Far infrared fiber thermal insulation fabric and preparation method and application thereof

Abstract

The invention discloses a far-infrared fiber thermal insulation fabric and a preparation method and application thereof, and relates to the field of fabrics. When preparing the far-infrared fiber thermal insulation fabric, the present invention polymerizes and deposits pyrrole and 1-(2-chloroethyl)pyrrole on the surface of tourmaline powder to obtain modified tourmaline powder; borneol and 3-N,N-dimethylaminomethyl acryloyl chloride are reacted to obtain grafted borneol; polyacrylonitrile powder is then reacted with grafted borneol and modified tourmaline powder in sequence to obtain modified polyacrylonitrile; modified polyacrylonitrile is used as a shell layer and polyvinyl pyrrolidone is used as a core layer for spinning to obtain spun fibers; viscose fibers are sequentially treated with sodium periodate and salicylaldehyde hydrazone to obtain modified viscose fibers; spun fibers and modified viscose fibers are twisted and then treated with iodine ion finishing liquid and then woven to obtain far-infrared fiber thermal insulation fabrics. The far-infrared fiber thermal insulation fabric prepared by the present invention has excellent warmth retention, antibacterial properties, antistatic properties, UV aging resistance and mechanical properties.

Description

Technical Field

[0001] The invention relates to the field of fabrics, in particular to a far-infrared fiber thermal insulation fabric and a preparation method and application thereof. Background Art

[0002] With the development of science and technology and the improvement of living standards, consumers' demand for textiles is not only to cover the body and keep warm, but also to put forward more demands on the functionality of textiles. Functional textiles can not only meet consumers' multi-scenario and personalized needs, but also increase the added value of textiles. While the research and development space of functional textiles is expanding, comfortable functional textiles have gradually become the focus of development and research. In the past few decades, limited fossil energy resources and increasing concerns about environmental pollution have accelerated people's desire to explore and develop sustainable and clean energy. As a clean energy, infrared radiation has received widespread attention and application in various fields such as military, energy conservation, medical care, construction, and textiles. It has brought vigorous development to the in-depth research and rapid development of high infrared emissivity materials.

[0003] In recent years, with the progress of society and the improvement of people's material living standards, people have higher and higher requirements for clothing. Some heavy and bulky winter clothes in the cold winter can no longer meet people's multi-functional requirements such as comfort, warmth, health care, beauty, fashion, etc. Therefore, the concept of active thermal insulation materials is proposed. The so-called active thermal insulation material is to use low thermal conductivity materials for warmth preservation, and also use appropriate technology to convert electrical energy, chemical energy, and solar energy into thermal energy to achieve the purpose of active warmth preservation. Far-infrared materials have the ability to absorb far-infrared light, store it, and then radiate it to the human body. Therefore, the present invention prepares a far-infrared fiber fabric with excellent warmth preservation. Summary of the invention

[0004] The purpose of the present invention is to provide a far-infrared fiber thermal insulation fabric and a preparation method and application thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a far-infrared fiber thermal insulation fabric, which is made by twisting spun fibers and modified viscose fibers and then treating them with iodine ion finishing liquid.

[0006] As an optimization, the modified viscose fiber is prepared by treating viscose fiber with sodium periodate and salicylaldehyde hydrazone in sequence.

[0007] As an optimization, the viscose fiber model has a fineness of 1.33dtex and a length of 38mm, and comes from Shandong Fuhui Textile Technology Co., Ltd.

[0008] As an optimization, the spun fiber is made by spinning polyacrylonitrile powder as a shell layer and polyvinyl pyrrolidone as a core layer after reacting with grafted borneol and modified tourmaline powder in sequence.

[0009] As an optimization, the polyacrylonitrile powder is of spinning grade and comes from Dongguan Xiuzhisheng Plastic Co., Ltd.

[0010] As an optimization, the grafted borneol is prepared by reacting borneol and 3-N,N-dimethylaminomethyl acryloyl chloride.

[0011] As an optimization, the modified tourmaline powder is prepared by polymerizing pyrrole and 1-(2-chloroethyl)pyrrole and depositing them on the surface of tourmaline powder.

[0012] As an optimization, the tourmaline powder model is 1250 mesh and comes from Hebei Hengyue Mineral Products Co., Ltd.

[0013] A method for preparing a far-infrared fiber thermal insulation fabric comprises the following preparation steps:

[0014] (1) Tourmaline powder, pyrrole, 1-(2-chloroethyl)pyrrole, p-toluenesulfonic acid and deionized water are mixed in a mass ratio of 1: (0.1-0.2): (0.02-0.04): (0.7-0.8): (10-20), deposited at a constant potential of 0.7-0.9 V for 60-180 s, filtered, washed with deionized water for 3-5 times, dried at 30-40° C. for 11-13 h, ground and sieved through 400-600 mesh to obtain modified tourmaline powder;

[0015] (2) Mix borneol, triethylamine and tetrahydrofuran in a mass ratio of 1: (0.97-0.99): (19-21), add 3-N,N-dimethylaminomethyl acryloyl chloride (0.87-0.89 times the mass of borneol) at -1-1°C, heat to 20-30°C, stir at 300-500 rpm for 8-12 hours, and filter. Concentrate the filtrate, wash with deionized water for 3-5 times, extract with dichloromethane for 2-4 times, dry with anhydrous sodium sulfate, filter, and concentrate with a developing agent prepared by mixing petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain grafted borneol;

[0016] (3) Mix polyacrylonitrile powder, grafted borneol, benzophenone and methanol in a mass ratio of 1: (0.4~0.5): (0.01~0.03): (20~30), filter after ultrasonic treatment at 45~55°C for 1~3 hours, irradiate under ultraviolet light of 385~395nm at a distance of 14~16cm for 25~35min, extract with acetone for 1~2h, wash with deionized water for 3~5 times, and dry at 50~60°C for 6~7h to obtain pre-modified polyacrylonitrile; mix pre-modified polyacrylonitrile, modified tourmaline powder and anhydrous ethanol in a mass ratio of 1: (0.03~0.05): (55~65), stir at 50~60°C and 400~500rpm for 7~9h, filter after stirring, wash with anhydrous ethanol and deionized water for 3~5 times respectively, and dry at 55~65°C for 11~13h to obtain modified polyacrylonitrile;

