothing decreased from 36.5℃ to 31.6℃, indicating that the moisture-absorbing and cooling garment has a significant cooling effect.

[0093] Figure 9 This is a graph showing the relative humidity change during the practical application of the multifunctional moisture-absorbing and cooling garment prepared above. The test results show that, compared with the control group, the relative humidity in the human microenvironment inside the special protective clothing decreased from 91.0% to 60.0%, indicating that the moisture-absorbing and cooling garment has a significant dehumidification effect.

[0094] Figure 10This is a graph showing the change in thermal index during the practical application of the multifunctional moisture-wicking and cooling garment prepared above. The test results show that, compared to the control group, the thermal index in the human body microenvironment inside the special protective clothing decreased from 65.0℃ to 39.5℃, indicating that the moisture-wicking and cooling garment has a significant cooling effect that reduces thermal stress on the human body and improves human comfort. Example 2

[0095] (1) The preparation of carboxylated cotton fabric is described in Example 1.

[0096] (2) The preparation of superhydrophobic MOF fabric is described in Example 1.

[0097] (3) Preparation of superabsorbent membrane

[0098] 0.6 mol of CuCl₂·2H₂O was ultrasonically dissolved in 150 mL of water, and then 3.6 mL of ethanolamine was added to obtain a 4 mol / L Cu complex solution. The Cu complex was then mixed with sodium polystyrene sulfonate (PSS) solution at a volume ratio of 1:1 and stirred for 3 h to obtain a Cu-PSS dispersion. The Cu-PSS dispersion was then poured into a petri dish mold and dried at 40 °C for 12 h to prepare a superhygroscopic Cu-PSS membrane. The amount of water adsorbed by the Cu-PSS membrane at different relative humidities in an environment of 35 °C was measured using an AquaLab vapor adsorption analyzer, and the amount of water adsorbed per unit mass of the Cu-PSS membrane (g g) was calculated. -1 The saturated water absorption rates of the Cu-PSS membrane were measured to be 0.6, 1.05, 1.85, 2.25, and 2.85 g / L at relative humidity levels of 60%, 70%, 80%, 90%, and 95%, respectively. −1 It exhibits excellent moisture absorption and water-carrying capacity.

[0099] (4) The super-hygroscopic membrane Cu-PSS prepared above is composited in the superhydrophobic MOF fabric interlayer to obtain a multifunctional moisture-absorbing and cooling fabric with a one-way moisture-wicking "sandwich" structure that has excellent moisture absorption performance and synergistic anti-fouling and antibacterial properties.

[0100] (5) Temperature, relative humidity and thermal index in the human microenvironment were tested in accordance with Example 1.

[0101] The temperature, relative humidity, and heat index of the control group increased to 36.8℃, 92.6%, and 67.0℃, respectively, while the temperature, relative humidity, and heat index of the experimental group were 32.4℃, 62%, and 40.5℃, respectively. The results show that Cu-PSS composite superhydrophobic MOF fabric clothing has excellent moisture absorption and cooling effects. Example 3

[0102] (1) The preparation of carboxylated cotton fabric is described in Example 1.

[0103] (2) The preparation of superhydrophobic MOF fabric is described in Example 1.

[0104] (3) Preparation of superabsorbent membrane

[0105] 0.6 mol of CaCl₂·2H₂O was ultrasonically dissolved in 150 mL of water, and then 3.6 mL of ethanolamine was added to obtain a 4 mol / L Ca complex solution. The Ca complex was then mixed with a polyvinyl alcohol (PVA, Mw ~145000, 20 wt%) solution at a volume ratio of 1:1 and stirred for 3 h to obtain a Ca-PVA dispersion. The Ca-PVA dispersion was then poured into a petri dish mold and dried at 40 °C for 12 h to prepare a superhygroscopic Ca-PVA membrane. The amount of water adsorbed by the Ca-PVA membrane at different relative humidities in an environment of 35 °C was determined using an AquaLab vapor adsorption analyzer, and the amount of water adsorbed per unit mass of the Ca-PVA membrane (gg) was calculated. -1 The saturated water absorption rates of the Ca-PVA film were measured to be 0.56, 1.15, 1.90, 2.45, and 2.96 g / L at relative humidity levels of 60%, 70%, 80%, 90%, and 95%, respectively. −1 It exhibits excellent moisture absorption and water-carrying capacity.

