Preparation method of a heat-insulating and breathable fiber

Abstract

The present invention belongs to the technical field of warm and breathable fibers, and discloses a preparation method of warm and breathable fibers. The preparation method is as follows: soaking linen fibers or cellulose fibers in glutaraldehyde aqueous solution I to obtain product I, then taking out product I and soaking it in molten polyethylene glycol to obtain product II, then taking out product II and soaking it in polyphenol aqueous solution and adding metal ion aqueous solution to the polyphenol aqueous solution for self-assembly of metal polyphenol network to obtain product III. The metal polyphenol network is obtained by coordination of metal ions and polyphenols. Finally, taking out product III and soaking it in glutaraldehyde aqueous solution II for reaction to obtain the final product, namely warm and breathable fibers; wherein, in the solution obtained by adding metal ion aqueous solution to polyphenol aqueous solution, the molar amount of metal ions is greater than the molar amount of polyphenols. The present invention forms a crosslinked interpenetrating network through multiple crosslinkings, so that the solid-phase material polyethylene glycol is fixed more firmly.

Description

Technical Field

[0001] The present invention belongs to the technical field of warm and breathable fibers, and relates to a preparation method of warm and breathable fibers. Background Art

[0002] Flax fibers or cellulose fibers have excellent comfort. In summer, flax fibers or cellulose fibers have a fast moisture absorption and release rate, can effectively regulate the ecological temperature environment on the surface of human skin, and have good breathability; phase change materials can undergo self-phase transitions according to changes in environmental temperature, storing heat or releasing heat. In winter, when flax fibers or cellulose fibers are used in combination with phase change materials, sufficient warmth retention effect can be obtained. However, when phase change materials are added to fibers, the content is often low and unstable, and there is a high possibility of overflowing from the fibers, so effective fixation is required.

[0003] For example, the literature ("Study on the preparation and properties of PAN / phase change microcapsule composite phase change fibers by wet spinning [J]. Synthetic Fiber Industry, 2024, 47(4): 1.") blends polyurea-coated n-octadecane phase change microcapsules (MPCM) with polyacrylonitrile (PAN) to prepare a spinning dope, and prepares PAN / MPCM composite phase change fibers with different MPCM contents by wet spinning. However, in practical applications, the shell materials of low-content phase change microcapsules will leak due to physical damage or chemical degradation, resulting in low wash resistance.

[0004] On this basis, Patent CN118127653A discloses a regenerated natural polymer-based solid-solid phase change fiber and its preparation method and application. This technical solution uses natural polymer materials as raw materials, grafts with monofunctional phase change materials to obtain natural polymer-based solid-solid phase change materials, and uses solution spinning to obtain regenerated natural polymer-based solid-solid phase change fibers. However, the crosslinking degree of the fibers prepared by this method is relatively low, and the crosslinked structure is easily damaged, resulting in the phase change materials not being densely encapsulated in the fibers and having low wash resistance.

[0005] Therefore, it is of great significance to study a preparation method of warm and breathable fibers to improve the fixation effect of phase change materials on fibers. Summary of the Invention

[0006] The object of the present invention is to solve the problems existing in the prior art and provide a preparation method of warm and breathable fibers.

[0007] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] A preparation method of a warm and breathable fiber, which comprises soaking linen fiber or cellulose fiber in glutaraldehyde aqueous solution I to obtain product I, then taking out product I and soaking it in molten polyethylene glycol to obtain product II, and then taking out product II and soaking it in polyphenol aqueous solution and adding metal ion aqueous solution to the polyphenol aqueous solution to perform self-assembly of a metal polyphenol network on the polyethylene glycol to obtain product III, and finally taking out product III and soaking it in glutaraldehyde aqueous solution II for reaction to obtain the final product, namely the warm and breathable fiber;

[0009] The metal polyphenol network is obtained by coordination of metal ions and polyphenols;

[0010] In the solution obtained by adding the metal ion aqueous solution to the polyphenol aqueous solution, the molar amount of the metal ions is greater than the molar amount of the polyphenols;