[0017] (4) Mix modified polyacrylonitrile, lithium chloride and N,N-dimethylformamide in a mass ratio of 1: (0.4-0.5): (5-6), stir at 75-85°C and 400-600 rpm for 11-13 h to obtain a fiber shell spinning solution; mix polyvinyl pyrrolidone and N,N-dimethylformamide in a mass ratio of 1: (85-95), ultrasonicate at 65-75°C for 4-6 h to obtain a fiber core spinning solution; The fiber shell spinning solution and the fiber core spinning solution are allowed to stand at 55-65°C for 35-45 minutes, coaxially spun using a coaxial spinneret, coagulated in an 85%-95% N,N-dimethylformamide aqueous solution at 45-55°C for 25-35 minutes, then drawn 11-13 times, immersed in deionized water for 21-23 hours, taken out and dried at 20-30°C for 11-13 hours to obtain spun fibers;

[0018] (5) Immerse the viscose fiber in a sodium periodate mixed solution, ultrasonicate at 60-70°C for 2-3 h, take it out and wash it with deionized water for 3-5 times, and dry it at 75-85°C to constant weight to obtain pre-modified viscose fiber; immerse the pre-modified viscose fiber in a salicylaldehyde hydrazone treatment solution for 1-2 h, take it out and air-dry it until no liquid drops within 5-15 seconds, stand it at 75-85°C for 5-7 h, wash it with deionized water for 3-5 times, and dry it at 60-70°C for 6-8 h to obtain modified viscose fiber;

[0019] (6) The spun fiber and the modified viscose fiber are mixed in a mass ratio of 1:(0.6-0.7), and the fibers are blended, opened, rolled, carded, drawn, and twisted to obtain a far-infrared precursor fiber with a fineness of 11.7-11.9 tex and a twist of 80-100 twists / 10 cm; the far-infrared precursor fiber is immersed in an iodine ion finishing solution, ultrasonicated for 5-15 min, allowed to stand at 40-60°C for 1-2 h, taken out, washed with deionized water for 3-5 times, and dried at 60-70°C for 6-8 h to obtain a far-infrared fiber; the far-infrared fiber is knitted using a JH / SD-2-4 double-sided multi-track small circular knitting machine with a horizontal density of 60-70 rows / 5 cm, a vertical density of 55-65 columns / 5 cm, and a weight of 230-250 g / m 2 The double rib weave produces a far-infrared fiber warm fabric.

[0020] As an optimization, the reaction equation of the modified tourmaline powder in step (1) is:

[0021] .

[0022] As an optimization, the reaction equation for grafting borneol in step (2) is:

[0023] .

[0024] As an optimization, the reaction equation for modifying polyacrylonitrile in step (3) is:

[0025] .

[0026] As an optimization, the process parameters of the coaxial spinning in step (4) are: inner diameter of the spinning needle 0.5~0.7mm, outer diameter of the spinning needle 1.1~1.3mm, shell layer flow rate 9~11mL / h, core layer flow rate 0.9~1.1mL / h.

[0027] As an optimization, the reaction equation of the modified viscose fiber in step (5) is:

[0028] .

[0029] As an optimization, the sodium periodate mixed solution in step (5) is obtained by mixing sodium periodate and deionized water in a mass ratio of 1:(45-55), and adding a hydrochloric acid solution with a mass fraction of 5%-7% to adjust the pH to 3-5.

[0030] As an optimization, the salicylaldehyde hydrazone treatment solution in step (5) is obtained by mixing salicylaldehyde hydrazone and anhydrous ethanol in a mass ratio of 1:(30-40).

[0031] As an optimization, the iodine ion finishing solution in step (6) is obtained by mixing potassium iodide and deionized water in a mass ratio of 1:(190~210).

[0032] An application of the far-infrared fiber thermal insulation fabric in home clothes.

[0033] Compared with the prior art, the invention has the following beneficial effects: when preparing the far-infrared fiber thermal insulation fabric, pyrrole and 1-(2-chloroethyl)pyrrole are polymerized and deposited on the surface of tourmaline powder to obtain modified tourmaline powder; borneol and 3-N,N-dimethylaminomethyl acryloyl chloride are reacted to obtain grafted borneol; polyacrylonitrile powder is sequentially reacted with the grafted borneol and the modified tourmaline powder to obtain modified polyacrylonitrile; the modified polyacrylonitrile is used as a shell layer and polyvinyl pyrrolidone is used as a core layer for spinning to obtain spun fibers; viscose fibers are sequentially treated with sodium periodate and salicylaldehyde hydrazone to obtain modified viscose fibers; the spun fibers and the modified viscose fibers are twisted, treated with iodine ion finishing liquid, and then spun to obtain the far-infrared fiber thermal insulation fabric.

[0034] Firstly, pyrrole and 1-(2-chloroethyl)pyrrole are polymerized and deposited on the surface of tourmaline powder to obtain modified tourmaline powder; borneol and 3-N,N-dimethylaminomethyl acryloyl chloride are reacted to obtain grafted borneol; polyacrylonitrile powder is then reacted with grafted borneol and modified tourmaline powder in sequence to obtain modified polyacrylonitrile; tourmaline is used as a filler to absorb far infrared rays released by the human body, thereby improving the warmth retention of far infrared fiber thermal insulation fabrics; a polypyrrole conductive layer is deposited on the surface of tourmaline powder by an electrochemical polymerization method, and the conjugated chain structure in the polypyrrole molecular structure allows electrons to move freely on the molecular chain, thereby enhancing the conductivity and improving the anti-static property of the far infrared fiber thermal insulation fabrics. At the same time, the doped 1-(2-chloroethyl)pyrrole can retain active chlorine atoms on the surface and undergo quaternary ammonium reaction to be grafted onto the main chain of polyacrylonitrile. The quaternary ammonium cation can neutralize and eliminate static electricity accumulation, further improving the antistatic property of the far-infrared fiber thermal insulation fabric. The grafted borneol is obtained by the reaction of hydroxyl and acyl chloride, and is grafted onto the main chain of polyacrylonitrile using ultraviolet light to introduce borneol and dimethylamino structures. The borneol structure can destroy bacterial cell membranes, interfere with DNA synthesis, and improve the antibacterial property of the far-infrared fiber thermal insulation fabric. The dimethylamino group can serve as a quaternary ammonium reaction site to form a quaternary ammonium salt, inhibit bacterial metabolism, and further enhance the antibacterial property of the far-infrared fiber thermal insulation fabric.