[0106] (4) The super-hygroscopic membrane Ca-PVA prepared above is composited in the superhydrophobic MOF fabric interlayer. The excellent moisture absorption properties of the membrane material are combined with the anti-fouling and antibacterial properties of the superhydrophobic MOF fabric to prepare a multifunctional moisture-absorbing and cooling clothing fabric with a one-way moisture-wicking "sandwich" structure.

[0107] (5) Temperature, relative humidity and thermal index in the human microenvironment were tested in accordance with Example 1.

[0108] The temperature, relative humidity, and heat index changes inside the special protective suit were monitored and recorded using a Kestrel D3 temperature and humidity meter during 20 minutes of running and 110 minutes of sitting to evaluate its moisture absorption and cooling effect. When the ambient temperature, relative humidity, and heat index were approximately 28.5℃, 75.0%, and 33.4℃, respectively, the temperature, relative humidity, and heat index of the control group increased to 36.3℃, 92.4%, and 66.2℃, respectively, while those of the experimental group were 32.4℃, 64%, and 40.2℃, respectively. These results indicate that the Ca-PVA composite superhydrophobic MOF fabric garment also exhibits excellent moisture absorption and cooling effects.

[0109] Comparative Example 1

[0110] Following the method described in Example 1, cotton T-shirts (size L) were processed, and tests were conducted on the temperature, relative humidity, and heat index in the human body microenvironment. The temperature, relative humidity, and heat index of the control group were 36.3℃, 91.2%, and 63.8℃, respectively, while those of the experimental group were 35.8℃, 90.6%, and 60.6℃, respectively. The test results showed that the values ​​of temperature, relative humidity, and heat index in the human body microenvironment were comparable to those of the control group. The results indicate that the superhydrophobic MOF fabric does not have the effect of absorbing sweat, dehumidifying, or cooling.

[0111] Comparative Example 2

[0112] (1) The preparation of the super-hygroscopic membrane is as described in Example 1.

[0113] (2) The super absorbent Ca-PSS membrane was sewn onto the inner walls of the front and back of the unfinished T-shirt. The inner layer (skin-contact layer) was also an unfinished T-shirt fabric. Referring to Example 1, temperature, relative humidity and heat index tests were conducted in the human body microenvironment, with an unfinished cotton T-shirt (size L) as a control.

[0114] Because unmodified cotton is a hydrophilic fabric, its contact angle is zero, therefore it does not have anti-fouling and self-cleaning properties.

[0115] The temperature, relative humidity, and heat index changes inside the special protective suit were monitored and recorded using a Kestrel D3 temperature and humidity meter during 20 minutes of running and 110 minutes of sitting to evaluate its moisture absorption and cooling effect. The temperature, relative humidity, and heat index of the control group were 36.8℃, 93.5%, and 66.8℃, respectively, while those of the experimental group were 35.4℃, 72%, and 51.6℃, respectively. The test results show that the temperature, humidity, and heat index in the microenvironment of the human body inside the protective suit decreased to some extent, but the effect was not very significant, and the improvement in human comfort was poor; at the same time, the damp clothing would stick to the surface of the human skin, which also caused discomfort.

[0116] (5) Antibacterial test

[0117] The antibacterial properties of cotton fabrics against *Escherichia coli* (ATCC 25922) and *Staphylococcus aureus* (ATCC 29213) were tested using a plate coating method. The inhibition rate of unmodified cotton fabric against both *Escherichia coli* and *Staphylococcus aureus* was found to be 0, indicating that unmodified cotton fabrics do not possess antibacterial function.