[0011] During the preparation process, multiple cross-linking structures are involved. In the following text, PEG represents polyethylene glycol, M represents metal ions, P represents polyphenols, -OH represents hydroxyl groups, and GA represents glutaraldehyde. When the linen fiber or cellulose fiber is soaked in glutaraldehyde aqueous solution I, since the linen fiber or cellulose fiber has its own hydroxyl groups, the glutaraldehyde in the glutaraldehyde aqueous solution I reacts with the hydroxyl groups on the linen fiber or cellulose. After being placed in molten polyethylene glycol, the other aldehyde group of glutaraldehyde reacts with the hydroxyl groups on the polyethylene glycol, thus forming a cross-linking structure O-GA-O; after adding the metal ion aqueous solution to the polyphenol aqueous solution, some metal ions coordinate with the hydroxyl groups in the polyphenols to form a metal polyphenol network outside the polyethylene glycol layer, and some metal ions coordinate with the hydroxyl groups in the polyethylene glycol to form a cross-linking structure PEG-M-P; after being placed in glutaraldehyde aqueous solution II, the glutaraldehyde in the glutaraldehyde aqueous solution II will react with the remaining reactive hydroxyl groups in PEG-M-P to form ; the glutaraldehyde in the glutaraldehyde aqueous solution II also reacts with the polyethylene glycol and polyphenols that have not undergone cross-linking reactions to obtain a cross-linking structure PEG-GA-P; the above various cross-linking structures interpenetrate with each other to form a cross-linked interpenetrating network, thereby making the solid-phase material polyethylene glycol more firmly fixed;

[0012] In addition, it should be noted that in the present invention, molten polyethylene glycol is more likely to be physically adsorbed onto the linen fiber or cellulose fiber than solid polyethylene glycol and liquid polyethylene glycol.

[0013] As a preferred technical solution:

[0014] The preparation method of a warm and breathable fiber as described above specifically comprises the following preparation steps:

[0015] (1) Soak the linen fiber or cellulose fiber in glutaraldehyde aqueous solution I with a concentration of 30 - 50 wt% for 6 - 24 h; the temperature of the glutaraldehyde aqueous solution I is 25 - 45 °C;

[0016] (2) Place the product after soaking in step (1) in molten polyethylene glycol for 0.5 - 2 h, and then vacuum dry at 40 - 60 °C for 4 - 8 h;

[0017] (3) Place the product after vacuum drying in step (2) in an aqueous polyphenol solution with a concentration of 1 - 10 wt% for 10 - 30 min. Subsequently, pour an aqueous metal ion solution at 10 - 25 °C into the aqueous polyphenol solution and let it stand for 2 - 8 h. Finally, dry the product after standing at 25 - 60 °C for 20 - 40 min;

[0018] (4) Place the product after drying in step (3) in an aqueous glutaraldehyde solution II with a concentration of 10 - 30 wt% for 6 - 24 h. Then take out the soaked fiber, remove the glutaraldehyde in the excess aqueous glutaraldehyde solution II with water, and dry at room temperature for 24 - 72 h to obtain the warm and breathable fiber.

[0019] For the preparation method of a warm and breathable fiber as described above, the mass - to - volume ratio of flax fiber or cellulose fiber to the aqueous glutaraldehyde solution I is 1:10 - 50.

[0020] For the preparation method of a warm and breathable fiber as described above, the mass - to - volume ratio of the product after soaking in step (1) to molten polyethylene glycol is 1:10 - 30; the mass - to - volume ratio of the product after vacuum drying in step (2) to the aqueous polyphenol solution is 1:5 - 25; the mass - to - volume ratio of the product after drying in step (3) to the aqueous glutaraldehyde solution II is 1:4 - 20.

[0021] For the preparation method of a warm and breathable fiber as described above, the molar ratio of polyphenol to metal ion is 1:2 - 10.

[0022] For the preparation method of a warm and breathable fiber as described above, the metal ion is one or more of copper ion, zinc ion, zirconium ion, iron ion and ferrous ion; the polyphenol is one or more of tannic acid, gallic acid, catechol and pyrogallol; the polyethylene glycol is one or more of polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 6000 and polyethylene glycol 10000.