[0035] Secondly, modified polyacrylonitrile is used as the shell layer and polyvinyl pyrrolidone is used as the core layer for spinning to prepare spun fibers; viscose fibers are treated with sodium periodate and salicylaldehyde hydrazone in sequence to prepare modified viscose fibers; the spun fibers and modified viscose fibers are twisted and treated with iodine ion finishing liquid before weaving to prepare far-infrared fiber thermal insulation fabrics; polyvinyl pyrrolidone is used as the core layer and dissolved in deionized water to form a hollow structure, thereby increasing a stable static air layer and improving the warmth retention of the far-infrared fiber thermal insulation fabrics; viscose fibers are oxidized with sodium periodate to form aldehyde groups, and salicylaldehyde hydrazone is grafted using a Schiff base reaction, and the hydrogen bonds in the molecular structure of salicylaldehyde hydrazone are oxidized by the presence of ultraviolet rays. It is easy to break after external irradiation, which causes the electron cloud density to transfer to N, forming an unstable tautomer, converting the absorbed ultraviolet light energy into heat energy and then restoring it to the original stable hydrogen bond ground state, thereby enhancing the anti-aging property of the far-infrared fiber thermal insulation fabric; using iodide ions for post-finishing, iodine ions can interfere with the synthesis of bacterial proteins and improve the antibacterial property of the far-infrared fiber thermal insulation fabric; at the same time, iodide ions can form electrostatic effects with the nitrogen atoms of the quaternary ammonium salt on the main chain of polyacrylonitrile, and can also coordinate with the electron pairs of the imine group on the viscose fiber to form a stable complex structure, enrich the cross-linked network, and improve the mechanical properties of the far-infrared fiber thermal insulation fabric. DETAILED DESCRIPTION

[0036] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0037] The raw materials used in the following examples and comparative examples are all commercially available: the viscose fiber model has a fineness of 1.33 dtex and a length of 38 mm, and is from Shandong Fuhui Textile Technology Co., Ltd.; the polyacrylonitrile powder model is spinning grade, and is from Dongguan Xiuzhisheng Plastic Co., Ltd.; the tourmaline powder model is 1250 mesh, and is from Hebei Hengyue Mineral Products Co., Ltd.

[0038] Example 1

[0039] A method for preparing a far-infrared fiber thermal insulation fabric, the method comprising the following preparation steps:

[0040] (1) Tourmaline powder, pyrrole, 1-(2-chloroethyl)pyrrole, p-toluenesulfonic acid and deionized water were mixed in a mass ratio of 1:0.1:0.02:0.7:10, deposited at a constant potential of 0.7 V for 180 s, filtered, washed with deionized water three times, dried at 30°C for 13 h, ground and sieved through 400 mesh to obtain modified tourmaline powder;

[0041] (2) borneol, triethylamine and tetrahydrofuran were mixed in a mass ratio of 1:0.97:19, 3-N,N-dimethylaminomethyl acryloyl chloride (0.87 times the mass of borneol) was added at -1°C, the temperature was raised to 20°C, stirred at 300 rpm for 12 hours and then filtered, the filtrate was concentrated, washed with deionized water three times, extracted with dichloromethane twice, dried with anhydrous sodium sulfate and filtered, and concentrated with a developing agent of a mixture of petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain grafted borneol;

[0042] (3) Polyacrylonitrile powder, grafted borneol, benzophenone and methanol were mixed in a mass ratio of 1:0.4:0.01:20, ultrasonicated at 45°C for 3 hours, filtered, irradiated under ultraviolet light at a distance of 14 cm and 385 nm for 35 minutes, extracted with acetone for 1 hour, washed with deionized water for 3 times, and dried at 50°C for 7 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, modified tourmaline powder and anhydrous ethanol were mixed in a mass ratio of 1:0.03:55, stirred at 50°C and 400 rpm for 9 hours, filtered, washed with anhydrous ethanol and deionized water for 3 times respectively, and dried at 55°C for 13 hours to obtain modified polyacrylonitrile;

[0043] (4) Modified polyacrylonitrile, lithium chloride and N,N-dimethylformamide were mixed in a mass ratio of 1:0.4:5, stirred at 75°C and 400 rpm for 13 h to obtain a fiber shell spinning solution; polyvinyl pyrrolidone and N,N-dimethylformamide were mixed in a mass ratio of 1:85, ultrasonicated at 65°C for 6 h to obtain a fiber core spinning solution; the fiber shell spinning solution and the fiber core spinning solution were allowed to stand at 55°C for 45 min, spun using a coaxial spinneret under the conditions of a spinning needle inner diameter of 0.5 mm, a spinning needle outer diameter of 1.1 mm, a shell layer flow rate of 9 mL / h, and a core layer flow rate of 0.9 mL / h, coagulated in an 85% volume fraction N,N-dimethylformamide aqueous solution at 45°C for 35 min, stretched 11 times, immersed in deionized water for 21 h, taken out and dried at 20°C for 13 h to obtain spun fibers;

[0044] (5) Sodium periodate and deionized water were mixed in a mass ratio of 1:45, and a 5% hydrochloric acid solution was added to adjust the pH to 3 to obtain a sodium periodate mixed solution; the viscose fiber was immersed in the sodium periodate mixed solution, ultrasonicated at 60°C for 3 hours, washed with deionized water for 3 times after being taken out, and dried at 75°C to constant weight to obtain a pre-modified viscose fiber; salicylaldehyde hydrazone and anhydrous ethanol were mixed in a mass ratio of 1:30 to obtain a salicylaldehyde hydrazone treatment solution; the pre-modified viscose fiber was immersed in the salicylaldehyde hydrazone treatment solution for 1 hour, taken out and aired until no liquid dripped within 5 seconds, allowed to stand at 75°C for 7 hours, washed with deionized water for 3 times, and dried at 60°C for 8 hours to obtain a modified viscose fiber;