[0118] Figure 11 This is a test chart showing the antibacterial performance of the unmodified fabric against Escherichia coli. The measured antibacterial rate against Escherichia coli was 0, indicating that the unmodified fabric does not possess antibacterial properties against Escherichia coli.

[0119] Figure 12This is a test chart showing the antibacterial performance of the unmodified fabric against Staphylococcus aureus. The measured antibacterial rate against Staphylococcus aureus was 0, indicating that the unmodified fabric does not possess antibacterial properties against Staphylococcus aureus.

[0120] Compare with Example 1

[0121] One-way moisture-wicking fabrics are a type of functional textile with moisture-absorbing, moisture-wicking, and quick-drying properties. They can control the flow and direction of water molecules, allowing sweat to transfer from the inner layer of the fabric to the outer surface while preventing external water molecules from penetrating the inner layer, thus improving the comfort of the garment. Using commercially available one-way moisture-wicking cotton clothing with good moisture-wicking properties as a control, a parallel experiment was conducted to test the thermal index in the human body microenvironment, following Example 1. The thermal index was 45.8℃.

[0122] Ambient temperature and humidity are combined to form the heat index, used to assess human thermal comfort. When the heat index exceeds 54°C, the risk of heatstroke is extremely high, potentially leading to heat exhaustion. Temperatures between 41 and 54°C are considered dangerous, and prolonged exposure can cause heatstroke, muscle cramps, and heat exhaustion. Therefore, reducing relative humidity and temperature plays a crucial role in lowering the risk of heatstroke and even heat exhaustion. This invention produces MOF fabric by in-situ growing a functionalized MOF coating on the surface of carboxylated fibers, followed by hydrophobic finishing to obtain a multifunctional superhydrophobic MOF fabric. Furthermore, a superabsorbent membrane material is obtained through thermosetting and loaded into the superhydrophobic MOF fabric interlayer, forming a double-sided, one-way moisture-wicking, multifunctional moisture-absorbing and cooling garment with a superhydrophobic outer layer and a superhydrophilic inner layer "sandwich" structure. See [link to relevant documentation]. Figure 13This is of great significance for developing moisture-wicking and cooling clothing suitable for special protective occupations. This invention uses carboxylated aniline to obtain carboxylated fabric via diazo radical polymerization; then, an MOF coating is grown in situ on the surface of the carboxylated fibers to obtain MOF fabric; finally, a superhydrophobic MOF fabric is obtained through thermal crosslinking and hydrophobic treatment. Alternatively, an inorganic metal salt is mixed with ethanolamine to form a metal complex, which is then mixed with a polymer and thermosetting to obtain a super-hygroscopic membrane material. Finally, a superabsorbent membrane was loaded into a superhydrophobic MOF fabric interlayer to prepare a multifunctional moisture-wicking and cooling garment with a "sandwich" structure. This garment possesses excellent antibacterial, self-cleaning, and stain-resistant properties without affecting its original wearability. It also exhibits excellent moisture-wicking and sweat-capturing capabilities, excellent recyclability, and strong adaptability. Furthermore, the designed "sandwich" structure features a unique double-sided unidirectional moisture-wicking property: a superhydrophobic outer fabric and a superhydrophilic inner absorbent membrane. This ensures that sweat is quickly guided to the middle absorbent membrane, maintaining effective sweat evaporation and preventing sweat buildup around the body, thus avoiding the formation of a high-temperature, high-humidity environment. This is expected to significantly reduce the risk of heatstroke among workers, truly achieving a moisture-wicking and cooling effect. This invention, while ensuring the garment's moisture-wicking and cooling effect, also endows it with valuable additional functions such as antibacterial and stain-resistant properties. The moisture-wicking and cooling garment prepared by this invention can effectively improve the comfort of workers, reduce heat discomfort and physiological stress caused by personal protective equipment, and lower the risk of dehydration, heatstroke, fatigue, and exercise-induced heat illness for medical staff or workers in high-temperature environments. It provides safety guarantees for relevant personnel, thereby improving their work efficiency, enthusiasm, sense of professional belonging, and pride, and generating a positive social effect for ensuring social safety. The multifunctional moisture-wicking and cooling garment has a simple preparation process, mild reaction conditions, and can be mass-produced. It has excellent performance and application prospects in special workplaces and can be expanded to include workers in high-temperature and high-humidity environments such as epidemic prevention medical personnel, firefighters, police officers, and outdoor construction workers.