[0023] For the preparation method of a warm and breathable fiber as described above, the moisture permeability of the cloth made of the warm and breathable fiber at 20 °C is 6174 - 6278 g·(m 2 ·24 h) -1 , the change rate of the moisture permeability after washing at 20 °C is 1.3 - 3.7%, and the moisture permeability at 30 °C is 7492 - 7597 g·(m 2 ·24 h) -1, the change rate of water vapor transmission rate after washing with water at 30 °C is 1.7 - 3%, and the water vapor transmission rate at 40 °C is 8795 - 8906 g·(m 2 ·24h) -1 , the change rate of water vapor transmission rate after washing with water at 40 °C is 1.9 - 3%.

[0024] Beneficial effects:

[0025] In the present invention, multiple cross - linked structures interpenetrate each other to form a cross - linked interpenetrating network, so that the solid - phase material polyethylene glycol is fixed more firmly; in addition, the present invention defines that polyethylene glycol is in a molten state, which can make it easier to physically adsorb onto linen fibers or cellulose fibers. Description of the drawings

[0026] Figure 1 It is the ultraviolet - visible absorption spectrum diagram of Product II in Example 3 of the present invention;

[0027] Figure 2 It is the ultraviolet - visible absorption spectrum diagram of the warm - keeping and breathable fiber prepared in Example 3 of the present invention. Detailed implementation manners

[0028] The present invention will be further described below in conjunction with specific implementation manners. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0029] To ensure that the performance of the substances used in each example and comparative example is disclosed sufficiently, the manufacturers and grades of the substances are specified. Products of other manufacturers and grades that meet the limitations of the present invention are also feasible.

[0030] The test methods for the relevant performance indicators in the following examples and comparative examples are as follows:

[0031] The test methods for the water vapor transmission rate and the change rate of water vapor transmission rate after washing are as follows, and the specific steps are as follows:

[0032] (1) First, the warm - keeping and breathable fibers prepared in each example are carded into single fibers (single filaments), then 50 single filaments are combined to form a continuous fiber strip, and finally the fiber strip is stretched and twisted to make fine yarn; among them, the stretching temperature is 40 °C, the stretching elongation is 30%, the stretching rate is 1 mm / min, and the twist is 20 turns / m;

[0033] (2) Using a shuttle loom, the fine yarn made in step (1) is used as the warp and weft to interweave into a cloth with a thickness of 1 mm;

[0034] (3)Refer to the standard of GB / T 12704.1-2009 "Textiles - Test method for water vapor permeability of fabrics - Part 1: Humid absorption method" to test the water vapor permeability of the prepared fabrics at 20 °C, 30 °C, and 40 °C respectively; then refer to the standard of GB / T 8629-2017 "Textiles - Domestic washing and drying procedures for testing" to wash the fabrics 40 times (test conditions: using type A washing machine, washing program 1 and standard detergent 2), finally dry the washed fabrics and make samples with a radius of 35 mm, and then refer to the standard of GB / T12704.1-2009 "Textiles - Test method for water vapor permeability of fabrics - Part 1: Humid absorption method" to test the water vapor permeability of the samples. Subsequently, calculate the change rate of the water vapor permeability according to the water vapor permeability of the fabrics before and after washing.

[0035] When there are multiple solutes in the polyphenol aqueous solution and the metal ion aqueous solution, the molar ratio of polyphenol to metal ion refers to the ratio of the sum of the molar amounts of all solutes in the polyphenol aqueous solution to the sum of the molar amounts of all solutes in the metal ion aqueous solution.

[0036] Example 1

[0037] A preparation method of a warm and breathable fiber is as follows:

[0038] (1)Soak flax fibers (wet-spun flax yarn, manufacturer is Jinda Holdings Co., Ltd., specification is 75NM) in glutaraldehyde aqueous solution I with a concentration of 30 wt% for 6 h to obtain product I; among them, the temperature of glutaraldehyde aqueous solution I is 25 °C, and the mass-volume ratio of flax fibers to glutaraldehyde aqueous solution I is 1:10;

[0039] (2)Place the product I obtained in step (1) in molten polyethylene glycol for 0.5 h, and then vacuum dry at 60 °C for 8 h to obtain product II; among them, polyethylene glycol is composed of polyethylene glycol 1000 (manufacturer is Sinopharm Chemical Reagent Co., Ltd., specification is CP (Shanghai Test)) and polyethylene glycol 2000 (manufacturer is Sinopharm Chemical Reagent Co., Ltd., specification is CP (Shanghai Test)) with a mass ratio of 1:1, and the mass-volume ratio of product I to molten polyethylene glycol is 1:10;