[0045] (6) The spun fiber and the modified viscose fiber were mixed at a mass ratio of 1:0.6, and the fibers were blended, opened, rolled, carded, drawn, and twisted to obtain a far-infrared precursor fiber with a fineness of 11.7 tex and a twist of 80 twists / 10 cm; potassium iodide and deionized water were mixed at a mass ratio of 1:190 to obtain an iodine ion finishing solution; the far-infrared precursor fiber was immersed in the iodine ion finishing solution, ultrasonicated for 5 minutes, allowed to stand at 40°C for 2 hours, taken out, washed with deionized water for 3 times, and dried at 60°C for 8 hours to obtain a far-infrared fiber; the far-infrared fiber was knitted using a JH / SD-2-4 double-sided multi-track small circular knitting machine with a horizontal density of 60 rows / 5 cm, a vertical density of 55 columns / 5 cm, and a thickness of 230 g / m 2 The double rib weave produces a far-infrared fiber warm fabric.

[0046] Example 2

[0047] A method for preparing a far-infrared fiber thermal insulation fabric, the method comprising the following preparation steps:

[0048] (1) Tourmaline powder, pyrrole, 1-(2-chloroethyl)pyrrole, p-toluenesulfonic acid and deionized water were mixed in a mass ratio of 1:0.15:0.03:0.75:15, deposited at a constant potential of 0.8 V for 120 seconds, filtered, washed with deionized water for 4 times, dried at 35°C for 12 hours, ground and sieved through 500 mesh to obtain modified tourmaline powder;

[0049] (2) borneol, triethylamine and tetrahydrofuran were mixed in a mass ratio of 1:0.98:20, and 3-N,N-dimethylaminomethyl acryloyl chloride (0.88 times the mass of borneol) was added at 0°C, the temperature was raised to 25°C, and the mixture was stirred at 400 rpm for 10 hours, and then filtered. The filtrate was concentrated, washed with deionized water for 4 times, extracted with dichloromethane for 3 times, dried with anhydrous sodium sulfate, filtered, and concentrated with a developing agent prepared by mixing petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain grafted borneol;

[0050] (3) Polyacrylonitrile powder, grafted borneol, benzophenone and methanol were mixed in a mass ratio of 1:0.45:0.02:25, and filtered after ultrasonic treatment at 50°C for 2 hours. The mixture was irradiated under ultraviolet light at a distance of 15 cm and 390 nm for 30 minutes, extracted with acetone for 1.5 hours, washed with deionized water for 4 times, and dried at 55°C for 6.5 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, modified tourmaline powder and anhydrous ethanol were mixed in a mass ratio of 1:0.04:60, stirred at 55°C and 450 rpm for 8 hours, filtered, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 60°C for 12 hours to obtain modified polyacrylonitrile;

[0051] (4) Modified polyacrylonitrile, lithium chloride and N,N-dimethylformamide were mixed in a mass ratio of 1:0.45:5.5, and stirred at 80°C and 500 rpm for 12 hours to obtain a fiber shell spinning solution; polyvinyl pyrrolidone and N,N-dimethylformamide were mixed in a mass ratio of 1:90, and ultrasonicated at 70°C for 5 hours to obtain a fiber core spinning solution; the fiber shell spinning solution and the fiber core spinning solution were allowed to stand at 60°C for 40 minutes, and spun using a coaxial spinneret under the conditions of a spinning needle inner diameter of 0.6 mm, a spinning needle outer diameter of 1.2 mm, a shell layer flow rate of 10 mL / h, and a core layer flow rate of 1 mL / h. The fibers were coagulated in a 90% volume fraction N,N-dimethylformamide aqueous solution at 50°C for 30 minutes, then stretched 12 times, immersed in deionized water for 22 hours, taken out and dried at 25°C for 12 hours to obtain spun fibers;

[0052] (5) Sodium periodate and deionized water were mixed in a mass ratio of 1:50, and a 6% hydrochloric acid solution was added to adjust the pH to 4 to obtain a sodium periodate mixed solution; the viscose fiber was immersed in the sodium periodate mixed solution, ultrasonicated at 65°C for 2.5 hours, washed with deionized water for 4 times, and dried at 80°C to constant weight to obtain a pre-modified viscose fiber; salicylaldehyde hydrazone and anhydrous ethanol were mixed in a mass ratio of 1:35 to obtain a salicylaldehyde hydrazone treatment solution; the pre-modified viscose fiber was immersed in the salicylaldehyde hydrazone treatment solution for 1.5 hours, taken out and aired until no liquid dripped within 10 seconds, allowed to stand at 80°C for 6 hours, washed with deionized water for 4 times, and dried at 65°C for 7 hours to obtain a modified viscose fiber;

[0053] (6) The spun fiber and the modified viscose fiber were mixed at a mass ratio of 1:0.65, and the fibers were blended, opened, rolled, carded, drawn, and twisted to obtain a far-infrared precursor fiber with a fineness of 11.8 tex and a twist of 90 twists / 10 cm; potassium iodide and deionized water were mixed at a mass ratio of 1:200 to obtain an iodine ion finishing solution; the far-infrared precursor fiber was immersed in the iodine ion finishing solution, ultrasonicated for 10 min, allowed to stand at 50°C for 1.5 h, taken out, washed with deionized water for 4 times, and dried at 65°C for 7 h to obtain a far-infrared fiber; the far-infrared fiber was knitted using a JH / SD-2-4 double-sided multi-track small circular knitting machine with a horizontal density of 65 rows / 5 cm, a vertical density of 60 columns / 5 cm, and a thickness of 240 g / m 2 The double rib weave produces a far-infrared fiber warm fabric.