Claims

1. A multifunctional moisture-wicking and cooling fabric, characterized in that, The multifunctional moisture-absorbing and cooling fabric includes a superhydrophobic fabric and a superabsorbent membrane material; the fabric is a cellulose-based fabric; the superhydrophobic fabric is located on both sides of the superabsorbent membrane material; the preparation method of the multifunctional moisture-absorbing and cooling fabric includes the following steps: immersing a carboxylated fabric in a solution of metal ions and organic ligands, and obtaining a MOF fabric through in-situ growth, wherein the MOF is ZIF-8 or ZIF-67; immersing the MOF fabric in an ethanol solution of a silane coupling agent for hydrophobic treatment, and baking to obtain a superhydrophobic fabric, wherein the silane coupling agent is n-octyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, n-octyltriethoxysilane, or tridecafluorooctyltriethoxysilane; mixing an ethanolamine solution of an inorganic metal salt with a polymer solution uniformly, and obtaining a superabsorbent membrane material through thermosetting; wherein the inorganic metal salt is calcium chloride, copper chloride, cobalt chloride, or lithium chloride; the polymer is sodium polystyrene sulfonate or polyvinyl alcohol; combining the superabsorbent membrane material and the superhydrophobic fabric to obtain the multifunctional moisture-absorbing and cooling fabric.

2. The multifunctional moisture-absorbing and cooling fabric according to claim 1, characterized in that, The fabric is cotton, linen, or a blend thereof.

3. The method for preparing the multifunctional moisture-absorbing and cooling fabric according to claim 1, characterized in that, Carboxylated fabric is impregnated in a solution of metal ions and organic ligands, and MOF fabric is obtained through in-situ growth. The MOF is ZIF-8 or ZIF-67. The MOF fabric is impregnated in an ethanol solution of a silane coupling agent for hydrophobic treatment and then baked to obtain a superhydrophobic fabric. The silane coupling agent is n-octyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, n-octyltriethoxysilane, or tridecafluorooctyltriethoxysilane. An ethanolamine solution of an inorganic metal salt is mixed uniformly with a polymer solution, and a superhygroscopic membrane material is obtained through thermosetting. The inorganic metal salt is calcium chloride, copper chloride, cobalt chloride, or lithium chloride. The polymer is sodium polystyrene sulfonate or polyvinyl alcohol. The superhygroscopic membrane material and the superhydrophobic fabric are combined to obtain a multifunctional moisture-absorbing and cooling fabric.

4. The method for preparing the multifunctional moisture-absorbing and cooling fabric according to claim 3, characterized in that, The fabric is added to a solution containing carboxyl aromatic free radicals, and the fabric fibers are subjected to in-situ diazo free radical grafting polymerization to obtain the carboxylated fabric.

5. The method for preparing the multifunctional moisture-absorbing and cooling fabric according to claim 3, characterized in that, During in-situ growth, the reaction temperature is 15–50℃ and the time is 4–20 h; during hydrophobic treatment, the temperature is 100–180℃ and the time is 0.5–5 h.

6. The method for preparing the multifunctional moisture-absorbing and cooling fabric according to claim 3, characterized in that, The mass ratio of inorganic metal salt to polymer is 5:1 to 1:2; the curing temperature is 30 to 80℃, and the curing time is 3 to 15 hours.

7. The method for preparing the multifunctional moisture-absorbing and cooling fabric according to claim 3, characterized in that, By loading superabsorbent membrane material into the interlayer of superhydrophobic fabric, a multifunctional moisture-absorbing and cooling fabric is formed.

8. The application of the multifunctional moisture-absorbing and cooling fabric according to claim 1 in the preparation of cooling clothing.

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