[0040] (3)At 25 °C, dissolve copper dichloride dihydrate and ferric chloride hexahydrate in deionized water and mix evenly to obtain an aqueous solution of copper ions and iron ions with a concentration of 0.1 wt%; among them, the mass ratio of copper dichloride dihydrate to ferric chloride hexahydrate is 2:1;

[0041] (4) Place the product II obtained in step (2) in an aqueous solution of gallic acid with a concentration of 1 wt% for 30 min. Subsequently, pour the aqueous solution of copper ions and iron ions prepared in step (3) at 10 °C into the aqueous solution of gallic acid and let it stand for 2 h while maintaining the temperature. Finally, dry the product after standing at 25 °C for 20 min to obtain product III; wherein, the mass-volume ratio of product II to the aqueous solution of gallic acid is 1:5, and the ratio of the molar amount of gallic acid to the sum of the molar amounts of copper ions and iron ions is 1:2;

[0042] (5) Place the product III obtained in step (4) into an aqueous solution of glutaraldehyde II with a concentration of 30 wt% for 6 h. Then, take out the soaked product III, remove the glutaraldehyde in the excess aqueous solution of glutaraldehyde II with water, and dry it at 25 °C for 24 h to obtain the warm and breathable fiber; wherein, the mass-volume ratio of product III to the aqueous solution of glutaraldehyde II is 1:20.

[0043] The moisture permeability of the cloth made of the above-prepared warm and breathable fiber is 6278 g·(m 2 ·24 h) -1 , the change rate of the moisture permeability of the cloth after washing with water at 20 °C is 1.8%, the moisture permeability at 30 °C is 7583 g·(m 2 ·24 h) -1 , the change rate of the moisture permeability of the cloth after washing with water at 30 °C is 2.3%, the moisture permeability at 40 °C is 8906 g·(m 2 ·24 h) -1 , the change rate of the moisture permeability of the cloth after washing with water at 40 °C is 2.8%.

[0044] Example 2

[0045] A method for preparing a warm and breathable fiber, the steps are as follows:

[0046] (1) Immerse linen fiber (wet-spun linen yarn, manufacturer is Jinda Holdings Co., Ltd., specification is 75 NM) in an aqueous solution of glutaraldehyde I with a concentration of 40 wt% for 15 h to obtain product I; wherein, the temperature of the aqueous solution of glutaraldehyde I is 35 °C, and the mass-volume ratio of linen fiber to the aqueous solution of glutaraldehyde I is 1:30;

[0047] (2) Place the product I obtained in step (1) in molten polyethylene glycol for 1.2 h, and then vacuum dry it at 50 °C for 6 h to obtain product II; wherein, polyethylene glycol is composed of polyethylene glycol 4000 (manufacturer is Sinopharm Chemical Reagent Co., Ltd., specification is CP (Shanghai Test)) and polyethylene glycol 10000 (manufacturer is Sinopharm Chemical Reagent Co., Ltd., specification is CP (Shanghai Test)) with a mass ratio of 3:2, and the mass-volume ratio of product I to molten polyethylene glycol is 1:20;

[0048] (3) At 25 °C, zinc chloride tetrahydrate and zirconium oxychloride octahydrate are dissolved in deionized water and mixed evenly to obtain an aqueous solution of zinc ions and zirconium ions with a concentration of 2 wt%; wherein, the mass ratio of zinc chloride tetrahydrate to zirconium oxychloride octahydrate is 1:2;

[0049] (4) The product II obtained in step (2) is placed in an aqueous solution of catechol and pyrogallol with a concentration of 10 wt% for 20 min. Subsequently, the aqueous solution of zinc ions and zirconium ions prepared in step (3) at 18 °C is poured into the aqueous solution of catechol and pyrogallol, and the temperature is kept static for 5 h. Finally, the product after standing is dried at 60 °C for 30 min to obtain product III; wherein, the mass ratio of catechol to pyrogallol in the aqueous solution of catechol and pyrogallol is 1:4, the mass-volume ratio of product II to the aqueous solution of catechol and pyrogallol is 1:25, and the ratio of the sum of the molar amounts of catechol and pyrogallol to the sum of the molar amounts of zinc ions and zirconium ions is 1:10;