[0054] Example 3

[0055] A method for preparing a far-infrared fiber thermal insulation fabric, the method comprising the following preparation steps:

[0056] (1) Tourmaline powder, pyrrole, 1-(2-chloroethyl)pyrrole, p-toluenesulfonic acid and deionized water were mixed in a mass ratio of 1:0.2:0.04:0.8:20, deposited at a constant potential of 0.9 V for 60 seconds, filtered, washed with deionized water for 5 times, dried at 40°C for 11 hours, ground and sieved through 600 mesh to obtain modified tourmaline powder;

[0057] (2) borneol, triethylamine and tetrahydrofuran were mixed in a mass ratio of 1:0.99:21, 3-N,N-dimethylaminomethyl acryloyl chloride (0.89 times the mass of borneol) was added at 1°C, the temperature was raised to 30°C, stirred at 500 rpm for 8 hours and then filtered, the filtrate was concentrated, washed with deionized water 5 times, extracted with dichloromethane 4 times, dried with anhydrous sodium sulfate and filtered, and concentrated with a developing agent prepared by mixing petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain grafted borneol;

[0058] (3) Polyacrylonitrile powder, grafted borneol, benzophenone and methanol were mixed in a mass ratio of 1:0.5:0.03:30, ultrasonicated at 55°C for 1 hour, filtered, irradiated under ultraviolet light of 395 nm at a distance of 16 cm for 25 minutes, extracted with acetone for 1 hour, washed with deionized water for 5 times, and dried at 60°C for 6 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, modified tourmaline powder and anhydrous ethanol were mixed in a mass ratio of 1:0.05:65, stirred at 60°C and 500 rpm for 7 hours, filtered, washed with anhydrous ethanol and deionized water for 5 times respectively, and dried at 65°C for 11 hours to obtain modified polyacrylonitrile;

[0059] (4) Modified polyacrylonitrile, lithium chloride and N,N-dimethylformamide were mixed in a mass ratio of 1:0.5:6, and stirred at 85°C and 600 rpm for 11 hours to obtain a fiber shell spinning solution; polyvinyl pyrrolidone and N,N-dimethylformamide were mixed in a mass ratio of 1:95, and ultrasonicated at 75°C for 4 hours to obtain a fiber core spinning solution; the fiber shell spinning solution and the fiber core spinning solution were allowed to stand at 65°C for 35 minutes, and spun using a coaxial spinneret under the conditions of a spinning needle inner diameter of 0.7 mm, a spinning needle outer diameter of 1.3 mm, a shell layer flow rate of 11 mL / h, and a core layer flow rate of 1.1 mL / h. The fibers were coagulated in a 95% volume fraction N,N-dimethylformamide aqueous solution at 55°C for 25 minutes, stretched 13 times, immersed in deionized water for 23 hours, taken out and dried at 30°C for 11 hours to obtain spun fibers;

[0060] (5) Sodium periodate and deionized water were mixed in a mass ratio of 1:55, and a 7% hydrochloric acid solution was added to adjust the pH to 5 to obtain a sodium periodate mixed solution; the viscose fiber was immersed in the sodium periodate mixed solution, ultrasonicated at 70°C for 2 hours, washed with deionized water 5 times, and dried at 85°C to constant weight to obtain a pre-modified viscose fiber; salicylaldehyde hydrazone and anhydrous ethanol were mixed in a mass ratio of 1:40 to obtain a salicylaldehyde hydrazone treatment solution; the pre-modified viscose fiber was immersed in the salicylaldehyde hydrazone treatment solution for 2 hours, taken out and aired until no liquid dripped within 15 seconds, allowed to stand at 85°C for 5 hours, washed with deionized water 5 times, and dried at 70°C for 6 hours to obtain a modified viscose fiber;

[0061] (6) The spun fiber and the modified viscose fiber were mixed at a mass ratio of 1:0.7, and the fibers were blended, opened, rolled, carded, drawn, and twisted to obtain a far-infrared precursor fiber with a fineness of 11.9 tex and a twist of 100 twists / 10 cm; potassium iodide and deionized water were mixed at a mass ratio of 1:210 to obtain an iodine ion finishing solution; the far-infrared precursor fiber was immersed in the iodine ion finishing solution, ultrasonicated for 15 min, allowed to stand at 60°C for 1 h, taken out and washed with deionized water for 5 times, and dried at 70°C for 6 h to obtain a far-infrared fiber; the far-infrared fiber was knitted using a JH / SD-2-4 double-sided multi-track small circular knitting machine with a horizontal density of 70 rows / 5 cm, a vertical density of 65 columns / 5 cm, and a thickness of 250 g / m 2 The double rib weave produces a far-infrared fiber warm fabric.

[0062] Comparative Example 1:

[0063] The preparation method of the far-infrared fiber thermal insulation fabric of Comparative Example 1 is different from that of Example 2 only in step (1), in which the tourmaline is not subjected to electrochemical deposition modification, and the remaining steps are the same as those of Example 2.

[0064] Comparative Example 2:

[0065] The preparation method of the far-infrared fiber thermal insulation fabric of Comparative Example 2 is different from that of Example 2 only in the difference between steps (2) and (3), and step (2) is omitted; step (3) is modified as follows: polyacrylonitrile powder, 3-N,N-dimethylaminomethyl acryloyl chloride, benzophenone and methanol are mixed in a mass ratio of 1:0.45:0.02:25, ultrasonicated at 50°C for 2 hours, filtered, irradiated at a distance of 15 cm and 390 nm ultraviolet light for 30 minutes, extracted with acetone for 1.5 hours, washed with deionized water for 4 times, and dried at 55°C for 6.5 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, modified tourmaline powder and anhydrous ethanol are mixed in a mass ratio of 1:0.04:60, stirred at 55°C and 450 rpm for 8 hours, filtered, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 60°C for 12 hours to obtain modified polyacrylonitrile. The remaining steps are the same as those of Example 2.

[0066] Comparative Example 3:

[0067] The preparation method of the far-infrared fiber thermal insulation fabric of Comparative Example 3 is different from that of Example 2 only in step (4), and step (4) is modified as follows: modifying polyacrylonitrile, lithium chloride and N,N-dimethylformamide in a mass ratio of 1:0.45:5.5 is mixed, and stirred at 80°C and 500 rpm for 12 hours to obtain a fiber shell spinning solution; the fiber shell spinning solution is allowed to stand at 60°C for 40 minutes, and is spun using a spinneret under the conditions of a spinning needle diameter of 1.2 mm and a flow rate of 10 mL / h, and is coagulated in a 90% N,N-dimethylformamide aqueous solution at 50°C for 30 minutes, and then drawn 12 times, and washed 4 times in deionized water, and then taken out and dried at 25°C for 12 hours to obtain spun fibers. The remaining steps are the same as those of Example 2.

[0068] Comparative Example 4:

[0069] The preparation method of the far-infrared fiber thermal insulation fabric of Comparative Example 4 is different from that of Example 2 only in steps (5) and (6), and step (5) is omitted; step (6) is modified as follows: the spun fiber and the viscose fiber are mixed at a mass ratio of 1:0.65, and the mixture is blended, opened, rolled, carded, drawn, and twisted to obtain a far-infrared precursor fiber with a fineness of 11.8 tex and a twist of 90 twists / 10 cm; potassium iodide and deionized water are mixed at a mass ratio of 1:200 to obtain an iodine ion finishing solution; the far-infrared precursor fiber is immersed in the iodine ion finishing solution, ultrasonicated for 10 minutes, allowed to stand at 50°C for 1.5 hours, taken out, washed with deionized water 4 times, and dried at 65°C for 7 hours to obtain a far-infrared fiber; the far-infrared fiber is kneaded using a JH / SD-2-4 double-sided multi-track small circular knitting machine with a horizontal density of 65 rows / 5 cm, a vertical density of 60 columns / 5 cm, and a thickness of 240 g / m 2 The far-infrared fiber thermal insulation fabric is obtained by double rib weaving. The remaining steps are the same as those in Example 2.

[0070] Comparative Example 5:

[0071] The preparation method of the far-infrared fiber thermal insulation fabric of Comparative Example 5 is different from that of Example 2 only in step (6). Step (6) is modified as follows: the spun fiber and the modified viscose fiber are mixed at a mass ratio of 1:0.65, and the mixture is blended, opened, rolled, carded, drawn, and twisted to obtain a far-infrared precursor fiber with a fineness of 11.8 tex and a twist of 90 twists / 10 cm; the far-infrared precursor fiber is knitted with a JH / SD-2-4 double-sided multi-track small circular knitting machine with a horizontal density of 65 rows / 5 cm, a vertical density of 60 columns / 5 cm, and a thickness of 240 g / m 2 The double rib weave produces a far-infrared fiber warm fabric.

[0072] Test Example 1:

[0073] 1. Far infrared performance

[0074] Test method: The far-infrared fiber thermal insulation fabrics obtained in each embodiment and comparative example were tested for far-infrared radiation temperature rise using FFZ411-I textile far-infrared temperature rise rate tester in accordance with GB / T30127.

[0075] 2. Warmth

[0076] Test method: The thermal resistance of the far-infrared fiber thermal insulation fabrics obtained in the embodiments and comparative examples was measured using a YG-606G thermal resistance tester according to GB / T11048.

[0077] 3. Antistatic

[0078] Test method: The far-infrared fiber thermal insulation fabrics obtained in each embodiment and comparative example were tested for half-life using a H0110 / V2 antistatic decay tester according to GB / T12703.

[0079] Table 1 below shows the analysis results of the far infrared performance, warmth retention and antistatic properties of the far infrared fiber thermal insulation fabrics of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0080]

[0081] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the far-infrared fiber thermal insulation fabric prepared by the present invention has good far-infrared performance, thermal insulation and antistatic properties.

[0082] By comparison, the far-infrared radiation temperature rise data of Examples 1, 2, 3 and Comparative Examples 1 to 5 are not much different, which shows that the use of tourmaline as a filler can absorb the far-infrared rays released by the human body and improve the warmth retention of the far-infrared fiber thermal insulation fabric.

[0083] By comparison, the half-life of Examples 1, 2, and 3 is shorter than that of Comparative Example 1, which indicates that the polypyrrole conductive layer is deposited on the surface of the tourmaline powder by electrochemical polymerization, and the conjugated chain structure in the polypyrrole molecular structure allows electrons to move freely on the molecular chain, thereby enhancing the conductivity and improving the antistatic property of the far-infrared fiber thermal insulation fabric; at the same time, the doped 1-(2-chloroethyl)pyrrole can retain active chlorine atoms on the surface, undergo quaternary ammonium reaction and be grafted onto the polyacrylonitrile main chain, and the quaternary ammonium cation can neutralize and eliminate static electricity accumulation, thereby further improving the antistatic property of the far-infrared fiber thermal insulation fabric.

[0084] By comparison, the thermal resistance of Examples 1, 2, and 3 is higher than that of Comparative Example 3, which illustrates that polyvinyl pyrrolidone is used as a core layer dissolved in deionized water to form a hollow structure, increase a stable static air layer, and improve the warmth retention of the far-infrared fiber thermal insulation fabric.

[0085] Test Example 2:

[0086] 1. Antibacterial

[0087] Test method: According to GB / T20944, 0.75g of the sterilized fragments of the far-infrared fiber thermal insulation fabrics obtained in each embodiment and comparative example were inoculated with 3×10 5 coli at 100 CFU / mL, mix well and pour into the culture medium, culture at 37℃ for 24h, and record the number of viable bacteria W 1 (The number of viable bacteria in the control group without adding samples W 0 ), calculate the inhibition rate = (W 0 -W 1 ) / W 0 *100%.

[0088] 2. Mechanical properties

[0089] Test method: The far-infrared fibers obtained in each embodiment and comparative example were tested for breaking strength Q using a YG061F electronic single yarn strength tester according to GB / T3916. 0 .