[0050] (5) The product III obtained in step (4) is placed in an aqueous solution II of glutaraldehyde with a concentration of 10 wt% for 15 h. After that, the soaked product III is taken out, and the glutaraldehyde in the excess aqueous solution II of glutaraldehyde is removed with water, and then dried at 25 °C for 48 h to obtain the warm and breathable fiber; wherein, the mass-volume ratio of product III to the aqueous solution II of glutaraldehyde is 1:12.

[0051] The moisture permeability of the cloth made of the above-prepared warm and breathable fiber is 6265 g·(m 2 ·24 h) -1 , the change rate of the moisture permeability of the cloth after washing with water at 20 °C is 3.7%, the moisture permeability at 30 °C is 7595 g·(m 2 ·24 h) -1 , the change rate of the moisture permeability of the cloth after washing with water at 30 °C is 2.7%, the moisture permeability at 40 °C is 8911 g·(m 2 ·24 h) -1 , the change rate of the moisture permeability of the cloth after washing with water at 40 °C is 3%.

[0052] Example 3

[0053] A preparation method of a warm and breathable fiber, the steps are as follows:

[0054] (1) The flax fiber (wet-spun flax yarn, manufacturer: Jinda Holdings Co., Ltd., specification: 75 NM) is soaked in an aqueous solution I of glutaraldehyde with a concentration of 50 wt% for 24 h to obtain product I; wherein, the temperature of the aqueous solution I of glutaraldehyde is 45 °C, and the mass-volume ratio of the flax fiber to the aqueous solution I of glutaraldehyde is 1:50;

[0055] (2) Place the product I obtained in step (1) in molten polyethylene glycol 6000 (manufactured by Sinopharm Chemical Reagent Co., Ltd., specification CP (Shanghai Test)) for 2 h, and then vacuum dry at 40 °C for 4 h to obtain product II; wherein, the mass-volume ratio of product I to molten polyethylene glycol is 1:30;

[0056] (3) At 25 °C, dissolve ferrous chloride tetrahydrate in deionized water and mix evenly to obtain an aqueous solution of ferrous ions with a concentration of 0.5 wt%.

[0057] (4) Place the product II obtained in step (2) in an aqueous solution of tannic acid with a concentration of 6 wt% for 10 min, then pour the aqueous solution of ferrous ions prepared in step (3) at 25 °C into the aqueous solution of tannic acid and keep the temperature for static settlement for 8 h. Finally, dry the settled product at 40 °C for 40 min to obtain product III; wherein, the mass-volume ratio of product II to the aqueous solution of tannic acid is 1:15, and the molar ratio of tannic acid to ferrous ions is 1:5;

[0058] (5) Place the product III obtained in step (4) into an aqueous solution II of glutaraldehyde with a concentration of 20 wt% for 24 h. Then take out the soaked product III, remove the glutaraldehyde in the excess aqueous solution II of glutaraldehyde with water, and dry at 25 °C for 72 h to prepare the warm and breathable fiber; wherein, the mass-volume ratio of product III to the aqueous solution II of glutaraldehyde is 1:4.

[0059] Wash the product II and the warm and breathable fiber prepared in this example 10 times, 20 times, and 40 times respectively in ultrapure water, and then test the ultraviolet-visible absorption spectra of the washed solutions respectively, as Figure 1 、 Figure 2 shown. It can be seen from the figure that as the number of water washing times of product II increases, the peak intensity increases significantly, indicating that its coating is unstable and the cross-linked structure is easily damaged. While for the warm and breathable fiber, the peak intensity basically does not change as the number of water washing times increases. Compared with product II, the warm and breathable fiber has a higher cross-linking degree and is not easily damaged, making it more difficult for the solid phase material to detach from the flax fiber.