[0090] 3. Anti-ultraviolet aging

[0091] Test method: Take the far-infrared fibers of the same size obtained in each embodiment and the comparative example, use a YG(B)611-Ⅳ type sunlight climate tester, age for 4 hours under 340nm wavelength ultraviolet light conditions, and test the breaking strength Q using a YG061F electronic single yarn strength tester in accordance with GB / T3916. 1 , calculate the anti-aging rate = Q 1 / Q 0 *100%.

[0092] Table 2 below shows the analysis results of the antibacterial properties, mechanical properties and anti-ultraviolet aging properties of the far-infrared fiber thermal insulation fabrics of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0093]

[0094] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 2, it can be found that the far-infrared fiber thermal insulation fabric prepared by the present invention has good antibacterial properties, mechanical properties and anti-ultraviolet aging properties.

[0095] By comparison, the antibacterial rate and breaking strength of Examples 1, 2, and 3 are higher than those of Comparative Example 1, which illustrates that the polypyrrole conductive layer is deposited on the surface of tourmaline powder by electrochemical polymerization, and the doped 1-(2-chloroethyl)pyrrole can retain active chlorine atoms on the surface, undergo quaternary ammonium reaction and be grafted on the main chain of polyacrylonitrile, and the formed quaternary ammonium salt structure can inhibit bacterial metabolism and enhance the antibacterial property of far-infrared fiber thermal insulation fabric; at the same time, quaternary ammonium cations can form electrostatic effects with iodide ions, enrich the cross-linked network, and improve the mechanical properties of the far-infrared fiber thermal insulation fabric.

[0096] By comparison, the antibacterial rates of Examples 1, 2, and 3 are higher than those of Comparative Example 2, indicating that the grafted borneol is obtained by the reaction of hydroxyl and acyl chloride, and is grafted onto the polyacrylonitrile main chain using ultraviolet light, introducing borneol and dimethylamino structures. The borneol structure can destroy bacterial cell membranes, interfere with DNA synthesis, and improve the antibacterial properties of far-infrared fiber thermal insulation fabrics.

[0097] By comparison, Examples 1, 2, and 3 have higher breaking strength and anti-aging rate than Comparative Example 4, which indicates that the viscose fiber is oxidized by sodium periodate to form aldehyde groups, and salicylaldehyde hydrazone is grafted by Schiff base reaction. The hydrogen bonds in the molecular structure of salicylaldehyde hydrazone are easily broken after being irradiated with ultraviolet light, which causes the electron cloud density to transfer to N, forming an unstable tautomer, converting the absorbed ultraviolet light energy into heat energy and then restoring it to the original stable hydrogen bond ground state, thereby enhancing the anti-aging property of the far-infrared fiber thermal insulation fabric; at the same time, the electron pairs of the imine group on the viscose fiber can coordinate with iodide ions to form a stable complex structure, enrich the cross-linked network, and improve the mechanical properties of the far-infrared fiber thermal insulation fabric.

[0098] By comparison, the antibacterial rate and breaking strength of Examples 1, 2, and 3 are higher than those of Comparative Example 5, which shows that the use of iodine ions for post-finishing can interfere with the synthesis of bacterial proteins and improve the antibacterial properties of the far-infrared fiber thermal insulation fabric; at the same time, iodine ions can form electrostatic effects with the nitrogen atoms of the quaternary ammonium salt on the main chain of polyacrylonitrile, and can also coordinate with the electron pairs of the imine group on the viscose fiber to form a stable complex structure, enrich the cross-linked network, and improve the mechanical properties of the far-infrared fiber thermal insulation fabric.

[0099] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a far-infrared fiber thermal insulation fabric, characterized in that: The method comprises the following preparation steps: (1) mixing tourmaline powder, pyrrole, 1-(2-chloroethyl)pyrrole, p-toluenesulfonic acid and deionized water, filtering after precipitation under a constant potential, washing, drying, grinding and sieving to obtain modified tourmaline powder; (2) Mix borneol, triethylamine and tetrahydrofuran, add 3-N,N-dimethylaminomethyl acryloyl chloride, heat and stir, filter, concentrate the filtrate, wash and extract, dry, filter and concentrate to obtain grafted borneol; (3) mixing polyacrylonitrile powder, grafted borneol, benzophenone and methanol, filtering after ultrasonic dispersion, extracting after ultraviolet light irradiation, washing and drying to obtain pre-modified polyacrylonitrile; The pre-modified polyacrylonitrile, modified tourmaline powder and anhydrous ethanol are mixed, filtered after reaction, washed and dried to obtain modified polyacrylonitrile; (4) mixing modified polyacrylonitrile, lithium chloride and N,N-dimethylformamide to obtain a fiber shell spinning solution; mixing polyvinyl pyrrolidone and N,N-dimethylformamide to obtain a fiber core spinning solution; coaxially spinning the fiber shell spinning solution and the fiber core spinning solution, coagulating and stretching them in an N,N-dimethylformamide aqueous solution, soaking them in deionized water, taking them out and drying them to obtain spun fibers; (5) Mixing sodium periodate and deionized water, adding hydrochloric acid solution to obtain a sodium periodate mixed solution; immersing viscose fiber in the sodium periodate mixed solution, ultrasonically dispersing, washing and drying to obtain pre-modified viscose fiber; mixing salicylaldehyde hydrazone and anhydrous ethanol to obtain a salicylaldehyde hydrazone treatment solution; immersing the pre-modified viscose fiber in the salicylaldehyde hydrazone treatment solution, taking out and hanging to dry, standing for reaction, washing and drying to obtain modified viscose fiber; (6) The spun fiber and the modified viscose fiber are mixed, and the mixture is subjected to blending, opening, rolling, carding, drawing and twisting to obtain far-infrared precursor fiber; potassium iodide and deionized water are mixed to obtain iodine ion finishing solution; the far-infrared precursor fiber is immersed in the iodine ion finishing solution, ultrasonically dispersed, allowed to stand for reaction, taken out, washed and dried to obtain far-infrared fiber; the far-infrared fiber is woven to obtain far-infrared fiber thermal insulation fabric.