[0060] The moisture permeability of the cloth made of the above-prepared warm and breathable fiber is 6271 g·(m 2 ·24 h) -1 at 20 °C, the change rate of the moisture permeability of the cloth after washing at 20 °C is 1.3%, the moisture permeability at 30 °C is 7597 g·(m 2 ·24 h) -1 and the change rate of the moisture permeability of the cloth after washing at 30 °C is 1.7%. The moisture permeability at 40 °C is 8885 g·(m 2 ·24 h) -1, the change rate of the moisture permeability of the fabric after washing with water at 40 °C is 1.9%.

[0061] Example 4

[0062] A method for preparing a warm and breathable fiber, the steps are as follows:

[0063] (1) Immerse cellulose fibers (manufactured by Sateri Holdings Limited, brand name Ucos, model BVF) in glutaraldehyde aqueous solution I with a concentration of 30 wt% for 6 h to obtain product I; wherein, the temperature of glutaraldehyde aqueous solution I is 25 °C, and the mass-to-volume ratio of cellulose fibers to glutaraldehyde aqueous solution I is 1:10;

[0064] (2) Place the product I obtained in step (1) in molten polyethylene glycol for 0.5 h, and then vacuum dry at 60 °C for 8 h to obtain product II; wherein, polyethylene glycol is composed of polyethylene glycol 1000 and polyethylene glycol 2000 (manufactured by Sinopharm Chemical Reagent Co., Ltd., specification CP (Shanghai Test)) with a mass ratio of 1:1, and the mass-to-volume ratio of product I to molten polyethylene glycol is 1:10;

[0065] (3) At 25 °C, dissolve copper dichloride dihydrate and ferric chloride hexahydrate in deionized water and mix evenly to obtain an aqueous solution of copper ions and iron ions with a concentration of 0.1 wt%; wherein, the mass ratio of copper dichloride dihydrate to ferric chloride hexahydrate is 2:1;

[0066] (4) Place the product II obtained in step (2) in a 1 wt% aqueous solution of gallic acid for 30 min, then pour the aqueous solution of copper ions and iron ions prepared in step (3) at 10 °C into the aqueous solution of gallic acid and keep the temperature static for 2 h, and finally dry the static product at 25 °C for 20 min to obtain product III; wherein, the mass-to-volume ratio of product II to the aqueous solution of gallic acid is 1:5, and the ratio of the molar amount of gallic acid to the sum of the molar amounts of copper ions and iron ions is 1:2;

[0067] (5) Put the product III obtained in step (4) into glutaraldehyde aqueous solution II with a concentration of 30 wt% for 6 h, then take out the soaked product III, remove the glutaraldehyde in the excess glutaraldehyde aqueous solution II with water, and dry at 25 °C for 24 h to obtain the warm and breathable fiber; wherein, the mass-to-volume ratio of product III to glutaraldehyde aqueous solution II is 1:20.

[0068] The moisture permeability of the fabric made of the above-prepared warm and breathable fiber at 20 °C is 6129 g·(m 2 ·24 h) -1 , the change rate of the moisture permeability of the fabric after washing with water at 20 °C is 2.2%, and the moisture permeability at 30 °C is 7492 g·(m2 ·24 h) -1 After washing the fabric at 30°C, the change rate of the moisture permeability is 3%, and the moisture permeability at 40°C is 8795 g·(m 2 ·24 h) -1 After washing the fabric at 40°C, the change rate of the moisture permeability is 2.9%.

[0069] Example 5

[0070] A method for preparing a warm and breathable fiber, the steps are as follows:

[0071] (1) Immerse cellulose fibers (manufacturer: Sateri Holdings Limited, brand: Ucos, model: BVF) in glutaraldehyde aqueous solution I with a concentration of 40 wt% for 15 h to obtain Product I; wherein, the temperature of glutaraldehyde aqueous solution I is 35°C, and the mass-volume ratio of cellulose fibers to glutaraldehyde aqueous solution I is 1:30;

[0072] (2) Place Product I obtained in step (1) in molten polyethylene glycol for 1.2 h, and then vacuum dry at 50°C for 6 h to obtain Product II; wherein, polyethylene glycol is composed of polyethylene glycol 4000 and polyethylene glycol 10000 (manufacturer: Sinopharm Chemical Reagent Co., Ltd., specification: CP (Shanghai Test)) with a mass ratio of 3:2, and the mass-volume ratio of Product I to molten polyethylene glycol is 1:20;