2. The method for preparing a far-infrared fiber thermal insulation fabric according to claim 1, characterized in that: The specific preparation process of step (1) is as follows: tourmaline powder, pyrrole, 1-(2-chloroethyl)pyrrole, p-toluenesulfonic acid and deionized water are mixed in a mass ratio of 1: (0.1-0.2): (0.02-0.04): (0.7-0.8): (10-20), deposited at a constant potential of 0.7-0.9 V for 60-180 seconds, filtered, washed with deionized water for 3-5 times, dried at 30-40° C. for 11-13 hours, ground and sieved through 400-600 mesh to obtain modified tourmaline powder.

3. The method for preparing a far-infrared fiber thermal insulation fabric according to claim 1, characterized in that: The specific preparation process of step (2) is as follows: borneol, triethylamine and tetrahydrofuran are mixed in a mass ratio of 1: (0.97~0.99): (19~21), 3-N, N-dimethylaminomethyl acryloyl chloride (0.87~0.89 times the mass of borneol) is added at -1~1°C, the temperature is raised to 20~30°C, and the mixture is stirred at 300~500rpm for 8~12h and then filtered, the filtrate is concentrated, washed with deionized water for 3~5 times, extracted with dichloromethane for 2~4 times, dried with anhydrous sodium sulfate, filtered, and concentrated with a developing agent prepared by mixing petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain grafted borneol.

4. The method for preparing a far-infrared fiber thermal insulation fabric according to claim 1, characterized in that: The specific preparation process of step (3) is as follows: polyacrylonitrile powder, grafted borneol, benzophenone and methanol are mixed in a mass ratio of 1: (0.4-0.5): (0.01-0.03): (20-30), ultrasonicated at 45-55°C for 1-3 hours and then filtered, irradiated at a distance of 14-16 cm and 385-395 nm ultraviolet light for 25-35 minutes, extracted with acetone for 1-2 hours, washed with deionized water for 3-5 times, and dried at 50-60°C for 6-7 hours to obtain pre-modified polyacrylonitrile; Pre-modified polyacrylonitrile, modified tourmaline powder and anhydrous ethanol are mixed in a mass ratio of 1: (0.03-0.05): (55-65), stirred at 50-60°C and 400-500rpm for 7-9h, filtered, washed with anhydrous ethanol and deionized water for 3-5 times respectively, and dried at 55-65°C for 11-13h to obtain modified polyacrylonitrile.

5. The method for preparing a far-infrared fiber thermal insulation fabric according to claim 1, characterized in that: The specific preparation process of step (4) is as follows: modifying polyacrylonitrile, lithium chloride and N,N-dimethylformamide are mixed in a mass ratio of 1: (0.4-0.5): (5-6), and stirred at 75-85°C and 400-600 rpm for 11-13 hours to obtain a fiber shell spinning solution; polyvinyl pyrrolidone and N,N-dimethylformamide are mixed in a mass ratio of 1: (85-95), and ultrasonicated at 65-75°C for 4-6 hours to obtain a fiber core spinning solution; the fiber shell spinning solution and the fiber core spinning solution are allowed to stand at 55-65°C for 3 hours. The spinning was carried out for 5 to 45 minutes using a coaxial spinneret under the conditions of an inner diameter of the spinning needle of 0.5 to 0.7 mm, an outer diameter of the spinning needle of 1.1 to 1.3 mm, a shell layer flow rate of 9 to 11 mL / h, and a core layer flow rate of 0.9 to 1.1 mL / h. The fibers were coagulated in an aqueous N,N-dimethylformamide solution with a volume fraction of 85% to 95% at 45 to 55°C for 25 to 35 minutes, stretched 11 to 13 times, immersed in deionized water for 21 to 23 hours, taken out and dried at 20 to 30°C for 11 to 13 hours to obtain spun fibers.

6. The method for preparing a far-infrared fiber thermal insulation fabric according to claim 1, characterized in that: The specific preparation process of step (5) is as follows: sodium periodate and deionized water are mixed in a mass ratio of 1: (45-55), and a hydrochloric acid solution with a mass fraction of 5%-7% is added to adjust the pH to 3-5 to obtain a sodium periodate mixed solution; viscose fiber is immersed in the sodium periodate mixed solution, ultrasonicated at 60-70°C for 2-3 hours, washed with deionized water for 3-5 times after being taken out, and dried at 75-85°C to constant weight to obtain pre-modified viscose fiber; salicylaldehyde hydrazone and anhydrous ethanol are mixed in a mass ratio of 1: (30-40) to obtain a salicylaldehyde hydrazone treatment solution; the pre-modified viscose fiber is immersed in the salicylaldehyde hydrazone treatment solution for 1-2 hours, taken out and aired until no liquid drops within 5-15 seconds, allowed to stand at 75-85°C for 5-7 hours, washed with deionized water for 3-5 times, and dried at 60-70°C for 6-8 hours to obtain modified viscose fiber.

7. The method for preparing a far-infrared fiber thermal insulation fabric according to claim 1, characterized in that: The specific preparation process of step (6) is as follows: the spun fiber and the modified viscose fiber are mixed at a mass ratio of 1: (0.6~0.7), and the far-infrared precursor fiber with a fineness of 11.7~11.9tex and a twist of 80~100 twists / 10cm is obtained by blending, opening, rolling, carding, drawing and twisting; potassium iodide and deionized water are mixed at a mass ratio of 1: (190~210) to obtain an iodine ion finishing solution; the far-infrared precursor fiber is immersed in the iodine ion finishing solution, ultrasonicated for 5~15min, allowed to stand at 40~60℃ for 1~2h, taken out and washed with deionized water for 3~5 times, and dried at 60~70℃ for 6~8h to obtain the far-infrared fiber; the far-infrared fiber is knitted with a JH / SD-2-4 double-sided multi-track small circular knitting machine with a horizontal density of 60~70 rows / 5cm, a vertical density of 55~65 columns / 5cm, and a thickness of 230~250g / m 2 The double rib weave produces a far-infrared fiber warm fabric.

8. A far-infrared fiber thermal insulation fabric prepared according to the preparation method of the far-infrared fiber thermal insulation fabric according to any one of claims 1 to 7.

9. Use of the far-infrared fiber thermal insulation fabric according to claim 8 in home clothes.

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