[0073] (3) At 25°C, dissolve zinc chloride tetrahydrate and zirconium oxychloride octahydrate in deionized water and mix evenly to obtain an aqueous solution of zinc ions and zirconium ions with a concentration of 2 wt%; wherein, the mass ratio of zinc chloride tetrahydrate to zirconium oxychloride octahydrate is 1:2;

[0074] (4) Place Product II obtained in step (2) in an aqueous solution of catechol and pyrogallol with a concentration of 10 wt% for 20 min, then pour the aqueous solution of zinc ions and zirconium ions prepared in step (3) at 18°C into the aqueous solution of catechol and pyrogallol and keep the temperature static for 5 h, and finally dry the static product at 60°C for 30 min to obtain Product III; wherein, the mass ratio of catechol to pyrogallol in the aqueous solution of catechol and pyrogallol is 1:4, the mass-volume ratio of Product II to the aqueous solution of catechol and pyrogallol is 1:25, and the ratio of the sum of the molar amounts of catechol and pyrogallol to the sum of the molar amounts of zinc ions and zirconium ions is 1:10;

[0075] (5) Put the product III obtained in step (4) into an aqueous glutaraldehyde solution II with a concentration of 10 wt% for 15 h. Then take out the soaked product III, remove the excess glutaraldehyde in the aqueous glutaraldehyde solution II with water, and dry it at 25 °C for 48 h to obtain the warm and breathable fiber; wherein, the mass-to-volume ratio of product III to the aqueous glutaraldehyde solution II is 1:12.

[0076] The moisture permeability of the cloth made of the above-prepared warm and breathable fiber is 6174 g·(m 2 ·24 h) -1 at 20 °C, the change rate of the moisture permeability of the cloth after washing with water at 20 °C is 2.3%, and the moisture permeability at 30 °C is 7524 g·(m 2 ·24 h) -1 at 30 °C, the change rate of the moisture permeability of the cloth after washing with water at 30 °C is 2.1%, and the moisture permeability at 40 °C is 8804 g·(m 2 ·24 h) -1 at 40 °C, the change rate of the moisture permeability of the cloth after washing with water at 40 °C is 2.8%.

[0077] Example 6

[0078] A method for preparing a warm and breathable fiber, the steps are as follows:

[0079] (1) Immerse the cellulose fiber (manufacturer: Sateri Holdings Limited, brand: Ucos, model: BVF) in an aqueous glutaraldehyde solution I with a concentration of 50 wt% for 24 h to obtain product I; wherein, the temperature of the aqueous glutaraldehyde solution I is 45 °C, and the mass-to-volume ratio of the cellulose fiber to the aqueous glutaraldehyde solution I is 1:50;

[0080] (2) Place the product I obtained in step (1) in molten polyethylene glycol 6000 (manufacturer: Sinopharm Chemical Reagent Co., Ltd., specification: CP (Shanghai Test)) for 2 h, and then vacuum dry it at 40 °C for 4 h to obtain product II; wherein, the mass-to-volume ratio of product I to the molten polyethylene glycol is 1:30;

[0081] (3) At 25 °C, dissolve ferrous chloride tetrahydrate in deionized water and mix evenly to obtain an aqueous ferrous ion solution with a concentration of 0.5 wt%;

[0082] (4) Place the product II obtained in step (2) in a 6 wt% aqueous tannic acid solution for 10 min, then pour the aqueous ferrous ion solution prepared in step (3) at 25 °C into the aqueous tannic acid solution and keep the temperature still for 8 h, and finally dry the still product at 40 °C for 20 min to obtain product III; wherein, the mass-to-volume ratio of product II to the aqueous tannic acid solution is 1:15, and the molar ratio of tannic acid to ferrous ion is 1:5;

[0083] (5) Put the product III obtained in step (4) into an aqueous glutaraldehyde solution II with a concentration of 20 wt% for 24 h. Then take out the soaked product III, remove the excess glutaraldehyde in the aqueous glutaraldehyde solution II with water, and dry it at 25 °C for 72 h to obtain the warm and breathable fiber; wherein, the mass-volume ratio of the product III to the aqueous glutaraldehyde solution II is 1:4.

[0084] The moisture permeability of the cloth made of the above-prepared warm and breathable fiber is 6205 g·(m 2 ·24 h) -1 at 20 °C, the change rate of the moisture permeability after washing with water at 20 °C is 2.4%, the moisture permeability at 30 °C is 7550 g·(m 2 ·24 h) -1 at 30 °C, the change rate of the moisture permeability after washing with water at 30 °C is 2.1%, the moisture permeability at 40 °C is 8853 g·(m 2 ·24 h) -1 at 40 °C, and the change rate of the moisture permeability after washing with water at 40 °C is 2.4%.

Claims

1. A method for preparing a thermal-retaining breathable fiber, characterized in that: The cellulose fiber is immersed in a glutaraldehyde aqueous solution I to obtain a product I, and then the product I is taken out and immersed in polyethylene glycol in a molten state to obtain a product II, and then the product II is taken out and immersed in a polyphenol aqueous solution and a metal ion aqueous solution is added to the polyphenol aqueous solution to perform self-assembly of a metal polyphenol network to obtain a product III, and finally the product III is taken out and immersed in a glutaraldehyde aqueous solution II to react to obtain a final product, i.e., a thermal insulation breathable fiber; The metal polyphenol network is obtained by the coordination of metal ions and polyphenols; In the solution obtained by adding the metal ion aqueous solution to the polyphenol aqueous solution, the molar amount of the metal ions is greater than the molar amount of the polyphenols.

2. The method for preparing a thermal-insulating and breathable fiber according to claim 1, characterized in that: The specific preparation steps are: (1) immersing cellulose fibers in a 30-50 wt% glutaraldehyde aqueous solution I for 6-24 hours; the temperature of the glutaraldehyde aqueous solution I is 25-45° C.; (2) placing the product soaked in step (1) in molten polyethylene glycol for 0.5 to 2 hours, and then vacuum drying at 40 to 60° C. for 4 to 8 hours; (3) placing the vacuum-dried product of step (2) in a polyphenol aqueous solution having a concentration of 1 to 10 wt% for 10 to 30 minutes, then pouring a 10 to 25° C. metal ion aqueous solution into the polyphenol aqueous solution and allowing the solution to stand for 2 to 8 hours, and finally drying the product at 25 to 60° C. for 20 to 40 minutes; (4) placing the dried product of step (3) into a 10-30 wt % glutaraldehyde aqueous solution II for 6-24 hours to obtain a thermal insulation breathable fiber.

3. The method for preparing a thermal-retaining breathable fiber according to claim 2, characterized in that: The mass volume ratio of the cellulose fiber to the glutaraldehyde aqueous solution I is 1:10-50.

4. The method for preparing a thermal-insulating and breathable fiber according to claim 2, characterized in that: The mass volume ratio of the product after immersion in step (1) to the polyethylene glycol in a molten state is 1:10 to 30; the mass volume ratio of the product after vacuum drying in step (2) to the polyphenol aqueous solution is 1:5 to 25; and the mass volume ratio of the product after drying in step (3) to the glutaraldehyde aqueous solution II is 1:4 to 20.

5. The method for preparing a thermal-retaining breathable fiber according to claim 1, characterized in that: The molar ratio of polyphenols to metal ions is 1:2-10.

6. The method for preparing a thermal-retaining breathable fiber according to claim 5, characterized in that: The metal ions are one or more selected from the group consisting of copper ions, zinc ions, zirconium ions, iron ions and ferrous ions; the polyphenols are one or more selected from the group consisting of tannic acid, gallic acid, catechol and pyrogallol; and the polyethylene glycol is one or more selected from the group consisting of polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 6000 and polyethylene glycol 10000.

7. The method for preparing a thermal-insulating and breathable fiber according to claim 1, characterized in that: The moisture permeability of the cloth made of thermal breathable fiber at 20℃ is 6174~6278g·(m 2 24h) -1 The change rate of moisture permeability after washing at 20°C is 1.3-3.7%, and the moisture permeability at 30°C is 7492-7597 g·(m 2 24h) -1 The change rate of moisture permeability after washing at 30°C is 1.7-3%, and the moisture permeability at 40°C is 8795-8906 g·(m 2 24h) -1 The change rate of moisture permeability after washing at 40°C is 1.9~3%.

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